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Sample records for allyl acetate allyl

  1. N-Allylation of amines with allyl acetates using chitosan-immobilized palladium

    Science.gov (United States)

    A simple procedure for N-Allylation of allyl Acetates has been developed using a biodegradable and easily recyclable heterogeneous chitosan-supported palladium catalyst. The general methodology, applicable to wide range of substrates, has sustainable features that include a ligan...

  2. Kinetic Resolution of Racemic and Branched Monosubstituted Allylic Acetates by a Ruthenium-Catalyzed Regioselective Allylic Etherification.

    Science.gov (United States)

    Shinozawa, Toru; Terasaki, Shou; Mizuno, Shota; Kawatsura, Motoi

    2016-07-01

    We demonstrated the kinetic resolution of racemic and branched monosubstituted allylic acetates by a ruthenium-catalyzed regioselective allylic etherification. The reaction was effectively catalyzed by the chiral ruthenium catalyst, which was generated by [RuCl2(p-cymene)]2 and (S,S)-iPr-pybox and a catalytic amount of TFA, and both the allylic etherification product and recovered allylic acetate were obtained as an enantiomerically enriched form with up to a 103 s value. PMID:27276556

  3. Temperature-controlled redox-neutral ruthenium(ii)-catalyzed regioselective allylation of benzamides with allylic acetates.

    Science.gov (United States)

    Manikandan, Rajendran; Jeganmohan, Masilamani

    2016-08-10

    Substituted aromatic amides reacted efficiently with allylic acetates in the presence of a cationic ruthenium complex in ClCH2CH2Cl at room temperature providing ortho allylated benzamides in a highly regioselective manner without any oxidant and base. The whole catalytic reaction occurred in a Ru(ii) oxidation state and thus the oxidation step is avoided. By tuning the reaction temperature, ortho allyl and vinyl benzamides were prepared exclusively. Later, ortho allyl and vinylated benzamides were converted into biologically useful six- and five-membered benzolactones in the presence of HCl. PMID:27456467

  4. Memory effects in palladium-catalyzed allylic Alkylations of 2-cyclohexen-1-yl acetate

    DEFF Research Database (Denmark)

    Svensen, Nina; Fristrup, Peter; Tanner, David Ackland;

    2007-01-01

    The objective of this work was to characterize the enantiospecificity of the allylic alkylation of enantioenriched 2-cyclohexen-1-yl acetate with the enolate ion of dimethyl malonate catalyzed by unsymmetrical palladium catalysts. The precatalysts employed were (eta(3)-allyl)PdLCl, where L...

  5. Solvent-Controlled, Tunable β-OAc and β-H Elimination in Rh(III)-Catalyzed Allyl Acetate and Aryl Amide Coupling via C-H Activation.

    Science.gov (United States)

    Dai, Huimin; Yu, Chao; Wang, Zihao; Yan, Hong; Lu, Changsheng

    2016-07-15

    The Heck reaction between arenes and allyl acetate has led to cinnamyl derivatives and allyl products depending on the regioselectivity of β-elimination. The regioselectivity can be controlled by the solvent in the Rh(III)-catalyzed arene-allyl acetate coupling via C-H activation: (1) in THF, cinnamyl derivatives via β-H elimination were generated; (2) in MeOH, allyl products via β-OAc elimination were produced. Both routes have advantages such as excellent γ-selectivity toward allyl acetate, good to excellent yields, and broad substrate scope. PMID:27351917

  6. Hydroxymethylation beyond Carbonylation: Enantioselective Iridium-Catalyzed Reductive Coupling of Formaldehyde with Allylic Acetates via Enantiotopic π-Facial Discrimination.

    Science.gov (United States)

    Garza, Victoria J; Krische, Michael J

    2016-03-23

    Chiral iridium complexes modified by SEGPHOS catalyze the 2-propanol-mediated reductive coupling of branched allylic acetates 1a-1o with formaldehyde to form primary homoallylic alcohols 2a-2o with excellent control of regio- and enantioselectivity. These processes, which rely on enantiotopic π-facial discrimination of σ-allyliridium intermediates, represent the first examples of enantioselective formaldehyde C-C coupling beyond aldol addition. PMID:26958737

  7. Allyl 4-hydroxyphenyl carbonate

    Directory of Open Access Journals (Sweden)

    Víctor Hugo Flores Ahuactzin

    2009-07-01

    Full Text Available The title molecule, C10H10O4, is a functionalized carbonate used in the synthetic route to organic glasses. The central CH fragment of the allyl group is disordered over two positions, with occupancies in a 0.758 (10:0.242 (10ratio. This disorder reflects the torsional flexibility of the oxygen–allyl group, although both disordered parts present the expected anticlinal conformation, with O—CH2—CH=CH2 torsion angles of −111 (2 and 119.1 (4°. The crystal structure is based on chains parallel to [010], formed by O...H—O hydrogen bonds involving hydroxyl and carbonyl groups as donors and acceptors, respectively. The molecular packing is further stabilized by two weak C—H...π contacts from the benzene ring of the asymmetric unit with two benzene rings of neighboring molecules.

  8. UV RADIATION INDUCED GRAFT COPOLYMERIZATION OF ALLYL ACETATE ONTO POLY(ETHYLENE TEREPHTHALATE) (PET) FILMS FOR FUEL CELL MEMBRANES

    Institute of Scientific and Technical Information of China (English)

    Mostak Ahmed; Mubarak A. Khan; Nazia Rahman; M. Anwar H. Khan

    2012-01-01

    Ultraviolet (UV)-induced graft copolymerization of allyl acetate (AA) monomer onto poly(ethylene terephthalate) (PET) films and the subsequent sulfonation on the monomer units in the grafting chain using chlorosulfonic acid (C1SO3H) were carried out to prepare proton exchange membranes (PEMs) for fuel cells.A maximum grafting value of 12.8% was found for 35 vol% allyl acetate after 3 h radiation time.Optimum concentration of ClSO3H was selected for the sulfonation reaction to be 0.05 mol/L based on the degree of sulfonation and the tensile strength studies of the membrane.The degree of sulfonation increased as the sulfonation reaction temperature and sulfonation time were increasing.The radiation grafting and the sulfonation have been confirmed by titrimetric and gravimetric analyses as well as FTIR spectroscopy.The maximum ion exchange capacity (IEC) of 0.04125 mmol g-1 was found at 12.1% degree of sulfonation and the maximum proton conductivity was found to be 0.035 S cm-1 at 30℃ and a relative humidity of 60%.The various physical and chemical properties of the PEMs such as water uptake,mechanical strength,thermal durability and oxidative stability were also studied.To investigate the suitability of the prepared membrane for fuel cell applications,its properties were compared with those of Nation 117.

  9. Allylation of Aromatic Aldehyde under Microwave Irradiation

    Institute of Scientific and Technical Information of China (English)

    ZHANG,Yu-Mei; JIA,Xue-Feng; WANG,Jin-Xian

    2004-01-01

    @@ Allylation of carbonyl compounds is one of the most interesting processes for the preparation of homoallylic alcohols. Over the past few decades, many reagents have been developed for such reactions[1~3]. In this paper, we first report allylic zinc reagent 1, which can be prepared from zinc dust and allyl bromide conveniently in THF, and reacted with aromatic aldehyde to give homo-allylic alcohols under microwave irradiation.

  10. The allylic chalcogen effect in olefin metathesis

    Directory of Open Access Journals (Sweden)

    Yuya A. Lin

    2010-12-01

    Full Text Available Olefin metathesis has emerged as a powerful tool in organic synthesis. The activating effect of an allylic hydroxy group in metathesis has been known for more than 10 years, and many organic chemists have taken advantage of this positive influence for efficient synthesis of natural products. Recently, the discovery of the rate enhancement by allyl sulfides in aqueous cross-metathesis has allowed the first examples of such a reaction on proteins. This led to a new benchmark in substrate complexity for cross-metathesis and expanded the potential of olefin metathesis for other applications in chemical biology. The enhanced reactivity of allyl sulfide, along with earlier reports of a similar effect by allylic hydroxy groups, suggests that allyl chalcogens generally play an important role in modulating the rate of olefin metathesis. In this review, we discuss the effect of allylic chalcogens in olefin metathesis and highlight its most recent applications in synthetic chemistry and protein modifications.

  11. The allylic chalcogen effect in olefin metathesis

    Science.gov (United States)

    Lin, Yuya A

    2010-01-01

    Summary Olefin metathesis has emerged as a powerful tool in organic synthesis. The activating effect of an allylic hydroxy group in metathesis has been known for more than 10 years, and many organic chemists have taken advantage of this positive influence for efficient synthesis of natural products. Recently, the discovery of the rate enhancement by allyl sulfides in aqueous cross-metathesis has allowed the first examples of such a reaction on proteins. This led to a new benchmark in substrate complexity for cross-metathesis and expanded the potential of olefin metathesis for other applications in chemical biology. The enhanced reactivity of allyl sulfide, along with earlier reports of a similar effect by allylic hydroxy groups, suggests that allyl chalcogens generally play an important role in modulating the rate of olefin metathesis. In this review, we discuss the effect of allylic chalcogens in olefin metathesis and highlight its most recent applications in synthetic chemistry and protein modifications. PMID:21283554

  12. Interplay of metal-allyl and metal-metal bonding in dimolybdenum allyl complexes.

    Energy Technology Data Exchange (ETDEWEB)

    Trovitch, R. J.; John, K. D.; Martin, R. L.; Obrey, S. J.; Sattelberger, A. P.; Scott, B. L.; Baker, R. T.; LANL; Univ. of Ottawa

    2009-01-01

    Addition of PMe{sub 3} to Mo{sub 2}(allyl){sub 4} afforded Mo{sub 2}(allyl){sub 4}(PMe{sub 3}){sub 2}, in which two of the allyl groups adopt an unprecedented {mu}{sub 2}-{eta}{sup 1}, {eta}{sup 3} bonding mode; theoretical studies elucidate the roles of the {sigma}- and {pi}-donor ligands in the interplay of metal-allyl and metal-metal bonding.

  13. Highly enantio- and diastereoselective allylic alkylation of Morita-Baylis-Hillman carbonates with allyl ketones

    KAUST Repository

    Tong, Guanghu

    2013-05-17

    The asymmetric allylic alkylation of Morita-Baylis-Hillman (MBH) carbonates with allyl ketones has been developed. The α-regioselective alkylation adducts, containing a hexa-1,5-diene framework with important synthetic value, were achieved in up to 83% yield, >99% ee, and 50:1 dr by using a commercially available Cinchona alkaloid as the catalyst. From the allylic alkylation adduct, a cyclohexene bearing two adjacent chiral centers was readily prepared. © 2013 American Chemical Society.

  14. Cationic ruthenium-cyclopentadienyl-diphosphine complexes as catalysts for the allylation of phenols with allyl alcohol: relation between structure and catalytic performance in O- vs. C-allylation

    NARCIS (Netherlands)

    van Rijn, J.A.; Lutz, M.; von Chrzanowski, L.S.; Spek, A.L.; Bouwman, E.; Drent, E.

    2009-01-01

    A new catalytic method has been investigated to obtain either O- or C-allylated phenolic products using allyl alcohol or diallyl ether as the allyl donor. With the use of new cationic ruthenium(II) complexes as catalyst, both reactions can be performed with good selectivity. Active cationic Ru(II) c

  15. Compound list: allyl alcohol [Open TG-GATEs

    Lifescience Database Archive (English)

    Full Text Available allyl alcohol AA 00010 ftp://ftp.biosciencedbc.jp/archive/open-tggates/LATEST/Human/in_vitro/allyl_alcohol....Human.in_vitro.Liver.zip ftp://ftp.biosciencedbc.jp/archive/open-tggates/LATEST/Rat/in_vitro/allyl_alcohol...dbc.jp/archive/open-tggates/LATEST/Rat/in_vivo/Liver/Repeat/allyl_alcohol.Rat.in_vivo.Liver.Repeat.zip ftp:/.../ftp.biosciencedbc.jp/archive/open-tggates/LATEST/Rat/in_vivo/Kidney/Single/allyl_alcohol.Rat.in_vivo.Kidney....Single.zip ftp://ftp.biosciencedbc.jp/archive/open-tggates/LATEST/Rat/in_vivo/Kidney/Repeat/allyl_alcohol.Rat.in_vivo.Kidney.Repeat.zip ...

  16. Magnetic silica supported palladium catalyst: synthesis of allyl aryl ethers in water

    Science.gov (United States)

    A simple and benign procedure for the synthesis of aryl allyl ethers has been developed using phenols, allyl acetates and magnetically recyclable silica supported palladium catalyst in water; performance of reaction in air and easy separation of the catalyst using an external mag...

  17. Enantioselective synthesis of fluorinated branched allylic compounds via Ir-catalyzed allylations of functionalized fluorinated methylene derivatives.

    Science.gov (United States)

    Zhang, Hongbo; Chen, Jiteng; Zhao, Xiao-Ming

    2016-08-14

    Enantioselective introduction of the functionalized monofluorinated methylenes into the allylic fragment under Ir catalysis has been realized, which gave the fluorinated branched allyl products in good to high yields with excellent regio- and enantioselectivities. PMID:27383920

  18. Allylic Nitro Compounds as Nitrite Donors

    OpenAIRE

    Chakrapani, Harinath; Gorczynski, Michael J.; King, S Bruce

    2006-01-01

    Allylic nitro compounds were synthesized and evaluated as organic sources of nitrite and nitric oxide. Unactivated allylic nitro compounds do not spontaneously release nitrite and nucleophile promoted nitrite release is slow. However, 2-(nitromethyl)-cyclohex-1-ene-3-one spontaneously dissociates in buffer (pH = 7.4) to release nitrite with a kobs = 1.6 × 10−5 s−1. In the presence of L-cysteine, this compound rapidly yields nitrite and reacts with hemoglobin similarly to sodium nitrite. Struc...

  19. Elementary reaction allyl radical with oxygen

    Institute of Scientific and Technical Information of China (English)

    DONG Feng; KONG Fanao

    2003-01-01

    The elementary reaction between allyl radical with oxygen molecule wasexperimentally investigated. The allyl radical was produced via laser photolysis of C3H5Br in gaseous phase. Nascent vibrational excited products HCO, CO2, CH3CHO and HCOOH were recorded by the time- resolved Fourier transform infrared spectroscopy. The product channels of C2H5+CO2, CH3CHO+HCO, and HCOOH + C2H3 have been identified. The vibrational populations of product CO2 are obtained by spectral simulation. A mechanism forming a series of three-membered ring-struc- ture intermediates is suggested.

  20. Palladium Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Engelin, Casper Junker; Fristrup, Peter

    2011-01-01

    The atom-efficiency of one of the most widely used catalytic reactions for forging C-C bonds, the Tsuji-Trost reaction, is limited by the need of preoxidized reagents. This limitation can be overcome by utilization of the recently discovered palladium-catalyzed C-H activation, the allylic C...

  1. Pressure Dependent Product Formation in the Photochemically Initiated Allyl + Allyl Reaction

    Directory of Open Access Journals (Sweden)

    Thomas Zeuch

    2013-11-01

    Full Text Available Photochemically driven reactions involving unsaturated radicals produce a thick global layer of organic haze on Titan, Saturn’s largest moon. The allyl radical self-reaction is an example for this type of chemistry and was examined at room temperature from an experimental and kinetic modelling perspective. The experiments were performed in a static reactor with a volume of 5 L under wall free conditions. The allyl radicals were produced from laser flash photolysis of three different precursors allyl bromide (C3H5Br, allyl chloride (C3H5Cl, and 1,5-hexadiene (CH2CH(CH22CHCH2 at 193 nm. Stable products were identified by their characteristic vibrational modes and quantified using FTIR spectroscopy. In addition to the (re- combination pathway C3H5+C3H5 → C6H10 we found at low pressures around 1 mbar the highest final product yields for allene and propene for the precursor C3H5Br. A kinetic analysis indicates that the end product formation is influenced by specific reaction kinetics of photochemically activated allyl radicals. Above 10 mbar the (re- combination pathway becomes dominant. These findings exemplify the specificities of reaction kinetics involving chemically activated species, which for certain conditions cannot be simply deduced from combustion kinetics or atmospheric chemistry on Earth.

  2. SYNTHESIS OF ALLYL PHENYL ETHER AND CLAISEN REARRANGEMENT

    Directory of Open Access Journals (Sweden)

    Gagik Torosyan

    2011-12-01

    Full Text Available It has been established the possibility for phenol allylation on natural zeolites and them analogs. Here is demonstrated the synthesis of allyl phenol, which has wide industrial applications. The offered method in comparison with the traditional methods has more advantages – higher selectivity, smaller material and power resources consumption. It has been obtained the mixture of allylating phenols (30% in general with allyl phenyl ether (1 with 80% yields. At 600 K is obtained allylphenyl ether, at 700 K beginning the formation of allyl phenols, which is the result of direct C-allylation of the aromatic ring. It has been investigated the possibility of Claisen rearrangement in the same conditions. All of that are established by gas-liquid chromatography and liquid chromatography data.

  3. Cp*Co(III)-Catalyzed Dehydrative C-H Allylation of 6-Arylpurines and Aromatic Amides Using Allyl Alcohols in Fluorinated Alcohols.

    Science.gov (United States)

    Bunno, Youka; Murakami, Nanami; Suzuki, Yudai; Kanai, Motomu; Yoshino, Tatsuhiko; Matsunaga, Shigeki

    2016-05-01

    Cp*Co(III)-catalyzed C-H allylation of various aromatic C-H bonds using allyl alcohols as allylating reagents is described. Improved reaction conditions using fluorinated alcohol solvents afforded efficient directed C-H allylation of 6-arylpurines, benzamides, and a synthetically useful Weinreb amide with good functional group compatibility.

  4. Resonance Raman spectrum of the allyl-d5 radical and the force field analysis of the allyl radical

    Science.gov (United States)

    Liu, Xianming; Getty, James D.; Kelly, Peter B.

    1993-08-01

    Resonance Raman spectra of the allyl-d5 radical have been obtained with excitation between 247 and 223 nm. Analysis of the spectra yields the first observation of fundamental frequencies, nu4, nu5, and nu7 and overtone frequencies 2nu9, 2nu10, and 2nu12. The new vibrational data are combined with previously observed frequencies of allyl-h5 and allyl-d5 radical to produce the force field analysis for the allyl radical. This study suggests reassignment of several previously observed infrared (IR) bands. Experimental frequencies and assignments for allyl-h5 and allyl-d5 are compared with results from ab initio calculations. Force constants obtained in the present work are compared with the force constants of other sp2 hybridization molecules such as benzene, allene, and ethylene.

  5. Toward Efficient Palladium-Catalyzed Allylic C-H Alkylation

    DEFF Research Database (Denmark)

    Jensen, Thomas; Fristrup, Peter

    2009-01-01

    Recent breakthroughs have proved that direct palladium (II)-catalyzed allylic C-H alkylation can be achieved. This new procedure shows that the inherent requirement for a leaving group in the Tsuji-Trost palladium-catalyzed allylic alkylation can be lifted. These initial reports hold great promise...

  6. Iridium-catalyzed allylic substitutions with cyclometalated phosphoramidite complexes bearing a dibenzocyclooctatetraene ligand: preparation of (π-allyl)Ir complexes and computational and NMR spectroscopic studies.

    Science.gov (United States)

    Raskatov, Jevgenij A; Jäkel, Mascha; Straub, Bernd F; Rominger, Frank; Helmchen, Günter

    2012-11-01

    (π-Allyl)Ir complexes derived from dibenzocyclooctatetraene and phosphoramidites by cyclometalation are effective catalysts for allylic substitution reactions of linear monosubstituted allylic carbonates. These catalysts provide exceptionally high degrees of regioselectivity and allow the reactions to be run under aerobic conditions. A series of (π-allyl)Ir complexes were prepared and characterized by X-ray crystal structure analyses. An allylic amination with aniline displayed different resting states depending on the presence of a strong base. DFT calculations were carried out on the mechanistic aspects of these reactions. The results suggest that for the (π-allyl)Ir complexes, the formation and reactions with nucleophiles proceed with comparable rates. PMID:23018807

  7. Zinc Mediated Tandem Fragmentation-Allylation of Methyl 5-Iodopentofuranosides

    DEFF Research Database (Denmark)

    Hyldtoft, Lene; Madsen, Robert

    1999-01-01

    In the presence of zinc and allyl bromide methyl 5-iodopentofuranosides undergo a tandem fragmentation alkylation to give functionalized dienes. These can undergo ring-closing olefin metathesis to produce cyclohexenes which on dihydroxylation give quercitols.......In the presence of zinc and allyl bromide methyl 5-iodopentofuranosides undergo a tandem fragmentation alkylation to give functionalized dienes. These can undergo ring-closing olefin metathesis to produce cyclohexenes which on dihydroxylation give quercitols....

  8. Scalable and sustainable electrochemical allylic C-H oxidation

    Science.gov (United States)

    Horn, Evan J.; Rosen, Brandon R.; Chen, Yong; Tang, Jiaze; Chen, Ke; Eastgate, Martin D.; Baran, Phil S.

    2016-05-01

    New methods and strategies for the direct functionalization of C-H bonds are beginning to reshape the field of retrosynthetic analysis, affecting the synthesis of natural products, medicines and materials. The oxidation of allylic systems has played a prominent role in this context as possibly the most widely applied C-H functionalization, owing to the utility of enones and allylic alcohols as versatile intermediates, and their prevalence in natural and unnatural materials. Allylic oxidations have featured in hundreds of syntheses, including some natural product syntheses regarded as “classics”. Despite many attempts to improve the efficiency and practicality of this transformation, the majority of conditions still use highly toxic reagents (based around toxic elements such as chromium or selenium) or expensive catalysts (such as palladium or rhodium). These requirements are problematic in industrial settings; currently, no scalable and sustainable solution to allylic oxidation exists. This oxidation strategy is therefore rarely used for large-scale synthetic applications, limiting the adoption of this retrosynthetic strategy by industrial scientists. Here we describe an electrochemical C-H oxidation strategy that exhibits broad substrate scope, operational simplicity and high chemoselectivity. It uses inexpensive and readily available materials, and represents a scalable allylic C-H oxidation (demonstrated on 100 grams), enabling the adoption of this C-H oxidation strategy in large-scale industrial settings without substantial environmental impact.

  9. Transition metal catalysed Grignard-like allylic activation across tetragonal tin(II) oxide

    Indian Academy of Sciences (India)

    Pradipta Sinha; Moloy Banerjee; Abhijit Kundu; Sujit Roy

    2002-08-01

    The reaction of allyl halide and a carbonyl compound under the aegis of tetragonal tin(II) oxide and catalytic 8, 10 metal complexes provides the corresponding homoallylic alcohol, via a novel allyl tin intermediate.

  10. Structurally defined allyl compounds of main group metals: coordination and reactivity.

    Science.gov (United States)

    Lichtenberg, Crispin; Okuda, Jun

    2013-05-10

    Organometallic allyl compounds are important as allylation reagents in organic synthesis, as polymerization catalysts, and as volatile metal precursors in material science. Whereas the allyl chemistry of synthetically relevant transition metals such as palladium and of the lanthanoids is well-established, that of main group metals has been lagging behind. Recent progress on allyl complexes of Groups 1, 2, and 12-16 now provides a more complete picture. This is based on a fundamental understanding of metal-allyl bonding interactions in solution and in the solid state. Furthermore, reactivity trends have been rationalized and new types of allyl-specific reactivity patterns have been uncovered. Key features include 1) the exploitation of the different types of metal-allyl bonding (highly ionic to predominantly covalent), 2) the use of synergistic effects in heterobimetallic compounds, and 3) the adjustment of Lewis acidity by variation of the charge of allyl compounds.

  11. A convenient procedure for the synthesis of allyl and benzyl ethers from alcohols and phenols

    Indian Academy of Sciences (India)

    H Surya Prakash Rao; S P Senthilkumar

    2001-06-01

    Allyl and benzyl ethers of alcohols can be prepared conveniently and in high yield with allyl and benzyl bromide in the presence of solid potassium hydroxide without use of any solvent. Phenols can be converted to allyl ethers but are inert to benzylation under above conditions.

  12. 40 CFR 721.7000 - Polymer of disodium maleate, allyl ether, and ethylene oxide.

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Polymer of disodium maleate, allyl... New Uses for Specific Chemical Substances § 721.7000 Polymer of disodium maleate, allyl ether, and... substance identified generically as a polymer of disodium maleate, allyl ether, and ethylene oxide...

  13. Iridium-Catalyzed Selective Isomerization of Primary Allylic Alcohols.

    Science.gov (United States)

    Li, Houhua; Mazet, Clément

    2016-06-21

    This Account presents the development of the iridium-catalyzed isomerization of primary allylic alcohols in our laboratory over the past 8 years. Our initial interest was driven by the long-standing challenge associated with the development of a general catalyst even for the nonasymmetric version of this seemingly simple chemical transformation. The added value of the aldehyde products and the possibility to rapidly generate molecular complexity from readily accessible allylic alcohols upon a redox-economical isomerization reaction were additional sources of motivation. Certainly influenced by the success story of the related isomerization of allylic amines, most catalysts developed for the selective isomerization of allylic alcohols were focused on rhodium as a transition metal of choice. Our approach has been based on the commonly accepted precept that hydrogenation and isomerization are often competing processes, with the latter being usually suppressed in favor of the former. The cationic iridium complexes [(Cy3P)(pyridine)Ir(cod)]X developed by Crabtree (X = PF6) and Pfaltz (X = BArF) are usually considered as the most versatile catalysts for the hydrogenation of allylic alcohols. Using molecular hydrogen to generate controlled amounts of the active form of these complexes but performing the reaction in the absence of molecular hydrogen enabled deviation from the typical hydrogenation manifold and favored exclusively the isomerization of allylic alcohols into aldehydes. Isotopic labeling and crossover experiments revealed the intermolecular nature of the process. Systematic variation of the ligand on the iridium center allowed us to identify the structural features beneficial for catalytic activity. Subsequently, three generations of chiral catalysts have been investigated and enabled us to reach excellent levels of enantioselectivity for a wide range of 3,3-disubstituted aryl/alkyl and alkyl/alkyl primary allylic alcohols leading to β-chiral aldehydes. The

  14. Highly Enantioselective Formation of α-Allyl-α-Arylcyclopentanones via Pd-Catalysed Decarboxylative Asymmetric Allylic Alkylation.

    Science.gov (United States)

    Akula, Ramulu; Doran, Robert; Guiry, Patrick J

    2016-07-11

    A highly enantioselective Pd-catalysed decarboxylative asymmetric allylic alkylation of cyclopentanone derived α-aryl-β-keto esters employing the (R,R)-ANDEN-phenyl Trost ligand has been developed. The product (S)-α-allyl-α-arylcyclopentanones were obtained in excellent yields and enantioselectivities (up to >99.9 % ee). This represents one of the most highly enantioselective formations of an all-carbon quaternary stereogenic center reported to date. This reaction was demonstrated on a 4.0 mmol scale without any deterioration of enantioselectivity and was exploited as the key enantioselective transformation in an asymmetric formal synthesis of the natural product (+)-tanikolide. PMID:27191198

  15. Sulfonium-based Ionic Liquids Incorporating the Allyl Functionality

    Directory of Open Access Journals (Sweden)

    Paul J. Dyson

    2007-04-01

    Full Text Available A series of sulfonium halides bearing allyl groups have been prepared andcharacterized. Anion metathesis with Li[Tf2N] and Ag[N(CN2] resulted in sulfonium-basedionic liquids which exhibit low viscosities at room temperature. The solid state structure ofone of the halide salts was determined by single crystal X-ray diffraction.

  16. Electrochemical Allylic Oxidation of Olefins: Sustainable and Safe.

    Science.gov (United States)

    Waldvogel, Siegfried R; Selt, Maximilian

    2016-10-01

    The power you're supplying: With the application of an optimized electrochemical approach, the allylic oxidation of olefins, which is an important C-H activation process that provides access to enones, becomes a sustainable, versatile, and potent key reaction for organic synthesis.

  17. Branching Out: Rhodium-Catalyzed Allylation with Alkynes and Allenes.

    Science.gov (United States)

    Koschker, Philipp; Breit, Bernhard

    2016-08-16

    We present a new and efficient strategy for the atom-economic transformation of both alkynes and allenes to allylic functionalized structures via a Rh-catalyzed isomerization/addition reaction which has been developed in our working group. Our methodology thus grants access to an important structural class valued in modern organic chemistry for both its versatility for further functionalization and the potential for asymmetric synthesis with the construction of a new stereogenic center. This new methodology, inspired by mechanistic investigations by Werner in the late 1980s and based on preliminary work by Yamamoto and Trost, offers an attractive alternative to other established methods for allylic functionalization such as allylic substitution or allylic oxidation. The main advantage of our methodology consists of the inherent atom economy in comparison to allylic oxidation or substitution, which both produce stoichiometric amounts of waste and, in case of the substitution reaction, require prefunctionalization of the starting material. Starting out with the discovery of a highly branched-selective coupling reaction of carboxylic acids with terminal alkynes using a Rh(I)/DPEphos complex as the catalyst system, over the past 5 years we were able to continuously expand upon this chemistry, introducing various (pro)nucleophiles for the selective C-O, C-S, C-N, and C-C functionalization of both alkynes and the double-bond isomeric allenes by choosing the appropriate rhodium/bidentate phosphine catalyst. Thus, valuable compounds such as branched allylic ethers, sulfones, amines, or γ,δ-unsaturated ketones were successfully synthesized in high yields and with a broad substrate scope. Beyond the branched selectivity inherent to rhodium, many of the presented methodologies display additional degrees of selectivity in regard to regio-, diastereo-, and enantioselective transformations, with one example even proceeding via a dynamic kinetic resolution. Many advances

  18. ION EXCHANGE SUBSTANCES BY SAPONIFICATION OF ALLYL PHOSPHATE POLYMERS

    Science.gov (United States)

    Kennedy, J.

    1959-04-14

    An ion exchange resin having a relatively high adsorption capacity tor uranyl ion as compared with many common cations is reported. The resin comprises an alphyl-allyl hydrogen phosphate polymer, the alphyl group being either allyl or a lower alkyl group having up to 5 carbon atoins. The resin is prepared by polymerizing compounds such as alkyl-diallyl phosphate and triallyl phosphate in the presence of a free radical generating substance and then partially hydrolyzing the resulting polymer to cause partial replacement of organic radicals by cations. A preferred free radical gencrating agent is dibenzoyl peroxide. The partial hydrolysis is brought about by refluxing the polymer with concentrated aqueous NaOH for three or four hours.

  19. Radiation initiated copolymerization of allyl alcohol with acrylonitrile

    Energy Technology Data Exchange (ETDEWEB)

    Solpan, Dilek; Guven, Olgun [Hacettepe Univ., Ankara (Turkey). Dept. of Chemistry

    1996-07-01

    Copolymerization of allyl alcohol (AA) with acrylonitrile (AN) initiated by {gamma}-rays has been investigated to determine the respective reactivity ratios. Three different experimental techniques, namely Fourier Transform Infrared (FTIR), Ultraviolet (UV/vis) and elemental analysis (EA) have been used for the determination of copolymer compositions. Fineman-Ross (FR), Kelen-Tudos (KT), Non-Linear Least Square (NLLS) Analysis and Q-e methods have been applied to the three sets of experimental data. It has been concluded that data obtained from elemental analysis as applied to the Non-Linear Least Square approach gave the most reliable reactivity ratios as 2.09 and 0.40 for acrylonitrile and allyl alcohol, respectively. (Author).

  20. Radiation initiated copolymerization of allyl alcohol with acrylonitrile

    Science.gov (United States)

    Şolpan, Dilek; Güven, Olgun

    1996-07-01

    Copolymerization of allyl alcohol (AA) with acrylonitrile (AN) initiated by γ-rays has been investigated to determine the respective reactivity ratios. Three different experimental techniques, namely Fourier Transform Infrared (FTIR), Ultraviolet (UV/vis) and elemental analysis (EA) have been used for the determination of copolymer compositions. Fineman-Ross (FR), Kelen-Tüdös (KT), Non-Linear Least Square (NLLS) Analysis and Q-e methods have been applied to the three sets of experimental data. It has been concluded that data obtained from elemental analysis as applied to the Non-Linear Least Square approach gave the most reliable reactivity ratios as 2.09 and 0.40 for acrylonitrile and allyl alcohol, respectively.

  1. Enantioconvergent synthesis by sequential asymmetric Horner-Wadsworth-Emmons and palladium-catalyzed allylic substitution reactions

    DEFF Research Database (Denmark)

    Pedersen, Torben Møller; Hansen, E. Louise; Kane, John;

    2001-01-01

    A new method for enantioconvergent synthesis has been developed. The strategy relies on the combination of an asymmetric Horner-Wadsworth-Emmons (HWE) reaction and a palladium-catalyzed allylic substitution. Different $alpha@-oxygen-substituted, racemic aldehydes were initially transformed by...... asymmetric HWE reactions into mixtures of two major $alpha@,$beta@-unsaturated esters, possessing opposite configurations at their allylic stereocenters as well as opposite alkene geometry. Subsequently, these isomeric mixtures of alkenes could be subjected to palladium-catalyzed allylic substitution...

  2. Gold(I)-Assisted α-Allylation of Enals and Enones with Alcohols.

    Science.gov (United States)

    Mastandrea, Marco Michele; Mellonie, Niall; Giacinto, Pietro; Collado, Alba; Nolan, Steven P; Miscione, Gian Pietro; Bottoni, Andrea; Bandini, Marco

    2015-12-01

    The intermolecular α-allylation of enals and enones occurs by the condensation of variously substituted allenamides with allylic alcohols. Cooperative catalysis by [Au(ItBu)NTf2] and AgNTf2 enables the synthesis of a range of densely functionalized α-allylated enals, enones, and acyl silanes in good yield under mild reaction conditions. DFT calculations support the role of an α-gold(I) enal/enone as the active nucleophilic species.

  3. Palladium(0)-Catalyzed Intermolecular Allylic Dearomatization of Indoles by a Formal [4+2] Cycloaddition Reaction.

    Science.gov (United States)

    Gao, Run-Duo; Xu, Qing-Long; Zhang, Bo; Gu, Yiting; Dai, Li-Xin; You, Shu-Li

    2016-08-01

    Bridged indoline derivatives were synthesized by an intermolecular Pd-catalyzed allylic dearomatization reaction of substituted indoles. The reaction between indoles and allyl carbonates bearing a nucleophilic alcohol side-chain proceeds in a cascade fashion, providing bridged indolines in excellent enantioselectivity. PMID:27321285

  4. Allyl sulphides in olefin metathesis: catalyst considerations and traceless promotion of ring-closing metathesis.

    Science.gov (United States)

    Edwards, Grant A; Culp, Phillip A; Chalker, Justin M

    2015-01-11

    Allyl sulphides are reactive substrates in ruthenium-catalysed olefin metathesis reactions, provided each substrate is matched with a suitable catalyst. A profile of catalyst activity is described, along with the first demonstration of allyl sulphides as traceless promoters in relayed ring-closing metathesis reactions.

  5. Pd-catalyzed cascade allylic alkylation and dearomatization reactions of indoles with vinyloxirane.

    Science.gov (United States)

    Gao, Run-Duo; Xu, Qing-Long; Dai, Li-Xin; You, Shu-Li

    2016-09-14

    We have developed Pd-catalyzed intermolecular Friedel-Crafts-type allylic alkylation and allylic dearomatization reactions of substituted indoles bearing a nucleophilic group with vinyloxirane, providing an efficient method to synthesize structurally diverse tetrahydrocarboline and spiroindolenine derivatives under mild conditions. PMID:27511802

  6. Allyl sulphides in olefin metathesis: catalyst considerations and traceless promotion of ring-closing metathesis.

    Science.gov (United States)

    Edwards, Grant A; Culp, Phillip A; Chalker, Justin M

    2015-01-11

    Allyl sulphides are reactive substrates in ruthenium-catalysed olefin metathesis reactions, provided each substrate is matched with a suitable catalyst. A profile of catalyst activity is described, along with the first demonstration of allyl sulphides as traceless promoters in relayed ring-closing metathesis reactions. PMID:25410944

  7. Green Synthesis and Regioselective Control of Sn/I2 Mediated Allylation of Carbonyl Compounds with Crotyl Halide in Water

    Institute of Scientific and Technical Information of China (English)

    ZHANG,Yan; ZHA,Zhang-Gen; ZHOU,Yu-Qing; WANG,Zhi-Yong

    2004-01-01

    @@ Barbier-type carbonyl allylation is particularly useful due to ease of operation and the availability and tractability of allylic substrates,[1] Metals such as indium, zinc and tin are often used as the mediator. Here we present a green approach toward the synthesis, that is, Sn/I2 mediated allylation of carbonyl compounds with crotyl halide in water.

  8. Polymer-Supported Chiral Monodentate Phosphoramidites in Palladium-Catalyzed Allylic Alkylation Reactions

    Institute of Scientific and Technical Information of China (English)

    JIANG,Zhi-Dong; MENG,Zhao-Hai

    2007-01-01

    A new and simple method for immobilization of monodentate chiral ligand on the cheap resin has been developed.A series of resin-immobilized phosphoramidite ligands based on BINOL and TADDOL backbones have been synthesized and characterized with gel-phase NMR.The immobilized ligands have been applied to the Pd-catalyzed asymmetric allylic alkylation of 1,3-diphenyl-2-propenyl acetate.Among four ligands,the supported bulky monodentate phosphoramidite ligand based on TADDOL backbone afforded the chiral product with ee up to 65%;moreover,this ligand could be recycled for 3 times without substantial decrease of the conversion and ee.

  9. Mechanistic Investigation of Palladium–Catalyzed Allylic C–H Activation

    DEFF Research Database (Denmark)

    Engelin, Casper Junker; Jensen, Thomas; Rodríguez-Rodríguez, Sergio;

    2013-01-01

    The mechanism for the palladium–catalyzed allylic C–H activation was investigated using a combination of experimental and theoretical methods. A Hammett study revealed a buildup of a partial negative charge in the rate-determining step, while determination of the kinetic isotope effect (KIE...... acetate acts as a base in an intramolecular fashion during the C–H activation step. The re-oxidation of palladium was found to reach a similar energy level as that of the C–H activation. Calculations of turnover frequencies (TOF) for the entire catalytic cycle for the C–H alkylation were used to acquire a...

  10. Construction of an Asymmetric Quaternary Carbon Center via Allylation of Hydrazones

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Jin Bum; Satyender, Apuri; Jang, Doo Ok [Yonsei Univ., Wonju (Korea, Republic of)

    2013-11-15

    Asymmetric indium-mediated allylation of imine derivatives bearing a chiral auxiliary is a reliable strategy for the synthesis of chiral homoallylic amines. Various techniques for indium-mediated stereoselective allylation of imines bearing a chiral auxiliary have been reported. In 1997 Loh and co-workers reported indium-mediated allylation with imines derived from L-valine methyl ester. Since then, many forms of indium-mediated allylation bearing a chiral auxiliary have been reported, including imines derived from (S)-valinol, (R)-phenylglycinol, uracil, (R)-phenylglycinol methyl ester, N-tert-butanesufinamide, and (1R,2S)-1-amino-2-indanol. However, the synthesis of chiral auxiliaries often involves a laborious multi-step synthesis with expensive reagents. Therefore, the development of readily accessible chiral auxiliaries for asymmetric indium-mediated all-ylation is in high demand.

  11. Enantioselective functionalization of allylic C-H bonds following a strategy of functionalization and diversification.

    Science.gov (United States)

    Sharma, Ankit; Hartwig, John F

    2013-11-27

    We report the enantioselective functionalization of allylic C-H bonds in terminal alkenes by a strategy involving the installation of a temporary functional group at the terminal carbon atom by C-H bond functionalization, followed by the catalytic diversification of this intermediate with a broad scope of reagents. The method consists of a one-pot sequence of palladium-catalyzed allylic C-H bond oxidation under neutral conditions to form linear allyl benzoates, followed by iridium-catalyzed allylic substitution. This overall transformation forms a variety of chiral products containing a new C-N, C-O, C-S, or C-C bond at the allylic position in good yield with a high branched-to-linear selectivity and excellent enantioselectivity (ee ≤97%). The broad scope of the overall process results from separating the oxidation and functionalization steps; by doing so, the scope of nucleophile encompasses those sensitive to direct oxidative functionalization. The high enantioselectivity of the overall process is achieved by developing an allylic oxidation that occurs without acid to form the linear isomer with high selectivity. These allylic functionalization processes are amenable to an iterative sequence leading to (1,n)-functionalized products with catalyst-controlled diastereo- and enantioselectivity. The utility of the method in the synthesis of biologically active molecules has been demonstrated.

  12. A Facile and Mild Synthesis of Trisubstituted Allylic Sulfones from Morita-Baylis-Hillman Carbonates

    Directory of Open Access Journals (Sweden)

    Lin Jiang

    2015-05-01

    Full Text Available An efficient and catalyst-free synthesis of trisubstituted allylic sulfones through an allylic sulfonylation reaction of Morita-Baylis-Hillman (MBH carbonates with sodium sulfinates has been developed. Under the optimized reaction conditions, a series of trisubstituted allylic sulfones were rapidly prepared in good to excellent yields (71%–99% with good to high selectivity (Z/E from 79:21 to >99:1. Compared with known synthetic methods, the current protocol features mild reaction temperature, high efficiency and easily available reagents.

  13. Studies on the Synthesis of Morphinan Alkaloid: Preparation of the Key Allylic Silyl Ether Precursor

    Institute of Scientific and Technical Information of China (English)

    Zhen Lei SONG; Yong Qiang TU; Shuan Hu GAO; Yi Jun JIANG; Shu Yu ZHANG

    2005-01-01

    A convergent strategy to the key allylic silyl ether precursor 4 in our synthetic efforts toward morphinan alkaloid is presented. The vital step is the selective 1,2-addition of the organocerium agent of 6 to ketene 5.

  14. Facile synthesis of allyl resinate monomer in an aqueous solution under microwave irradiation

    Indian Academy of Sciences (India)

    Yanju Lu; Mixia Wang; Zhendong Zhao; Yuxiang Chen; Shichao Xu; Jing Wang; Liangwu Bi

    2015-07-01

    We have developed a facile method for production of allyl resinate monomer (allyl rosin ester) via a phase transfer reaction under microwave irradiation. The synthesis of allyl resinate was conducted using allyl chloride and sodium resinate as starting materials in aqueous solution at 50°C for 30 min with a yield of 94.7%, which is 20% higher than conventional heating method. The products precipitated spontaneously from the aqueous phase after reaction, which significantly facilitated the subsequent separation of monomer products. The synthesized monomer product appeared as a viscous liquid, with a viscosity of 460 mPa·s at 25°C and a density of 1.0469 g/cm3. The physical and chemical properties suggested that the synthesized monomer has great potential for free radical polymerization.

  15. Synthesis of acrylic and allylic bifunctional cross-linking monomers derived from PET waste

    Science.gov (United States)

    Cruz-Aguilar, A.; Herrera-González, A. M.; Vázquez-García, R. A.; Navarro-Rodríguez, D.; Coreño, J.

    2013-06-01

    An acrylic and two novel allylic monomers synthesized from bis (hydroxyethyl) terephthalate, BHET, are reported. This was obtained by glycolysis of post-consumer PET with boiling ethylene glycol. The bifunctional monomer bis(2-(acryloyloxy)ethyl) terephthalate was obtained from acryloyl chloride, while the allylic monomers 2-(((allyloxi)carbonyl)oxy) ethyl (2-hydroxyethyl) terephthalate and bis(2-(((allyloxi)carbonyl)oxy)ethyl) terephthalate, from allyl chloroformate. Cross-linking was studied in bulk polymerization using two different thermal initiators. Monomers were analyzed by means of 1H NMR and the cross-linked polymers by infrared spectroscopy. Gel content higher than 90% was obtained for the acrylic monomer. In the case of the mixture of the allylic monomers, the cross-linked polymer was 80 % using BPO initiator, being this mixture 24 times less reactive than the acrylic monomer.

  16. Total Synthesis of Clavosolide A via Tandem Allylic Oxidation/Oxa-Conjugate Addition Reaction

    Science.gov (United States)

    Baker, Joseph B.; Kim, Hyoungsu; Hong, Jiyong

    2015-01-01

    The tandem allylic oxidation/oxa-conjugate addition reaction promoted by the gem-disubstituent effect in conjunction with the NHC-mediated oxidative esterification was explored for the facile synthesis of clavosolide A. PMID:26236051

  17. Crystal structure of (E)-4-(acet­oxy­imino)-N-allyl-3-isopropyl-2,6-di­phenyl­piperi­dine-1-carbo­thio­amide

    OpenAIRE

    Mohandas, T; Krishnan, K. Gokula; Balamurugan, S.; Harrison, William T. A.; Thanikachalam, V.; Sakthivel, P.

    2015-01-01

    The title compound, C26H31N3O2S, crystallizes with two mol­ecules (A and B) in the asymmetric unit. In each case, the piperidine ring exists in a twist-boat conformation. The dihedral angle between the phenyl rings is 46.16 (12)° in mol­ecule A and 44.95 (12)° in mol­ecule B. In both mol­ecules, the allyl side chain is disordered over two orientations in a 0.649 (9):0.351 (9) ratio for mol­ecule A and 0.826 (10):0.174 (10) ratio for mol­ecule B. In the crystal, neither mol­ecule forms a hydro...

  18. Highly selective palladium–benzothiazole carbene-catalyzed allylation of active methylene compounds under neutral conditions

    OpenAIRE

    Antonio Monopoli; Pietro Cotugno; Zambonin, Carlo G.; Francesco Ciminale; Angelo Nacci

    2015-01-01

    The Pd–benzothiazol-2-ylidene complex I was found to be a chemoselective catalyst for the Tsuji–Trost allylation of active methylene compounds carried out under neutral conditions and using carbonates as allylating agents. The proposed protocol consists in a simplified procedure adopting an in situ prepared catalyst from Pd2dba3 and 3-methylbenzothiazolium salt V as precursors. A comparison of the performance of benzothiazole carbene with phosphanes and an analogous imidazolium carbene ligand...

  19. Selective epoxidation of allylic alcohols with a titania-silica aerogel

    Energy Technology Data Exchange (ETDEWEB)

    Dusi, M.; Mallat, T.; Baiker, A. [Lab. of Technical Chemistry, Swiss Federal Inst. of Technology, ETH-Zentrum, Zuerich (Switzerland)

    1998-12-31

    An amorphous mesoporous titania-silica aerogel (20 wt%TiO{sub 2} - 80 wt% SiO{sub 2}) and tert.-butylhydroperoxide (TBHP) have been used for the epoxidation of various allylic alcohols. Allylic alcohols possessing an internal double bond were more reactive than those with a terminal C=C bond. Epoxide selectivities could be improved by addition of (basic) zeolite 4 A and NaHCO{sub 3} to the reaction mixture. (orig.)

  20. Palladium-Catalyzed Dearomative Allylic Alkylation of Indoles with Alkynes To Synthesize Indolenines with C3-Quarternary Centers.

    Science.gov (United States)

    Gao, Shang; Wu, Zijun; Fang, Xinxin; Lin, Aijun; Yao, Hequan

    2016-08-01

    A palladium-catalyzed dearomative allylic alkylation of indoles with alkynes to construct indolenines with C3-quarternary centers was reported. The in situ formed arylallene intermediate omitted the need to install leaving groups on the allylic compounds and employ extra oxidants to oxidize the allylic C-H bonds. The reaction exhibited good functional group tolerance and high atom economy. Moreover, the reaction was further expanded to synthesize pyrroloindolines and furanoindolines. PMID:27442021

  1. Molecular cytotoxicity mechanisms of allyl alcohol (acrolein) in budding yeast.

    Science.gov (United States)

    Golla, Upendarrao; Bandi, Goutham; Tomar, Raghuvir S

    2015-06-15

    Allyl alcohol (AA) is one of the environmental pollutants used as a herbicide and industrial chemical. AA undergoes enzymatic oxidation in vivo to form Acrolein (Acr), a highly reactive and ubiquitous environmental toxicant. The exposure to AA/Acr has detrimental effects on cells and is highly fatal. In corroboration to the current literature describing AA/Acr toxicity, this study aimed to investigate the molecular cytotoxicity mechanisms of AA/Acr using budding yeast as a eukaryotic model organism. Genome-wide transcriptome analysis of cells treated with a sublethal dose of AA (0.4 mM) showed differential regulation of approximately 30% of the yeast genome. Functional enrichment analysis of the AA transcriptome revealed that genes belong to diverse cellular processes including the cell cycle, DNA damage repair, metal homeostasis, stress response genes, ribosomal biogenesis, metabolism, meiosis, ubiquitination, cell morphogenesis, and transport. Moreover, we have identified novel molecular targets of AA/Acr through genetic screening, which belongs to oxidative stress, DNA damage repair, iron homeostasis, and cell wall integrity. This study also demonstrated the epigenetic basis of AA/Acr toxicity mediated through histone tails and chromatin modifiers. Interestingly, our study disclosed the use of pyrazole and ethanol as probable antidotes for AA intoxication. For the first time, this study also demonstrated the reproductive toxicity of AA/Acr using the yeast gametogenesis (spermatogenesis) model. Altogether, this study unravels the molecular mechanisms of AA/Acr cytotoxicity and facilitates the prediction of biomarkers for toxicity assessment and therapeutic approaches. PMID:25919230

  2. Rapid formation of β-allyl substituted isotetronic acid derivatives via Claisen rearrangement using a microfludic device

    Institute of Scientific and Technical Information of China (English)

    Xia Ping Ma; Zhi Ming Li; Quan Rui Wang

    2011-01-01

    The thermal Claisen rearrangement of O-allyl substituted isotetronic acids 1 was successfully carried out within a glass microreactor operated with temperature at 150 ℃ and a flow rate of 1 mL/h. The strategy provides an efficient alternative way to β-allyl substituted isotetronic acid derivatives 2 in high yields with much accelerated reaction speed.

  3. Dicyano-Functionalized MCM-41-Supported Palladium Complex as An Efficient Catalyst for Allylation of Aldehydes and Ketones

    Institute of Scientific and Technical Information of China (English)

    ZHAO Hong; CAI Ming-Zhong

    2006-01-01

    Dicyano-functionalized MCM-41-supported palladium complex was prepared from dicyano-functionalized MCM-41 and palladium chloride. This complex exhibited high catalytic activity in the allylation of aldehydes and ketones with allylic chlorides in the presence of SnCl2. This polymeric palladium complex can be recovered and reused without noticeable loss of activity.

  4. How phenyl makes a difference: mechanistic insights into the ruthenium( ii )-catalysed isomerisation of allylic alcohols

    KAUST Repository

    Manzini, Simone

    2013-10-16

    [RuCl(η5-3-phenylindenyl)(PPh3)2] (1) has been shown to be a highly active catalyst for the isomerisation of allylic alcohols to the corresponding ketones. A variety of substrates undergo the transformation, typically with 0.25-0.5 mol% of catalyst at room temperature, outperforming commonly-used complexes such as [RuCl(Cp)(PPh3) 2] and [RuCl(η5-indenyl)(PPh3) 2]. Mechanistic experiments and density functional theory have been employed to investigate the mechanism and understand the effect of catalyst structure on reactivity. These investigations suggest a oxo-π-allyl mechanism is in operation, avoiding intermediate ruthenium hydride complexes and leading to a characteristic 1,3-deuterium shift. Important mechanistic insights from DFT and experiments also allowed for the design of a protocol that expands the scope of the transformation to include primary allylic alcohols. © 2013 The Royal Society of Chemistry.

  5. Kinetic Studies that Evaluate the Solvolytic Mechanisms of Allyl and Vinyl Chloroformate Esters

    Directory of Open Access Journals (Sweden)

    Malcolm J. D'Souza

    2013-04-01

    Full Text Available At 25.0 °C the specific rates of solvolysis for allyl and vinyl chloroformates have been determined in a wide mix of pure and aqueous organic mixtures. In all the solvents studied, vinyl chloroformate was found to react significantly faster than allyl chloroformate. Multiple correlation analyses of these rates are completed using the extended (two-term Grunwald-Winstein equation with incorporation of literature values for solvent nucleophilicity (NT and solvent ionizing power (YCl. Both substrates were found to solvolyze by similar dual bimolecular carbonyl-addition and unimolecular ionization channels, each heavily dependent upon the solvents nucleophilicity and ionizing ability.

  6. Highly selective palladium–benzothiazole carbene-catalyzed allylation of active methylene compounds under neutral conditions

    Directory of Open Access Journals (Sweden)

    Antonio Monopoli

    2015-06-01

    Full Text Available The Pd–benzothiazol-2-ylidene complex I was found to be a chemoselective catalyst for the Tsuji–Trost allylation of active methylene compounds carried out under neutral conditions and using carbonates as allylating agents. The proposed protocol consists in a simplified procedure adopting an in situ prepared catalyst from Pd2dba3 and 3-methylbenzothiazolium salt V as precursors. A comparison of the performance of benzothiazole carbene with phosphanes and an analogous imidazolium carbene ligand is also proposed.

  7. Chemoselective and stereoselective lithium carbenoid mediated cyclopropanation of acyclic allylic alcohols.

    Science.gov (United States)

    Durán-Peña, M J; Flores-Giubi, M E; Botubol-Ares, J M; Harwood, L M; Collado, I G; Macías-Sánchez, A J; Hernández-Galán, R

    2016-03-01

    The reaction of geraniol with different lithium carbenoids generated from n-BuLi and the corresponding dihaloalkane has been evaluated. The reaction occurs in a chemo and stereoselective manner, which is consistent with a directing effect from the oxygen of the allylic moiety. Furthermore, a set of polyenes containing allylic hydroxyl or ether groups were chemoselectively and stereoselectively converted into the corresponding gem-dimethylcyclopropanes in one single step in moderate to good yields mediated by a lithium carbenoid generated in situ by the reaction of n-BuLi and 2,2-dibromopropane.

  8. One-pot synthesis and characterization of a new, branched polycarbosilane bearing allyl groups

    Institute of Scientific and Technical Information of China (English)

    Tian Hua Huang; Zhao Ju Yu; Xu Min He; Mu He Huang; Li Fu Chen; Hai Ping Xia; Li Tong Zhang

    2007-01-01

    A highly branched polycarbosilane bearing allyl groups has been prepared by a one-pot synthesis with chloromethyltrichlorosilane, chloromethylmethyldichlorosilane and allyl chloride as the starting materials.The resultant polymer, with the approximate formula [SiH1.2(CH)30.71(CH2CH=CH2)0.09CH2]n,has been characterized by 1H, 13C, and 29Si NMR, GPC, TG and elemental analysis.It could be cross-linked thermally at 170℃ in the absence of oxygen.Pyrolysis of the polymer gave a ceramic with a yield of about 70%.

  9. Synthesis of (-)-Piperitylmagnolol Featuring ortho-Selective Deiodination and Pd-Catalyzed Allylation.

    Science.gov (United States)

    Ikoma, Atsushi; Ogawa, Narihito; Kondo, Daiki; Kawada, Hiroki; Kobayashi, Yuichi

    2016-05-01

    A 1,4-addition strategy using an enone and a copper reagent was studied for the synthesis of (-)-piperitylmagnolol. A MOM-protected biphenol copper reagent was added to BF3·OEt2-activated 4-isopropylcyclohexenone, whereas 1,4-addition of protected monophenol reagents possessing an allyl group was found to be unsuccessful. The allyl group was later attached to the p-,p'-diiodo-biphenol ring by Pd-catalyzed coupling with allylborate. The aforementioned iodide was synthesized using a new method for ortho-selective deiodination of o-,p-diiodophenols. PMID:27109890

  10. In(OTf)3 catalyzed allylation reaction of imines with tetraallyltin

    Institute of Scientific and Technical Information of China (English)

    Xiao Ning Wei; Ling Yan Liu; Bing Wang; Wei Xing Chang; Jing Li

    2009-01-01

    In the presence of catalytic amount of In(OTf)3 (10 mol%), a series of aldimines reacted with tetraallyltin in a 2:1 molar ratio to afford the corresponding homoallylic amines in good yields. The good atom efficiency was achieved under mild reaction conditions and a new protocol (allyl)4Sn/In(OTf)3 for simple imines was developed.

  11. Enantioselective copper catalyzed allylic alkylation using Grignard reagents; Applications in synthesis

    NARCIS (Netherlands)

    Zijl, Anthoni Wouter van

    2009-01-01

    Enantioselective copper catalyzed allylic alkylation is a powerful carbon-carbon bond forming reaction. In this thesis the development of a new catalyst for the use of Grignard reagents in this reaction is described. This catalyst is based on copper and the ligand Taniaphos. The high regio- and enan

  12. Electrochemical studies and self diffusion coefficients in cyclic ammonium based ionic liquids with allyl substituents

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Tzi-Yi [Department of Chemistry, National Cheng Kung University, Tainan 701, Taiwan (China); Department of Polymer Materials, Kun Shan University, Tainan 71003, Taiwan (China); Su, Shyh-Gang [Department of Chemistry, National Cheng Kung University, Tainan 701, Taiwan (China); Wang, H. Paul [Department of Environmental Engineering, National Cheng Kung University, Tainan, Taiwan (China); Lin, Yuan-Chung [Institute of Environmental Engineering, National Sun Yat-Sen University, Kaohsiung 804, Taiwan (China); Gung, Shr-Tusen; Lin, Ming-Wei [Department of Chemistry, National Cheng Kung University, Tainan 701, Taiwan (China); Sun, I.-Wen, E-mail: iwsun@mail.ncku.edu.t [Department of Chemistry, National Cheng Kung University, Tainan 701, Taiwan (China)

    2011-03-30

    Research highlights: Cyclic ammonium-based ionic liquids with allyl substituent have high conductivity. Ionic liquids with allyl substituent have wide electrochemical window. Electrochemical and self diffusion coefficients are available for comparison. The Stokes-Einstein plots of DT{sup -1} vs. {eta}{sup -1} for redox couples in ILs are evaluated. Stokes-Einstein product of ferrocene is larger than that of cobaltocenium in ILs. - Abstract: Several cyclic ammonium-based ionic liquids (ILs) with allyl substituent are synthesized, these allyl substituent ILs have high ionic conductivity (up to 4.72 mS cm{sup -1} at 30 {sup o}C) and wide electrochemical window of 5 V. The electrochemical behaviors of two organometallic redox couples Fc/Fc{sup +} (ferrocene/ferrocenium) and Cc/Cc{sup +} (cobaltocene/cobaltocenium) have been studied in these ILs, the calculated Stokes-Einstein product (D{eta} T{sup -1}) of ferrocene in ILs is larger than that of cobaltocenium in ILs. The self-diffusion coefficients of cation and anion in these ILs are studied using pulsed gradient spin-echo NMR technique. There are very few reports where electrochemically derived diffusion coefficients and self diffusion coefficients are available for comparison, so a new key concept in electrochemistry could be developed in this paper.

  13. α-Regioselective Barbier Reaction of Carbonyl Compounds and Allyl Halides Mediated by Praseodymium.

    Science.gov (United States)

    Wu, San; Li, Ying; Zhang, Songlin

    2016-09-01

    The first utility of praseodymium as a mediating metal in the Barbier reaction of carbonyl compounds with allyl halides was reported in this paper. In contrast to the traditional metal-mediated or catalyzed Barbier reactions, exclusive α-adducts were obtained in this one-pot reaction with a broad scope of substrates and feasible reaction conditions. PMID:27490708

  14. Reactions of unsaturated compounds. CXXIV. Claisen rearrangement of allyl and propargyloxydienyl phosphonates

    Energy Technology Data Exchange (ETDEWEB)

    Dangyan, Yu.M.; Tirakyan, M.R.; Panosyan, G.A.; Badanyan, Sh.O.

    1986-12-20

    O,O-Dialkyl-1-ethylidene-2-allyl(propargyl)oxy-2-butenyl phosphonates have been obtained from vinylallenyl phosphonates and undergo thermal Claisen rearrangement to form highly unsaturated ketophosphonates. Comprehensive coupling constant and chemical shift figures from an NMR analysis are given.

  15. Organocatalytic asymmetric allylic amination of Morita–Baylis–Hillman carbonates of isatins

    Directory of Open Access Journals (Sweden)

    Hang Zhang

    2012-08-01

    Full Text Available The investigation of a Lewis base catalyzed asymmetric allylic amination of Morita–Baylis–Hillman carbonates derived from isatins afforded an electrophilic pathway to access multifunctional oxindoles bearing a C3-quaternary stereocenter, provided with good to excellent enantioselectivity (up to 94% ee and in high yields (up to 97%.

  16. Zirconium-allyl complexes as resting states in zirconocene-catalyzed α-olefin polymerization.

    Science.gov (United States)

    Panchenko, Valentina N; Babushkin, Dmitrii E; Brintzinger, Hans H

    2015-01-01

    UV-vis spectroscopic data indicate that zirconocene cations with Zr-bound allylic chain ends are generally formed during olefin polymerization with zirconocene catalysts. The rates and extent of their formation and of their re-conversion to the initial pre-catalyst cations depend on the types of zirconocene complexes and activators used.

  17. Synthesis of telechelic vinyl/allyl functional siloxane copolymers with structural control

    DEFF Research Database (Denmark)

    Madsen, Frederikke Bahrt; Javakhishvili, Irakli; Jensen, Rasmus Egekjær;

    2014-01-01

    Multifunctional siloxane copolymers with terminal vinyl or allyl functional groups are synthesised through the borane-catalysed polycondensation of hydrosilanes and alkoxysilanes. Copolymers of varying mole- cular weights ( M ̄ w =13200 – 70 300 g mol − 1 ), spatially well-distributed functional...

  18. Allylic and benzylic sp3 C-H oxidation in water.

    Science.gov (United States)

    Ang, Wei Jie; Lam, Yulin

    2015-01-28

    A copper-catalyzed method for the oxidation of allylic and benzylic sp(3) C-H by aqueous tert-butyl hydroperoxide (T-Hydro) in water using a recyclable fluorous ligand has been developed. The reaction procedure is tolerant to additional functional groups and the fluorous ligand could be reused with little loss of catalytic activity. PMID:25412371

  19. Polystyrene-supported Selenides and Selenoxide:Versatile Routes to Synthesize Allylic Alcohols

    Institute of Scientific and Technical Information of China (English)

    Wei Ming XU; You Chu ZHANG; Xian HUANG

    2003-01-01

    Several polystyrene-supported selenides and selenoxide have been prepared firstly. These novel reagents were treated with LDA to produce selenium stabilized carbanions, which reacted with aldehydes and alkyl halides, followed by selenoxide syn-elimination and [2,3] sigmatropic rearrangement respectively to give Z-allylic alcohols stereoselectively.

  20. Silylene-mediated ring contraction of homoallylic ethers to form allylic silanes.

    Science.gov (United States)

    Bourque, Laura E; Haile, Pamela A; Woerpel, K A

    2009-09-18

    (-)-Isopulegol derivatives undergo a ring contraction under silylene-mediated conditions to provide cyclopentane products. Silylene transfer to other homoallylic ethers did not provide the ring contraction products. Allylic silane products were elaborated to determine the stereochemical course of the ring contraction reaction. A mechanism for the transformation is proposed. PMID:19681592

  1. The Wacker oxidation of allyl alcohol along cyclic-intermediate routes: An ab initio molecular dynamics investigation

    Science.gov (United States)

    Imandi, Venkataramana; Nair, Nisanth N.

    2016-09-01

    The absence of isotope scrambling observed by Henry and coworkers in the Wacker oxidation of deuterated allylic alcohol was used by them as support for the inner-sphere mechanism hydroxypalladation mechanism. One of the assumptions used to interpret their experimental data was that allyl alcohol oxidation takes place through non-cyclic intermediate routes as in the case of ethene. Here we verify this assumption through ab initio metadynamics simulations of the Wacker oxidation of allyl alcohol in explicit solvent. Importance of our results in interpreting the isotope scrambling experiments is discussed.

  2. Gold(I)-Catalyzed Intramolecular Hydroamination of N-Allylic,N′-Aryl Ureas to form Imidazolidin-2-ones

    OpenAIRE

    Li, Hao; Song, Feijie; Widenhoefer, Ross A.

    2011-01-01

    Treatment of N-allylic,N′-aryl ureas with a catalytic 1:1 mixture of di-tert-butyl-o-biphenylphoshphine gold(I) chloride and silver hexafluorophosphate (1 mol %) in chloroform at room temperature led to 5-exo hydroamination to form the corresponding imidazolidin-2-ones in excellent yield. In the case of N-allylic ureas that possessed an allylic alkyl, benzyloxymethyl, or acetoxymethyl substituent, gold(I)-catalyzed 5-exo hydroamination leads to formation of the corresponding trans-3,4-disubst...

  3. Gold(I)-Catalyzed Intramolecular Hydroamination of N-Allylic,N'-Aryl Ureas to form Imidazolidin-2-ones.

    Science.gov (United States)

    Li, Hao; Song, Feijie; Widenhoefer, Ross A

    2011-04-18

    Treatment of N-allylic,N'-aryl ureas with a catalytic 1:1 mixture of di-tert-butyl-o-biphenylphoshphine gold(I) chloride and silver hexafluorophosphate (1 mol %) in chloroform at room temperature led to 5-exo hydroamination to form the corresponding imidazolidin-2-ones in excellent yield. In the case of N-allylic ureas that possessed an allylic alkyl, benzyloxymethyl, or acetoxymethyl substituent, gold(I)-catalyzed 5-exo hydroamination leads to formation of the corresponding trans-3,4-disubstituted imidazolidin-2-ones in excellent yield with ≥50:1 diastereoselectivity. PMID:21709731

  4. Vibronic spectra of the allyl radical at 6-8 eV with resonance-enhanced multiphoton ionization technique

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The allyl radical was produced in molecular beam by pyrolysis of allyl iodide. The vibronic spectra from ground state to six new electronic states of the allyl radical at 6-8 eV, p?3dxz , p?3dxy, and p?ns (n=4, 6, 7, 8) were observed firstly with the aid of time-of-flight mass spectroscopy and resonance-enhanced multiphoton ionization technique. Vibrational progression of n7 (C3 bend) with gross spacing of about 430 cm-1 was observed in ns Rydberg states. The adiabatic ionization potential of the allyl radical was obtained to be (65641 ± 20) cm-1 ((8.138 ± 0.002) eV) by fitting the term values of ns (n=4,6,7,8) Rydberg states with Rydberg formula.

  5. Enantioselective Allylic C-H Oxidation of Terminal Olefins to Isochromans by Palladium(II)/Chiral Sulfoxide Catalysis.

    Science.gov (United States)

    Ammann, Stephen E; Liu, Wei; White, M Christina

    2016-08-01

    The enantioselective synthesis of isochroman motifs has been accomplished by palladium(II)-catalyzed allylic C-H oxidation from terminal olefin precursors. Critical to the success of this goal was the development and utilization of a novel chiral aryl sulfoxide-oxazoline (ArSOX) ligand. The allylic C-H oxidation reaction proceeds with the broadest scope and highest levels of asymmetric induction reported to date (avg. 92 % ee, 13 examples with greater than 90 % ee). PMID:27376625

  6. Synthetic Studies on Tricyclic Diterpenoids: Direct Allylic Amination Reaction of Isopimaric Acid Derivatives.

    Science.gov (United States)

    Timoshenko, Mariya A; Kharitonov, Yurii V; Shakirov, Makhmut M; Bagryanskaya, Irina Yu; Shults, Elvira E

    2016-02-01

    A selective synthesis of 7- or 14-nitrogen containing tricyclic diterpenoids was completed according to a strategy in which the key step was the catalyzed direct allylic amination of methyl 14α-hydroxy-15,16-dihydroisopimarate with a wide variety of nitrogenated nucleophiles. It was revealed that the selectivity of the reaction depends on the nature of nucleophile. The catalyzed reaction of the mentioned diterpenoid allylic alcohol with 3-nitroaniline, 3-(trifluoromethyl)aniline, and 4-(trifluoromethyl)aniline yield the subsequent 7α-, 7β- and 14αnitrogen-containing diterpenoids. The reaction with 2-nitroaniline, 4-nitro-2-chloroaniline, 4-methoxy-2-nitroaniline, phenylsulfamide, or tert-butyl carbamate proceeds with the formation of 7α-nitrogen-substituted diterpenoids as the main products. PMID:27308214

  7. Rheology and viscosity scaling of gelatin/1-allyl-3-methylimidazolium chloride solution

    Science.gov (United States)

    Qiao, Congde; Li, Tianduo; Zhang, Ling; Yang, Xiaodeng; Xu, Jing

    2014-05-01

    Gelatin/1-allyl-3-methylimidazolium chloride solutions are prepared by using the ionic liquid 1-allyl-3-methylimidazolium chloride as solvent. The rheological properties of the gelatin solutions have been investigated by steady shear and oscillatory shear measurements. In the steady shear measurements, the gelatin solutions with high concentration show a shear-thinning flow behavior at high shear rates, while another shear thinning region can be found in the dilute gelatin solutions at low shear rates. The overlap concentration of gelatin in [amim]Cl is 1.0 wt% and the entanglement concentration is a factor of 4 larger (4.0 wt%). The high intrinsic viscosity (295 mL/g) indicates that the gelatin chains dispersed freely in the ionic liquid and no aggregation phenomenon occurs in dilute gelatin solution. The frequency dependences of modulus changed obviously with an increase in gelatin concentration. The empirical time-temperature superposition principle holds true at the experimental temperatures.

  8. [Characterization of surface properties of 1-allyl-3-methylimidazolium chloride ionic liquid by inverse gas chromatography].

    Science.gov (United States)

    Chen, Yali; Wang, Qiang; Deng, Lishuang; Zhang, Zhengfang; Tang, Jun

    2013-02-01

    The determination of the dispersive component of surface free energies (gamma(s)d) at different temperatures and Lewis acid-base parameters of 1-allyl-3-methylimidazolium chloride ionic liquid ([AMIM]Cl) were investigated by means of inverse gas chromatography (IGC). Four n-alkanes, including n-hexane (C6), n-heptane (C7), n-octane (C8) and n-nonane (C9), were chosen as the apolar probes to characterize the dispersive component of the surface free energies at 343.15, 353.15, 363.15 and 373.15 K, respectively; and dichloromethane (DCM), trichloromethane (TCM), tetrahydrofuran (THF), ethyl acetate (EtAc), acetone (Acet) as the polar probes to estimate the Lewis acid-base parameters to judge the interactions between [AMIM] Cl and the solvents. The IGC characterizations encompassed the adsorption thermodynamic parameters to acid-base surface interactions, including the standard enthalpy (deltaHa(s)) and the free energy change of adsorption (deltaGa(s)) at different temperatures. The results showed that the Lewis acid parameter Ka of [AMIM] Cl was 0.34, and the base parameter Kb was 1.68, which indicated it was Lewis amphoteric with predominantly basic character. Furthermore, the free energy of adsorption deltaGa(s) was also figured out. It was found that the gamma(s)d of the [AMIM] Cl were 52.26, 50.82, 46.08 and 42.05 mJ/m2 at 343.15, 353.15, 363.15 and 373.15 K, respectively. The results are of great importance to the study of the surface properties and the application of ionic liquid.

  9. On the key role of water in the allylic activation catalysed by Pd (II) bisphosphinite complexes

    Indian Academy of Sciences (India)

    Rakesh Kumar Sharma; Ashoka G Samuelson

    2006-11-01

    Palladium and platinum complexes of bisphosphinites and bisphosphines derived from mandelic acid have been prepared and characterized. Their ability to catalyze allylation of imines with allyltributylstannane has been studied. Bisphophinite complexes of Pd (II) are shown to be ideal and they work best in the presence of one equivalent of water. The near neutral conditions employed make the catalysts suitable for a wide variety of substrates.

  10. Highly Regioselective Palladium-Catalyzed Carboxylation of Allylic Alcohols with CO2.

    Science.gov (United States)

    Mita, Tsuyoshi; Higuchi, Yuki; Sato, Yoshihiro

    2015-11-01

    Various allylic alcohols were carboxylated in the presence of a catalytic amount of PdCl2 and PPh3 using ZnEt2 as a stoichiometric transmetalation agent under a CO2 atmosphere (1 atm). This carboxylation proceeded in a highly regioselective manner to afford branched carboxylic acids predominantly. The β,γ-unsaturated carboxylic acid thus obtained was successfully converted into an optically active γ-butyrolactone, a known intermediate of (R)-baclofen.

  11. Iron(III) chloride catalyzed glycosylation of peracylated sugars with allyl/alkynyl alcohols

    Energy Technology Data Exchange (ETDEWEB)

    Narayanaperumal, Senthil; Silva, Rodrigo Cesar da; Monteiro, Julia L.; Correa, Arlene G.; Paixao, Marcio W., E-mail: mwpaixao@ufscar.br [Universidade Federal de Sao Carlos (UFSCAR), SP (Brazil). Dept. de Quimica

    2012-11-15

    In this work, the use of ferric chloride as an efficient catalyst in glycosylation reactions of sugars in the presence of allyl and alkynyl alcohols is described. The corresponding glycosides were obtained with moderate to good yields. This new procedure presented greater selectivity when compared to classic methods found in the literature. Principal features of this simple method include non-hazardous reaction conditions, low-catalyst loading, good yields and high anomeric selectivity (author)

  12. Lewis base catalyzed enantioselective allylic hydroxylation of Morita-Baylis-Hillman carbonates with water

    KAUST Repository

    Zhu, Bo

    2011-08-19

    A Lewis base catalyzed allylic hydroxylation of Morita-Baylis-Hillman (MBH) carbonates has been developed. Various chiral MBH alcohols can be synthesized in high yields (up to 99%) and excellent enantioselectivities (up to 94% ee). This is the first report using water as a nucleophile in asymmetric organocatalysis. The nucleophilic role of water has been verified using 18O-labeling experiments. © 2011 American Chemical Society.

  13. Tether-directed synthesis of highly substituted oxasilacycles via an intramolecular allylation employing allylsilanes

    Directory of Open Access Journals (Sweden)

    Cox Liam R

    2007-02-01

    Full Text Available Abstract Background Using a silyl tether to unite an aldehyde electrophile and allylsilane nucleophile into a single molecule allows a subsequent Lewis-acid-mediated allylation to proceed in an intramolecular sense and therefore receive all the benefits associated with such processes. However, with the ability to cleave the tether post allylation, a product that is the result of a net intermolecular reaction can be obtained. In the present study, four diastereoisomeric β-silyloxy-α-methyl aldehydes, which contain an allylsilane tethered through the β-carbinol centre, have been prepared, in order to probe how the relative configuration of the two stereogenic centres affects the efficiency and selectivity of the intramolecular allylation. Results Syn-aldehydes, syn-4a and syn-4b, both react poorly, affording all four possible diastereoisomeric oxasilacycle products. In contrast, the anti aldehydes anti-4a and anti-4b react analogously to substrates that lack substitution at the α-site, affording only two of the four possible allylation products. Conclusion The outcome of the reaction with anti-aldehydes is in accord with reaction proceeding through a chair-like transition state (T.S.. In these systems, the sense of 1,3-stereoinduction can be rationalised by the aldehyde electrophile adopting a pseudoaxial orientation, which will minimise dipole-dipole interactions in the T.S. The 1,4-stereoinduction in these substrates is modest and seems to be modulated by the R substituent in the starting material. In the case of the syn-substrates, cyclisation through a chair T.S. is unlikely as this would require the methyl substituent α to the reacting carbonyl group to adopt an unfavourable pseudoaxial position. It is therefore proposed that these substrates react through poorly-defined T.S.s and consequently exhibit essentially no stereoselectivity.

  14. Experimental and Kinetic Modeling Study of 2-Methyl-2-Butene: Allylic Hydrocarbon Kinetics.

    Science.gov (United States)

    Westbrook, Charles K; Pitz, William J; Mehl, Marco; Glaude, Pierre-Alexandre; Herbinet, Olivier; Bax, Sarah; Battin-Leclerc, Frederique; Mathieu, Olivier; Petersen, Eric L; Bugler, John; Curran, Henry J

    2015-07-16

    Two experimental studies have been carried out on the oxidation of 2-methyl-2-butene, one measuring ignition delay times behind reflected shock waves in a stainless steel shock tube, and the other measuring fuel, intermediate, and product species mole fractions in a jet-stirred reactor (JSR). The shock tube ignition experiments were carried out at three different pressures, approximately 1.7, 11.2, and 31 atm, and at each pressure, fuel-lean (ϕ = 0.5), stoichiometric (ϕ = 1.0), and fuel-rich (ϕ = 2.0) mixtures were examined, with each fuel/oxygen mixture diluted in 99% Ar, for initial postshock temperatures between 1330 and 1730 K. The JSR experiments were performed at nearly atmospheric pressure (800 Torr), with stoichiometric fuel/oxygen mixtures with 0.01 mole fraction of 2M2B fuel, a residence time in the reactor of 1.5 s, and mole fractions of 36 different chemical species were measured over a temperature range from 600 to 1150 K. These JSR experiments represent the first such study reporting detailed species measurements for an unsaturated, branched hydrocarbon fuel larger than iso-butene. A detailed chemical kinetic reaction mechanism was developed to study the important reaction pathways in these experiments, with particular attention on the role played by allylic C-H bonds and allylic pentenyl radicals. The results show that, at high temperatures, this olefinic fuel reacts rapidly, similar to related alkane fuels, but the pronounced thermal stability of the allylic pentenyl species inhibits low temperature reactivity, so 2M2B does not produce "cool flames" or negative temperature coefficient behavior. The connections between olefin hydrocarbon fuels, resulting allylic fuel radicals, the resulting lack of low-temperature reactivity, and the gasoline engine concept of octane sensitivity are discussed. PMID:25822578

  15. Synthesis of alkenyl boronates from allyl-substituted aromatics using an olefin cross-metathesis protocol.

    Science.gov (United States)

    Hemelaere, Rémy; Carreaux, François; Carboni, Bertrand

    2013-07-01

    An efficient synthesis of 3-aryl-1-propenyl boronates from pinacol vinyl boronic ester and allyl-substituted aromatics by cross metathesis is reported. Although the allylbenzene derivatives are prone to isomerization reaction under metathesis conditions, we found that some ruthenium catalysts are effective for this methodology. This strategy thus provides an interesting alternative approach to alkyne hydroboration, leading to the preparation of unknown compounds. Moreover, the boron substituent can be replaced by various functional groups in good yields.

  16. Surprisingly Mild Enolate-Counterion-Free Pd(0)-Catalyzed Intramolecular Allylic Alkylations

    DEFF Research Database (Denmark)

    Madec, David; Prestat, Guillaume; Martini, Elisabetta;

    2005-01-01

    Palladium-catalyzed intramolecular allylic alkylations of unsaturated EWG-activated amides can take place under phase-transfer conditions or in the presence of a crown ether. These new reaction conditions are milder and higher yielding than those previously reported. A rationalization for such an...... for such an unexpected result is put forth and validated by DFT-B3LYP calculations. The results suggest cyclization via a counterion-free (E)-enolate TS....

  17. Allyl isothiocyanate induced stress response in Caenorhabditis elegans

    OpenAIRE

    Saini AkalRachna K; Tyler Robert T; Shim Youn; Reaney Martin JT

    2011-01-01

    Abstract Background Allyl isothiocyanate (AITC) from mustard is cytotoxic; however the mechanism of its toxicity is unknown. We examined the effects of AITC on heat shock protein (HSP) 70 expression in Caenorhabditis elegans. We also examined factors affecting the production of AITC from its precursor, sinigrin, a glucosinolate, in ground Brassica juncea cv. Vulcan seed as mustard has some potential as a biopesticide. Findings An assay to determine the concentration of AITC in ground mustard ...

  18. Rhodium-catalysed asymmetric allylic arylation of racemic halides with arylboronic acids

    Science.gov (United States)

    Sidera, Mireia; Fletcher, Stephen P.

    2015-11-01

    Csp2-Csp2 cross-coupling reactions between arylboronic acid and aryl halides are widely used in both academia and industry and are strategically important in the development of new agrochemicals and pharmaceuticals. Csp2-Csp3 cross-coupling reactions have been developed, but enantioselective variations are rare and simply retaining the stereochemistry is a problem. Here we report a highly enantioselective Csp2-Csp3 bond-forming method that couples arylboronic acids to racemic allyl chlorides. Both enantiomers of a cyclic chloride are converted into a single enantiomer of product via a dynamic kinetic asymmetric transformation. This Rh-catalysed method uses readily available and inexpensive building blocks and is mild and broadly applicable. For electron-deficient, electron-rich or ortho-substituted boronic acids better results are obtained with racemic allyl bromides. Oxygen substitution in the allyl halide is tolerated and the products can be functionalized to provide diverse building blocks. The approach fills a significant gap in the methods for catalytic asymmetric synthesis.

  19. The soft X-ray absorption spectrum of the allyl free radical.

    Science.gov (United States)

    Alagia, M; Bodo, E; Decleva, P; Falcinelli, S; Ponzi, A; Richter, R; Stranges, S

    2013-01-28

    The first experimental study of the X-ray absorption spectrum (XAS) of the allyl free radical, CH(2)CHCH(2), is reported. A supersonic He seeded beam of hyperthermal allyl radicals was crossed by a high resolution synchrotron radiation (SR) in the focus of a 3D ion momentum imaging time-of-flight (TOF) spectrometer to investigate the soft X-ray absorption and fragmentation processes. The XAS, recorded as Total-Ion-Yield (TIY), is dominated by C1s electron excitations from either the central carbon atom, C(C), or the two terminal carbon atoms, C(T), to the frontier orbitals, the semi-occupied-molecular-orbital (SOMO) and the lowest-unoccupied-molecular-orbital (LUMO). All of the intense features in the XAS could only be assigned with the aid of ab initio spectral simulation at the Multi-Configuration Self-Consistent-Field (MCSCF) level of theory, this level being required because of the multi-reference nature of the core-excited state wavefunctions of the open shell molecule. The ionization energies (IEs) of the singlet and triplet states of the C1s ionized allyl radical (XPS) were also calculated at the MCSCF level. PMID:23232557

  20. Nouvelles Réactions d'Allylation Radicalaire : Exploitation de la Rupture homolytique de Liaisons Carbone-Oxygène et Carbone-Carbone

    OpenAIRE

    Debien, Laurent

    2013-01-01

    This PhD thesis is divided in eight chapters. The first three bibliographic chapters present the general principles of radical chemistry, the possibility offered by the xanthate radical chemistry and a review of the radical allylation methods, main focus of this work. The three next chapters are dedicated to the exploitation of the radical allylation of allylic alcohols, recently discovered in our laboratory. The use of such a technology enabled the preparation of functionalized enol ethers, ...

  1. On the Nature of the Intermediates and the Role of Chloride Ions in Pd-Catalyzed Allylic Alkylations: Added Insight from Density Functional Theory

    DEFF Research Database (Denmark)

    Fristrup, Peter; Ahlquist, Mårten Sten Gösta; Tanner, David Ackland;

    2008-01-01

    The reactivity of intermediates in palladium-catalyzed allylic alkylation was investigated using DFT (B3LYP) calculations including a PB-SCRF solvation model. In the presence of both phosphine and chloride ligands, the allyl intermediate is in equilibrium between a cationic eta(3)-allylPd complex...... with two phosphine ligands, the corresponding neutral complex with one phosphine and one chloride ligand, and a neutral eta(1)-allylPd complex with one chloride and two phosphine ligands. The eta(1)-complex is unreactive toward nucleophiles. The cationic eta(3)-complex is the intermediate most...

  2. Genome wide association mapping in Arabidopsis thaliana identifies novel genes involved in linking allyl glucosinolate to altered biomass and defense

    Directory of Open Access Journals (Sweden)

    Marta Francisco

    2016-07-01

    Full Text Available A key limitation in modern biology is the ability to rapidly identify genes underlying newly identified complex phenotypes. Genome wide association studies (GWAS have become an increasingly important approach for dissecting natural variation by associating phenotypes with genotypes at a genome wide level. Recent work is showing that the Arabidopsis thaliana defense metabolite, allyl glucosinolate (GSL, may provide direct feedback regulation, linking defense metabolism outputs to the growth and defense responses of the plant. However, there is still a need to identify genes that underlie this process. To start developing a deeper understanding of the mechanism(s that modulate the ability of exogenous allyl GSL to alter growth and defense, we measured changes in plant biomass and defense metabolites in a collection of natural 96 A. thaliana accessions fed with 50 µM of allyl GSL. Exogenous allyl GSL was introduced exclusively to the roots and the compound transported to the leaf leading to a wide range of heritable effects upon plant biomass and endogenous GSL accumulation. Using natural variation we conducted GWAS to identify a number of new genes which potentially control allyl responses in various plant processes. This is one of the first instances in which this approach has been successfully utilized to begin dissecting a novel phenotype to the underlying molecular/polygenic basis.

  3. New [Mo(eta3-allyl)(CO)2L3]+ complexes with monodentate or tridentate nitrogen-donor ligands.

    Science.gov (United States)

    Pérez, Julio; Morales, Dolores; Nieto, Sonia; Riera, Lucía; Riera, Víctor; Miguel, Daniel

    2005-03-01

    Cationic complexes [Mo(eta(3)-allyl)(CO)2L3]+ (L3 = either nitrogen-donor tridentate ligand or three monodentate ligands) were prepared in high yield and under mild conditions using as precursors either the triflato complex [Mo(eta(3)-allyl)(OTf)(CO)2(NCMe)2] or the combination of the chloro complex [Mo(eta(3)-allyl)Cl(CO)2(NCMe)2] and the salt NaBAr'(4)(Ar'= 3,5-bis(trifluoromethyl)phenyl). The tridentate ligands employed were 2,2':6',2'-terpyridine (terpy) and cis,cis-1,3,5-cyclohexanetriamine (CHTA), whereas the monodentate ligands imidazole (im) and 3,5-dimethylpyrazole (dmpz) were chosen. In order to stabilize the labile intermediates, an excess of acetonitrile was used in most of the syntheses. However, the pyrazole complex was prepared through a nitrile-free route to avoid reactions at the coordinated nitrile. The solid state structures of [Mo(eta(3)-methallyl)(CO)2(terpy)]OTf (2), [Mo(eta(3)-methallyl)(CO)2(CHTA)]BAr'4 (3), [Mo(eta(3)-methallyl)(CO)2(NCMe)3]BAr'4 (4), [Mo(eta(3)-allyl)(CO)2(im)3]OTf (5) and [Mo(eta(3)-allyl)(CO)2(dmpz)3]BAr'4 (6) were determined by means of single-crystal X-ray diffraction. PMID:15726140

  4. Enhanced performance of the catalytic conversion of allyl alcohol to 3-hydroxypropionic acid using bimetallic gold catalysts.

    Science.gov (United States)

    Falletta, Ermelinda; Della Pina, Cristina; Rossi, Michele; He, Qian; Kiely, Christopher J; Hutchings, Graham J

    2011-01-01

    One of the strategic building blocks in organic synthesis is 3-hydroxypropionic acid, which is particularly important for the manufacture of high performance polymers. However, to date, despite many attempts using both biological and chemical routes, no large scale effective process for manufacturing 3-hydroxypropionic acid has been developed. One potentially useful starting point is from allyl alcohol, as this can be obtained in principle from the dehydration of glycerol, thereby presenting a bio-renewable green pathway to this important building block. The catalytic transformation of allyl alcohol to 3-hydroxypropionic acid presents interesting challenges in catalyst design, particularly with respect to the control of selectivity among the products that can be expected, as acrylic acid, acrolein and glyceric acid can also be formed. In this paper, we present a novel eco-sustainable catalytic pathway leading to 3-hydroxypropionic acid, which highlights the outstanding potential of gold-based and bimetallic catalysts in the aerobic oxidation of allyl alcohol. PMID:22455056

  5. Study on the Preparation of Allyl-modified Starch in Isopropyl/Water Medium for Warp Sizing

    Institute of Scientific and Technical Information of China (English)

    LI Man-li; ZHU Zhi-feng; ZHANG Long-qiu

    2008-01-01

    A new method for the pretreatment of starch by etherification was developed to eliminate the problems of lower grafting efficiency associated with the preparation of starch graft copolymers as warp sizing agents.The etherification of starch with allyl chloride was investigated in order to effectively enhance the reaction efficiency.The technological variables of the reaction considered for evaluating the etherification included sodium hydroxide amount,water content in water-isopropyi alcohol medium,allyl cldoride concentration,reaction temperature and reaction time.The experimental result demonstrated that the variables considered showed evident effect on the reaction efficiency.For the etherification,a condition of 20% for the water content,1.5:1 for the molar ratio of sodium hydroxide to allyl chloride.and at 30℃ under 24h reaction is Sufficient to retain the reaction efficiency above 50%.Furthermore,a contrast test demonstrated that the graft efficiency can be increased with the etherification pretreatment.

  6. Thermophysical properties and reaction kinetics of γ-irradiated poly allyl diglycol carbonates nuclear track detector

    Science.gov (United States)

    Elmaghraby, Elsayed K.; Seddik, Usama

    2015-07-01

    Kinetic thermogravimetric technique was used to study the effect of gamma irradiation on the poly allyl diglycol carbonates (PADC) within the dose range from 50 to ? Gy. The approach of Coats-Redfern was used to analyze the data. Results showed that low doses around 50 Gy make the polymer slightly more resistive to heat treatment. Higher radiation doses cause severe effects in the samples accompanied by the formation of lower molecular mass species and consequent crosslinking. Results support the domination of re-polymerization and crosslinking for the γ radiation interaction PADC at dose below about ? Gy, while the situation is inverted above ? Gy in which chain secession dominates.

  7. Synthesis of Aminophosphine Ligands with Binaphthyl Backbones for Silver(I)-catalyzed Enantioselective Allylation of Benzaldehyde

    Institute of Scientific and Technical Information of China (English)

    WANG,Yi(王以); JI,Bao-Ming(吉保明); DING,Kui-Ling(丁奎岭)

    2002-01-01

    A series of aminophosphine ligands was synthesized from 2amino-2′-hydroxy-1,1′-binaphthyl (NOBIN). Their asymmetric induction efficiency was examined for silver(I)catalyzed enantioselective allylation reaction of benzaldehyde with allyltributyltin.Under the optimized reaction conditions,quantitative yield as well as moderate ee value (54.5% ee)of product was achieved by the catalysis with silver(I)/3 complex. The effects of the binaphthyl backbone and the substituted situated at chelating N, Patoms on enantioselectivity of the reaction were also discussed.

  8. Unusual selectivity-determining factors in the phosphine-free Heck arylation of allyl ethers

    DEFF Research Database (Denmark)

    Ambrogio, I.; Fabrizi, G.; Cacchi, S.;

    2008-01-01

    The Heck reaction of aryl iodides and bromides with allyl ethers has been investigated. Using phosphinefree Pd(OAc)(2) in DNIF at 90 degrees C in the presence of Bu4NOAc, the reaction gave cinnamyl derivatives, usually in good to high yields, with a wide range of aryl halides. The reaction tolera...... for cinnamyl ether over enol ether products. Interestingly, it was found that the product selectivity does not arise from competing beta-hydride eliminations but rather from a competition between beta-elimination and hindered single-bond rotation in the initial carbopalladation product....

  9. Non-thermal plasma destruction of allyl alcohol in waste gas: kinetics and modelling

    Science.gov (United States)

    DeVisscher, A.; Dewulf, J.; Van Durme, J.; Leys, C.; Morent, R.; Van Langenhove, H.

    2008-02-01

    Non-thermal plasma treatment is a promising technique for the destruction of volatile organic compounds in waste gas. A relatively unexplored technique is the atmospheric negative dc multi-pin-to-plate glow discharge. This paper reports experimental results of allyl alcohol degradation and ozone production in this type of plasma. A new model was developed to describe these processes quantitatively. The model contains a detailed chemical degradation scheme, and describes the physics of the plasma by assuming that the fraction of electrons that takes part in chemical reactions is an exponential function of the reduced field. The model captured the experimental kinetic data to less than 2 ppm standard deviation.

  10. Lanthanum triflate triggered synthesis of tetrahydroquinazolinone derivatives of N-allyl quinolone and their biological assessment

    Directory of Open Access Journals (Sweden)

    Jardosh Hardik H.

    2012-01-01

    Full Text Available A series of 24 derivatives of tetrahydroquinazolinone has been synthesized by one-pot cyclocondensation reaction of N-allyl quinolones, cyclic β-diketones and (thiourea/N-phenylthiourea in presence of lanthanum triflate catalyst. This methodology allowed us to achieve the products in excellent yield by stirring at room temperature. All the synthesized compounds were investigated against a representative panel of pathogenic strains using broth microdilution MIC (minimum inhibitory concentration method for their in vitro antimicrobial activity. Amongst these sets of heterocyclic compounds 5h, 6b, 6h, 5f, 5l, 5n and 6g found to have admirable activity.

  11. Nano-Aluminum Powder Mediated Allylation of Carbonyl Compounds in Aqueous Media

    Institute of Scientific and Technical Information of China (English)

    YUAN Shi-Zhen; LIU Jin

    2008-01-01

    A new and effective Barbier-Grignard allylation of aldehydes or ketones has been carried out with nano-aluminum powder in aqueous 0.1 mol·L-1 NH4Cl (aq.) under an atmosphere of nitrogen. Aromatic carbonyl compounds gave homoallylic alcohols in good yields. The effectiveness of reaction was strongly influenced by the steric environment surrounding the carbonyl group. Aliphatic carbonyl compounds proceeded in low yields. The dominant stereoisomer was an erythro-isomer when an ortho-hydroxyl carbonyl compound was reacted under such a reaction condition.

  12. Non-thermal plasma destruction of allyl alcohol in waste gas: kinetics and modelling

    International Nuclear Information System (INIS)

    Non-thermal plasma treatment is a promising technique for the destruction of volatile organic compounds in waste gas. A relatively unexplored technique is the atmospheric negative dc multi-pin-to-plate glow discharge. This paper reports experimental results of allyl alcohol degradation and ozone production in this type of plasma. A new model was developed to describe these processes quantitatively. The model contains a detailed chemical degradation scheme, and describes the physics of the plasma by assuming that the fraction of electrons that takes part in chemical reactions is an exponential function of the reduced field. The model captured the experimental kinetic data to less than 2 ppm standard deviation

  13. Organocatalytic Enantioselective Nucleophilic Alkynylation of Allyl Fluorides Affording Chiral Skipped Ene-ynes.

    Science.gov (United States)

    Okusu, Satoshi; Okazaki, Hiroki; Tokunaga, Etsuko; Soloshonok, Vadim A; Shibata, Norio

    2016-06-01

    Asymmetric methods for preparation of chiral alkynyl-containing compounds are in extremely high demand in many sectors of chemical research. In this work, we report the discovery of a general organocatalytic enantioselective alkynylation based on the idea of Si/F activation of the allylic C-F bond. This approach features reasonably broad substrate scope, functional group tolerance, and relatively neutral, mild, and operationally convenient reaction conditions; all of which bode well for the synthetic value of the discovered method. In particular, this method provides unique chiral skipped 1,4-ene-ynes having two kinds of versatile functional groups. PMID:27111713

  14. Combined experimental and theoretical mechanistic investigation of the Barbier allylation in aqueous media

    DEFF Research Database (Denmark)

    Dam, Johan Hygum; Fristrup, Peter; Madsen, Robert

    2008-01-01

    -determining step. For Zn, In, Sn, Sb, and Bi, an inverse secondary kinetic isotope effect was found (k(H)/k(D) = 0.75-0.95), which was compatible with the formation of a discrete organometallic species prior to allylation via a closed six-membered transition state. With Mg, a significantly larger build...... with the effect of solvent described by a polarized continuum model. The calculated secondary deuterium isotope effects based on this mechanism were found to be in good agreement with experimental values, thus adding further support to this mechanistic scenario....

  15. Allyl Isothiocyanate Increases MRP1 Function and Expression in a Human Bronchial Epithelial Cell Line

    OpenAIRE

    Dian-lei Wang; Chen-yin Wang; Yin Cao; Xian Zhang; Xiu-hua Tao; Li-li Yang; Jin-pei Chen; Shan-shan Wang; Ze-geng Li

    2014-01-01

    Multidrug resistance-associated protein 1 (MRP1), a member of the ATP-binding cassette (ABC) superfamily of transporters, plays an important role in normal lung physiology by protecting cells against oxidative stress and toxic xenobiotics. The present study investigates the effects of allyl isothiocyanate (AITC) on MRP1 mRNA and MRP1 protein expression and transporter activity in the immortalised human bronchial epithelial cell line 16HBE14o-. MRP1 mRNA and MRP1 protein expression in 16HBE14o...

  16. Direct asymmetric allylic alkenylation of N-itaconimides with Morita-Baylis-Hillman carbonates

    KAUST Repository

    Yang, Wenguo

    2012-08-03

    The asymmetric allylic alkenylation of Morita-Baylis-Hillman (MBH) carbonates with N-itaconimides as nucleophiles has been developed using a commercially available Cinchona alkaloid catalyst. A variety of multifunctional chiral α-methylene-β-maleimide esters were attained in moderate to excellent yields (up to 99%) and good to excellent enantioselectivities (up to 91% ee). The origin of the regio- and stereoselectivity was verified by DFT methods. Calculated geometries and relative energies of various transition states strongly support the observed regio- and enantioselectivity. © 2012 American Chemical Society.

  17. Synthesis of Aryl Allyl Ether in the Recyclable Ionic Liquid [bmim]PF6

    Institute of Scientific and Technical Information of China (English)

    Zhou Mei-Yun; Li Yi-Qun; Xu Xin-Ming

    2004-01-01

    Ionic liquids, especially imidazonium salts, have recently gained recognition as possible environmentally benign alternative chemical process solvents. This is mainly due to their nonvolatile nature, insolubility in some solvents as well as their ability to dissolve a wide range of organic and inorganic materials, allowing the ionic liquids easy recovery and recycling. Examples of their application in organic reactions have been summarized in a number of recent review articles.1Aryl allyl ether is very useful intermediate in organic synthesis. The Williamson reaction is a well knows method for the preparation ethers. However, the reaction of alkylating agents with the phenoxide ions was conventionally carried out in the organic solvents. The usual solvents for this type of reaction are DCM, 2 DMSO, 3 DMF, 4 CH3CN5 etc. With the current desire to avoid the use of organic molecular solvents in organic synthesis, we decide to investigate the use of the ionic liquid for the alternative solvent for the Williamson reaction to prepare the aryl allyl ethers. The ionic liquid employed here was the moisture stable 1-butyl-3-methylimidazolium hexafluorophosphate [bmim]PF6.6 The ionic liquid is non-volatile, thermally stable, and depending on the anion, can present low immiscible with water,alkanes and dialky ethers. We have now found that aryl allyl ethers can have been obtained from various phenols and allyl bromide in the presence of potassium hydroxide in [bmim]PF6 as a replacement for classical organic solvents in the ambient temperature. The results are shown in Scheme 1.The reaction were carried out by simple mixing the phenolwith the ally bromide and potassium hydroxide in [bmim]PF6 and stirred at room temperature for 4h. The results are summarized in Table 1.In conclusion, Williamson reaction can be successfully conducted in ionic liquid [bmim]PF6 with a number of advantages: the procedure is simple, the reaction condition is mild and the yields are excellent

  18. Synthesis of oxacyclic scaffolds via dual ruthenium hydride/Brønsted acid-catalyzed isomerization/cyclization of allylic ethers.

    Science.gov (United States)

    Ascic, Erhad; Ohm, Ragnhild G; Petersen, Rico; Hansen, Mette R; Hansen, Casper L; Madsen, Daniel; Tanner, David; Nielsen, Thomas E

    2014-03-17

    A ruthenium hydride/Brønsted acid-catalyzed tandem sequence is reported for the synthesis of 1,3,4,9-tetrahydropyrano[3,4-b]indoles (THPIs) and related oxacyclic scaffolds. The process was designed on the premise that readily available allylic ethers would undergo sequential isomerization, first to enol ethers (Ru catalysis), then to oxocarbenium ions (Brønsted acid catalysis) amenable to endo cyclization with tethered nucleophiles. This methodology provides not only an attractive alternative to the traditional oxa-Pictet-Spengler reaction for the synthesis of THPIs, but also convenient access to THPI congeners and other important oxacycles such as acetals. PMID:24616060

  19. [3,3]-sigmatropic rearrangements of fluorinated allyl (Thio)cyanates - a tool for the synthesis of fluorinated (Thio)ureas.

    Science.gov (United States)

    Ramb, Daniel C; Kost, Lisa; Haufe, Günter

    2014-01-01

    The first (thio)cyanate to iso(thio)cyanate rearrangements based on 2-fluoroallylic alcohols are presented. Long-chain 2-fluoroallylic alcohols were converted to corresponding N-unsubstituted carbamates by treatment with trichloroacetyl isocyanate. Dehydration using trifluoroacetic anhydride in the presence of triethylamine formed intermediate allylic cyanates, which immediately underwent sigmatropic rearrangement to fluorinated allyl isocyanates. Without isolation the latter delivered fluorinated ureas by addition of amines. The thiocyanate to isothiocyanate rearrangements started from the same fluorinated allylic alcohols, which were first converted to mesylates. Heating in THF with potassium thiocyanate led to fluorinated allyl isothiocyanates, via [3,3]-sigmatropic rearrangement of intermediate allyl thiocyanates. The formed products were further reacted with amines to fluorinated thioureas.

  20. From a Sequential to a Concurrent Reaction in Aqueous Medium: Ruthenium-Catalyzed Allylic Alcohol Isomerization and Asymmetric Bioreduction.

    Science.gov (United States)

    Ríos-Lombardía, Nicolás; Vidal, Cristian; Liardo, Elisa; Morís, Francisco; García-Álvarez, Joaquín; González-Sabín, Javier

    2016-07-18

    The ruthenium-catalyzed redox isomerization of allylic alcohols was successfully coupled with the enantioselective enzymatic ketone reduction (mediated by KREDs) in a concurrent process in aqueous medium. The overall transformation, formally the asymmetric reduction of allylic alcohols, took place with excellent conversions and enantioselectivities, under mild reaction conditions, employing commercially and readily available catalytic systems, and without external coenzymes or cofactors. Optimization resulted in a multistep approach and a genuine cascade reaction where the metal catalyst and biocatalyst coexist from the beginning. PMID:27258838

  1. Iodine-Catalyzed Decarboxylative Amidation of β,γ-Unsaturated Carboxylic Acids with Chloramine Salts Leading to Allylic Amides.

    Science.gov (United States)

    Kiyokawa, Kensuke; Kojima, Takumi; Hishikawa, Yusuke; Minakata, Satoshi

    2015-10-26

    The iodine-catalyzed decarboxylative amidation of β,γ-unsaturated carboxylic acids with chloramine salts is described. This method enables the regioselective synthesis of allylic amides from various types of β,γ-unsaturated carboxylic acids containing substituents at the α- and β-positions. In the reaction, N-iodo-N-chloroamides, generated by the reaction of a chloramine salt with I2 , function as a key active species. The reaction provides an attractive alternative to existing methods for the synthesis of useful secondary allylic amine derivatives. PMID:26493878

  2. Role of allyl group in the hydroxyl and peroxyl radical scavenging activity of S-allylcysteine.

    Science.gov (United States)

    Maldonado, Perla D; Alvarez-Idaboy, J Raúl; Aguilar-González, Adriana; Lira-Rocha, Alfonso; Jung-Cook, Helgi; Medina-Campos, Omar Noel; Pedraza-Chaverrí, José; Galano, Annia

    2011-11-17

    S-Allylcysteine (SAC) is the most abundant compound in aged garlic extracts, and its antioxidant properties have been demonstrated. It is known that SAC is able to scavenge different reactive species including hydroxyl radical (•OH), although its potential ability to scavenge peroxyl radical (ROO•) has not been explored. In this work the ability of SAC to scavenge ROO• was evaluated, as well as the role of the allyl group (-S-CH(2)-CH═CH(2)) in its free radical scavenging activity. Two derived compounds of SAC were prepared: S-benzylcysteine (SBC) and S-propylcysteine (SPC). Their abilities to scavenge •OH and ROO• were measured. A computational analysis was performed to elucidate the mechanism by which these compounds scavenge •OH and ROO•. SAC was able to scavenge •OH and ROO•, in a concentration-dependent way. Such activity was significantly ameliorated when the allyl group was replaced by benzyl or propyl groups. It was shown for the first time that SAC is able to scavenge ROO•.

  3. Iron complexes of tetramine ligands catalyse allylic hydroxyamination via a nitroso–ene mechanism

    Directory of Open Access Journals (Sweden)

    David Porter

    2015-12-01

    Full Text Available Iron(II complexes of the tetradentate amines tris(2-pyridylmethylamine (TPA and N,N′-bis(2-pyridylmethyl-N,N′-dimethylethane-1,2-diamine (BPMEN are established catalysts of C–O bond formation, oxidising hydrocarbon substrates via hydroxylation, epoxidation and dihydroxylation pathways. Herein we report the capacity of these catalysts to promote C–N bond formation, via allylic amination of alkenes. The combination of N-Boc-hydroxylamine with either FeTPA (1 mol % or FeBPMEN (10 mol % converts cyclohexene to the allylic hydroxylamine (tert-butyl cyclohex-2-en-1-yl(hydroxycarbamate in moderate yields. Spectroscopic studies and trapping experiments suggest the reaction proceeds via a nitroso–ene mechanism, with involvement of a free N-Boc-nitroso intermediate. Asymmetric induction is not observed using the chiral tetramine ligand (+-(2R,2′R-1,1′-bis(2-pyridylmethyl-2,2′-bipyrrolidine ((R,R′-PDP.

  4. Further exploration of the heterocyclic diversity accessible from the allylation chemistry of indigo

    Directory of Open Access Journals (Sweden)

    Alireza Shakoori

    2015-04-01

    Full Text Available Diversity-directed synthesis based on the cascade allylation chemistry of indigo, with its embedded 2,2’-diindolic core, has resulted in rapid access to new examples of the hydroxy-8a,13-dihydroazepino[1,2-a:3,4-b']diindol-14(8H-one skeleton in up to 51% yield. Additionally a derivative of the novel bridged heterocycle 7,8-dihydro-6H-6,8a-epoxyazepino[1,2-a:3,4-b']diindol-14(13H-one was produced when the olefin of the allylic substrate was terminally disubstituted. Further optimisation also produced viable one-pot syntheses of derivatives of the spiro(indoline-2,9'-pyrido[1,2-a]indol-3-one (65% and pyrido[1,2,3-s,t]indolo[1,2-a]azepino[3,4-b]indol-17-one (72% heterocyclic systems. Ring-closing metathesis of the N,O-diallylic spiro structure and subsequent Claisen rearrangement gave rise to the new (1R,8aS,17aS-rel-1,2-dihydro-1-vinyl-8H,17H,9H-benz[2',3']pyrrolizino[1',7a':2,3]pyrido[1,2-a]indole-8,17-(2H,9H-dione heterocyclic system.

  5. Further exploration of the heterocyclic diversity accessible from the allylation chemistry of indigo

    Science.gov (United States)

    Shakoori, Alireza; Bremner, John B; Abdel-Hamid, Mohammed K; Willis, Anthony C; Haritakun, Rachada

    2015-01-01

    Summary Diversity-directed synthesis based on the cascade allylation chemistry of indigo, with its embedded 2,2’-diindolic core, has resulted in rapid access to new examples of the hydroxy-8a,13-dihydroazepino[1,2-a:3,4-b']diindol-14(8H)-one skeleton in up to 51% yield. Additionally a derivative of the novel bridged heterocycle 7,8-dihydro-6H-6,8a-epoxyazepino[1,2-a:3,4-b']diindol-14(13H)-one was produced when the olefin of the allylic substrate was terminally disubstituted. Further optimisation also produced viable one-pot syntheses of derivatives of the spiro(indoline-2,9'-pyrido[1,2-a]indol)-3-one (65%) and pyrido[1,2,3-s,t]indolo[1,2-a]azepino[3,4-b]indol-17-one (72%) heterocyclic systems. Ring-closing metathesis of the N,O-diallylic spiro structure and subsequent Claisen rearrangement gave rise to the new (1R,8aS,17aS)-rel-1,2-dihydro-1-vinyl-8H,17H,9H-benz[2',3']pyrrolizino[1',7a':2,3]pyrido[1,2-a]indole-8,17-(2H,9H)-dione heterocyclic system. PMID:25977722

  6. Polymerizations of beta-substituted allylic arsonium ylides with catalytic amounts of organoboron compounds

    International Nuclear Information System (INIS)

    My Ph.D. work consisted in the generalization and optimization of a new polymerization reaction involving allylic arsonium ylides and catalytic amounts of various boron compounds. Thus, various β-substituted allylic arsonium salts were produced according to synthetic strategies that depended on the nature of the functional group born by the salt. These salts were converted in situ to the corresponding arsonium ylides which were then treated with boron compounds to yield polymers. Our new method of polymerization afforded either non conjugated polyenes that are functionalized every three atoms of carbon, or statistic copolymers, depending on the nature of the group R born on the β position of the ylide. These new polymers cannot be synthesized by usual methods of polymerization. Initial molar ratios of reactants were found to give molar mass control of the synthesized polymers. This controlled polymerization allowed us to produce several bloc copolymers. All the polymers were characterized by NMR techniques, by size exclusion chromatography and, for some of them, by mass spectrometry. Investigation of their physicochemical properties will need additional experiments. (author)

  7. Asymmetric allylic alkylation in combination with ring-closing metathesis for the preparation of chiral N-heterocycles

    NARCIS (Netherlands)

    Teichert, Johannes F.; Zhang, Suyan; Zijl, Anthoni W. van; Slaa, Jan Willem; Minnaard, Adriaan J.; Feringa, Bernard

    2010-01-01

    Asymmetric copper-catalyzed allylic substitution with methylmagnesium bromide is employed in combination with ring-closing olefin metathesis or ene-yne metathesis to achieve the synthesis of chiral, unsaturated nitrogen heterocycles. The resulting six- to eight-membered chiral heterocycles are acces

  8. The NBS Reaction: A Simple Explanation for the Predominance of Allylic Substitution over Olefin Addition by Bromine at Low Concentrations.

    Science.gov (United States)

    Wamser, Carl C.; Scott, Lawrence T.

    1985-01-01

    Examines mechanisms related to use of N-bromosuccinimide (NBS) for bromination at an allylic position. Also presents derived rate laws for three possible reactions of molecular bromine with an alkene: (1) free radical substitution; (2) free radical addition; and (3) electrophilic addition. (JN)

  9. Organoselenium-catalyzed, hydroxy-controlled regio- and stereoselective amination of terminal alkenes: efficient synthesis of 3-amino allylic alcohols.

    Science.gov (United States)

    Deng, Zhimin; Wei, Jialiang; Liao, Lihao; Huang, Haiyan; Zhao, Xiaodan

    2015-04-17

    An efficient route to prepare 3-amino allylic alcohols in excellent regio- and stereoselectivity in the presence of bases by orangoselenium catalysis has been developed. In the absence of bases α,β-unsaturated aldehydes were formed in up to 97% yield. Control experiments reveal that the hydroxy group is crucial for the direct amination. PMID:25849818

  10. Aldehyde Selective Wacker Oxidations of Phthalimide Protected Allylic Amines : A New Catalytic Route to beta(3)-Amino Acids

    NARCIS (Netherlands)

    Weiner, Barbara; Baeza Garcia, Alejandro; Jerphagnon, Thomas; Feringa, Ben L.

    2009-01-01

    A new method for the synthesis of B-3-amino acids is presented. Phthalimide protected allylic amines are oxidized under Wacker conditions selectively to aldehydes using PdCl2 and CuCl or Pd(MeCN)(2)Cl(NO2) and CuCl2 as complementary catalyst systems. The aldehydes are produced in excellent yields an

  11. Thiol addition to protected allyl glycosides: an improved method for the preparation of spacer-arm glycosides

    NARCIS (Netherlands)

    Vliegenthart, J.F.G.; Seeventer, P.B. van; Dorst, J.A.L.M. van; Siemerink, J.F.; Kamerling, J.P.

    1997-01-01

    A useful method for the preparation of differently functionalized sulfide spacer-arm glycosides is presented. Several protected allyl glycosides were variously elongated via a radical addition reaction with pentanethiol, methyl 3-mercaptopropionate, or 2-mercaptoethanol. The hydroxyl function of pro

  12. Synthesis of novel chiral phosphine-triazine ligand derived from α-phenylethylamine for Pd-catalyzed asymmetric allylic alkylation

    Institute of Scientific and Technical Information of China (English)

    Jia Di Huang; Xiang Ping Hu; Zhuo Zheng

    2008-01-01

    A novel chiral phosphine-triazine ligand was synthesized from chiral model reaction of Pd-catalyzed allylic alkylation of rac-l,3-diphenylprop-2-en-l-yl pivalate with dimethyl malonate, good enantioselectivity (90% e.e.) was obtained by using this ligand.

  13. Growth behavior prediction of fresh catfish fillet with Pseudomonas aeruginosa under stresses of allyl isothiocyanate, temperature and modified atmosphere

    Science.gov (United States)

    Pseudomonas aeruginosa, a common spoilage microorganism in fish, grows rapidly when temperature rises above 4 degree C. The combination of allyl isothiocyanate (AIT) and modified atmosphere (MA) was applied and proved to be effective to retard the growth of P. aeruginosa. The objective of this resea...

  14. Antimicrobial activity of allyl isothiocyanate used to coat biodegradable composite films as affected by storage and handling conditions

    Science.gov (United States)

    We evaluated the effects of storage and handling conditions on the antimicrobial activity of biodegradable composite films (polylactic acid and sugar beet pulp) coated with allyl isothiocyanate (AIT). Polylactic acid (PLA) and chitosan were incorporated with AIT and coated on one side of the film. T...

  15. Enantioselective construction of quaternary N-heterocycles by palladium-catalysed decarboxylative allylic alkylation of lactams

    KAUST Repository

    Behenna, Douglas C.

    2011-12-18

    The enantioselective synthesis of nitrogen-containing heterocycles (N-heterocycles) represents a substantial chemical research effort and resonates across numerous disciplines, including the total synthesis of natural products and medicinal chemistry. In this Article, we describe the highly enantioselective palladium-catalysed decarboxylative allylic alkylation of readily available lactams to form 3,3-disubstituted pyrrolidinones, piperidinones, caprolactams and structurally related lactams. Given the prevalence of quaternary N-heterocycles in biologically active alkaloids and pharmaceutical agents, we envisage that our method will provide a synthetic entry into the de novo asymmetric synthesis of such structures. As an entry for these investigations we demonstrate how the described catalysis affords enantiopure quaternary lactams that intercept synthetic intermediates previously used in the synthesis of the Aspidosperma alkaloids quebrachamine and rhazinilam, but that were previously only available by chiral auxiliary approaches or as racemic mixtures. © 2012 Macmillan Publishers Limited. All rights reserved.

  16. Cutting thin sheets of allyl diglycol carbonate (CR-39) with a CW CO2, laser

    International Nuclear Information System (INIS)

    Recent studies have shown that Allyl Diglycol Carbonate, commercially known as CR-39 (the most sensitive among etch track detectors) can detect relativistic oxygen and other heavier nuclei. We are using large sheets of special grade CR-39 (DOP) in our experiment in Space Shuttle-Spacelab-3. As CR-39 is a highly brittle substance, special care is required to cut CR-39 shetts, especially in case of large sheets and circular cuts. A study of cutting of CR-39 sheets using laser light is described in this paper. It has been found that this method is sufficiently fast to handle large number of sheets and also equally safe for big sheets. A maximum speed up to 200 cm/min with a 5 x 104 W/cm2 laser is obtained during the present study. This study also shows that laser cutting does not affect the track properties of CR-39. (orig.)

  17. Theoretical study on the gas phase reaction of allyl chloride with hydroxyl radical.

    Science.gov (United States)

    Zhang, Yunju; Chao, Kai; Sun, Jingyu; Zhang, Wanqiao; Shi, Haijie; Yao, Cen; Su, Zhongmin; Pan, Xiumei; Zhang, Jingping; Wang, Rongshun

    2014-02-28

    The reaction of allyl chloride with the hydroxyl radical has been investigated on a sound theoretical basis. This is the first time to gain a conclusive insight into the reaction mechanism and kinetics for important pathways in detail. The reaction mechanism confirms that OH addition to the C=C double bond forms the chemically activated adducts, IM1 (CH2CHOHCH2Cl) and IM2 (CH2OHCHCH2Cl) via low barriers, and direct H-abstraction paths may also occur. Variational transition state model and multichannel RRKM theory are employed to calculate the temperature-, pressure-dependent rate constants. The calculated rate constants are in good agreement with the experimental data. At 100 Torr with He as bath gas, IM6 formed by collisional stabilization is the major products in the temperature range 200-600 K; the production of CH2CHCHCl via hydrogen abstractions becomes dominant at high temperatures (600-3000 K). PMID:24588171

  18. Theoretical study on the gas phase reaction of allyl chloride with hydroxyl radical

    Science.gov (United States)

    Zhang, Yunju; Chao, Kai; Sun, Jingyu; Zhang, Wanqiao; Shi, Haijie; Yao, Cen; Su, Zhongmin; Pan, Xiumei; Zhang, Jingping; Wang, Rongshun

    2014-02-01

    The reaction of allyl chloride with the hydroxyl radical has been investigated on a sound theoretical basis. This is the first time to gain a conclusive insight into the reaction mechanism and kinetics for important pathways in detail. The reaction mechanism confirms that OH addition to the C=C double bond forms the chemically activated adducts, IM1 (CH2CHOHCH2Cl) and IM2 (CH2OHCHCH2Cl) via low barriers, and direct H-abstraction paths may also occur. Variational transition state model and multichannel RRKM theory are employed to calculate the temperature-, pressure-dependent rate constants. The calculated rate constants are in good agreement with the experimental data. At 100 Torr with He as bath gas, IM6 formed by collisional stabilization is the major products in the temperature range 200-600 K; the production of CH2CHCHCl via hydrogen abstractions becomes dominant at high temperatures (600-3000 K).

  19. Low-temperature Electrodeposition of Aluminium from Lewis Acidic 1-Allyl-3-methylimidazolium Chloroaluminate Ionic Liquids

    Institute of Scientific and Technical Information of China (English)

    郑勇; 张锁江; 吕兴梅; 王倩; 左勇; 刘恋

    2012-01-01

    Lewis acidic 1-allyl-3-methylimidazolium chloroaluminate ionic liquids were used as promising electrolytes in the low-temperature electrodeposition of aluminium. Systematic studies on deposition process have been performed by cYClic voltammetry and chronoamperometry. The surface morphology and X-ray diffraction (XRD) patterns of deposits prepared at different experimental conditions were also investigated. It was shown that the nucleation density and growth rate of crystallites had a great effect on the structure of aluminium deposited. The crys- tallographic orientation of deposits was mainly influenced by temperature and current density. Smooth, dense and well adherent aluminium coatings were obtained on copper substrates at 10-25 mA.cm^-2 and 313.2-353.2 K. More- over, the current efficiency of deposition and purity of aluminium have been significantly improved, demonstrating that the ionic liquids tested have a prospectful potential in electroplating and electrorefining of aluminium.

  20. Preservation of acidified cucumbers with a natural preservative combination of fumaric acid and allyl isothiocyanate that target lactic acid bacteria and yeasts.

    Science.gov (United States)

    Pérez-Díaz, I M; McFeeters, R F

    2010-05-01

    Without the addition of preservative compounds cucumbers acidified with 150 mM acetic acid with pH adjusted to 3.5 typically undergo fermentation by lactic acid bacteria. Fumaric acid (20 mM) inhibited growth of Lactobacillus plantarum and the lactic acid bacteria present on fresh cucumbers, but spoilage then occurred due to growth of fermentative yeasts, which produced ethanol in the cucumbers. Allyl isothiocyanate (2 mM) prevented growth of Zygosaccharomyces globiformis, which has been responsible for commercial pickle spoilage, as well as the yeasts that were present on fresh cucumbers. However, allyl isothiocyanate did not prevent growth of Lactobacillus plantarum. When these compounds were added in combination to acidified cucumbers, the cucumbers were successfully preserved as indicated by the fact that neither yeasts or lactic acid bacteria increased in numbers nor were lactic acid or ethanol produced by microorganisms when cucumbers were stored at 30 degrees C for at least 2 mo. This combination of 2 naturally occurring preservative compounds may serve as an alternative approach to the use of sodium benzoate or sodium metabisulfite for preservation of acidified vegetables without a thermal process.

  1. Formation of gold clusters on La-Ni mixed oxides and its catalytic performance for isomerization of allylic alcohols to saturated aldehydes

    International Nuclear Information System (INIS)

    Au/NiO catalyzed the isomerization of allylic alcohols to afford saturated aldehydes. La-Ni mixed oxide could stabilize Au(III) and afford gold clusters smaller than 1 nm by H2 reduction. The resulting Au clusters on La-Ni-O exhibited superior catalytic performance to Au/NiO for the isomerization of internal allylic alcohol, 2-octen-1-ol to octanal. (author)

  2. An Efficient Protocol for the Palladium-catalyzed Asymmetric Decarboxylative Allylic Alkylation Using Low Palladium Concentrations and a Palladium(II) Precatalyst

    OpenAIRE

    Marziale, Alexander N.; Duquette, Douglas C.; Craig, Robert A.; Kim, Kelly E.; Liniger, Marc; Numajiri, Yoshitaka; Stoltz, Brian M.

    2015-01-01

    Enantioselective catalytic allylic alkylation for the synthesis of 2-alkyl-2-allylcycloalkanones and 3,3-disubstituted pyrrolidinones, piperidinones and piperazinones has been previously reported by our laboratory. The efficient construction of chiral all-carbon quaternary centers by allylic alkylation was previously achieved with a catalyst derived in situ from zero valent palladium sources and chiral phosphinooxazoline (PHOX) ligands. We now report an improved reaction protocol with broad a...

  3. A chemical assessment of the suitability of allyl- iso-propyltelluride as a Te precursor for metal organic vapour phase epitaxy

    Science.gov (United States)

    Hails, Janet E.; Cole-Hamilton, David J.; Stevenson, John; Bell, William; Foster, Douglas F.; Ellis, David

    2001-04-01

    The chemical studies, which led to the testing of allyl- iso-propyltelluride (allylTePr i) as a Te precursor in metal organic vapour phase epitaxy are presented. The pyrolysis in hydrogen of allylTePr i gave products including 1,5-hexadiene, propane and propene. Co-pyrolysis of dimethylcadmium (Me 2Cd) and allylTePr i gave the hydrocarbons expected from the pyrolysis of the individual precursors plus additional hydrocarbons including 2-methylpropane and 1-butene. Plots of percentage decomposition versus temperature, which proved extremely useful in determining the likely growth temperatures for both CdTe and HgTe, showed that allylTePr i is less stable than both Pr 2iTe (di- iso-propyltelluride) and Me 2Cd. The possible role of Hg in the growth of CdTe is also discussed. The chemistry of allylTePr i is well suited for use as an efficient precursor for epitaxial growth of tellurium containing semiconductors since there is very little formation of other organotellurium compounds on pyrolysis.

  4. One-pot synthesis of enantiomerically pure N-protected allylic amines from N-protected α-amino esters

    Science.gov (United States)

    Silveira-Dorta, Gastón; Álvarez-Méndez, Sergio J; Martín, Víctor S

    2016-01-01

    Summary An improved protocol for the synthesis of enantiomerically pure allylic amines is reported. N-Protected α-amino esters derived from natural amino acids were submitted to a one-pot tandem reduction–olefination process. The sequential reduction with DIBAL-H at −78 °C and subsequent in situ addition of organophosphorus reagents yielded the corresponding allylic amines without the need to isolate the intermediate aldehyde. This circumvents the problem of instability of the aldehydes. The method tolerates well both Wittig and Horner–Wadsworth–Emmons organophosphorus reagents. A better Z-(dia)stereoselectivity was observed when compared to the previous one-pot method. The (dia)stereoselectivity of the process was affected neither by the reaction solvent nor by the amount of DIBAL-H employed. The method is compatible with the presence of free hydroxy groups as shown with serine and threonine derivatives. PMID:27340486

  5. The pure rotational spectrum of a Claisen rearrangement precursor Allyl Phenyl Ether using CP-FTMW spectroscopy

    Science.gov (United States)

    Grubbs, G. S.; Frank, Derek S.; Obenchain, Daniel A.; Cooke, S. A.; Novick, Stewart E.

    2016-06-01

    The pure rotational spectrum of a Claisen rearrangement precursor, Allyl Phenyl Ether (APE), has been measured on a chirped pulse Fourier transform microwave (CP-FTMW) spectrometer in the 8-14 GHz region. Rotational and centrifugal distortion constants for multiple conformations have been determined and are reported for the first time. This is the first study of a phenyl-containing ether where multiple conformers were experimentally observed all within their ground vibrational states. Quantum chemical calculations have been performed to isolate low energy geometries of APE and are implemented to aid in spectral assignment. Other structural parameters such as planar moments and inertial defects for the Allyl Phenyl Ether conformers are presented and compared to similar molecules.

  6. REDUCING NONSELECTIVE PROTEIN ADSORPTION AND CELL ADHESION ON POLYACRYLONITRILE FILMS BY COPOLYMERIZATION OF ACRYLONITRILE WITH α-ALLYL GLUCOSIDE

    Institute of Scientific and Technical Information of China (English)

    Rui-qiang Kou; Chao Qu; Zhi-kang Xu; You-yi Xu; Ke Yao

    2003-01-01

    In this work, the surface properties of novel sugar-containing polymers, α-allyl glucoside (AG)/acrylonitrile (AN)copolymers, were studied by contact angle, protein adsorption and cell adhesion measurements. It was found that the contact angle of the copolymer films decreased from 68° to 30° with the increase of AG content in the copolymer. The adsorption amount of bovine serum albumin (BSA) and the adhesive macrophage onto the film surface also decreased significantly with increasing α-allyl glucoside content from 0 to 42 wt% in the copolymer. These preliminary results reveal that both the hydrophilicity and the biocompatibility of polyacrylonitrile-based membranes could be improved by copolymerizing acrylonitrile with vinyl carbohydrates.

  7. Inhibition of Listeria monocytogenes on cooked cured chicken breasts by acidified coating containing allyl isothiocyanate or deodorized Oriental mustard extract.

    Science.gov (United States)

    Olaimat, Amin N; Holley, Richard A

    2016-08-01

    Ready-to-eat meats are considered foods at high risk to cause life-threatening Listeria monocytogenes infections. This study screened 5 L. monocytogenes strains for their ability to hydrolyze sinigrin (a glucosinolate in Oriental mustard), which formed allyl isothiocyanate (AITC) and reduced L. monocytogenes viability on inoculated vacuum-packed, cooked, cured roast chicken slices at 4 °C. Tests involved incorporation of 25-50 μl/g AITC directly or 100-250 mg/g Oriental mustard extract in 0.5% (w/v) κ-carrageenan/2% (w/v) chitosan-based coatings prepared using 1.5% malic or acetic acid. L. monocytogenes strains hydrolyzed 33.6%-48.4% pure sinigrin in MH broth by 21 d at 25 °C. Acidified κ-carrageenan/chitosan coatings containing 25-50 μl/g AITC or 100-250 mg/g mustard reduced the viability of L. monocytogenes and aerobic bacteria on cooked, cured roast chicken slices by 4.1 to >7.0 log10 CFU/g compared to uncoated chicken stored at 4 °C for 70 d. Coatings containing malic acid were significantly more antimicrobial than those with acetic acid. During storage for 70 d, acidified κ-carrageenan/chitosan coatings containing 25-50 μl/g AITC or 250 mg/g mustard extract reduced lactic acid bacteria (LAB) numbers 3.8 to 5.4 log10 CFU/g on chicken slices compared to uncoated samples. Acidified κ-carrageenan/chitosan-based coatings containing either AITC or Oriental mustard extract at the concentrations tested had the ability to control L. monocytogenes viability and delay growth of potential spoilage bacteria on refrigerated, vacuum-packed cured roast chicken. PMID:27052706

  8. Statistic evaluation of cysteine and allyl alcohol as additives for Cu-Zn coatings from citrate baths

    OpenAIRE

    Julyana Ribeiro Garcia; Dalva Cristina Baptista do Lago; Fernando Lucas Gonçalves Silva; Eliane D'Elia; Aderval Severino Luna; Lilian Ferreira de Senna

    2013-01-01

    In the present work, cysteine and allyl alcohol were added to citrate baths as additives to Cu-Zn coatings on steel substrates. In order to verify the effects of the deposition parameters (current density, mechanical stirring speed, and additives) on the coating composition, electrochemical behavior, morphology, and microstructure properties of Cu-Zn coatings, the electrodeposition of the alloy was carried out using an experimental composite design 2³, in which these parameters were considere...

  9. Synchrotron Photoionization Mass Spectrometry Measurements of Kinetics and Product Formation in the Allyl Radical (H2CCHCH2)Self Reaction

    Science.gov (United States)

    Selby, Talitha M.; Melini, giovanni; Goulay, Fabien; Leone, Stephen R.; Fahr, Askar; Taatjes, Craig A.; Osborn, David L.

    2008-01-01

    Product channels for the self-reaction of the resonance-stabilized allyl radical, C3H5 + C3H5, have been studied with isomeric specificity at temperatures from 300-600 K and pressures from 1-6 Torr using time-resolved multiplexed photoionization mass spectrometry. Under these conditions 1,5-hexadiene was the only C6H10 product isomer detected. The lack of isomerization of the C6H10 product is in marked contrast to the C6H6 product in the related C3H3 + C3H3 reaction, and is due to the more saturated electronic structure of the C6H10 system. The disproportionation product channel, yielding allene + propene, was also detected, with an upper limit on the branching fraction relative to recombination of 0.03. Analysis of the allyl radical decay at 298 K yielded a total rate coefficient of (2.7 +/- 0.8) x 10(exp -11) cu cm/molecule/s, in good agreement with pre.vious experimental measurements using ultraviolet kinetic absorption spectroscopy and a recent theoretical determination using variable reaction coordinate transition state theory. This result provides independent indirect support for the literature value of the allyl radical ultraviolet absorption cross-section near 223 nm.

  10. 烯丙基酚醛树脂的固化动力学%Curing Kinetics of Allyl Phenolic Resin

    Institute of Scientific and Technical Information of China (English)

    刘洋; 刘诗薇; 李志强; 于景坤

    2012-01-01

    The curing behavior of allyl phenolic resin was analyzed at different heating rates using differential scanning calorimetry.The obtained kinetic data were treated by Kissinger and KAS(Kissinger-Akahira-Sunose) methods to obtain the curing reaction kinetic parameters.A curing kinetics model was established for allyl phenolic resin.Compared with phenolic resin,the curing temperature of allyl phenolic resin is higher,the reaction order is closer to 1,and the average activation energy of the curing reaction is lower,111.45 kJ/mol.The activation energy of allyl phenolic resin is almost constant and changes little with temperature in the curing process.The curing kinetics model of allyl phenolic resin provides a theoretical basis for the study of curing process parameters.%利用差示扫描量热法分析了烯丙基酚醛树脂在不同升温速率下的固化行为,用Kissinger法和KAS(Kissinger-Akahira-Sunose)法对获得的动力学数据进行处理,得到了固化反应动力学参数,并建立了烯丙基酚醛树脂的固化动力学模型.结果表明:与纯酚醛树脂相比,烯丙基酚醛树脂固化温度较高,反应级数更接近于1,固化反应所需的平均表观活化能较低,为111.45kJ/mol;在整个固化过程中,烯丙基酚醛树脂的活化能较为恒定,随温度变化不大;烯丙基酚醛树脂固化动力学模型为研究该体系固化工艺参数提供了理论依据.

  11. Increased presevation of sliced mozzarella cheese by antimibrobial sachet incorporated with allyl isothiocyanate

    Directory of Open Access Journals (Sweden)

    Ana Clarissa dos Santos Pires

    2009-12-01

    Full Text Available There is an increasing tendency to add natural antimicrobials of plant origin into food. The objective of this work was to develop a microbial sachet incorporated with allyl isothiocyanate (AIT, a volatile compound of plant origin, and to test its efficiency against growth of yeasts and molds, Staphylococcus sp. and psychrotrophic bacteria on sliced mozzarella cheese. Another objective was to quantify the concentration of AIT in the headspace of cheese packaging. A reduction of 3.6 log cycles was observed in yeasts and molds counts in the mozzarella packed with the antimicrobial sachet over 15-day storage time. The sachet also showed an antibacterial effect on Staphylococcus sp., reducing 2.4 log cycles after 12-day storage. Psychrotrophic bacteria species were the most resistant to the antimicrobial action. The highest concentration of AIT (0.08µg.mL-1 inside the active packaging system was observed at the 6-day of storage at 12 ºC ± 2 ºC. At the end of the storage time, AIT concentration decreased to only 10% of the initial concentration. Active packaging containing antimicrobial sachet has a potential use for sliced mozzarella, with molds and yeasts being the most sensitive to the antimicrobial effects.

  12. Merging allylic carbon-hydrogen and selective carbon-carbon bond activation

    Science.gov (United States)

    Masarwa, Ahmad; Didier, Dorian; Zabrodski, Tamar; Schinkel, Marvin; Ackermann, Lutz; Marek, Ilan

    2014-01-01

    Since the nineteenth century, many synthetic organic chemists have focused on developing new strategies to regio-, diastereo- and enantioselectively build carbon-carbon and carbon-heteroatom bonds in a predictable and efficient manner. Ideal syntheses should use the least number of synthetic steps, with few or no functional group transformations and by-products, and maximum atom efficiency. One potentially attractive method for the synthesis of molecular skeletons that are difficult to prepare would be through the selective activation of C-H and C-C bonds, instead of the conventional construction of new C-C bonds. Here we present an approach that exploits the multifold reactivity of easily accessible substrates with a single organometallic species to furnish complex molecular scaffolds through the merging of otherwise difficult transformations: allylic C-H and selective C-C bond activations. The resulting bifunctional nucleophilic species, all of which have an all-carbon quaternary stereogenic centre, can then be selectively derivatized by the addition of two different electrophiles to obtain more complex molecular architecture from these easily available starting materials.

  13. Computational study of dissociative electron attachment to π-allyl ruthenium (II) tricarbonyl bromide

    Science.gov (United States)

    Thorman, Rachel M.; Bjornsson, Ragnar; Ingólfsson, Oddur

    2016-08-01

    Motivated by the current interest in low energy electron induced fragmentation of organometallic complexes in focused electron beam induced deposition (FEBID) we have evaluated different theoretical protocols for the calculation of thermochemical threshold energies for DEA to the organometallic complex π-allyl ruthenium (II) tricarbonyl bromide. Several different computational methods including density functional theory (DFT), hybrid-DFT and coupled cluster were evaluated for their ability to predict these threshold energies and compared with the respective experimental values. Density functional theory and hybrid DFT methods were surprisingly found to have poor reliability in the modelling of several DEA reactions; however, the coupled cluster method LPNO-pCCSD/2a was found to produce much more accurate results. Using the local correlation pair natural orbital (LPNO) methodology, high level coupled cluster calculations for open-shell systems of this size are now affordable, paving the way for reliable theoretical DEA predictions of such compounds. Contribution to the Topical Issue "Advances in Positron and Electron Scattering", edited by Paulo Limao-Vieira, Gustavo Garcia, E. Krishnakumar, James Sullivan, Hajime Tanuma and Zoran Petrovic.

  14. Allylic amination reactivity of Ni, Pd, and Pt heterobimetallic and monometallic complexes.

    Science.gov (United States)

    Carlsen, Ryan W; Ess, Daniel H

    2016-06-14

    Transition metal heterobimetallic complexes with dative metal-metal interactions have the potential for novel fast reactivity. There are few studies that both compare the reactivity of different metal centers in heterobimetallic complexes and compare bimetallic reactivity to monometallic reactivity. Here we report density-functional calculations that show the reactivity of [Cl2Ti(N(t)BuPPh2)2M(II)(η(3)-methallyl)] heterobimetallic complexes for allylic amination follows M = Ni > Pd > Pt. This reactivity trend was not anticipated since the amine addition transition state involves M(II) to M(0) reduction and this could disadvantage Ni. Comparison of heterobimetallic complexes to the corresponding monometallic (CH2)2(N(t)BuPPh2)2M(II)(η(3)-methallyl) complexes reveals that this reactivity trend is due to the bimetallic interaction and that the bimetallic interaction significantly lowers the barrier height for amine addition by >10 kcal mol(-1). The impact of the early transition metal center on the amination addition barrier height depends on the late transition metal center. The lowest barrier heights for this reaction occur when late and early transition metal centers are from the same periodic table row. PMID:26893287

  15. Theoretical kinetic estimates for the recombination of hydrogen atoms with propargyl and allyl radicals

    Energy Technology Data Exchange (ETDEWEB)

    Harding, L. B.; Klippenstein, S. J.

    2000-01-12

    Ab initio quantum chemical simulations are coupled with variational transition state theory in estimating rate constants for the H+C{sub 3}H{sub 3} and H+C{sub 3}H{sub 5} recombination reactions. The energy of interaction between the H atom and each of the radicals is evaluated at the CAS+1+2 level for the range of separations and relative orientations spanning the transition state region. An analytic representation of these interaction energies is then implemented in variable reaction coordinate transition state theory calculations of the high pressure limit recombination rate constant for temperatures ranging from 200 to 2000 K. For the propargyl reaction the overall addition rate is separated into contributions correlating with the initial formation of allene and propyne. These theoretical results are compared with the available experimental data as well as with corresponding theoretical estimates for the H+C{sub 2}H{sub 3} and H+C{sub 2}H{sub 5} reactions. The H+propargyl and H+allyl total recombination rates are remarkably similar, with both being greater than the H+vinyl and H+ethyl rates, due to the presence of twice as many addition channels.

  16. Allyl m-Trifluoromethyldiazirine Mephobarbital: An Unusually Potent Enantioselective and Photoreactive Barbiturate General Anesthetic

    Energy Technology Data Exchange (ETDEWEB)

    Savechenkov, Pavel Y.; Zhang, Xi; Chiara, David C.; Stewart, Deirdre S.; Ge, Rile; Zhou, Xiaojuan; Raines, Douglas E.; Cohen, Jonathan B.; Forman, Stuart A.; Miller, Keith W.; Bruzik, Karol S. (Harvard-Med); (Mass. Gen. Hosp.); (UIC)

    2012-12-10

    We synthesized 5-allyl-1-methyl-5-(m-trifluoromethyl-diazirynylphenyl)barbituric acid (14), a trifluoromethyldiazirine-containing derivative of general anesthetic mephobarbital, separated the racemic mixture into enantiomers by chiral chromatography, and determined the configuration of the (+)-enantiomer as S by X-ray crystallography. Additionally, we obtained the {sup 3}H-labeled ligand with high specific radioactivity. R-(-)-14 is an order of magnitude more potent than the most potent clinically used barbiturate, thiopental, and its general anesthetic EC{sub 50} approaches those for propofol and etomidate, whereas S-(+)-14 is 10-fold less potent. Furthermore, at concentrations close to its anesthetic potency, R-(-)-14 both potentiated GABA-induced currents and increased the affinity for the agonist muscimol in human {alpha}1{beta}2/3{gamma}2L GABA{sub A} receptors. Finally, R-(-)-14 was found to be an exceptionally efficient photolabeling reagent, incorporating into both {alpha}1 and {beta}3 subunits of human {alpha}1{beta}3 GABAA receptors. These results indicate R-(-)-14 is a functional general anesthetic that is well-suited for identifying barbiturate binding sites on Cys-loop receptors.

  17. Allyl Isothiocyanate Inhibits Actin-Dependent Intracellular Transport in Arabidopsis thaliana

    Directory of Open Access Journals (Sweden)

    Bjørnar Sporsheim

    2015-12-01

    Full Text Available Volatile allyl isothiocyanate (AITC derives from the biodegradation of the glucosinolate sinigrin and has been associated with growth inhibition in several plants, including the model plant Arabidopsis thaliana. However, the underlying cellular mechanisms of this feature remain scarcely investigated in plants. In this study, we present evidence of an AITC-induced inhibition of actin-dependent intracellular transport in A. thaliana. A transgenic line of A. thaliana expressing yellow fluorescent protein (YFP-tagged actin filaments was used to show attenuation of actin filament movement by AITC. This appeared gradually in a time- and dose-dependent manner and resulted in actin filaments appearing close to static. Further, we employed four transgenic lines with YFP-fusion proteins labeling the Golgi apparatus, endoplasmic reticulum (ER, vacuoles and peroxisomes to demonstrate an AITC-induced inhibition of actin-dependent intracellular transport of or, in these structures, consistent with the decline in actin filament movement. Furthermore, the morphologies of actin filaments, ER and vacuoles appeared aberrant following AITC-exposure. However, AITC-treated seedlings of all transgenic lines tested displayed morphologies and intracellular movements similar to that of the corresponding untreated and control-treated plants, following overnight incubation in an AITC-absent environment, indicating that AITC-induced decline in actin-related movements is a reversible process. These findings provide novel insights into the cellular events in plant cells following exposure to AITC, which may further expose clues to the physiological significance of the glucosinolate-myrosinase system.

  18. Enhanced biocompatibility and wound healing properties of biodegradable polymer-modified allyl 2-cyanoacrylate tissue adhesive.

    Science.gov (United States)

    Lee, Young Ju; Son, Ho Sung; Jung, Gyeong Bok; Kim, Ji Hye; Choi, Samjin; Lee, Gi-Ja; Park, Hun-Kuk

    2015-06-01

    As poly L-lactic acid (PLLA) is a polymer with good biocompatibility and biodegradability, we created a new tissue adhesive (TA), pre-polymerized allyl 2-cyanoacrylate (PACA) mixed with PLLA in an effort to improve biocompatibility and mechanical properties in healing dermal wound tissue. We determined optimal mixing ratios of PACA and PLLA based on their bond strengths and chemical structures analyzed by the thermal gravimetric analysis (TGA) and Fourier transform infrared (FT-IR) spectroscopy. In vitro biocompatibility of the PACA/PLLA was evaluated using direct- and indirect-contact methods according to the ISO-10993 cytotoxicity test for medical devices. The PACA/PLLA have similar or even better biocompatibility than those of commercially available cyanoacrylate (CA)-based TAs such as Dermabond® and Histoacryl®. The PACA/PLLA were not different from those exposed to Dermabond® and Histoacryl® in Raman spectra when biochemical changes of protein and DNA/RNA underlying during cell death were compared utilizing Raman spectroscopy. Histological analysis revealed that incised dermal tissues of rats treated with PACA/PLLA showed less inflammatory signs and enhanced collagen formation compared to those treated with Dermabond® or Histoacryl®. Of note, tissues treated with PACA/PLLA were stronger in the tensile strength compared to those treated with the commercially available TAs. Therefore, taking all the results into consideration, the PACA/PLLA we created might be a clinically useful TA for treating dermal wounds. PMID:25842106

  19. Allyl Isothiocyanate Induces Cell Toxicity by Multiple Pathways in Human Breast Cancer Cells.

    Science.gov (United States)

    Bo, Peng; Lien, Jin-Cherng; Chen, Ya-Yin; Yu, Fu-Shun; Lu, Hsu-Feng; Yu, Chun-Shu; Chou, Yu-Cheng; Yu, Chien-Chih; Chung, Jing-Gung

    2016-01-01

    Isothiocyanates (ITCs) occur in many cruciferous vegetables. These compounds, which have significant anticancer actions, can induce apoptosis in different human cancer cell lines. In the present study, we investigated if allyl isothiocyanate (AITC) would induce toxicity in human breast cancer MCF-7 (estrogen receptor positive) and MDA-MB-231 (estrogen receptor negative) cells. We found that AITC stimulated reactive oxygen species and Ca[Formula: see text] production, and decreased the mitochondrial membrane potential. Activity of caspase-8, -9 and -3 was increased by AITC in both cell lines. AITC also induced mitochondrial-mediated apoptosis, as shown by cytochrome c, AIF and Endo G release from mitochondria, activation of caspase-9 and caspase-3, and formation of DAPI-positive cells. There was a significant reduction in the levels of the anti-apoptotic protein Bcl-2 along with a marked increase in the pro-apoptotic protein Bax in both cell lines. AITC induced apoptosis in human breast cancer MCF-7 cells via AIF and Endo G signaling pathways, but in MDA-MB-231 cells apoptosis occurred via the GADD153 pathway. This study has revealed novel anti-cancer mechanisms of AITC, a compound that is ordinarily present in human diets and may have potential therapeutic effects in various cancers. PMID:27080949

  20. Allyl isothiocyanates and cinnamaldehyde potentiate miniature excitatory postsynaptic inputs in the supraoptic nucleus in rats.

    Science.gov (United States)

    Yokoyama, Toru; Ohbuchi, Toyoaki; Saito, Takeshi; Sudo, Yuka; Fujihara, Hiroaki; Minami, Kouichiro; Nagatomo, Toshihisa; Uezono, Yasuhito; Ueta, Yoichi

    2011-03-25

    Allyl isothiocyanates (AITC) and cinnamaldehyde are pungent compounds present in mustard oil and cinnamon oil, respectively. These compounds are well known as transient receptor potential ankyrin 1 (TRPA1) agonists. TRPA1 is activated by low temperature stimuli, mechanosensation and pungent irritants such as AITC and cinnamaldehyde. TRPA1 is often co-expressed in TRPV1. Recent study showed that hypertonic solution activated TRPA1 as well as TRPV1. TRPV1 is involved in excitatory synaptic inputs to the magnocellular neurosecretory cells (MNCs) that produce vasopressin in the supraoptic nucleus (SON). However, it remains unclear whether TRPA1 may be involved in this activation. In the present study, we examined the role of TRPA1 on the synaptic inputs to the MNCs in in vitro rat brain slice preparations, using whole-cell patch-clamp recordings. In the presence of tetrodotoxin, AITC (50μM) and cinnamaldehyde (30μM) increased the frequency of miniature excitatory postsynaptic currents without affecting the amplitude. This effect was significantly attenuated by previous exposure to ruthenium red (10μM), non-specific TRP channels blocker, high concentration of menthol (300μM) and HC-030031 (10μM), which are known to antagonize the effects of TRPA1 agonists. These results suggest that TRPA1 may exist at presynaptic terminals to the MNCs and enhance glutamate release in the SON. PMID:21266172

  1. Allyl functionalized phosphinite and phosphonite ligands: Synthesis, transition metal chemistry and orthopalladation reactions

    Indian Academy of Sciences (India)

    Singappagudem Govindaraju; Guddekoppa S Ananthnag; Susmita Naik; Shaikh M Mobin; Maravanji S Balakrishn

    2012-07-01

    Allyl functionalized phosphinite PPh2(OAr) [Ar=C6H4(-C3H5)] (1) and phosphonite PPh(OAr)2 (2) ligands were prepared by the reactions of 2-allylphenol with PPh2Cl and PPhCl2, respectively. The ruthenium(II) complexes, [Ru(6--cymene)(PPh2(OAr))Cl2] (3) and [Ru(6--cymene)(PPh(OAr)2Cl2)] (4) were obtained by reacting 1 or 2 with [Ru(6--cymene)Cl2]2 in 2:1 molar ratios, respectively. Reactions of 1 or 2 with AuCl(SMe2) gave [Au{PPh2(OAr)}Cl] (5) or [Au{PPh(OAr)2}Cl] (6) in good yield. The palladium complex, [Pd{PPh(OAr)2}2Cl2] (7) was prepared by reacting Pd(COD)Cl2 with 2 in 1:2 molar ratio. The reaction between Pd(COD)Cl2 and 1 yielded a mixture of orthopalladated cis- and trans-[Pd(Ph2P(OAr))Cl]2 (8a and 8b). The treatment of 8 with PPh3 and Ph2PCH2PPh2 resulted in the cleavage of chloro bridge to give respectively, [Ph2(OAr)PPd(PPh3)Cl] (9) and [Ph2(ArO)PPd(2-dppm)]OTf (10). Single crystal X-ray structure of the ruthenium complex 3 is described.

  2. CuCl-Catalyzed Aerobic Oxidation of Allylic and Propargylic Alcohols to Aldehydes or Ketones with 1 : 1 Combination of Phenanthroline and Bipyridine as the Ligandst%CuCl-Catalyzed Aerobic Oxidation of Allylic and Propargylic Alcohols to Aldehydes or Ketones with 1 : 1 Combination of Phenanthroline and Bipyridine as the Ligandst

    Institute of Scientific and Technical Information of China (English)

    刘宇; 麻生明

    2012-01-01

    We developed a modified protocol for the oxidation of 2,3-allenyl alcohols using CuCI with l : 1 combination of phenanthroline and bipyridine as the catalyst. To further investigate the applicability of this system, other types of alcohols such as allylic and propargylic alcohols have been tested: we found that both allylic and propargylic alcohols may be oxidized to the corresponding aldehydes or ketones using molecular oxygen in air as the oxidant with moderate to excellent yields.

  3. Allyl/propenyl phenol synthases from the creosote bush and engineering production of specialty/commodity chemicals, eugenol/isoeugenol, in Escherichia coli.

    Science.gov (United States)

    Kim, Sung-Jin; Vassão, Daniel G; Moinuddin, Syed G A; Bedgar, Diana L; Davin, Laurence B; Lewis, Norman G

    2014-01-01

    The creosote bush (Larrea tridentata) harbors members of the monolignol acyltransferase, allylphenol synthase, and propenylphenol synthase gene families, whose products together are able to catalyze distinct regiospecific conversions of various monolignols into their corresponding allyl- and propenyl-phenols, respectively. In this study, co-expression of a monolignol acyltransferase with either substrate versatile allylphenol or propenylphenol synthases in Escherichia coli established that various monolignol substrates were efficiently converted into their corresponding allyl/propenyl phenols, as well as providing proof of concept for efficacious conversion in a bacterial platform. This capability thus potentially provides an alternate source to these important plant phytochemicals, whether for flavor/fragrance and fine chemicals, or ultimately as commodities, e.g., for renewable energy or other intermediate chemical purposes. Previous reports had indicated that specific and highly conserved amino acid residues 84 (Phe or Val) and 87 (Ile or Tyr) of two highly homologous allyl/propenyl phenol synthases (circa 96% identity) from a Clarkia species mainly dictate their distinct regiospecific catalyzed conversions to afford either allyl- or propenyl-phenols, respectively. However, several other allyl/propenyl phenol synthase homologs isolated by us have established that the two corresponding amino acid 84 and 87 residues are not, in fact, conserved.

  4. Fluorinated alcohols as promoters for the metal-free direct substitution reaction of allylic alcohols with nitrogenated, silylated, and carbon nucleophiles.

    Science.gov (United States)

    Trillo, Paz; Baeza, Alejandro; Nájera, Carmen

    2012-09-01

    The direct allylic substitution reaction using allylic alcohols in 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) and 2,2,2-trifluoroethanol (TFE) as reaction media is described. The developed procedure is simple, works under mild conditions (rt, 50 and 70 °C), and proves to be very general, since different nitrogenated nucleophiles and carbon nucleophiles can be used achieving high yields, especially when HFIP is employed as solvent and aromatic allylic alcohols are the substrates. Thus, sulfonamides, carbamates, carboxamides, and amines can be successfully employed as nitrogen-based nucleophiles. Likewise, silylated nucleophiles such as trimethylsilylazide, allyltrimethylsilane, trimethylsilane, and trimethylsilylphenylacetylene give the corresponding allylic substitution products in high yields. Good results for the Friedel-Crafts adducts are also achieved with aromatic compounds (phenol, anisole, indole, and anilines) as nucleophiles. Particularly interesting are the results obtained with electron-rich anilines, which can behave as nitrogenated or carbon nucleophiles depending on their electronic properties and the solvent employed. In addition, 1,3-dicarbonyl compounds (acetylacetone and Meldrum's acid) are also successfully employed as soft carbon nucleophiles. Studies for mechanism elucidation are also reported, pointing toward the existence of carbocationic intermediates and two working reaction pathways for the obtention of the allylic substitution product.

  5. Stereoselective coordination: a six-membered P,N-chelate tailored for asymmetric allylic alkylation.

    Science.gov (United States)

    Császár, Z; Farkas, G; Bényei, A; Lendvay, G; Tóth, I; Bakos, J

    2015-10-01

    Six-membered chelate complexes [Pd(1a-b)Cl2], (2a-b) and [Pd(1a-b)(η(3)-PhCHCHCHPh)]BF4, (3a-b) of P,N-type ligands 1a, ((2S,4S)-2-diphenyl-phosphino-4-isopropylamino-pentane) and 1b, ((2S,4S)-2-diphenyl-phosphino-4-methylamino-pentane) have been prepared. The Pd-complexes have been characterized in solution by 1D and 2D NMR spectroscopy. The observed structures were confirmed by DFT calculations and in the case of 2a also by X-ray crystallography. Unexpectedly, the coordination of the all-carbon-backbone aminophosphine 1a resulted in not only a stereospecific locking of the donor nitrogen atom into one of the two possible configurations but also the conformation of the six-membered chelate rings containing three alkyl substituents was forced into the same single chair structure showing the axially placed isopropyl group on the coordinated N-atom. The stereodiscriminative complexation of 1a led to the formation of a palladium catalyst with a conformationally rigid chelate having a configurationally fixed nitrogen and electronically different coordination sites due to the presence of P and N donors. The stereochemically fixed catalyst provided excellent ee's (up to 96%) and activities in asymmetric allylic alkylation reactions. In contrast, the chelate rings formed by 1b exist in two different chair conformations, both containing axial methyl groups, but with the opposite configurations of the coordinated N-atom. Pd-complexes of 1b provided low enantioselectivities in similar alkylations, therefore emphasizing the importance of the stereoselective coordination of N-atoms in analogous P-N chelates. The factors determining the coordination of the ligands were also studied with respect to the chelate ring conformation and the nitrogen configuration.

  6. Does 1-Allyl-3-methylimidazolium chloride Act as a Biocompatible Solvent for Stem Bromelain?

    Science.gov (United States)

    Jha, Indrani; Bisht, Meena; Venkatesu, Pannuru

    2016-06-30

    The broader scope of ILs in chemical sciences particularly in pharmaceutical, bioanalytical and many more applications is increasing day by day. Hitherto, a very less amount of research is available in the depiction of conformational stability, activity, and thermal stability of enzymes in the presence of ILs. In the present study, the perturbation in the structure, stability, and activity of stem bromelain (BM) has been observed in the presence of 1-allyl-3-methylimidazolium chloride ([Amim][Cl]) using various techniques. This is the first report in which the influence of [Amim][Cl] has been studied on the enzyme BM. Fluorescence spectroscopy has been utilized to map out the changes in the environment around tryptophan (Trp) residues of BM and also to discuss the variations in the thermal stability of BM as an outcome of its interaction with the IL at different concentrations. Further, the work delineates the denaturing effect of high concentration of IL on enzyme structure and activity. It dictates the fact that low concentrations (0.01-0.10 M) of [Amim][Cl] are only changing the structural arrangement of the protein without having harsh consequences on its activity and stability. However, high concentrations of IL proved to be totally devastating for both activity and stability of BM. The observed decrease in the stability of BM at high concentration may be due to the combined effect of cation and anion interactions with the protein residues. The present work is successful in dictating the probable mechanism of interaction between BM and [Amim][Cl]. These results can prove to be fruitful in the studies of enzymes in aqueous IL systems since the used IL is thermally stable and nonvolatile in nature thereby providing a pathway of alteration in the activity of enzymes in potentially green systems. PMID:27268069

  7. Antibacterial activity of starch/acrylamide/allyl triphenyl phosphonium bromide copolymers synthesized by gamma irradiation

    International Nuclear Information System (INIS)

    Starch/acrylamide/allyl triphenyl phosphonium bromide (St/AM/TP) copolymers were synthesized by simultaneous gamma irradiation and characterized by FTIR and 1H NMR techniques, weight measurement and titration method. Moreover, their antibacterial activities against Staphylococcus aureus were explored by the viable cell counting method in sterile distilled water. At St/AM/TP 6:8.4:5.6 g, copolymers with higher graft ratio (G) and higher (AM+TP) graft efficiency (EAM+TP) were obtained at 3 and 6 kGy, while cationic degree (CD) and TP graft efficiency (ETP) continuously increased with absorbed dose from 1 to 6 kGy. All of the copolymers were capable of killing >99.75% of 107 CFU/ml S. aureus within 30 mins. Moreover, at 3 kGy, G, EAM+TP and ETP increased with AM/TP from 0:14 to 11.2:2.8 g at St/(AM+TP) 6:14 g, while the optimum CD and antibacterial activity were achieved at AM/TP 7:7 and 8.4:5.6 g. In addition, at 3 kGy, G, EAM+TP and CD increased with St/(AM+TP) from 6:3 to 6:18 g at AM/TP 8.4:5.6 g, while the optimum antibacterial activity was achieved at 6:10 to 6:18 g, and the optimum ETP was achieved at 6:14. - Highlights: • Cationic starch is prepared from AM and TP by Gamma irradiation. • Cationic starch is characterized by FTIR, NMR, weight method and titration method. • Grafting ratio and cationic degree depend on absorbed dose and composition. • Cationic starch shows good antibacterial activity against Staphylococcus aureus

  8. S-Allyl-Cysteines Reduce Amelioration of Aluminum Induced Toxicity in Rats

    Directory of Open Access Journals (Sweden)

    Sadhana Shrivastava

    2011-01-01

    Full Text Available Problem statement: Aluminum (Al is a trivalent cation found in its ionic form in most kinds of animal tissues and in natural waters everywhere. Approach: It is a potent neurotoxin and has been associated in the pathogenesis of several clinical disorders including Alzheimer’s disease. Results: The aim of the study was to demonstrate the protective effect of S-Allyl-Cysteines (SAC against Al-induced toxicity in rat model on certain biochemical parameters, lipid peroxidation and oxidative stress enzymes of white albino rats. Six rats per group were divided into various treatment groups. Group one rats were given normal saline and served as control group. Group two animals received Al as aluminum nitrate 32.5 mg (i.p. for the induction of toxicity. Group three to five received different doses of SAC (25, 50 and 100 mg kg-1 for 3 days after 24 h of Al toxicity. Rats were orally administered their respective doses every day for 3 days. Evaluations were made in blood and tissues. The activity of Acetylcholinesterase (AchE was inhibited in all the parts of brain after Al intoxication. Significant rise were observed the Activities of Serum Transaminases (AST and ALT after toxicant exposure. The activity of â-Aminolevulinic acid Dehydratase (ALAD in blood and â-Aminolevulinic Acid Synthetase (ALAS in brain was decreased after Al exposure. Al significant increased cholesterol, triglyceride, creatinine and urea level in serum. TBARS level was significantly higher and GSH content were significantly lower during toxicity. Total and esterified cholesterol in liver, kidney and brain were increased after Al exposure. Histopathological changes in liver, kidney and brain were also recouped with the therapy. Conclusion/Recommendations: Our data proved that SAC which is a bioactive and bioavailable component of garlic has organosulfur compounds which regulates the thiol status of the cell and scavenges free radicals and work as an antioxidant. Thus SAC

  9. Proton conductive membranes based on poly (styrene-co-allyl alcohol semi-IPN

    Directory of Open Access Journals (Sweden)

    Felipe Augusto Moro Loureiro

    2014-01-01

    Full Text Available The optimization of fuel cell materials, particularly polymer membranes, for PEMFC has driven the development of methods and alternatives to achieve systems with more adequate properties to this application. The sulfonation of poly (styrene-co-allyl alcohol (PSAA, using sulfonating agent:styrene ratios of 2:1, 1:1, 1:2, 1:4, 1:6, 1:8 and 1:10, was previously performed to obtain proton conductive polymer membranes. Most of those membranes exhibited solubility in water with increasing temperature and showed conductivity of approximately 10-5 S cm-1. In order to optimize the PSAA properties, especially decreasing its solubility, semi-IPN (SIPN membranes are proposed in the present study. These membranes were obtained from the diglycidyl ether of bisphenol A (DGEBA, curing reactions in presence of DDS (4,4-diaminodiphenyl sulfone and PSAA. Different DGEBA/PSAA weight ratios were employed, varying the PSAA concentration between 9 and 50% and keeping the mass ratio of DGEBA:DDS as 1:1. The samples were characterized by FTIR and by electrochemical impedance spectroscopy. Unperturbed bands of PSAA were observed in the FTIR spectra of membranes, suggesting that chemical integrity of the polymer is maintained during the synthesis. In particular, bands involving C-C stretching (1450 cm-1, C=C (aromatic, ~ 3030 cm-1 and C-H (2818 and 2928 cm-1 were observed, unchanged after the synthesis. The disappearance or reduction of the intensity of the band at 916 cm-1, attributed to the DGEBA epoxy ring, is evidenced for all samples, indicating the epoxy ring opening and the DGEBA crosslinking. Conductivity of H3PO4 doped membranes increases with temperature, reaching 10-4 S cm-1.

  10. N-allyl epiderpride: An extremely potent SPECT radioligand for the dopamine D2 receptor

    Energy Technology Data Exchange (ETDEWEB)

    Kessler, R.M.; Mason, N.S.; Ansari, M.S. [Vanderbilt Univ., Nashville, TN (United States)] [and others

    1994-05-01

    We have previously reported that epidepride is a potent (K{sub D} 24pM) and specific SPECT radioligand for the dopamine D2 receptor which can be used to study striatal and extrastriatal dopamine D2 receptors in man. We have synthesized and evaluated the N-allyl analogue of epiderpride (APID) as a potential SPECT radioligand for the dopamine D2 receptor. In comparison to epidepride it is even more potent at the dopamine D2 receptor, the K{sub D} for APID being 11 frontal cortical homogenate. The lipophilicity, evaluated using the log kw pH 7.5, was 2.9 versus 2.05 for epidepride. Competitive binding studies using rat striatal, hippocampal and frontal cortical homogenates showed high affinity for only dopamine D2 like cerebellar ratio of 275:1 at 320 minutes post injection-similar to that seen with epidepride, but with nearly four times higher brain uptake. Of interest was the off-rate from the dopamine D2 receptor; it was 0.0046 min{sup -1} in vitro at 25{degrees}C-corresponding to an t 1/2 of 150 minutes. Studies in rhesus monkeys show an in vivo off rate (following 2.5 mg/kg raclopride IV) of about 0.0082 min{sup -1} seen that with epidepride. SPECT studies in rhesus monkeys reveal APID is a promising SPECT radioligand that appears to be similar to epidepride, but with higher brain uptake due to its more optimal lipophilicity for entry into brain.

  11. Elucidation of the regio- and chemoselectivity of enzymatic allylic oxidations with Pleurotus sapidus – conversion of selected spirocyclic terpenoids and computational analysis

    Directory of Open Access Journals (Sweden)

    Verena Weidmann

    2013-10-01

    Full Text Available Allylic oxidations of olefins to enones allow the efficient synthesis of value-added products from simple olefinic precursors like terpenes or terpenoids. Biocatalytic variants have a large potential for industrial applications, particularly in the pharmaceutical and food industry. Herein we report efficient biocatalytic allylic oxidations of spirocyclic terpenoids by a lyophilisate of the edible fungus Pleurotus sapidus. This ‘’mushroom catalysis’’ is operationally simple and allows the conversion of various unsaturated spirocyclic terpenoids. A number of new spirocyclic enones have thus been obtained with good regio- and chemoselectivity and chiral separation protocols for enantiomeric mixtures have been developed. The oxidations follow a radical mechanism and the regioselectivity of the reaction is mainly determined by bond-dissociation energies of the available allylic CH-bonds and steric accessibility of the oxidation site.

  12. Antimicrobial activity of allyl isothiocyanate used to coat biodegradable composite films as affected by storage and handling conditions.

    Science.gov (United States)

    Li, Weili; Liu, Linshu; Jin, Tony Z

    2012-12-01

    We evaluated the effects of storage and handling conditions on the antimicrobial activity of biodegradable composite films (polylactic acid and sugar beet pulp) coated with allyl isothiocyanate (AIT). Polylactic acid and chitosan were incorporated with AIT and used to coat one side of the film. The films were subjected to different storage conditions (storage time, storage temperature, and packed or unpacked) and handling conditions (washing, abrasion, and air blowing), and the antimicrobial activity of the films against Salmonella Stanley in tryptic soy broth was determined. The films (8.16 μl of AIT per cm(2) of surface area) significantly (P packaging.

  13. Allyl- iso-propyltelluride, a new MOVPE precursor for CdTe, HgTe and (Hg,Cd)Te

    Science.gov (United States)

    Hails, Janet E.; Cole-Hamilton, David J.; Stevenson, John; Bell, William

    2000-06-01

    The use of allyl- iso-propyltelluride as the tellurium precursor for the growth of CdTe, HgTe and (Hg,Cd)Te by metal organic vapour-phase epitaxy has been investigated. It has proved to be an efficient source of tellurium with growth rates for HgTe and (Hg,Cd)Te of up to 10 μm h -1 at 300°C. The best CdTe was grown at 4.5 μm h -1 under Me 2Cd-rich conditions at 300°C in the presence of Hg vapour.

  14. The utilization of the mesoporous Ti-SBA-15 catalyst in the epoxidation of allyl alcohol to glycidol and diglycidyl ether in the water medium

    Directory of Open Access Journals (Sweden)

    Wróblewska Agnieszka

    2015-12-01

    Full Text Available This work presents the studies on the optimization the process of allyl alcohol epoxidation over the Ti-SBA-15 catalyst. The optimization was carried out in an aqueous medium, wherein water was introduced into the reaction medium with an oxidizing agent (30 wt% aqueous solution of hydrogen peroxide and it was formed in the reaction medium during the processes. The main investigated technological parameters were: the temperature, the molar ratio of allyl alcohol/hydrogen peroxide, the catalyst content and the reaction time. The main functions the process were: the selectivity of transformation to glycidol in relation to allyl alcohol consumed, the selectivity of transformation to diglycidyl ether in relation to allyl alcohol consumed, the conversion of allyl alcohol and the selectivity of transformation to organic compounds in relation to hydrogen peroxide consumed. The analysis of the layer drawings showed that in water solution it is best to conduct allyl alcohol epoxidation in direction of glycidol (selectivity of glycidol 54 mol% at: the temperature of 10–17°C, the molar ratio of reactants 0.5–1.9, the catalyst content 2.9–4.0 wt%, the reaction time 2.7–3.0 h and in direction of diglycidyl ether (selectivity of diglycidyl ether 16 mol% at: the temperature of 18–33°C, the molar ratio of reactants 0.9–1.65, the catalyst content 2.0–3.4 wt%, the reaction time 1.7–2.6 h. The presented method allows to obtain two very valuable intermediates for the organic industry.

  15. 烯丙基异硫氰酸酯的熏蒸毒力研究%FUMIGATION ACTIVITY OF THE ALLYL ISOTHIOCYANATE

    Institute of Scientific and Technical Information of China (English)

    陈春武; 谢令德; 陈雅群; 何君; 贺艳萍

    2012-01-01

    以玉米象和赤拟谷盗作为实验对象,采用熏蒸方式对烯丙基异硫氰酸酯的毒力进行测定.结果表明,烯丙基异硫氰酸酯对所研究的两种害虫有较好的快速致死作用,同时研究发现在相同熏蒸时间内烯丙基异硫氰酸酯对玉米象熏蒸的LC50和LC99均小于对赤拟谷盗的LC50和LC99,这说明烯丙基异硫氰酸酯对玉米象的熏蒸效果比对赤拟谷盗的好.%Chosing Si tophilus zesmais (Motschulsky) and Tribolium castaneun (Herbst) as experimental objects, the toxicity for the allyl isothiocyanate (AITC) is tested systematically by fumigation method. The result demonstrates that the allyl isothiocyanate presents rapid lethal effect against both of the two types of insects. The research also shows that both the LC50 and the LC99 of the fumigation of the allyl isothiocyanate to the Sitophilus zeamais are less than those of the allyl isothiocyanate to the Tribolium castaneum exposuring the same fumigating time, which indicates that the fumigating effect of the allyl isothiocyanate to the Sitophilus zeamais is more effective than that of the allyl isothiocyanate to the Tribolium castaneum.

  16. 烯丙基苯并恶嗪改性BT树脂的研究%Study on Bismaleimide-Triazine Resin Modiifed by Allyl Benzoxazine

    Institute of Scientific and Technical Information of China (English)

    陈虹; 寇开昌; 王益群; 张宇; 卓龙海

    2014-01-01

    采用熔融缩聚法合成了烯丙基苯并恶嗪(Boz-allyl),并利用傅立叶变换红外光谱,磁共振氢谱对其表征。用动态扫描量热与热重分析研究了其固化过程及热性能,随后用其对双马来酰亚胺-三嗪树脂(BT树脂)改性,并分析了改性树脂的力学性能。结果表明,Boz-allyl存在两种固化机理,固化物5%和10%热失重温度分别为325,385℃,在800℃时质量保持率仍可达34%,说明其具有优良的热稳定性和耐烧蚀性,用其改性后BT树脂韧性明显提高,当Boz-allyl质量分数为8%时冲击和弯曲强度达到最大值,分别为11.32 kJ/m2和127.11 MPa。%An allyl benzoxazine(Boz-allyl) was synthesized by melt polycondensation method and the structures of Boz-allyl was confirmed by Fourier transform infrared spectroscopy and nuclear magnetic resonance. Using differential scanning calorimetery and thermal gravimetric analysis,the curing behavior and thermal property of it were probed. Then the bismaleimide-triazine resin modified by Boz-allyl was prepared and its mechanical properties was investigated. The results show a dual cure pattern of Boz-allyl ,while the 5%and 10%weight loss temperatures of polybenzoxazine is 325℃and 385℃respectively,with quality retention rate up to 34%at 800℃,which reveals good heat resistance and ablation resistance. The addition of Boz-allyl into BT resin significantly improves toughness and strength,its impact strength and flexural strength is up to their maximums of 11.32 kJ/m2 and 127.11 MPa when the mass fraction of Boz-allyl is 8%.

  17. Allyl thiourea as a corrosion inhibitor for cold rolled steel in H{sub 3}PO{sub 4} solution

    Energy Technology Data Exchange (ETDEWEB)

    Li Xianghong, E-mail: xianghong-li@163.com [Faculty of Science, Southwest Forestry University, Kunming 650224 (China) and Key Laboratory for Forest Resources Conservation and Use in the Southwest Mountains of China Ministry of Education, Southwest Forestry University, Kunming 650224 (China); Deng Shuduan [Faculty of Materials Engineering, Southwest Forestry University, Kunming 650224 (China); Fu Hui [Faculty of Science, Southwest Forestry University, Kunming 650224 (China)

    2012-02-15

    Highlights: Black-Right-Pointing-Pointer Allyl thiourea (ATU) acts as a good inhibitor for steel in 1.0 M H{sub 3}PO{sub 4}. Black-Right-Pointing-Pointer Inhibition efficiency increases slightly with the temperature at 0.2-0.5 mM. Black-Right-Pointing-Pointer The adsorption of ATU on steel surface obeys Langmuir adsorption isotherm. Black-Right-Pointing-Pointer ATU behaves as a mixed-type inhibitor. - Abstract: The inhibition effect of allyl thiourea (ATU) on the corrosion of cold rolled steel (CRS) in 1.0 M H{sub 3}PO{sub 4} solution at 20-50 Degree-Sign C was studied by weight loss, potentiodynamic polarisation, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) methods. The results show that ATU is a good inhibitor, and the maximum inhibition efficiency of 0.5 mM inhibitor is higher than 95% at all studied temperatures. The adsorption of ATU obeys Langmuir adsorption isotherm. Polarisation curves show that ATU behaves as a mixed-type inhibitor. EIS spectra exhibit one capacitive loop. The inhibition action is also evidenced by SEM.

  18. A recyclable heavy fluorous tag carrying an allyl alcohol pendant group: design and evaluation toward applications in synthetic carbohydrate chemistry.

    Science.gov (United States)

    Fukuda, Kazuo; Tojino, Mami; Goto, Kohtaro; Dohi, Hirofumi; Nishida, Yoshihiro; Mizuno, Mamoru

    2015-04-30

    Toward applications in synthetic carbohydrate chemistry, we converted our previous acid-resistant heavy fluorous tag [(Rf)3C-CH2-OH, 1] to allyl alcohol derivatives [(Rf)3C-CH2-O-(CH2)n-CH=CH-CH2-OH, 3 (n=1) or 4 (n=3)] by means of olefin cross metathesis. They were then subjected to β-glycosylation reactions by using a series of glycosyl donors, including glycosyl bromide and trichloroacetimidates. The terminal OH group in 3 and 4 was found to be β-glycosylated in moderate yield when 2,3,4,6-tetra-O-benzoyl-D-galactosyl trichloroacetimidate was used as the glycosyl donor. Upon a detachment reaction using Pd(PPh3)4, the initial heavy fluorous tag 1 was recovered in high yield (>90%) together with 1-hydroxy sugar, indicating that not only the allyl ether linkage in the glycosides but also the internal di-alkyl ether linkage in 4 be cleaved by the action of the Pd-catalyst enabling long-range olefin transmigration. Potential utility was demonstrated by using the tetra-O-benzoyl-β-D-galactosylated derivative of 3 in a series of deprotection, protection and glycosylation reactions, which were conductible in high yields without using chromatographic purification process. These findings prompt us to propose a general scheme in which the acid-resistant heavy fluorous compound 1 is applied as a recyclable tag in synthetic carbohydrate chemistry. PMID:25753904

  19. Molecular detection and in vitro antioxidant activity of S-allyl-L-cysteine (SAC) extracted from Allium sativum.

    Science.gov (United States)

    Sun, Y-E; Wang, W-D

    2016-01-01

    It is well known that Allium sativum has potential applications to clinical treatment of various cancers due to its remarkable ability in eliminating free radicals and increasing metabolism. An allyl-substituted cysteine derivative - S-allyl-L-cysteine (SAC) was separated and identified from Allium sativum. The extracted SAC was reacted with 1-pyrenemethanol to obtain pyrene-labelled SAC (Py-SAC) to give SAC fluorescence properties. Molecular detection of Py-SAC was conducted by steady-state fluorescence spectroscopy and time-resolved fluorescence method to quantitatively measure concentrations of Py-SAC solutions. The ability of removing 1,1-diphenyl-2-picrylhydrazyl (DPPH) and hydroxyl radical using Py-SAC was determined through oxygen radical absorbance capacity (ORAC). Results showed the activity of Py-SAC and Vitamin C (VC) with ORAC as index, the concentrations of Py-SAC and VC were 58.43 mg/L and 5.72 mg/L respectively to scavenge DPPH, and 8.16 mg/L and 1.67 mg/L to scavenge •OH respectively. Compared with VC, the clearance rates of Py-SAC to scavenge DPPH were much higher, Py-SAC could inhibit hydroxyl radical. The ability of removing radical showed a dose-dependent relationship within the scope of the drug concentration. PMID:27453278

  20. Inhibition of bladder cancer cell proliferation by allyl isothiocyanate (mustard essential oil)

    Energy Technology Data Exchange (ETDEWEB)

    Sávio, André Luiz Ventura, E-mail: savio.alv@gmail.com [UNESP – Universidade Estadual Paulista, Faculdade de Medicina de Botucatu, Departamento de Patologia, Botucatu, SP (Brazil); Nicioli da Silva, Glenda [UFOP – Universidade Federal de Ouro Preto, Escola de Farmácia, Departamento de Análises Clínicas, Ouro Preto, MG (Brazil); Salvadori, Daisy Maria Fávero [UNESP – Universidade Estadual Paulista, Faculdade de Medicina de Botucatu, Departamento de Patologia, Botucatu, SP (Brazil)

    2015-01-15

    Highlights: • AITC inhibits mutant and wild-type TP53 cell proliferation. • Morphological changes and cells debris were observed after AITC treatment in both cells. • BAX and BCL2 expression modulation was observed in wild-type TP53 cells. • BCL2, BAX and ANLN increased and S100P decreased expression was detected in mutated TP53 cells. • AITC effects in gene modulation are dependent TP53 gene status. - Abstract: Natural compounds hold great promise for combating antibiotic resistance, the failure to control some diseases, the emergence of new diseases and the toxicity of some contemporary medical products. Allyl isothiocyanate (AITC), which is abundant in cruciferous vegetables and mustard seeds and is commonly referred to as mustard essential oil, exhibits promising antineoplastic activity against bladder cancer, although its mechanism of action is not fully understood. Therefore, the aim of this study was to investigate the effects of AITC activity on bladder cancer cell lines carrying a wild type (wt; RT4) or mutated (T24) TP53 gene. Morphological changes, cell cycle kinetics and CDK1, SMAD4, BAX, BCL2, ANLN and S100P gene expression were evaluated. In both cell lines, treatment with AITC inhibited cell proliferation (at 62.5, 72.5, 82.5 and 92.5 μM AITC) and induced morphological changes, including scattered and elongated cells and cellular debris. Gene expression profiles revealed increased S100P and BAX and decreased BCL2 expression in RT4 cells following AITC treatment. T24 cells displayed increased BCL2, BAX and ANLN and decreased S100P expression. No changes in SMAD4 and CDK1 expression were observed in either cell line. In conclusion, AITC inhibits cell proliferation independent of TP53 status. However, the mechanism of action of AITC differed in the two cell lines; in RT4 cells, it mainly acted via the classical BAX/BCL2 pathway, while in T24 cells, AITC modulated the activities of ANLN (related to cytokinesis) and S100P. These data confirm

  1. Highly efficient redox isomerization of allylic alcohols at ambient temperature catalyzed by novel ruthenium-cyclopentadienyl complexes--new insight into the mechanism.

    Science.gov (United States)

    Martín-Matute, Belén; Bogár, Krisztián; Edin, Michaela; Kaynak, F Betül; Bäckvall, Jan-E

    2005-10-01

    A range of ruthenium cyclopentadienyl (Cp) complexes have been prepared and used for isomerization of allylic alcohols to the corresponding saturated carbonyl compounds. Complexes bearing CO ligands show higher activity than those with PPh3 ligands. The isomerization rate is highly affected by the substituents on the Cp ring. Tetra(phenyl)methyl-substituted catalysts rapidly isomerize allylic alcohols under very mild reaction conditions (ambient temperature) with short reaction times. Substituted allylic alcohols have been isomerized by employing Ru-Cp complexes. A study of the isomerization catalyzed by [Ru(Ph5Cp)(CO)2H] (14) indicates that the isomerization catalyzed by ruthenium hydrides partly follows a different mechanism than that of ruthenium halides activated by KOtBu. Furthermore, the lack of ketone exchange when the isomerization was performed in the presence of an unsaturated ketone (1 equiv), different from that obtained by dehydrogenation of the starting allylic alcohol, supports a mechanism in which the isomerization takes place within the coordination sphere of the ruthenium catalyst. PMID:16028298

  2. Chiral N-1-adamantyl-N-trans-cinnamylaniline type ligands: synthesis and application to palladium-catalyzed asymmetric allylic alkylation of indoles.

    Science.gov (United States)

    Mino, Takashi; Nishikawa, Kenji; Asano, Moeko; Shima, Yamato; Ebisawa, Toshibumi; Yoshida, Yasushi; Sakamoto, Masami

    2016-08-21

    Such chiral phosphine-internal olefin hybrid type ligands as N-1-adamantyl-N-cinnamylaniline derivatives 1 with C(aryl)-N(amine) bond axial chirality were synthesized and utilized for the palladium-catalyzed asymmetric allylic alkylation of indoles to afford the desired products in high enantioselectivities (up to 98% ee). PMID:27425209

  3. Nickel-catalyzed enantioselective hydrovinylation of silyl-protected allylic alcohols:An efficient access to homoallylic alcohols with a chiral quaternary center

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Asymmetric hydrovinylation of silyl-protected allylic alcohols catalyzed by nickel complexes of chiral spiro phosphoramidite ligands was developed.A series of homoallylic alcohols with a chiral quaternary center were produced in high yields(up to 97%) and high enantioselectivities(up to 95% ee).The reaction provides an efficient method for preparing bifunctional compounds with a chiral quaternary carbon center.

  4. γ‐ and δ-Lactams through Palladium-Catalyzed Intramolecular Allylic Alkylation: Enantioselective Synthesis, NMR Investigation, and DFT Rationalization

    DEFF Research Database (Denmark)

    Bantreil, Xavier; Prestat, Guillaume; Moreno, Aitor;

    2011-01-01

    The Pd-catalyzed intramolecular allylic alkylation of unsaturated amides to give gamma- and delta-lactams has been studied in the presence of chiral ligands. Ligand (R)-3,5-tBu-MeOBIPHEP (MeOBIPHEP=6,6'-dimethoxybiphenyl-2,2-diyl)bis(diphenylphosphine)) afforded the best results and allowed the c...

  5. The adsorption stability & inhibition by allyl-thiourea of bulk nanocrystalline ingot iron in dilute HCl solution

    Science.gov (United States)

    Shen, C. B.; Wang, S. G.; Yang, H. Y.; Long, K.; Wang, F. H.

    2006-12-01

    The inhibitive effect of thiourea's (TU) alkyl derivative—allyl-thiourea (ATU) on the corrosion behaviors of bulk nanocrystalline and conventional polycrystalline ingot iron (BNII & CPII) was tested. Results indicate that BNII is less prone to get corrosive than its coarse grain counterpart in blank 1 mol L -1 HCl at room temperature. When CPII and BNII were immersed for a very short time in the corrosive solution inhibited by ATU, namely, 5 min, no inductive loop appears at different concentrations. When time became prolonged, for BNII, a Warburg impedance appeared. Inhibited by ATU, the electrodes composed of the samples are polarized anodically during the potentiodynamic polarization tests, the phenomena of desorption happens at the concentration of 100 mg L -1, but the variation between potential Edes is obvious. The inhibition effect of ATU for BNII is very limited by comparison with CPII in dilute HCl.

  6. Practical and Broadly Applicable Catalytic Enantioselective Additions of Allyl-B(pin) Compounds to Ketones and α-Ketoesters.

    Science.gov (United States)

    Robbins, Daniel W; Lee, KyungA; Silverio, Daniel L; Volkov, Alexey; Torker, Sebastian; Hoveyda, Amir H

    2016-08-01

    A set of broadly applicable methods for efficient catalytic additions of easy-to-handle allyl-B(pin) (pin=pinacolato) compounds to ketones and acyclic α-ketoesters was developed. Accordingly, a large array of tertiary alcohols can be obtained in 60 to >98 % yield and up to 99:1 enantiomeric ratio. At the heart of this development is rational alteration of the structures of the small-molecule aminophenol-based catalysts. Notably, with ketones, increasing the size of a catalyst moiety (tBu to SiPh3 ) results in much higher enantioselectivity. With α-ketoesters, on the other hand, not only does the opposite hold true, since Me substitution leads to substantially higher enantioselectivity, but the sense of the selectivity is reversed as well.

  7. Crystal structure of (E-4-(acetoxyimino-N-allyl-3-isopropyl-2,6-diphenylpiperidine-1-carbothioamide

    Directory of Open Access Journals (Sweden)

    T. Mohandas

    2015-08-01

    Full Text Available The title compound, C26H31N3O2S, crystallizes with two molecules (A and B in the asymmetric unit. In each case, the piperidine ring exists in a twist-boat conformation. The dihedral angle between the phenyl rings is 46.16 (12° in molecule A and 44.95 (12° in molecule B. In both molecules, the allyl side chain is disordered over two orientations in a 0.649 (9:0.351 (9 ratio for molecule A and 0.826 (10:0.174 (10 ratio for molecule B. In the crystal, neither molecule forms a hydrogen bond from its N—H group, presumably due to steric hindrance. A+A and B+B inversion dimers are formed, linked by pairs of weak C—H...O hydrogen bonds enclosing R22(22 ring motifs.

  8. Crystal structure of (E)-4-(acetoxyimino)-N-allyl-3-isopropyl-2,6-diphenylpiperidine-1-carbothioamide

    OpenAIRE

    Mohandas, T; K. Gokula Krishnan; Balamurugan, S.; Harrison, William T. A.; Thanikachalam, V.; Sakthivel, P.

    2015-01-01

    The title compound, C26H31N3O2S, crystallizes with two molecules (A and B) in the asymmetric unit. In each case, the piperidine ring exists in a twist-boat conformation. The dihedral angle between the phenyl rings is 46.16 (12)° in molecule A and 44.95 (12)° in molecule B. In both molecules, the allyl side chain is disordered over two orientations in a 0.649 (9):0.351 (9) ratio for molecule A and 0.826 (10):0.174 (10) ratio for molecule B. In the crystal, neither molecule forms a hydrogen bon...

  9. Improved synthesis of cyclic tertiary allylic alcohols by asymmetric 1,2-addition of AlMe3 to enones.

    Science.gov (United States)

    Kolb, Andreas; Zuo, Wei; Siewert, Jürgen; Harms, Klaus; von Zezschwitz, Paultheo

    2013-11-25

    The development of an improved protocol for the enantioselective Rh(I) /binap-catalysed 1,2-addition of AlMe3 to cyclic enones is reported. (31)P NMR analysis of the reaction revealed that the catalyst in its resting state is a chloride-bridged dimer. This insight led to the use of AgBF4 as an additive for in situ activation of the dimeric precatalyst. Thus, the catalyst loading can now be reduced to only 1 mol% with respect to rhodium. Various 5-7-membered cyclic enones can be transformed into tertiary allylic alcohols with excellent levels of enantioselectivity and high yields. The obtained products are versatile synthetic building blocks, shown by a highly enantioselective formal total synthesis of the pheromone (-)-frontalin as well as formation of a bicyclic lactone that has the core structure of the natural flavour component "wine lactone".

  10. SYNTHESIS, STRUCTURE AND BIOLOGICAL ACTIVITY OF N(4-ALLYL-3-THIOSEMICARBAZONES AND THEIR COORDINATION COMPOUNDS WITH SOME 3D METALS

    Directory of Open Access Journals (Sweden)

    Vasilii GRAUR

    2016-02-01

    Full Text Available The paper presents a review of different N(4-allyl-3-thiosemicarbazones and their coordination compounds described in literature. N(4-allyl-3-thiosemicarbazide can form corresponding thiosemicarbazones with aliphatic, aromatic and heteroaromatic carbonyl compounds. In the presence of transitional metal ions they can form coordination compounds of different structures. Both coordination compounds and proligands manifest antitumor, antibacterial, antiviral, and antimalarial activities. Copper(II coordination compounds with these ligands manifest better antitumor activity than corresponding proligands. SINTEZA, STRUCTURA ŞI ACTIVITATEA BIOLOGICĂ A N(4-ALIL-3-TIOSEMICARBAZONELOR ŞI A COMPUŞILOR COORDINATIVI AI UNOR METALE 3D CU ACEŞTI LIGANZILucrarea prezintă o revistă a N(4-alil-3-tiosemicarbazonelor şi a compuşilor coordinativi cu aceşti liganzi descrise în literatura de specialitate. N(4-alil-3-tiosemicarbazida formează tiosemicarbazone cu aldehide şi cetone alifatice, aro­matice şi heteroaromatice. În prezenţa ionilor de metale de tranziţie acestea pot forma compuşi coordinativi cu diferite structuri. N(4-alil-3-tiosemicarbazonele şi compuşii coordinativi manifestă activitate antitumorală, antibacterială, antivirală şi antimalarică. Compuşii coordinativi ai cuprului cu aceşti liganzi manifestă activitate antitumorală sporită în comparaţie cu N(4-alil-3-tiosemicarbazonele corespunzătoare. 

  11. A Review on Mutagenicity Testing for Hazard Classification of Chemicals at Work: Focusing on in vivo Micronucleus Test for Allyl Chloride.

    Science.gov (United States)

    Rim, Kyung-Taek; Kim, Soo-Jin

    2015-09-01

    Chemical mutagenicity is a major hazard that is important to workers' health. Despite the use of large amounts of allyl chloride, the available mutagenicity data for this chemical remains controversial. To clarify the mutagenicity of allyl chloride and because a micronucleus (MN) test had not yet been conducted, we screened for MN induction by using male ICR mice bone marrow cells. The test results indicated that this chemical is not mutagenic under the test conditions. In this paper, the regulatory test battery and several assay combinations used to determine the genotoxic potential of chemicals in the workplace have been described. Further application of these assays may prove useful in future development strategies of hazard evaluations of industrial chemicals. This study also should help to improve the testing of this chemical by commonly used mutagenicity testing methods and investigations on the underlying mechanisms and could be applicable for workers' health. PMID:26929826

  12. A formal [3,3]-sigmatropic rearrangement route to quaternary alpha-vinyl amino acids: use of allylic N-PMP trifluoroacetimidates.

    Science.gov (United States)

    Berkowitz, David B; Wu, Bin; Li, Huijie

    2006-03-01

    Pd(II)-mediated rearrangement of allylic N-PMP (p-methoxyphenyl) trifluoroacetimidates provides the first formal sigmatropic route to quaternary, alpha-vinylic amino acids, potential suicide substrates for PLP enzymes. The amino acid side chains enter via transition-metal-mediated C-C bond constructions, including (i) Cu(I)-mediated conjugate addition (Ala); (ii) Pd(0)/AsPh3-mediated Stille coupling (allyl-Gly, Phe, DOPA, m-Tyr); and (iii) Pd(0)/Pt-Bu3-mediated Negishi coupling (Leu). In the synthesis of the DOPA decarboxylase inactivator, alpha-vinyl-m-tyrosine, the new N-PMP trifluoroacetimidate rearranges much more efficiently than the corresponding trichloroacetimidate.

  13. Intramolecular carbolithiation of N-allyl-ynamides: an efficient entry to 1,4-dihydropyridines and pyridines – application to a formal synthesis of sarizotan

    Directory of Open Access Journals (Sweden)

    Wafa Gati

    2012-12-01

    Full Text Available We have developed a general synthesis of polysubstituted 1,4-dihydropyridines and pyridines based on a highly regioselective lithiation/6-endo-dig intramolecular carbolithiation from readily available N-allyl-ynamides. This reaction, which has been successfully applied to the formal synthesis of the anti-dyskinesia agent sarizotan, further extends the use of ynamides in organic synthesis and further demonstrates the synthetic efficiency of carbometallation reactions.

  14. Anti-inflammatory potential of allyl-isothiocyanate – role of Nrf2, NF-κB and microRNA-155

    OpenAIRE

    Wagner, Anika Eva; Boesch-Saadatmandi, Christine; Dose, Janina; Schultheiss, Gerhard; Rimbach, Gerald

    2012-01-01

    Abstract In this study, the underlying mechanisms of the potential anti-inflammatory properties of allyl-isothiocyanate (AITC) were analysed in vitro and in vivo. Murine RAW264.7 macrophages stimulated with lipopolysaccharide (LPS) were supplemented with increasing concentrations of AITC. In addition, C57BL/6 mice (n= 10 per group) were fed a pro-inflammatory high-fat diet and AITC was administered orally via gavage for 7 days. Biomarkers of inflammation were determined both in cultured cells...

  15. Identifying Barbiturate Binding Sites in a Nicotinic Acetylcholine Receptor with [3H]Allyl m-Trifluoromethyldiazirine Mephobarbital, a Photoreactive Barbiturate

    OpenAIRE

    Hamouda, Ayman K.; Stewart, Deirdre S.; Chiara, David C.; Savechenkov, Pavel Y.; Bruzik, Karol S.; Cohen, Jonathan B.

    2014-01-01

    At concentrations that produce anesthesia, many barbituric acid derivatives act as positive allosteric modulators of inhibitory GABAA receptors (GABAARs) and inhibitors of excitatory nicotinic acetylcholine receptors (nAChRs). Recent research on [3H]R-mTFD-MPAB ([3H]R-5-allyl-1-methyl-5-(m-trifluoromethyldiazirinylphenyl)barbituric acid), a photoreactive barbiturate that is a potent and stereoselective anesthetic and GABAAR potentiator, has identified a second class of intersubunit binding si...

  16. Palladium-Catalyzed C-H Arylation of α,β-Unsaturated Imines: Catalyst-Controlled Synthesis of Enamine and Allylic Amine Derivatives.

    Science.gov (United States)

    Li, Minyan; González-Esguevillas, María; Berritt, Simon; Yang, Xiaodong; Bellomo, Ana; Walsh, Patrick J

    2016-02-18

    A unique chemo- and regioselective α- and γ-arylation of palladium azapentadienyl intermediates is presented. Two distinct catalysts and sets of conditions successfully controlled the regioselectivity of the arylation. These methods provide the first umpolung C-H functionalization of azapentadienyl palladium intermediates and enable the divergent synthesis of allylic amine and enamine derivatives, which are of significant interest in the pharmaceutical industry. PMID:26846375

  17. Effect of three 2-allyl-p-mentha-6,8-dien-2-ols on inhibition of mild steel corrosion in 1 M HCl

    Directory of Open Access Journals (Sweden)

    S. Kharchouf

    2014-11-01

    Full Text Available 2-Allyl-p-mentha-6,8-dien-2-ols P1−P3 synthesized from carvone P are tested as corrosion inhibitors of steel in 1 M HCl using weight loss measurements, potentiodynamic polarisation and impedance spectroscopy (EIS methods. The addition of 2-allyl-p-mentha-6,8-dien-2-ols reduced the corrosion rate. Potentiodynamic polarisation studies clearly reveal that the presence of inhibitors does not change the mechanism of hydrogen evolution and that they act essentially as cathodic inhibitors. 2-Allyl-p-mentha-6,8-dien-2-ols tested adsorb on the steel surface according to Langmuir isotherm. From the adsorption isotherm some thermodynamic data for the adsorption process are calculated and discussed. EIS measurements show the increase of the charge-transfer resistance with the inhibitor concentration. The highest inhibition efficiency (92% is obtained for P1 at 3 g/L. The corrosion rate decreases with the rise of temperature. The corresponding activation energies are determined.

  18. Reaction of zearalenone and α-zearalenol with allyl isothiocyanate, characterization of reaction products, their bioaccessibility and bioavailability in vitro.

    Science.gov (United States)

    Bordin, K; Saladino, F; Fernández-Blanco, C; Ruiz, M J; Mañes, J; Fernández-Franzón, M; Meca, G; Luciano, F B

    2017-02-15

    This study investigates the reduction of zearalenone (ZEA) and α-zearalenol (α-ZOL) on a solution model using allyl isothiocyanate (AITC) and also determines the bioaccessibility and bioavailability of the reaction products isolated and identified by MS-LIT. Mycotoxin reductions were dose-dependent, and ZEA levels decreased more than α-ZOL, ranging from 0.2 to 96.9% and 0 to 89.5% respectively, with no difference (p⩽0.05) between pH 4 and 7. Overall, simulated gastric bioaccessibility was higher than duodenal bioaccessibility for both mycotoxins and mycotoxin-AITC conjugates, with duodenal fractions representing ⩾63.5% of the original concentration. Simulated bioavailability of reaction products (α-ZOL/ZEA-AITC) were lower than 42.13%, but significantly higher than the original mycotoxins. The cytotoxicity of α-ZOL and ZEA in Caco-2/TC7 cells was also evaluated, with toxic effects observed at higher levels than 75μM. Further studies should be performed to evaluate the toxicity and estrogenic effect of α-ZOL/ZEA-AITC. PMID:27664682

  19. Computational insight into complex structures of thorium coordination with N, N'- bis(3-allyl salicylidene)-o-phenylenediamine.

    Science.gov (United States)

    Lan, Wenbo; Gao, Sha; Lin, Ying-Wu; Liao, Lifu; Wang, Xiaofeng; Nie, Changming

    2016-09-01

    Theoretical calculations on the structure of Th(IV) complex containing N, N'- bis(3-allyl salicylidene)-o-phenylenediamine (BASPDA) were performed using density functional theory (DFT) at the B3LYP/6-311G** level. The geometrical structural parameters and infrared spectra results of the Th(BASPDA)2 from the calculation were compared with the parallel dislocated structure (PDS) obtained in laboratory. The calculated structural parameters were in good agreement with the experimental results. In addition, based on the calculations, a stereoisomer SFS (staggered finger " + " structure) of the Th(BASPDA)2 complex was forecasted by the analysis of a comprehensive method. The charge distribution, structural parameters, bond order indices, spectral properties and thermodynamic properties as well as the molecular orbitals of the two possible crystal structures of Th(BASPDA)2 were also systematically studied. It was expected that this work could provide insightful information for understanding the properties of Th (BASPDA)2 complex at the molecular level.

  20. A dioxygenase of Pleurotus sapidus transforms (+)-valencene regio-specifically to (+)-nootkatone via a stereo-specific allylic hydroperoxidation.

    Science.gov (United States)

    Krügener, Sven; Krings, Ulrich; Zorn, Holger; Berger, Ralf G

    2010-01-01

    A selective and highly efficient allylic oxidation of the sesquiterpene (+)-valencene to the grapefruit flavour compound (+)-nootkatone was achieved with lyophilisate of the edible mushroom Pleurotus sapidus. The catalytic reaction sequence was elucidated through the identification of intermediate, (+)-valencene derived hydroperoxides. A specific staining of hydroperoxides allowed the semi-preparative isolation of two secondary (+)-valencene hydroperoxides, 6(R)-Isopropenyl-4(R),4a(S)-dimethyl-2,3,4,4a,5,6,7,8-octahydro-naphthalen-4(S)-yl-hydroperoxide and 6(R)-Isopropenyl-4(R),4a(S)-dimethyl-2,3,4,4a,5,6,7,8-octahydro-naphthalen-2(R)-yl-hydroperoxide. Chemical reduction of the biotransformation products yielded a tertiary alcohol identified as 2(R)-Isopropenyl-8(R),8a(S)-dimethyl-1,3,4,7,8,8a-hexahydro-2H-naphthalen-4a(R)-ol. This suggested a lipoxygenase-type oxidation of (+)-valencene via secondary and tertiary hydroperoxides and confirmed homology data of the key enzyme obtained previously from amino acid sequencing. PMID:19765983

  1. Influence of the antimicrobial compound allyl isothiocyanate against the Aspergillus parasiticus growth and its aflatoxins production in pizza crust.

    Science.gov (United States)

    Quiles, Juan M; Manyes, Lara; Luciano, Fernando; Mañes, Jordi; Meca, Giuseppe

    2015-09-01

    Aflatoxins (AFs) are secondary metabolites produced by different species of Aspergillus, such as Aspergillus flavus and Aspergillus parasiticus, which possess mutagenic, teratogenic and carcinogenic activities in humans. In this study, active packaging devices containing allyl isothiocyanate (AITC) or oriental mustard flour (OMF) + water were tested to inhibit the growth of A. parasiticus and AFs production in fresh pizza crust after 30 d. The antimicrobial and anti-aflatoxin activities were compared to a control group (no antimicrobial treatment) and to a group added with commercial preservatives (sorbic acid + sodium propionate). A. parasiticus growth was only inhibited after 30 d by AITC in filter paper at 5 μL/L and 10 μL/L, AITC sachet at 5 μL/L and 10 μL/L and OMF sachet at 850 mg + 850 μL of water. However, AFs production was inhibited by all antimicrobial treatments in a dose-dependent manner. More importantly, AITC in a filter paper at 10 μL/L, AITC sachet at 10 μL/L, OMF sachet at 850 mg + 850 μL of water and sorbic acid + sodium propionate at 0.5-2.0 g/Kg completely inhibited AFs formation. The use of AITC in active packaging devices could be a natural alternative to avoid the growth of mycotoxinogenic fungi in refrigerated bakery products in substitution of common commercial preservatives.

  2. Statistic evaluation of cysteine and allyl alcohol as additives for Cu-Zn coatings from citrate baths

    Directory of Open Access Journals (Sweden)

    Julyana Ribeiro Garcia

    2013-04-01

    Full Text Available In the present work, cysteine and allyl alcohol were added to citrate baths as additives to Cu-Zn coatings on steel substrates. In order to verify the effects of the deposition parameters (current density, mechanical stirring speed, and additives on the coating composition, electrochemical behavior, morphology, and microstructure properties of Cu-Zn coatings, the electrodeposition of the alloy was carried out using an experimental composite design 2³, in which these parameters were considered the entry variables and the measured properties were the response variables. The confidence level was 95% and the results were shown as response surface diagrams. It was possible to verify that the current density affected the zinc content in the coating, while the coating produced from cysteine-contained bath presented the worse anticorrosive performance. In a general way, it was possible to observe that the studied parameters affected the morphology, grain size, and the electrochemical behavior of these coatings, although only a few response variables were statistically influenced by them.

  3. Statistic evaluation of cysteine and allyl alcohol as additives for Cu-Zn coatings from citrate baths

    Directory of Open Access Journals (Sweden)

    Julyana Ribeiro Garcia

    2012-01-01

    Full Text Available In the present work, cysteine and allyl alcohol were added to citrate baths as additives to Cu-Zn coatings on steel substrates. In order to verify the effects of the deposition parameters (current density, mechanical stirring speed, and additives on the coating composition, electrochemical behavior, morphology, and microstructure properties of Cu-Zn coatings, the electrodeposition of the alloy was carried out using an experimental composite design 2³, in which these parameters were considered the entry variables and the measured properties were the response variables. The confidence level was 95% and the results were shown as response surface diagrams. It was possible to verify that the current density affected the zinc content in the coating, while the coating produced from cysteine-contained bath presented the worse anticorrosive performance. In a general way, it was possible to observe that the studied parameters affected the morphology, grain size, and the electrochemical behavior of these coatings, although only a few response variables were statistically influenced by them.

  4. Mesoporous sol-gel WO{sub 3} thin films via poly(styrene-co-allyl-alcohol) copolymer templates

    Energy Technology Data Exchange (ETDEWEB)

    Ozkan Zayim, Esra [Department of Physics, Faculty of Science and Letters, Istanbul Technical University, Maslak, Istanbul 80626 (Turkey); Liu, Ping; Lee, Se-Hee; Tracy, C. Edwin; Pitts, J. Roland; Deb, Satyen K. [National Renewable Energy Laboratory, Golden, CO 80401 (United States); Turner, John A.

    2003-12-01

    In this study a copolymer poly(styrene-co-allyl-alcohol), [-CH{sub 2}CH(C{sub 6}H{sub 5})-]{sub x}[-CH{sub 2}CH-(CH{sub 2}OH)-]{sub y} has been employed as a novel template in a sol-gel synthesis process to direct the formation of mesoporous tungsten oxide. The copolymer, due to its rigid hydrophobic block of polystyrene, is a more effective surfactant in an alcohol solution than polypropylene oxide-polyethylene oxide based compounds. The films have been prepared by a spin-coating technique from an ethanol solution of tungsten hexachloride. At room temperature, ultraviolet illumination method has been found to be very suitable for removing the polymer template, leading to the formation of a high-quality mesoporous structure. The electrochromic and optical properties of the mesoporous films are described and compared to standard sol-gel tungsten oxide films. Mesoporous materials exhibit superior high-rate ion-insertion performance when used as electrochromic layers.

  5. Allyl isothiocyanate that induces GST and UGT expression confers oxidative stress resistance on C. elegans, as demonstrated by nematode biosensor.

    Directory of Open Access Journals (Sweden)

    Koichi Hasegawa

    Full Text Available BACKGROUND: Electrophilic xenobiotics and endogenous products from oxidative stresses induce the glutathione S-transferases (GSTs, which form a large family within the phase II enzymes over both animal and plant kingdoms. The GSTs thus induced in turn detoxify these external as well as internal stresses. Because these stresses are often linked to ageing and damage to health, the induction of phase II enzymes without causing adverse effects would be beneficial in slowing down ageing and keeping healthy conditions. METHODOLOGY/PRINCIPAL FINDINGS: We have tested this hypothesis by choosing allyl isothiocyanate (AITC, a functional ingredient in wasabi, as a candidate food ingredient that induces GSTs without causing adverse effects on animals' lives. To monitor the GST induction, we constructed a gst::gfp fusion gene and used it to transform Caenorhabditis elegans for use as a nematode biosensor. With the nematode biosensor, we found that AITC induced GST expression and conferred tolerance on the nematode against various oxidative stresses. We also present evidence that the transcription factor SKN-1 is involved in regulating the GST expression induced by AITC. CONCLUSIONS/SIGNIFICANCE: We show the applicability of the nematode biosensor for discovering and evaluating functional food substances and chemicals that would provide anti-ageing or healthful benefits.

  6. Structure formation of soil dispersions in the presence of polyelectrolytes on the basis of allyl alcohol and acryl acid derivatives

    Directory of Open Access Journals (Sweden)

    Amankait Asanov

    2015-09-01

    Full Text Available Some changes of structural composition and surface properties of soil dispersions in the presence of polyelectrolytes, based on allyl alcohol and acryl acid derivatives, have been studied. The results show, that the changes in the structure of soil dispersions composition are connected with the added concentration and pH value, that depend on mole ratio and nature of functional groups, as well as on the nature of counterions and concomitant electrolytes, changing with the conditions of polymer analogous conversion and neutralization reaction. Experimental data show, that the change in the conformational state and the length of the macromolecule has a significant impact on the structure-forming effect and the amount of polyelectrolyte, needed to achieve the same degree of structure-forming effect of soil dispersions. The causes for the revealed reasons are shown on the basis of the results of the experiment. Along with this, it was found that particular changes of structural composition and surface properties of the soil dispersions depend on the type and concentration of the added polyelectrolyte.

  7. Synthesis, structural characterization and biological activities of organotin(IV) complexes with 5-allyl-2-hydroxy-3-methoxybenzaldehyde-4-thiosemicarbazone

    Indian Academy of Sciences (India)

    Rosenani A Haque; M A Salam

    2015-09-01

    The organotin(IV) complexes [MeSnCl(L)] (2), [BuSnCl(L)] (3), [PhSnCl(L)] (4) and [Me2Sn(L)] (5) were synthesized by reacting organotin(IV) chloride(s) with 5-allyl-2-hydroxy-3-methoxybenzaldehyde- 4-thiosemicarbazone [H2L], (1)] in presence of KOH in 1:2:1 molar ratio (metal salt: base:ligand). All the complexes have been characterized by elemental analyses, UV-Vis, FT-IR, 1H, 13C and 119Sn NMR spectral studies. The molecular structure of complex 5 has been confirmed by single crystal X-ray diffraction analysis. The ligand, H2L coordinates to Sn(IV) in thiolate form through phenoxide-O, azomethine-N and thiolate-S atoms. The C-Sn-C angle measured from coupling constant 1 (119Sn, 13C) for dimethyltin(IV) complex 5 is 123.4°. The 2 (119Sn, 1H) coupling constant values for complex 2 and 5 are 72.4 and 76.3 Hz, respectively. Proposed geometry for five coordinated Sn(IV) atom is a strongly distorted trigonal bipyramid. Biological studies were preformed in vitro against four bacterial strains which have shown better activities and potential as antibacterial agents.

  8. Influence of the antimicrobial compound allyl isothiocyanate against the Aspergillus parasiticus growth and its aflatoxins production in pizza crust.

    Science.gov (United States)

    Quiles, Juan M; Manyes, Lara; Luciano, Fernando; Mañes, Jordi; Meca, Giuseppe

    2015-09-01

    Aflatoxins (AFs) are secondary metabolites produced by different species of Aspergillus, such as Aspergillus flavus and Aspergillus parasiticus, which possess mutagenic, teratogenic and carcinogenic activities in humans. In this study, active packaging devices containing allyl isothiocyanate (AITC) or oriental mustard flour (OMF) + water were tested to inhibit the growth of A. parasiticus and AFs production in fresh pizza crust after 30 d. The antimicrobial and anti-aflatoxin activities were compared to a control group (no antimicrobial treatment) and to a group added with commercial preservatives (sorbic acid + sodium propionate). A. parasiticus growth was only inhibited after 30 d by AITC in filter paper at 5 μL/L and 10 μL/L, AITC sachet at 5 μL/L and 10 μL/L and OMF sachet at 850 mg + 850 μL of water. However, AFs production was inhibited by all antimicrobial treatments in a dose-dependent manner. More importantly, AITC in a filter paper at 10 μL/L, AITC sachet at 10 μL/L, OMF sachet at 850 mg + 850 μL of water and sorbic acid + sodium propionate at 0.5-2.0 g/Kg completely inhibited AFs formation. The use of AITC in active packaging devices could be a natural alternative to avoid the growth of mycotoxinogenic fungi in refrigerated bakery products in substitution of common commercial preservatives. PMID:26146190

  9. Synthesis and structural characterization of [eta superscript 3]-allyl([alpha]-diimine)nickel(II) complexes bearing trimethylsilyl groups

    Energy Technology Data Exchange (ETDEWEB)

    Ionkin, Alex S.; Marshall, William J. (Dupont)

    2012-02-10

    A set of isomeric para- and meta-trimethylsilylphenyl ortho-substituted N,N-phenyl {alpha}-diimine ligands [(Ar-N C(Me)-(Me)C N-Ar) Ar=2,6-di(4-trimethylsilylphenyl)phenyl (16); Ar=2,6-di(3-trimethylsilylphenyl)phenyl (17)] have been synthesized through a two-step procedure. The palladium-catalyzed cross-coupling reaction between 2,6-dibromophenylamine (7) and 4-trimethylsilylphenylboronic acid (8), 3-trimethylsilylphenylboronic acid (9) was used to prepare 4,4-bis(trimethylsilyl)-[1,1;3,1]terphenyl-2-ylamine (10) and 3,3-bis(trimethylsilyl)-[1,1;3,1]terphenyl-2-ylamine (11). The di-1-adamantylphosphine oxide Ad{sub 2}P(O)H (13) and di-tert-butyl-trimethylsilylanylmethylphosphine tert-Bu{sub 2}P-CH{sub 2}-SiMe{sub 3} (14) were used for the first time as ligands for the Suzuki coupling. The condensation of 2,2,3,3-tetramethoxybutane (15) with anilines 10 and 11 afforded {alpha}-diimines 16 and 17. The reaction of {pi}-allylnickel chloride dimer (18), {alpha}-diimines (16), (17) and sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (BAF) (19) or silver hexafluoroantimonate (20) led to two sets of isomeric complexes [{eta}{sup 3}-allyl(Ar-N C(Me)-(Me)C N-Ar)Ni]{sup +} X{sup -}, [Ar=2,6-di(4-trimethylsilylphenyl)phenyl, X=BAF (3), X=SbF6 (4); Ar=2,6-di(3-trimethylsilylphenyl)phenyl, X=BAF (5), X=SbF6 (6)]. The steric repulsion of closely positioned trimethylsilyl groups in 4 caused the distortion of the nickel square planar coordination by 17.6{sup o} according to X-ray analysis.

  10. Structural analysis by reductive cleavage with LiAlH4 of an allyl ether choline-phospholipid, archaetidylcholine, from the hyperthermophilic methanoarchaeon Methanopyrus kandleri

    Directory of Open Access Journals (Sweden)

    Masateru Nishihara

    2002-01-01

    Full Text Available A choline-containing phospholipid (PL-4 in Methanopyrus kandleri cells was identified as archaetidylcholine, which has been described by Sprott et al. (1997. The PL-4 consisted of a variety of molecular species differing in hydrocarbon composition. Most of the PL-4 was acid-labile because of its allyl ether bond. The identity of PL-4 was confirmed by thin-layer chromatography (TLC followed by positive staining with Dragendorff-reagent and fast-atom bombardment–mass spectrometry. A new method of LiAlH4 hydrogenolysis was developed to cleave allyl ether bonds and recover the corresponding hydrocarbons. We confirmed the validity of the LiAlH4 method in a study of the model compound synthetic unsaturated archaetidic acid (2,3-di-O-geranylgeranyl-sn-glycerol-1-phosphate. Saturated ether bonds were not cleaved by the LiAlH4 method. The hydrocarbons formed following LiAlH4 hydrogenolysis of PL-4 were identified by gas–liquid chromatography and mass spectrometry. Four kinds of hydrocarbons with one to four double bonds were detected: 47% of the hydrocarbons had four double bonds; 11% had three double bonds; 14% had two double bonds; 7% had one double bond; and 6% were saturated species. The molecular species composition of PL-4 was also estimated based on acid lability: 77% of the molecular species had two acid-labile hydrocarbons; 11% had one acid-labile and one acid-stable hydrocarbon; and 11% had two acid-stable hydrocarbons. To our knowledge, this is the first report of a specific chemical degradation method for the structural analysis of allyl ether phospholipid in archaea.

  11. Substrate and stereocontrolled iodocycloetherification of highly functionalized enantiomerically pure allylic alcohols: application to synthesis of cytotoxic 2-epi jaspine B and its biological evaluation.

    Science.gov (United States)

    Kundooru, Somireddy; Das, Pintu; Meena, Sanjeev; Kumar, Vikash; Siddiqi, Mohammad Imran; Datta, Dipak; Shaw, Arun K

    2015-08-14

    Stereoselectivities of electrophilic additions of molecular iodine to enantiomerically pure highly functionalized allylic alcohols with internal nucleophiles have been investigated. The intramolecular nucleophilic attack on the I2-π complex by an oxygen nucleophile to obtain tri- and tetrasubstituted THFs is highly regio-, stereoselective and substrate controlled. The application of this study has been shown by utilizing one of the THFs 4a as a key intermediate to complete the total synthesis of marine anti-cancer natural product 2-epi jaspine B. PMID:26133669

  12. Effective production of S-allyl-L-cysteine through a homogeneous reaction with activated endogenous γ-glutamyltranspeptidase in garlic (Allium Sativum)

    OpenAIRE

    Xu, Xiaobian; Miao, Yelian; Chen, Jie Yu; Zhang, Qimei; Wang, Jining

    2013-01-01

    S-allyl-L-cysteine (SAC) is a bioactive compound in garlic (Allium sativum). A novel process including soaking and homogeneous reaction was applied for the effective production of SAC with endogenous γ-glutamyltranspeptidase (γ-GTP, EC 2.3.2.2) in garlic. The effects of temperature and CaCl2 concentration on γ-GTP activity in soaking, and the relationship of SAC production with γ-GTP activity in homogeneous reaction were investigated, using fresh garlic as raw material. The experimental resul...

  13. Synthesis of functionalized 5-substituted thiazolidine-2-thiones via adscititious xanthate-promoted radical cyclization of allyl(alkyl/aryl)dithiocarbamates.

    Science.gov (United States)

    Gao, Simiao; Zhang, Yu; Dong, Jun; Chen, Ning; Xu, Jiaxi

    2016-01-21

    Functionalized 5-substituted thiazolidine-2-thiones were synthesized efficiently from alkyl allyl(alkyl/aryl)-dithiocarbamates via radical cyclization with the corresponding S-alkyl O-ethyl xanthates as the adscititious radical precursors. The application of the adscititious radical precursors improves not only the yields, but also the efficiency in the radical cyclization reaction significantly. The current adscititious radical precursor method provides a new strategy for the achievement and improvement of some radical reactions which are hardly or difficultly realized by the traditional direct methods. PMID:26626401

  14. Platinum-Catalyzed Friedel-Crafts-Type C-H Coupling-Allylic Amination Cascade to Synthesize 3,4-Fused Tricyclic Indoles.

    Science.gov (United States)

    Suzuki, Yuta; Tanaka, Yuito; Nakano, Shun-ichi; Dodo, Kosuke; Yoda, Natsumi; Shinohara, Ken-Ichi; Kita, Kazuko; Kaneda, Atsushi; Sodeoka, Mikiko; Hamada, Yasumasa; Nemoto, Tetsuhiro

    2016-03-18

    A novel platinum-catalyzed cascade cyclization reaction was developed by intramolecular Friedel-Crafts-type C-H coupling of aniline derivatives with a propargyl carbonate unit-allylic amination sequence. Treatment of various propargyl carbonates tethered to meta-aniline derivatives with a Pt(dba)3/DPEphos catalyst system afforded the corresponding 3,4-fused tricyclic 3-alkylidene indolines in 42-99% yield, which were transformed into 3,4-fused indole derivatives by reaction with trifluoroacetic acid. The reaction products exhibited antiproliferative activities against cancer cells, but not normal cells, revealing the potential usefulness of this reaction for medicinal chemistry. PMID:26833557

  15. α-Allyl-ω-Methoxy-polyethylenglykol-co-maleat-basierte Polycarboxylat-Fließmittel für ultra-hochfesten Beton (UHPC): Synthese, Eigenschaften, Wirkmechanismus und Funktionalisierung

    OpenAIRE

    Gruber, Mirko

    2010-01-01

    Polycarboxylat-Fließmittel auf Basis von α-Allyl-ω-Methoxypolyethylenglykol-co-maleat wurden hinsichtlich Ankergruppe und Seitenkette chemisch so modifiziert, dass eine optimale Verflüssigung von ultra-hochfestem Beton erzielt wurde. Ergänzend wurde ein Scale-up dieser hocheffizienten Polymere von Labor- in den technischen 20L-Maßstab durchgeführt. Eine weitere Effektivitätssteigerung dieser Fließmittel wurde durch Kombination mit synergistisch wirkenden α-Hydroxycarbonsäuresalzen erzielt. Ei...

  16. (4R-4-(2-Allyl-2H-1,2,3-triazol-4-yl-1,2-O-isopropylidene-l-threose

    Directory of Open Access Journals (Sweden)

    David J. Watkin

    2008-12-01

    Full Text Available X-ray crystallography unequivocally confirmed the structure of the title compound, C12H17N3O4, as (4R-4-(2-allyl-2H-1,2,3-triazol-4-yl-1,2-O-isopropylidene-l-threose. The absolute configuration was determined by the use of d-glucorono-3,6-lactone as the starting material. The crystal structure consists of hydrogen-bonded chains of molecules running parallel to the a axis. There are no unusual packing features.

  17. Synthesis of allyl acrylate by phase-transfer catalysis%相转移催化法制备丙烯酸烯丙酯

    Institute of Scientific and Technical Information of China (English)

    李连贵; 马岩; 王永伟; 敖玉辉

    2011-01-01

    Allyl acrylate (ALA) was synthesized using sodium acrylate, allyl chloride (ALC) as raw materials, with phase-transfer catalysis as catalyst.The ALA was obtained from die crude product by centrifugation,drying,distillation and other purification measures.The optimal synthesis conditions were:TBAB (4% ofreactants) as catalyst,VALC∶ V水 = 1∶1 ,t = 1.75 h,T = 40 ℃.The total ALA yield was 94% and purity was 98%.%以丙烯酸钠与氯丙烯(ALC)为原料,在相转移催化剂存在下合成出丙烯酸烯丙酯(ALA)粗产品,经离心、干燥、蒸馏等纯化手段得ALA产品.最佳反应条件为:以四丁基溴化铵为相转移催化剂,用量为反应物物质的量的4%,VALC∶V水=1∶1,在40℃下反应1.75 h,ALA产率达94%以上,纯度达98%以上.

  18. Catalyst-Directed Diastereoselective Isomerization of Allylic Alcohols for the Stereoselective Construction of C(20) in Steroid Side Chains: Scope and Topological Diversification.

    Science.gov (United States)

    Li, Houhua; Mazet, Clément

    2015-08-26

    The stereoselective construction of C20 in steroidal derivatives by a highly diastereoselective Ir-catalyzed isomerization of primary allylic alcohols is reported. A key aspect of this strategy is a straightforward access to geometrically pure steroidal enol tosylate and enol triflate intermediates for subsequent high yielding stereoretentive Negishi cross-coupling reactions to allow structural diversity to be introduced. A range of allylic alcohols participates in the diastereoselective isomerization under the optimized reaction conditions. Electron-rich and electron-poor aryl or heteroaryl substituents are particularly well-tolerated, and the stereospecific nature of the reaction provides indifferently access to the natural C20-(R) and unnatural C20-(S) configurations. Alkyl containing substrates are more challenging as they affect regioselectivity of iridium-hydride insertion. A rationale for the high diastereoselectivities observed is proposed for aryl containing precursors. The scope of our method is further highlighted through topological diversification in the side chain and within the polycyclic domain of advanced and complex steroidal architectures. These findings have the potential to greatly simplify access to epimeric structural analogues of important steroid scaffolds for applications in biological, pharmaceutical, and medical sciences.

  19. Investigation of the O+allyl addition/elimination reaction pathways from the OCH(2)CHCH(2) radical intermediate.

    Science.gov (United States)

    Fitzpatrick, Benjamin L; Lau, Kai-Chung; Butler, Laurie J; Lee, Shih-Huang; Lin, Jim Jr-Min

    2008-08-28

    These experiments study the preparation of and product channels resulting from OCH(2)CHCH(2), a key radical intermediate in the O+allyl bimolecular reaction. The data include velocity map imaging and molecular beam scattering results to probe the photolytic generation of the radical intermediate and the subsequent pathways by which the radicals access the energetically allowed product channels of the bimolecular reaction. The photodissociation of epichlorohydrin at 193.3 nm produces chlorine atoms and c-OCH(2)CHCH(2) radicals; these undergo a facile ring opening to the OCH(2)CHCH(2) radical intermediate. State-selective resonance-enhanced multiphoton ionization (REMPI) detection resolves the velocity distributions of ground and spin-orbit excited state chlorine independently, allowing for a more accurate determination of the internal energy distribution of the nascent radicals. We obtain good agreement detecting the velocity distributions of the Cl atoms with REMPI, vacuum ultraviolet (VUV) photoionization at 13.8 eV, and electron bombardment ionization; all show a bimodal distribution of recoil kinetic energies. The dominant high recoil kinetic energy feature peaks near 33 kcalmol. To elucidate the product channels resulting from the OCH(2)CHCH(2) radical intermediate, the crossed laser-molecular beam experiment uses VUV photoionization and detects the velocity distribution of the possible products. The data identify the three dominant product channels as C(3)H(4)O (acrolein)+H, C(2)H(4)+HCO (formyl radical), and H(2)CO (formaldehyde)+C(2)H(3). A small signal from C(2)H(2)O (ketene) product is also detected. The measured velocity distributions and relative signal intensities at me=27, 28, and 29 at two photoionization energies show that the most exothermic product channel, C(2)H(5)+CO, does not contribute significantly to the product branching. The higher internal energy onset of the acrolein+H product channel is consistent with the relative barriers en route to

  20. Ultraviolet Photodissociation Dynamics of the Allyl Radical via the B̃(2)A1(3s), C̃(2)B2(3py), and Ẽ(2)B1(3px) Electronic Excited States.

    Science.gov (United States)

    Song, Yu; Lucas, Michael; Alcaraz, Maria; Zhang, Jingsong; Brazier, Christopher

    2015-12-17

    Ultraviolet (UV) photodissociation dynamics of jet-cooled allyl radical via the B̃(2)A1(3s), C̃(2)B2(3py), and Ẽ(2)B1(3px) electronically excited states are studied at the photolysis wavelengths from 249 to 216 nm using high-n Rydberg atom time-of-flight (HRTOF) and resonance-enhanced multiphoton ionization (REMPI) techniques. The photofragment yield (PFY) spectra of the H atom products are measured using both allyl chloride and 1,5-hexadiene as precursors of the allyl radical and show a broad peak centered near 228 nm, whereas the previous UV absorption spectra of the allyl radical peak around 222 nm. This difference suggests that, in addition to the H + C3H4 product channel, another dissociation channel (likely CH3 + C2H2) becomes significant with increasing excitation energy. The product translational energy release of the H + C3H4 products is modest, with the P(ET) distributions peaking near 8.5 kcal/mol and the fraction of the average translational energy in the total excess energy, ⟨fT⟩, in the range 0.22-0.18 from 249 to 216 nm. The P(ET)'s are consistent with production of H + allene and H + propyne, as suggested by previous experimental and theoretical studies. The angular distributions of the H atom products are isotropic, with the anisotropy parameter β ≈ 0. The H atom dissociation rate constant from the pump-probe study gives a lower limit of 1 × 10(8)/s. The dissociation mechanism is consistent with unimolecular decomposition of the hot allyl radical on the ground electronic state after internal conversion of the electronically excited state. PMID:26334360

  1. Velocity Map Imaging Study of Ion-Radical Chemistry: Charge Transfer and Carbon-Carbon Bond Formation in the Reactions of Allyl Radicals with C(.).

    Science.gov (United States)

    Pei, Linsen; Farrar, James M

    2016-08-11

    We present an experimental and computational study of the dynamics of collisions of ground state carbon cations with allyl radicals, C3H5, at a collision energy of 2.2 eV. Charge transfer to produce the allyl cation, C3H5(+), is exoergic by 3.08 eV and proceeds via energy resonance such that the electron transfer occurs without a significant change in nuclear velocities. The products have sufficient energy to undergo the dissociation process C3H5(+) → C3H4(+) + H. Approximately 80% of the reaction products are ascribed to charge transfer, with ∼40% of those products decaying via loss of a hydrogen atom. We also observe products arising from the formation of new carbon-carbon bonds. The experimental velocity space flux distributions for the four-carbon products are symmetric about the centroid of the reactants, providing direct evidence that the products are mediated by formation of a C4H5(+) complex living at least a few rotational periods. The primary four-carbon reaction products are formed by elimination of molecular hydrogen from the C4H5(+) complex. More than 75% of the nascent C4H3(+) products decay by C-H bond cleavage to yield a C4H2(+) species. Quantum chemical calculations at the MP2/6-311+g(d,p) level of theory support the formation of a nonplanar cyclic C4H5(+) adduct that is produced when the p-orbital containing the unpaired electron on C(+) overlaps with the unpaired spin density on the terminal carbon atoms in allyl. Product formation then occurs by 1,2-elimination of molecular hydrogen from the cyclic intermediate to form a planar cyclic C4H3(+) product. The large rearrangement in geometry as the C4H3(+) products are formed is consistent with high vibrational excitation in that product and supports the observation that the majority of those products decay to form the C4H2(+) species. PMID:27434380

  2. Induction of apoptosis in human liver carcinoma HepG2 cell line by 5-allyl-7-gen-difluoromethylenechrysin

    Institute of Scientific and Technical Information of China (English)

    Xiang-Wen Tan; Hong Xia; Jin-Hua Xu; Jian-Guo Cao

    2009-01-01

    AIM: To investigate the effect of 5-allyl-7-gen-difluoromethylenechrysin (ADFMChR) on apoptosis of human liver carcinoma HepG2 cell line and the molecular mechanisms involved. METHODS: HepG2 cells and L-02 cells were cultured in vitro and the inhibitory effect of ADFMChR on their proliferation was measured by MTT assay. The apoptosis of HepG2 cells was determined by flow cytometry (FCM) using propidium iodide (PI) fluorescence staining.DNA ladder bands were observed by DNA agarose gel electrophoresis. The influence of ADFMChR on the proxisome proliferator-activated receptor γ (PPARγ), NF-κB, Bcl-2 and Bax protein expression of HepG2 cells were analyzed by Western blotting. RESULTS: MTT assay showed that ADFMChR significantly inhibited proliferation of HepG2 cells in a dosedependent manner, with little effect on growth of L-02 cells, and when IC50 was measured as 8.45 μmol/L and 191.55 μmol/L respectively, the potency of ADFMChR to HepG2 cells, was found to be similar to 5-fluorouracil (5-FU, IC50 was 9.27 μmol/L). The selective index of ADFMChR cytotoxicity to HepG2 cells was 22.67 (191.55/8.45), higher than 5-FU (SI was 7.05 (65.37/9.27). FCM with PI staining demonstrated that the apoptosis rates of HepG2 cells treated with 3.0, 10.0 and 30.0 μmol/L ADFMChR for 48 h were 5.79%, 9.29% and 37.8%, respectively, and were significantly higher when treated with 30.0 μmol/L ADFMChR than when treated with 30.0 μmol/L ChR (16.0%) ( P < 0.05) and were similar to those obtained with 30.0 μmol/L 5-FU (41.0%). DNA agarose gel electrophoresis showed that treatment of HepG2 cells with 10.0 μmol/L ADFMChR for 48 h and 72 h resulted in typical DNA ladders which could be reversed by 10.00 μmol/L GW9662, a blocker of PPARγ. Western blotting analysis revealed that after 24 h of treatment with 3.0, 10.0, 30.0 μmol/L ADFMChR, PPARγ and Bax protein expression in HepG2 cells increased but Bcl-2 and NF-κB expression decreased; however, pre-incubation with 10.0 μmol/L GW

  3. 1-Allyl-3-methyl-3′,5′-diphenylspiro[quinoxaline-2(1H,2′(3′H-[1,3,4]thiadiazole

    Directory of Open Access Journals (Sweden)

    Seik Weng Ng

    2010-12-01

    Full Text Available In the title spiro compound, C25H22N4S, the planar quinoxaline (r.m.s. deviation = 0.070 Å and planar thiadiazole (r.m.s. deviation = 0.060 Å ring systems share a common C atom; their mean planes are aligned at 89.7 (1°. The thiazole ring possesses two aromatic ring substituents and is nearly coplanar with these rings [the dihedral angles between the thiadiazole and phenyl rings are 5.7 (1 and 10.7 (1°]. The allyl unit is disordered over two positions in a 0.65 (1:0.35 (1 ratio.

  4. Enhancement of the fungicidal activity of amphotericin B by allicin, an allyl-sulfur compound from garlic, against the yeast Saccharomyces cerevisiae as a model system.

    Science.gov (United States)

    Ogita, Akira; Fujita, Ken-ichi; Taniguchi, Makoto; Tanaka, Toshio

    2006-10-01

    Amphotericin B (AmB) is a representative antibiotic for the control of serious fungal infections, and its fungicidal activity was greatly enhanced by allicin, an allyl-sulfur compound from garlic. In addition to the plasma membrane permeability change, AmB induced vacuole membrane damage so that the organelles were visible as small discrete particles. Although allicin was ineffective in promoting AmB-induced plasma membrane disability, this compound enhanced AmB-induced structural damage to the vacuolar membrane even at a non-lethal dose of the antibiotic. Allicin could also enhance the antifungal activity of AmB against the pathogenic fungus Candida albicans and against Aspergillus fumigatus. In contrast, allicin did not enhance the cytotoxic activity of AmB against cells of human promyelocytic leukemia (HL-60), a vacuole-less organism.

  5. Time-resolved fluorescence sensing of pesticides chlorpyrifos, crotoxyphos and endosulfan by the luminescent Eu(III)-8-allyl-3-carboxycoumarin probe

    Science.gov (United States)

    Azab, Hassan A.; Khairy, Gasser M.; Kamel, Rasha M.

    2015-09-01

    This work describes the application of time resolved fluorescence in microtiter plates for investigating the interactions of europium-allyl-3-carboxycoumarin with pesticides chlorpyrifos, endosulfan and crotoxyphos. Stern-Volmer studies at different temperatures for chlorpyrifos and crotoxyphos shows dynamic and static quenching mechanisms respectively. Direct methods for the determination of the pesticides under investigation have been developed using the luminescence variations of the probe in solution. The detection limits are 6.53, 0.004, 3.72 μmol/L for chlorpyrifos, endosulfan, and crotoxyphos, respectively. The binding constants and thermodynamic parameters of the pesticides with probe were evaluated. A thermodynamic analysis showed that the reaction is spontaneous with negative ΔG. Effect of some relevant interferents on the detection of pesticides has been investigated. The new method was applied to the determination of the pesticides in different types of water samples (tap, mineral, and waste water).

  6. Synthesis and Crystal Structure of 1-(4-Nitrobenzyl-3-allyl-1H-benzo[d]imidazol-2(3H-one

    Directory of Open Access Journals (Sweden)

    Dounia Belaziz

    2013-01-01

    Full Text Available A functionalized benzimidazole, 1-(4-nitrobenzyl-3-allyl-1H-benzo[d]imidazol-2(3H-one, has been synthesized, and the crystal structure was determined and analyzed. This compound crystallizes in the monoclinic, space group P21/n (number 14 c with cell parameters, a=7.12148(8 Å, b=16.12035(17 Å, c=13.04169(17 Å, β=93.3043(11, V=1494.71(3 Å3, and Dcalc = 1.375 g/mm3. The solid state geometry is stabilized by intermolecular π–π interactions along with the van der Waals interactions which contribute to the stability of the crystal packing. Computational calculations have been used to properly understand the main intermolecular interactions present in the crystal.

  7. Research on Industrial Catalytic Synthesis of Allyl Isothiocyanate%烯丙基异硫氰酸酯的工业催化合成研究

    Institute of Scientific and Technical Information of China (English)

    王咏梅

    2014-01-01

    Allyl isothiocyanate is an important Intermediate products in organic Production , it is widely used in va-rious fields such as pesticides , medicine and soil disinfection etc . This paper describes different methods from dif -ferent starting materials and routes of synthesis of isothiocyanates , and the temperature , pressure , ratio of raw materials was studied in detail . We also made the effect for the catalyst in this reaction , the influences of solvents on the reaction . Under catalytic conditions , to stage a way of industrial synthesis of allyl isothiocyanate , achieves better purification and reduce the cost of products of dual urpose .%烯丙基异硫氰酸酯是一种重要的有机合成中间体,在合成农药、医药等方面都有比较重要的用途,在土壤消毒方面也有应用。本文叙述了用不同起始原料,不同技术路线合成异硫氰酸酯的方法,并对温度、压力、配料比进行了细致的研究试验。特别研究了催化剂对反应的影响,探讨了溶剂对反应的影响。在催化条件下,以阶段升温的方式工业合成烯丙基异硫氰酯的方法,达到了纯化产品和降低成本的双重目的。

  8. Sterically shielded pyramidal amino groups in two 4,4′-(aryl­methyl­ene)bis­(6-allyl-3-chloro-2-methyl­aniline) derivatives

    OpenAIRE

    Blanco, Maria C.; Palma, Alirio; Bahsas, Ali; Hursthouse, Michael B.; Cobo, Justo; Glidewell, Christopher

    2009-01-01

    4,4′-(Phenyl­methyl­ene)bis­(6-allyl-3-chloro-2-methyl­aniline), C27H28Cl2N2, (I), and 4,4′-(2-thienylmethyl­ene)bis­(6-allyl-3-chloro-2-methyl­aniline), C25H26Cl2N2S, (II), adopt similar mol­ecular conformations, although the thienyl group in (II) exhibits orientational disorder over two sets of sites with occupancies of 0.614 (3) and 0.386 (3). The amino groups in both compounds are pyramidal. A single N—H⋯N hydrogen bond links the mol­ecules of (I) into cyclic centrosymmetric dimers. Mol­e...

  9. Bromoallenes as allyl dication equivalents in the presence or absence of palladium(0): direct construction of bicyclic sulfamides containing five- to eight-membered rings by tandem cyclization of bromoallenes.

    Science.gov (United States)

    Hamaguchi, Hisao; Kosaka, Shohei; Ohno, Hiroaki; Fujii, Nobutaka; Tanaka, Tetsuaki

    2007-01-01

    A highly regioselective synthesis of bicyclic sulfamides is described. Based on our recent discovery that bromoallenes can act as allyl dication equivalents in the presence of a palladium catalyst and alcohol, we investigated tandem cyclization of bromoallenes bearing a sulfamide group. It is found that some bromoallenes act as allyl dication equivalents even in the absence of a palladium(0) catalyst to afford cyclosulfamides containing five- or six-membered rings. While the palladium-free cyclization is dependent on the substrate structure affording the bicyclic sulfamides through the first cyclization onto the proximal or central carbon atom of the bromoallenes, the palladium-catalyzed reaction strongly promotes the first cyclization onto the central allenic carbon atom to afford bicyclic sulfamides containing a seven- or eight-membered ring. Formation of two types of bicyclic sulfamides from single bromoallenes by simply changing the reaction conditions is also described. PMID:17200916

  10. Synthesis, Molecular Structure and Characterization of Allylic Derivatives of 6-Amino-3-methyl-1,2,4-triazolo[3,4-f][1,2,4]-triazin-8(7H-one

    Directory of Open Access Journals (Sweden)

    Gene-Hsiang Lee

    2006-06-01

    Full Text Available 1-Allyl- (2 and 7-allyl-6-amino-3-methyl-1,2,4-triazolo[3,4-f][1,2,4]triazin-8(7H-one (3 were obtained via the 18-crown-6-ether catalyzed room temperature reactionof 6-amino-3-methyl-1,2,4-triazolo[3,4-f][1,2,4]triazin-8(7H-one (1 with potassiumcarbonate and allyl bromide in dry acetone. The structures of these two derivatives wereverified by 2D-NMR measurements, including gHSQC and gHMBC measurements. Theminor compound 2 may possess aromatic character. A single crystal X-ray diffractionexperiment indicated that the major compound 3 crystallizes from dimethyl sulfoxide in themonoclinic space group P21/n and its molecular structure includes an attached dimethylsulfoxide molecule, resulting in the molecular formula C10H16N6O2S. Molecular structuresof 3 are linked by extensive intermolecular N-H···N hydrogen bonding [graph set C 1 (7]. 1Each molecule is attached to the dimethyl sulfoxide oxygen via N-H···O intermolecularhydrogen bonding. The structure is further stabilized by π-π stacking interactions.

  11. Pressure Effects on Product Channels of the Allyl Radical Reactions; C3H5+C3H5 and C3H5+CH3

    Science.gov (United States)

    Halpern, J. B.; N'Doumi, M.; Fahr, A.

    2011-12-01

    Relatively large hydrocarbon molecules (C4, C6 and larger) have been detected in several planetary environments. The mechanism for the formation of such large molecular species and detailed mechanism for their potential destruction are not well understood and are of considerable current interest. Previously we have studied the kinetics and product channels of small unsaturated hydrocarbon radical (C2 and C3s) reactions relevant to planetary atmospheric modeling. Reactions of C2 radicals (such as vinyl, H2CCH and ethynyl C2H) and C3 radicals (such as propargyl, HCCCH2) can affect the abundances of a large number of stable observable C3, C4, C5, C6 and larger molecules, including linear, aromatic and even poly aromatic molecules. Pressure-dependent product yields have been determined experimentally for the self- and cross-radical reactions performed at 298 K and at pressures between ~4 Torr (0.5 kPa) and 760 Torr (101 kPa). Final reaction products were quantitatively determined using a gas chromatograph with mass spectrometry/flame ionization detection (GC/MS/FID). In some cases complementary computational studies extended the pressure and temperature range of the experiments and provided valuable information on the complex reaction mechanisms. Theses studies provide a systematic framework so that important energetic and structural parameters for radical-radical reactions can be assessed. Here we report recent results for the allyl radical reactions H2CCCH3+ H2CCCH3 and H2CCCH3+CH3. For the allyl radical self-reaction, at high pressures the "head -to-head", combination channel forming 1,5-hexadiene is dominant with a combination/disproportionation = 1,5-hexadiene/propyne ratio of about 24 at 500 Torr (67 kPa, T=298K). At low pressures the ratio is substantially reduced to about 1.2 (at 0.3 kPa) and other major products are observed including allene, propene, 1-butene and propyne.

  12. Effective production of S-allyl-L-cysteine through a homogeneous reaction with activated endogenous γ-glutamyltranspeptidase in garlic (Allium Sativum).

    Science.gov (United States)

    Xu, Xiaobian; Miao, Yelian; Chen, Jie Yu; Zhang, Qimei; Wang, Jining

    2015-03-01

    S-allyl-L-cysteine (SAC) is a bioactive compound in garlic (Allium sativum). A novel process including soaking and homogeneous reaction was applied for the effective production of SAC with endogenous γ-glutamyltranspeptidase (γ-GTP, EC 2.3.2.2) in garlic. The effects of temperature and CaCl2 concentration on γ-GTP activity in soaking, and the relationship of SAC production with γ-GTP activity in homogeneous reaction were investigated, using fresh garlic as raw material. The experimental results showed that the γ-GTP in fresh garlic was activated by soaking. The yield rate and the final content of SAC increased linearly with increasing initial γ-GTP activity in the homogeneous reaction at 37 °C. The final SAC content reached 606.3 μg/g (i.e. 32 times higher than that in fresh garlic) after soaking for 72 h in a 10-mM CaCl2 solution at 10 °C, and the homogeneous reaction for 8 h at 37 °C. SAC was produced effectively through the homogeneous reaction with activated endogenous γ-GTP in garlic. PMID:25745247

  13. Isomerisation and controlled condensation in an aqueous medium of allyl alcohol catalysed by new water-soluble rhodium complexes with 1,3,5-triaza-7-phosphaadamantane (PTA).

    Science.gov (United States)

    Smoleński, Piotr; Kirillova, Marina V; Guedes da Silva, M Fátima C; Pombeiro, Armando J L

    2013-08-14

    New aqua-soluble rhodium(I) [Rh(CO)(PTA)4]Cl (1) (PTA = 1,3,5-triaza-7-phosphaadamantane) and rhodium(III) [RhCl2(PTA)4]Cl (2) complexes have been synthesized via the reaction of [{Rh(CO)2(μ-Cl)}2] or RhCl3·3H2O, respectively, with stoichiometric amounts of PTA in ethanol. Compound 1 is also obtained upon reduction of 2 in an H2/CO atmosphere. They have been characterized by IR, (1)H and (31)P{H} NMR spectroscopies, elemental and single crystal X-ray diffraction analyses. While compound 1 shows distorted square-pyramid geometry (τ5 = 0.09) with a P3C-type basal plane, compound 2 is octahedral with the chloro ligands in the cis position. The hydride rhodium(I) complex [RhH(PTA)4] (3) is formed upon the addition of NaBH4 to an aqueous solution of 1 or 2. Compounds 1-3 (in the case of 2 upon reduction by H2) act as homogeneous catalysts, or catalyst precursors, in the isomerisation and condensation of allyl alcohol at room temperature and in an aqueous medium. The product selectivity is easily controlled by changing the concentration of the base in the reaction mixture, thus resulting in the exclusive formation of either 3-hydroxy-2-methylpentanal (HP) or 2-methyl-2-pentenal (MP) in quantitative yields. PMID:23793921

  14. Synthesis, molecular modeling and biological evaluation of novel 2-allyl amino 4-methyl sulfanyl butyric acid as α-amylase and α-glucosidase inhibitor

    Science.gov (United States)

    Balan, Kannan; Perumal, Perumal; Sundarabaalaji, Narayanan; Palvannan, Thayumanavan

    2015-02-01

    In the present study 2-allyl amino 4-methyl sulfanyl butyric acid (AMSB) was synthesized in good yield. AMSB was characterized by Fourier transforms infrared spectroscopy (FTIR), Nuclear magnetic resonance (NMR) (1H and 13C) and Liquid chromatography mass spectrometry (LCMS). The radical scavenging activity and reducing power assay of AMSB was assessed using 1-1-diphenyl 2-picryl hydrazyl (DPPH), 2,2‧-azino-bis (3-ethyl benzothiazoline-6-sulfonic acid) (ABTS) and ferric ion reducing antioxidant power assay (FRAP) and was found to be 44.1, 34.71 and 41.7 μg/ml respectively. The compound showed effective inhibition against α-amylase and α-glucosidase. AMSB was identified to be a reversible mixed noncompetitive inhibitor of α-amylase and α-glucosidase. The molecular docking study was carried out to evaluate the specific groove binding properties and affords valuable information of AMSB binding mode in the active site of α-glucosidase the study may lead to the which leads to the rational design of new class of antidiabetic drugs targeting α-glucosidase based on AMSB in near future.

  15. Decreased glycation and structural protection properties of γ-glutamyl-S-allyl-cysteine peptide isolated from fresh garlic scales (Allium sativum L.).

    Science.gov (United States)

    Tan, Dehong; Zhang, Yao; Chen, Lulu; Liu, Ling; Zhang, Xuan; Wu, Zhaoxia; Bai, Bing; Ji, Shujuan

    2015-01-01

    The antiglycative effect of γ-glutamyl-S-allyl-cysteine (GSAC) peptide isolated from fresh garlic scales was investigated in the bovine serum albumin (BSA)/glucose system. GSAC inhibited the increase of fluorescence intensity at about 440 nm in a concentration-dependent manner and reduced reacted free lysine side chains by 10.9%, 24.7% and 37.7%, as the GSAC concentrations increased from 0.1 to 2.5 mg mL(-1). Glycation-specific decline in BSA α-helix content (from 61.3% to 55.6%) and increase in β-sheet (from 2.1% to 5.4%) were prevented by GSAC (2.5 mg mL(-1)) in vitro, implying its stabilisation effect. GSAC treatment (2.5 mg mL(-1)) suppressed protein crosslinking to form polymers. Additionally, GSAC (10, 40, and 160 μg mL(-1)) showed radical-scavenging and metal-chelating capacities. In conclusion, GSAC has an antiglycative effect, which may involve its radical-scavenging and metal-chelating capacities. PMID:25631559

  16. Isolation determination of garlic allyl sulfides and their antioxidant activity%大蒜烯丙基硫化物的分离鉴定及抗氧化性

    Institute of Scientific and Technical Information of China (English)

    刘玲; 陈琭璐; 张瑶; 白冰; 纪淑娟

    2015-01-01

    为了研究大蒜烯丙基硫化物的抗氧化活性,该文利用离子交换层析与制备液相技术从大蒜中分离得到 S-烯丙基-L-半胱氨酸(S-allyl-L-cysteine,SAC)、S-烯丙基-L-半胱氨酸亚砜(S-allyl-L-cysteine sulfoxide,ACSO)和γ-谷氨酰-S-烯丙基-L-半胱氨酸(γ-L-glutamyl-S-allyl-L-cysteine,GSAC)3种水溶性烯丙基硫化物。分离产物利用高效液相色谱-电喷雾离子化串联质谱联用(high performance liquid chromatography-electrospray ionization-mass/mass spectrometry, HPLC-ESI-MS/MS)、核磁共振氢谱(proton nuclear magnetic resonance,1H NMR)和核磁共振碳谱(carbon-13 nuclear magnetic resonance,13C NMR)技术及比旋光度检测方法鉴定,并与合成标准品比对分析确定。同时,该文以具有半胱氨酸结构的还原型谷胱甘肽(glutathione,GSH)为参照测定了 SAC、ACSO、GSAC 的1,1-二苯基-2-三硝基苯肼(1,1-diphenyl-2-picrylhydrazyl,DPPH)自由基清除能力及铁离子螯合能力。结果表明,SAC和GSAC对DPPH自由基的清除率较高(73.55%,72.68%)且与 GSH(71.14%)无显著性差异(P<0.05);SAC 和 ACSO 对铁离子的螯合率较高(81.21%,79.18%)且与GSH(78.13%)无显著性差异(P<0.05),尤其是GSAC对铁离子螯合率(92.76%)显著性高于GSH(P<0.05),证实了3种硫化物均具有很好的抗氧化性能。研究结果进一步解释和阐述大蒜硫化物的螯合能力,进而为大蒜硫化物以抗氧化为基础的其他功能活性研究提供参考。%The allyl-substituted cysteine derivatives were major components of sulfur compounds in garlic. This study separated and identified 3 allyl-substituted cysteine derivatives, i.e.S-allyl-L-cysteine (SAC),S-allyl-L-cysteine sulfoxide (ACSO) andγ-L-glutamyl-S-allyl-L-cysteine (GSAC). Furthermore, scavenging ability of 1,1-Diphenyl-2-picrylhydrazyl (DPPH) free radical and iron chelating ability were tested

  17. Primary photodissociation pathways of epichlorohydrin and analysis of the C-C bond fission channels from an O((3)P)+allyl radical intermediate.

    Science.gov (United States)

    Fitzpatrick, Benjamin L; Alligood, Bridget W; Butler, Laurie J; Lee, Shih-Huang; Lin, Jim Jr-Min

    2010-09-01

    This study initially characterizes the primary photodissociation processes of epichlorohydrin, c-(H(2)COCH)CH(2)Cl. The three dominant photoproduct channels analyzed are c-(H(2)COCH)CH(2)+Cl, c-(H(2)COCH)+CH(2)Cl, and C(3)H(4)O+HCl. In the second channel, the c-(H(2)COCH) photofission product is a higher energy intermediate on C(2)H(3)O global potential energy surface and has a small isomerization barrier to vinoxy. The resulting highly vibrationally excited vinoxy radicals likely dissociate to give the observed signal at the mass corresponding to ketene, H(2)CCO. The final primary photodissociation pathway HCl+C(3)H(4)O evidences a recoil kinetic energy distribution similar to that of four-center HCl elimination in chlorinated alkenes, so is assigned to production of c-(H(2)COC)=CH(2); the epoxide product is formed with enough vibrational energy to isomerize to acrolein and dissociate. The paper then analyzes the dynamics of the C(3)H(5)O radical produced from C-Cl bond photofission. When the epoxide radical photoproduct undergoes facile ring opening, it is the radical intermediate formed in the O((3)P)+allyl bimolecular reaction when the O atom adds to an end C atom. We focus on the HCO+C(2)H(4) and H(2)CO+C(2)H(3) product channels from this radical intermediate in this report. Analysis of the velocity distribution of the momentum-matched signals from the HCO+C(2)H(4) products at m/e=29 and 28 shows that the dissociation of the radical intermediate imparts a high relative kinetic energy, peaking near 20 kcal/mol, between the products. Similarly, the energy imparted to relative kinetic energy in the H(2)CO+C(2)H(3) product channel of the O((3)P)+allyl radical intermediate also peaks at high-recoil kinetic energies, near 18 kcal/mol. The strongly forward-backward peaked angular distributions and the high kinetic energy release result from tangential recoil during the dissociation of highly rotationally excited nascent radicals formed photolytically in this

  18. Ruthenium Catalyzed Diastereo- and Enantioselective Coupling of Propargyl Ethers with Alcohols: Siloxy-Crotylation via Hydride Shift Enabled Conversion of Alkynes to π-Allyls

    Science.gov (United States)

    Liang, Tao; Zhang, Wandi; Chen, Te-Yu; Nguyen, Khoa D.; Krische, Michael J.

    2015-01-01

    The first enantioselective carbonyl crotylations through direct use of alkynes as chiral allylmetal equivalents are described. Chiral ruthenium(II) complexes modified by Josiphos (SL-J009-1) catalyze the C-C coupling of TIPS-protected propargyl ether 1a with primary alcohols 2a-2o to form products of carbonyl siloxy-crotylation 3a-3o, which upon silyl deprotection-reduction deliver 1,4-diols 5a-5o with excellent control of regio-, anti-diastereo- and enantioselectivity. Structurally related propargyl ethers 1b and 1c bearing ethyl- and phenyl-substituents engage in diastereo- and enantioselective coupling, as illustrated in the formation of adducts 5p and 5q, respectively. Selective mono-tosylation of diols 5a, 5c, 5e, 5f, 5k and 5m is accompanied by spontaneous cyclization to deliver the trans-2,3-disubstituted furans 6a, 6c, 6e, 6f, 6k and 6m, respectively. Primary alcohols 2a, 2l and 2p were converted to the siloxy-crotylation products 3a, 3l and 3p, which upon silyl deprotection-lactol oxidation were transformed to the trans-4,5-disubstituted γ-butyrolactones 7a, 7l and 7p. The formation of 7p represents a total synthesis of (+)-trans-whisky lactone. Unlike closely related ruthenium catalyzed alkyne-alcohol C-C couplings, deuterium labeling studies provide clear evidence of a novel 1,2-hydride shift mechanism that converts metal-bound alkynes to π-allyls in the absence of intervening allenes. PMID:26418572

  19. SYNTHESIS AND ANTITUMOR ACTIVITY OF COPPER, NICKEL AND COBALT COORDINATION COMPOUNDS WITH 1-(2-HYDROXYPHENYLETHANONE N(4-ALLYL-3-THIOSEMICARBAZONE

    Directory of Open Access Journals (Sweden)

    Vasilii GRAUR

    2015-12-01

    Full Text Available The paper presents the synthesis of the ligand 1-(2-hydroxyphenylethanone N(4-allyl-3-thiosemicarbazone (H2L and six coordination compounds of copper, nickel and cobalt with this ligand. The structure of thiosemicarbazone H2L was studied using 1H and 13С NMR spectroscopy. The synthesized coordination compounds were studied using elemental analysis, gravimetric analysis of water content, molar conductivity, and magnetochemistry. For H2L the antitumor activity towards human leukemia HL-60 cells and cervical cancer HeLa cells was determined. It was established that the substitution of hydrogen atom with methyl group in the azomethinic fragment leads to the growth of antitumor activity.SINTEZA ŞI ACTIVITATEA ANTITUMORALĂ A COMPUŞILOR COMPLECŞI AI CUPRULUI, NICHELULUI ŞI COBALTULUI CU N(4-ALIL-3-TIOSEMICARBAZONA 1-(2-HIDROXIFENILETANONEILucrarea conţine descrierea sintezei N(4-alil-3-tiosemicarbazonei 1-(2-hidroxifeniletanonei (H2L şi a şase compuşi coordinativi ai cuprului, nichelului şi cobaltului cu acest ligand. Structura tiosemicarbazonei H2L a fost stabilită în baza datelor spectroscopiei RMN 1H şi 13C. Compuşi coordinativi au fost studiaţi cu ajutorul analizei elementale, analizei gravimetrice a conţinutului de apă, conductivitaţii molare şi magnetochimiei. Pentru H2L a fost determinată activitatea antitumorală faţă de celulele leucemiei umane HL-60 şi ale cancerului cervical HeLa. S-a stabilit că înlocuirea atomului de hidrogen cu o grupare metil în fragmentul azomethinic conduce la creşterea activitaţii antitumorale.

  20. Anti-inflammatory potential of allyl-isothiocyanate--role of Nrf2, NF-(κ) B and microRNA-155.

    Science.gov (United States)

    Wagner, Anika Eva; Boesch-Saadatmandi, Christine; Dose, Janina; Schultheiss, Gerhard; Rimbach, Gerald

    2012-04-01

    In this study, the underlying mechanisms of the potential anti-inflammatory properties of allyl-isothiocyanate (AITC) were analysed in vitro and in vivo. Murine RAW264.7 macrophages stimulated with lipopolysaccharide (LPS) were supplemented with increasing concentrations of AITC. In addition, C57BL/6 mice (n= 10 per group) were fed a pro-inflammatory high-fat diet and AITC was administered orally via gavage for 7 days. Biomarkers of inflammation were determined both in cultured cells and in mice. AITC significantly decreased tumour necrosis factor α mRNA levels and its secretion in LPS stimulated RAW264.7 macrophages. Furthermore, gene expression of other pro-inflammatory markers including interleukin-1β and inducible nitric oxide synthase were down-regulated following AITC treatment. AITC decreased nuclear p65 protein levels, a subunit of the transcription factor NF-κB. Importantly, our data indicate that AITC significantly attenuated microRNA-155 levels in LPS-stimulated RAW264.7 macrophages in a dose-dependent manner. The anti-inflammatory effects of AITC were accompanied by an increase in Nrf2 nuclear translocation and consequently by an increase of mRNA and protein levels of the Nrf2 target gene heme-oxygenase 1. AITC was slightly less potent than sulforaphane (used as a positive control) in down-regulating inflammation in LPS-stimulated macrophages. A significant increase in nuclear Nrf2 and heme-oxygenase 1 gene expression and only a moderate down-regulation of interleukin-1β and microRNA-155 levels due to AITC was found in mouse liver. Present data suggest that AITC exhibits potent anti-inflammatory activity in cultured macrophages in vitro but has only little anti-inflammatory activity in mice in vivo. PMID:21692985

  1. Ruthenium Catalyzed Diastereo- and Enantioselective Coupling of Propargyl Ethers with Alcohols: Siloxy-Crotylation via Hydride Shift Enabled Conversion of Alkynes to π-Allyls.

    Science.gov (United States)

    Liang, Tao; Zhang, Wandi; Chen, Te-Yu; Nguyen, Khoa D; Krische, Michael J

    2015-10-14

    The first enantioselective carbonyl crotylations through direct use of alkynes as chiral allylmetal equivalents are described. Chiral ruthenium(II) complexes modified by Josiphos (SL-J009-1) catalyze the C-C coupling of TIPS-protected propargyl ether 1a with primary alcohols 2a-2o to form products of carbonyl siloxy-crotylation 3a-3o, which upon silyl deprotection-reduction deliver 1,4-diols 5a-5o with excellent control of regio-, anti-diastereo-, and enantioselectivity. Structurally related propargyl ethers 1b and 1c bearing ethyl- and phenyl-substituents engage in diastereo- and enantioselective coupling, as illustrated in the formation of adducts 5p and 5q, respectively. Selective mono-tosylation of diols 5a, 5c, 5e, 5f, 5k, and 5m is accompanied by spontaneous cyclization to deliver the trans-2,3-disubstituted furans 6a, 6c, 6e, 6f, 6k, and 6m, respectively. Primary alcohols 2a, 2l, and 2p were converted to the siloxy-crotylation products 3a, 3l, and 3p, which upon silyl deprotection-lactol oxidation were transformed to the trans-4,5-disubstituted γ-butyrolactones 7a, 7l, and 7p. The formation of 7p represents a total synthesis of (+)-trans-whisky lactone. Unlike closely related ruthenium catalyzed alkyne-alcohol C-C couplings, deuterium labeling studies provide clear evidence of a novel 1,2-hydride shift mechanism that converts metal-bound alkynes to π-allyls in the absence of intervening allenes. PMID:26418572

  2. Control of Salmonella on fresh chicken breasts by κ-carrageenan/chitosan-based coatings containing allyl isothiocyanate or deodorized Oriental mustard extract plus EDTA.

    Science.gov (United States)

    Olaimat, Amin N; Holley, Richard A

    2015-06-01

    Control of Salmonella in poultry is a public health concern as salmonellosis is one of the most common foodborne diseases worldwide. This study aimed to screen the ability of 5 Salmonella serovars to degrade the mustard glucosinolate, sinigrin (by bacterial myrosinase) in Mueller-Hinton broth at 25 °C for 21 d and to reduce Salmonella on fresh chicken breasts by developing an edible 0.2% (w/v) κ-carrageenan/2% (w/v) chitosan-based coating containing Oriental mustard extract, allyl isothiocyanate (AITC), EDTA or their combinations. Individual Salmonella serovars degraded 50.2%-55.9% of the sinigrin present in 21 d. κ-Carrageenan/chitosan-based coatings containing 250 mg Oriental mustard extract/g or 50 μl AITC/g reduced the numbers of Salmonella on chicken breasts 2.3 log10 CFU/g at 21 d at 4 °C. However, when either mustard extract or AITC was combined with 15 mg/g EDTA in κ-carrageenan/chitosan-based coatings, Salmonella numbers were reduced 2.3 log10 CFU/g at 5 d and 3.0 log10 CFU/g at 21 d. Moreover, these treatments reduced numbers of lactic acid bacteria and aerobic bacteria by 2.5-3.3 log10 CFU/g at 21 d. κ-Carrageenan/chitosan coatings containing either 50 μl AITC/g or 250 mg Oriental mustard extract/g plus 15 mg EDTA/g have the potential to reduce Salmonella on raw chicken.

  3. 铜表面烯丙基硫脲自组装膜的电化学行为%Electrochemical evaluation of allyl thiourea layers on copper surface

    Institute of Scientific and Technical Information of China (English)

    高洪峰; 康万利; 孟令伟; 王轶男

    2011-01-01

    To elaborate the corrosion behavior of copper in sodium chloride solutions in the presence of allyl thiourea (AT) ,serf-assembled monolayers (SAMs) derived from adsorption of AT onto the surface of copper were evaluated in neutral aqueous sodium chloride solutions. The electrochemical behaviors and inhibition efficiency of copper in neutral sodium chloride solutions containing allyl thiourea were investigated by using electrochemical techniques. It was found that SAMs of AT against copper hinder cathodic reaction enormously. Protective properties of allyl thiourea layers on copper surfaces depend on the corrosion potential,the concentration of AT, and the chloride ions in the environment. The coneentrations of AT have effect on the conditions of the SAMs, which has been proved by SEM observations.%为阐明金属Cu在含稀丙基硫脲NaCl溶液中的腐蚀行为和规律,利用自组装技术在铜表面制备了烯丙基硫脲自组装膜,并在中性氯化钠体系中测试了该自组装膜的电化学行为和缓蚀效率.电化学测定表明,烯丙基硫脲自组装膜对阴极过程有明显的抑制,并且发现自组装膜的保护性质与腐蚀电位、烯丙基硫脲的浓度和溶液中Cl-浓度密切相关.烯丙基硫脲的浓度对自组装膜的状态有很大影响.通过SEM实验验证了不同浓度的稀丙基硫脲形成的自组装膜状态不相同.

  4. Synthesis and reactivity of {alpha}-phenylseleno-{beta}-substituted styrenes: preparation of (Z)-allyl alcohols, (E)-{alpha}-phenyl-{alpha},{beta}-unsaturated aldehydes and {alpha}-aryl acetophenones

    Energy Technology Data Exchange (ETDEWEB)

    Lenardao, Eder J.; Jacob, Raquel G.; Silva, Thiago B. da [Universidade Federal de Pelotas, RS (Brazil). Dept. de Quimica Analitica e Inorganica]. E-mail: lenardao@ufpel.edu.br; Cella, Rodrigo [Santa Maria Univ., RS (Brazil). Dept. de Quimica; Perin, Gelson [Universidade Federal de Pelotas, RS (Brazil). Dept. de Quimica Organica

    2006-09-15

    A new and efficient method was developed to prepare {alpha}-phenylseleno-{beta}-substituted styrenes by reaction of diethyl {alpha}-phenylseleno benzylphosphonate with NaH and aldehydes. Selenium-lithium exchange by reaction with n-BuLi yielded the vinyl lithium species, which were captured with several electrophiles, like aldehydes and DMF, affording exclusively (Z)-allyl alcohols, and (E)-{alpha}-phenyl-{alpha}-{beta}-unsaturated aldehydes, respectively in good yields. The hydrolysis of the vinyl selenides in presence of TiCl{sub 4} allowed the corresponding {alpha}-aryl acetophenones. (author)

  5. Oxidation stability of biodiesel fuels and blends using the Rancimat and PetroOXY methods. Effect of 4-allyl-2,6-dimethoxyphenol and catechol as biodiesel additives on oxidation stability.

    Science.gov (United States)

    Botella, Lucía; Bimbela, Fernando; Martín, Lorena; Arauzo, Jesús; Sánchez, José L

    2014-01-01

    IN THE PRESENT WORK, SEVERAL FATTY ACID METHYL ESTERS (FAME) HAVE BEEN SYNTHESIZED FROM VARIOUS FATTY ACID FEEDSTOCKS: used frying olive oil, pork fat, soybean, rapeseed, sunflower, and coconut. The oxidation stabilities of the biodiesel samples and of several blends have been measured simultaneously by both the Rancimat method, accepted by EN14112 standard, and the PetroOXY method, prEN16091 standard, with the aim of finding a correlation between both methodologies. Other biodiesel properties such as composition, cold filter plugging point (CFPP), flash point (FP), and kinematic viscosity have also been analyzed using standard methods in order to further characterize the biodiesel produced. In addition, the effect on the biodiesel properties of using 4-allyl-2,6-dimethoxyphenol and catechol as additives in biodiesel blends with rapeseed and with soybean has also been analyzed. The use of both antioxidants results in a considerable improvement in the oxidation stability of both types of biodiesel, especially using catechol. Adding catechol loads as low as 0.05% (m/m) in blends with soybean biodiesel and as low as 0.10% (m/m) in blends with rapeseed biodiesel is sufficient for the oxidation stabilities to comply with the restrictions established by the European EN14214 standard. An empirical linear equation is proposed to correlate the oxidation stability by the two methods, PetroOXY and Rancimat. It has been found that the presence of either catechol or 4-allyl-2,6-dimethoxyphenol as additives affects the correlation observed. PMID:25101258

  6. Oxidation stability of biodiesel fuels and blends using the Rancimat and PetroOXY methods. Effect of 4-allyl-2,6-dimetoxiphenol and cathecol as biodiesel additives on oxidation stability

    Science.gov (United States)

    Botella, Lucía; Bimbela, Fernando; Martín, Lorena; Arauzo, Jesús; Sanchez, Jose Luis

    2014-07-01

    In the present work, several fatty acid methyl esters (FAME) have been synthesized from various fatty acid feedstocks: used frying olive oil, pork fat, soybean, rapeseed, sunflower and coconut. The oxidation stabilities of the biodiesel samples and of several blends have been measured simultaneously by both the Rancimat method, accepted by EN14112 standard, and the PetroOXY method, prEN16091 standard, with the aim of finding a correlation between both methodologies. Other biodiesel properties such as composition, cold filter plugging point (CFPP), flash point (FP) and kinematic viscosity have also been analyzed using standard methods in order to further characterize the biodiesel produced. In addition, the effect on the biodiesel properties of using 4-allyl-2,6-dimetoxiphenol and cathecol as additives in biodiesel blends with rapeseed and with soybean has also been analyzed. The use of both antioxidants results in a considerable improvement in the oxidation stability of both types of biodiesel, especially using cathecol. Adding cathecol loads as low as 0.05 % (m/m) in blends with soybean biodiesel and as low as 0.10 % (m/m) in blends with rapeseed biodiesel is sufficient for the oxidation stabilities to comply with the restrictions established by the European EN14214 standard.An empirical linear equation is proposed to correlate the oxidation stability by the two methods, PetroOXY and Rancimat. It has been found that the presence of either cathecol or 4-allyl-2,6-dimetoxiphenol as additives affects the correlation observed.

  7. Oxidation stability of biodiesel fuels and blends using the Rancimat and PetroOXY methods. Effect of 4-allyl-2,6-dimethoxyphenol and catechol as biodiesel additives on oxidation stability.

    Science.gov (United States)

    Botella, Lucía; Bimbela, Fernando; Martín, Lorena; Arauzo, Jesús; Sánchez, José L

    2014-01-01

    IN THE PRESENT WORK, SEVERAL FATTY ACID METHYL ESTERS (FAME) HAVE BEEN SYNTHESIZED FROM VARIOUS FATTY ACID FEEDSTOCKS: used frying olive oil, pork fat, soybean, rapeseed, sunflower, and coconut. The oxidation stabilities of the biodiesel samples and of several blends have been measured simultaneously by both the Rancimat method, accepted by EN14112 standard, and the PetroOXY method, prEN16091 standard, with the aim of finding a correlation between both methodologies. Other biodiesel properties such as composition, cold filter plugging point (CFPP), flash point (FP), and kinematic viscosity have also been analyzed using standard methods in order to further characterize the biodiesel produced. In addition, the effect on the biodiesel properties of using 4-allyl-2,6-dimethoxyphenol and catechol as additives in biodiesel blends with rapeseed and with soybean has also been analyzed. The use of both antioxidants results in a considerable improvement in the oxidation stability of both types of biodiesel, especially using catechol. Adding catechol loads as low as 0.05% (m/m) in blends with soybean biodiesel and as low as 0.10% (m/m) in blends with rapeseed biodiesel is sufficient for the oxidation stabilities to comply with the restrictions established by the European EN14214 standard. An empirical linear equation is proposed to correlate the oxidation stability by the two methods, PetroOXY and Rancimat. It has been found that the presence of either catechol or 4-allyl-2,6-dimethoxyphenol as additives affects the correlation observed.

  8. 3-(alphaR)-alpha-((2S,5R)-4-allyl-2,5-dimethyl-1-piperazinyl)-3-hydroxybenzyl)-N-alkyl-N-arylbenzamides: potent, non-peptidic agonists of both the micro and delta opioid receptors.

    Science.gov (United States)

    Bishop, Michael J; Garrido, Dulce M; Boswell, G Evan; Collins, Mark A; Harris, Philip A; McNutt, Robert W; O'Neill, Scott J; Wei, Ke; Chang, Kwen-Jen

    2003-02-13

    Opioid analgesics with both micro and delta opioid receptor activation represent a new approach to the treatment of severe pain with an improved safety profile. Compounds with this profile may exhibit strong analgesic properties due to micro agonism, with a reduced side effect profile resulting from delta agonism. Replacing the p-diethylamide of the known potent delta opioid receptor selective agonist BW373U86 with a m-diethylamide resulted in a compound with agonist activity at both the micro and delta opioid receptors. Modifying the amide to an N-methyl-N-phenylamide increased agonist potency at both receptors. A series of 3-(alphaR)-alpha-((2S,5R)-4-allyl-2,5-dimethyl-1-piperazinyl)-3-hydroxybenzyl)-N-alkyl-N-arylbenzamides have been made to explore the structure-activity relationship (SAR) around the N-methyl-N-phenylamide. Several potent agonists of both the micro and delta opioid receptors have been identified, including (+)-3-((alphaR)-alpha-((2S,5R)-4-allyl-2,5-dimethyl-1-piperazinyl)-3-hydroxybenzyl)-N-(4-fluorophenyl)-N-methylbenzamide (23), which has EC50 values of 0.67 and 1.1 nM at the micro (guinea pig ileum assay) and delta (mouse vas deferens assay) opioid receptors, respectively.

  9. Ruthenium(II) carbonyl complexes bearing quinoline-based NNO tridentate ligands as catalyst for one-pot conversion of aldehydes to amides and o-allylation of phenols

    Science.gov (United States)

    Manikandan, R.; Prakash, G.; Kathirvel, R.; Viswanathamurthi, P.

    2013-12-01

    Six new octahedral ruthenium(II) carbonyl complexes having the general molecular formula [RuCl(CO)(B)L1-2] (B = PPh3, AsPh3 or py; L1-2 = quinoline based NNO ligand) were synthesized. The quinoline based ligands behave as monoanionic tridentate donor and coordinated to ruthenium via ketoenolate oxygen, azomethine nitrogen and quinoline nitrogen. The composition of the complexes has been established by elemental analysis and spectral methods (FT-IR, electronic, 1H NMR, 13C NMR, 31P NMR and ESI-Mass). The complexes were used as efficient catalysts for one-pot conversion of various aldehydes to their corresponding primary amides in presence of NH2OH·HCl and NaHCO3. The effect of catalyst loading and reaction temperature on catalytic activity of the ruthenium(II) carbonyl complexes were also investigated. The synthesized complexes also possess good catalytic activity for the o-allylation of phenols in the presence of K2CO3 under mild conditions. The complexes afforded branched allyl aryl ethers according to a regioselective reaction.

  10. Asymmetric allylic substitution catalyzed by C1-symmetrical complexes of molybdenum: structural requirements of the ligand and the stereochemical course of the reaction.

    Science.gov (United States)

    Malkov, Andrei V; Gouriou, Laure; Lloyd-Jones, Guy C; Starý, Ivo; Langer, Vratislav; Spoor, Paul; Vinader, Victoria; Kocovský, Pavel

    2006-09-01

    Application of new chiral ligands (R)-(-)-12 a and (S)-(+)-12 c (VALDY), derived from amino acids, to the title reaction, involving cinnamyl (linear) and isocinnamyl (branched) type substrates (4 and 5 --> 6), led to excellent regio- and enantioselectivities (>30:1, < or =98 % ee), showing that ligands with a single chiral center are capable of high asymmetric induction. The structural requirements of the ligand and the mechanism are discussed. The application of single enantiomers of deuterium-labeled substrates (both linear 38 c and branched 37 c) and analysis of the products (41-43) by (2)H{(1)H} NMR spectroscopy in a chiral liquid crystal matrix allowed the stereochemical pathways of the reaction to be distinguished. With ligand (S)-(+)-12 c, the matched enantiomer of branched substrate was found to be (S)-5, which was converted into (R)-6 with very high regio- and stereoselectivity via a process that involves net retention of stereochemistry. The mismatched enantiomer of the branched substrate was found to be (R)-5, which was also converted into (R)-6, that is, with apparent net inversion, but at a lower rate and with lower overall enantioselectivity. This latter feature, which may be termed a "memory effect", reduced the global enantioselectivity in the reaction of the racemic substrate (+/-)-5. The stereochemical pathway of the mismatched manifold has been shown also to be one of net retention, the apparent inversion occurring through equilibration via an Mo-allyl intermediate prior to nucleophilic attack. Incomplete equilibration leads to the memory effect and thus to lower enantioselectivity. Analysis of the mismatched manifold over the course of the reaction revealed that the memory effect is progressively attenuated with the nascent global selectivity increasing substantially as the reaction proceeds. The origin of this effect is suggested to be the depletion of CO sources in the reaction mixture, which attenuates turnover rate and thus facilitates

  11. DFT-Based Explanation of the Effect of Simple Anionic Ligands on the Regioselectivity of the Heck Arylation of Acrolein Acetals

    DEFF Research Database (Denmark)

    Henriksen, Signe Teuber; Tanner, David Ackland; Cacchi, Sandro;

    2009-01-01

    The Heck arylation of acrolein acetal has been studied computationally and compared to the corresponding reaction with allyl ethers. The reaction can be controlled to give either cinnamaldehydes or arylpropanoic esters by addition of different coordinating anions, acetate, or chloride. The comput...

  12. Oxidation stability of biodiesel fuels and blends using the Rancimat and PetroOXY methods. Effect of 4-allyl-2,6-dimetoxiphenol and cathecol as biodiesel additives on oxidation stability

    Directory of Open Access Journals (Sweden)

    Lucía eBotella

    2014-07-01

    Full Text Available In the present work, several fatty acid methyl esters (FAME have been synthesized from various fatty acid feedstocks: used frying olive oil, pork fat, soybean, rapeseed, sunflower and coconut. The oxidation stabilities of the biodiesel samples and of several blends have been measured simultaneously by both the Rancimat method, accepted by EN14112 standard, and the PetroOXY method, prEN16091 standard, with the aim of finding a correlation between both methodologies. Other biodiesel properties such as composition, cold filter plugging point (CFPP, flash point (FP and kinematic viscosity have also been analyzed using standard methods in order to further characterize the biodiesel produced. In addition, the effect on the biodiesel properties of using 4-allyl-2,6-dimetoxiphenol and cathecol as additives in biodiesel blends with rapeseed and with soybean has also been analyzed. The use of both antioxidants results in a considerable improvement in the oxidation stability of both types of biodiesel, especially using cathecol. Adding cathecol loads as low as 0.05 % (m/m in blends with soybean biodiesel and as low as 0.10 % (m/m in blends with rapeseed biodiesel is sufficient for the oxidation stabilities to comply with the restrictions established by the European EN14214 standard.An empirical linear equation is proposed to correlate the oxidation stability by the two methods, PetroOXY and Rancimat. It has been found that the presence of either cathecol or 4-allyl-2,6-dimetoxiphenol as additives affects the correlation observed.

  13. Research in biotransformation of allyl-phenol compounds to produce natural flavors%生物转化烯丙基酚类化合物生产天然香料的研究

    Institute of Scientific and Technical Information of China (English)

    李巧峰; 余旭亚; 孟庆雄; 王亚明

    2011-01-01

    Allyl-phenol compounds is a kind of common aromatic compounds that are often used as starting compounds for the production of various flavors.Recently, biotransformation has emerged as an important approach for producing natural flavors in high quantities.Because the biotransformation processes are environmentally friendly and the products are considered ‘ natural’, flavor production using this method is attracting more and more attention.The recent advances in the synthesis, biotransformation of allyl- phenol compounds and its production of relevant natural flavors were reviewed.Using vanillin as a model to show recent progress in high-value natural flavor production, and the significance of future research in metabolic mechanism character and optimization of biotransformation to improve the yields of target products for scale-up and industrial use were discussed.%烯丙基苯酚类化合物是常见的芳香化合物,是香料生产的常用原料.生物转化已成为生产天然香料的一个重要方法.生物转化过程以其环境友好性、产品是"天然的"等优点,越来越被大家关注.综述了烯丙基苯酚类化合物的生物转化及其生产相关香料的最新进展,并以香草醛为例阐述了生物转化生产高附加值天然香料的潜力.同时,展望了研究生物转化的代谢机制及其工艺优化的现实意义.

  14. Spectroscopic and thermal characterization of Cu(II), Co(II), Ni(II) and Mn(II) complexes of fluorescent dye 4-N,N-dimethyl-ethanolamine-N-allyl-1,8-naphthalimide (4DMEAN)

    Science.gov (United States)

    Refat, Moamen S.; Killa, Hamada M. A.; Fetooh, Hammad

    2010-11-01

    Compounds having general formula: [M(4DMEAN) X (Cl) 2(H 2O) Y]· ZH 2O, where (M = Cu(II), Co(II), Ni(II) and Mn(II), 4DMEAN = 4-N,N-dimethyl-ethanolamine-N-allyl-1,8-naphthalimide, X = 1 or 2, Y = 0 or 2 and Z = 1, 2, 4 or 6) have been prepared. The resulted compounds were characterized by elemental analysis, conductivity measurements, magnetic measurements, (infrared, 1H NMR, mass and electronic) spectra and thermogravimetric analysis. The results were suggested that all 4DMEAN complexes formed have a 1:1 M ratio (metal: 4DMEAN) except for Co(II) complex exist as 1:2. The 4DMEAN ligand acts as a neutral bidentate through both of the oxygen atom of ( sbnd C sbnd OCH 2) group and the lone pair of electron on the nitrogen atom of (N(CH 3) 2 group. The molar conductance measurements proved that the 4DMEAN complexes are non-electrolytes. The kinetic thermodynamic parameters such as: E*, Δ H*, Δ S* and Δ G* were estimated from the DTG curves.

  15. Preservation of acidified cucumbers with a natural preservative combination of fumaric acid and allyl isothiocyanate that target lactic acid bacteria and yeasts

    Science.gov (United States)

    Without the addition of preservative compounds cucumbers acidified with 150 mM acetic acid with pH adjusted to 3.5 typically undergo fermentation by lactic acid bacteria. Fumaric acid (20 mM) inhibited growth of Lactobacillus plantarum and the lactic acid bacteria present on fresh cucumbers, but sp...

  16. Reaction Dynamics Behavior of Epoxidation of Allyl Chloride with Hydrogen Peroxide Catalyzed by Ti-MWW%Ti-MWW催化氯丙烯环氧化反应动力学行为

    Institute of Scientific and Technical Information of China (English)

    方向青; 王钰宁; 邓秀娟; 吴海虹; 吴鹏; 刘月明; 何鸣元

    2011-01-01

    The reaction mechanism for epoxidation of allyl chloride (ALC) with H2O2 catalyzed by Ti-MWW was studied in detail. The results showed that the epoxidation of ALC is first order reaction with respect to the catalyst amount and is the reactions between zero and first order with respect to the substrate concentration and the oxidant concentration. For H2O2, the epoxidation is first order reaction when its concentration is lower than 0.67 mol/L and zero order when its concentration is higher than 2 mol/L. For ALC, only when its concentration is very high, the obvious decrease of the reaction order from I to 0 was observed. And the epoxidation reaction rate is an S-type curve when the Ti content in Ti-MWW increases.%以Ti-MWW分子筛为催化剂,以H2O2为氧化剂,系统研究了氯丙烯环氧化反应的动力学行为.结果表明,该反应速率与Ti-MWW分子筛的用量成正比,是1级反应.当H2O2浓度小于0.67 mol/L时,环氧化反应为1级反应;大于2 mol/L时,为0级反应.随着氯丙烯浓度的增加,环氧化反应级数从1级向0级转变;且只有当其浓度很高时,反应级数才会明显降低.随着分子筛中Ti含量的增加,氯丙烯环氧化反应速率呈S形变化.

  17. Well-defined mono(η3-allyl)nickel complex MONi(η3-C3H5) (M = Si or Al) grafted onto silica or alumina: A molecularly dispersed nickel precursor for syntheses of supported small size nickel nanoparticles

    KAUST Repository

    Li, Lidong

    2014-01-01

    Preparing evenly-dispersed small size nickel nanoparticles over inert oxides remains a challenge today. In this context, a versatile method to prepare supported small size nickel nanoparticles (ca. 1-3 nm) with narrow size distribution via a surface organometallic chemistry (SOMC) route is described. The grafted mono(η3-allyl)nickel complexes MONi(η 3-C3H5) (M = Si or Al) as precursors are synthesized and fully characterized by elemental analysis, FTIR spectroscopy and paramagnetic solid-state NMR. © 2014 the Partner Organisations.

  18. 离子液体1-烯丙基-3-甲基咪唑分离毛竹半纤维素研究%Isolation of hemicelluloses by 1-allyl-3-methyl imidazole ionic liquids from bamboo

    Institute of Scientific and Technical Information of China (English)

    林妲; 彭红; 阮榕生; 余紫苹; 刘玉环

    2012-01-01

    以毛竹为原料,通过1-烯丙基-3-甲基咪唑室温离子液体([Amim]Cl)直接分离半纤维素,并利用红外光谱检测、热动力学分析、中性糖成分检测、糖醛酸含量测定和一维核磁共振成像等分析手段证明氯化1-烯丙基-3-甲基咪唑离子液体可直接分离毛竹半纤维素.所得组分中不含有木质素杂质但混有少量纤维素和果胶质,毛竹半纤维素结构是以(1→4)-β-D-木聚糖为主链,以阿拉伯糖和4-O-甲基-α-D-葡糖醛酸为侧链的木聚糖,其中阿拉伯糖以C-3位与木聚糖主链相连,4-O-甲基-α-D-葡糖醛酸则以O-2位与木糖主链相连.%In this paper, hemicellulose was directly separated through the l-allyl-3-methyl imidazolium room temperature ionic liquid ( [Amim]Cl) from Moso bamboo. The structures of the hemicelluloses were elucidated by FTIR, thermal analysis,l3 CNMR spectroscopy, content of neutral sugars and uronic acids. The results show that the room temperature ionic liquid treatment are effective on the separation of hemicelluloses from bamboo, and the components mixed with a small amount of pectin but not contain lignin and cellulose. The hemicellulosic fraction has a backbone of ( 1→4)-β-D-xylan and aere branched mainly through arabinose and 4-0-methyl-a-D-glucuronic acid,which arabinose at C-3 position of main chain and 4-0-methyl-a-Z)-glucuronic acid at 0-2 position.

  19. Inhibition Action of Allyl Thiourea for Steel in H2 SO4 Solution%烯丙基硫脲对硫酸溶液中钢的吸附与缓蚀作用机理

    Institute of Scientific and Technical Information of China (English)

    李向红; 邓书端; 付惠; 李自美

    2011-01-01

    The inhibition action of allyl thiourea (ATU) on cold rolled steel (CRS) in 1.0 mol/L H2 SO4 solution at 20℃-50 ℃ was investigated by weight loss, potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS). The results showed that ATU is a good inhibitor for CRS in H2SO4 solution, and inhibition efficiency was higher than 94% with the inhibitor concentration of 0. 2 mmol/L. Three adsorption thermodynamic parameters including adsorption free energy AGo , adsorption enthalpy △H0 and adsorption entropy △S0 were also calculated. The inhibition mechanism was discussed in detail according to the parameters. The adsorption of ATU on CRS surface obeys Langmuir adsorption isotherm equation. Polarization curves showed that ATU acts as a mixed-type inhibitor. All EIS spectra exhibit one capacitive loop at high frequency followed by a small inductive loop at low frequency, and the charge transfer resistance increases remarkably after adding ATU inhibitor.%用失重法、动电位极化曲线和电化学阻抗谱(EIS)研究了在1.0mol/L H2S(1)1中20~50℃烯丙基硫脲(ATU)在冷轧钢表面的吸附及缓蚀作用。结果表明:ATU对钢具有好的缓蚀作用,当ATU浓度仅为2.0mmol/L时,缓蚀率大于94%。ATU在钢表面的吸附符合Langmuir吸附模型,得出相应的吸附热力学参数(吸附自由能△G0,吸附焓△H0,吸附熵△S0),并根据这些参数详细讨论了缓蚀作用机理。ATU为混合抑制型缓蚀剂;EIS谱高频区呈半圆容抗弧而低频区呈小段感抗弧,添加ATU后电荷转移电阻显著增大。

  20. Inhibition of lipopolysaccharide-inducible nitric oxide synthase and IL-1beta through suppression of NF-kappaB activation by 3-(1'-1'-dimethyl-allyl)-6-hydroxy-7-methoxy-coumarin isolated from Ruta graveolens L.

    Science.gov (United States)

    Raghav, Sunil Kumar; Gupta, Bhawna; Shrivastava, Anju; Das, Hasi Rani

    2007-03-29

    The Ruta graveolens L. plant is used in traditional medicine to treat a large number of diseases. The methanol (50%) extract of the whole plant was observed to inhibit the expression of inducible nitric oxide synthase (iNOS) and the cycloxygenase-2 (COX-2) gene in lipopolysaccharide (LPS)-induced macrophage cells (J774A.1, [Raghav, S.K., Gupta, B., Agrawal, C., Goswami, K., Das, H.R., 2006b. Anti-inflammatory effect of Ruta graveolens L. in murine macrophage cells. J. Ethnopharmacol. 104, 234-239]). The effect of whole plant extract on the expression of other pro-inflammatory genes such as tumor necrosis factor-alpha (TNF-alpha), interleukin-1beta (IL-1beta), IL-12, interferon-gamma (IFN-gamma) and the activation of nuclear factor-kB (NF-kappaB) were investigated in LPS stimulated macrophage cells. An active compound was isolated from this methanol extract by further solvent fractionation and reverse phase high performance liquid chromatography (RP-HPLC). The purified compound was identified as 3-(1'-1'-dimethyl-allyl)-6-hydroxy-7-methoxy-coumarin having IUPAC nomenclature of 6-hydroxy-7-methoxy-3-(2-methyl but-3-en-2yl)-2H-chromen-2-one by ESI-MS, MALDI, FT-IR and NMR. Effect of this purified compound was assessed on iNOS, COX-2 and various pro-inflammatory cytokine genes and was observed to inhibit both the protein and mRNA expression of iNOS and IL-1beta in LPS challenged macrophages. Electrophoretic mobility shift assay (EMSA) and Western blot analyses indicated that the plant extract and the isolated active compound blocked the LPS-induced activation of NF-kappaB through the prevention of inhibitor-kB (IkB) degradation. The purified compound also showed the anti-oxidant activity. The active compound at a dose of 40 mg/kg body weight was observed to inhibit the iNOS and IL-1beta gene expression significantly in endotoxin-induced inflammatory model of BALB/c mice. The low level of nitric oxide production was also observed in the sera of compound treated mice

  1. Radiation polymerization of allyl derivatives of glycerin

    International Nuclear Information System (INIS)

    Radiation polymerization of 1 allyloxi-3-(chlorine)-alkoxipropanol-2, 1-cro otoxy-3=ethyloxypropanol-2, 1-allylamino-3-amyloxypropanol-2, 1-butoxy-2-allyloxi-3-chlorpropane has been carried out. Some kinetic character ristics of the polymerization process have been obtained. A dependence of the polymerization rate on exposure doze rate, on the persence of modifier (orthopho osphoric acid) and its ratio to the manometer has been studied

  2. Fault locator of an allyl chloride plant

    Directory of Open Access Journals (Sweden)

    Savković-Stevanović Jelenka B.

    2004-01-01

    Full Text Available Process safety analysis, which includes qualitative fault event identification, the relative frequency and event probability functions, as well as consequence analysis, was performed on an allye chloride plant. An event tree for fault diagnosis and cognitive reliability analysis, as well as a troubleshooting system, were developed. Fuzzy inductive reasoning illustrated the advantages compared to crisp inductive reasoning. A qualitative model forecast the future behavior of the system in the case of accident detection and then compared it with the actual measured data. A cognitive model including qualitative and quantitative information by fuzzy logic of the incident scenario was derived as a fault locator for an ally! chloride plant. The obtained results showed the successful application of cognitive dispersion modeling to process safety analysis. A fuzzy inductive reasoner illustrated good performance to discriminate between different types of malfunctions. This fault locator allowed risk analysis and the construction of a fault tolerant system. This study is the first report in the literature showing the cognitive reliability analysis method.

  3. Gas-phase chemistry of Sc(CH{sub 3}){sub 2}{sup +} with alkenes: Activation of allylic C-H bonds by a d{sup 0} system and the migratory insertion of C=C bonds into Sc{sup +}-CH{sub 3} bonds

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Yongqing; Hill, Y.D.; Freiser, B.S. [Purdue Univ., West Lafayette, IN (United States)] [and others

    1992-11-04

    The gas-phase chemistry of Sc(CH{sub 3}){sub 2}{sup +} with alkenes was studied by Fourier transform mass spectrometry. The metal center on Sc(CH{sub 3}){sub 2}{sup +} is d{sup 0}, providing an opportunity to study alternative mechanisms of C-C or C-H activation other than the most common one involving oxidative addition. The elimination of H{sub 2} is observed in the reaction of Sc(CH{sub 3}){sub 2}{sup +} with ethylene, and the product ScC{sub 4}H{sub 8}{sup +} and ScC{sub 6}H{sub 10}{sup +} ions have a metal(methyl)(allyl) and metal-bisallyl structure, respectively, consistent with a proposed reaction mechanism involving the consecutive migratory insertion of ethylenes into the scandium-methyl bonds. In addition, theoretical calculations indicate that the metal(methyl)(allyl) structure is between 10 and 20 kcal/mol more stable than the metal(1-butene) isomer. Sc(CH{sub 3}){sub 2}{sup +} reacts with propene to form predominantly ScC{sub 4}H{sub 8}{sup +} by loss of CH{sub 4}, with minor amounts of ScC{sub 3}H{sub 4}{sup +} and ScC{sub 4}H{sub 6}{sup +} also observed. ScC{sub 4}H{sub 6}{sup +} is formed as either the exclusive or the predominant product ion in the reactions of Sc(CH{sub 3}){sub 2}{sup +} with butenes. Sc(CH{sub 3}){sub 2} reacts with cyclopentene to form predominantly ScC{sub 6}H{sub 8}{sup +} by losing CH{sub 4} and H{sub 2}. Isotope labeling studies with Sc(CD{sub 3}){sub 2}{sup +} and other structure studies indicate that all of the alkenes studied, with the exception of ethylene, react with Sc(CH{sub 3}){sub 2}{sup +} via a multicentered {sigma}-bond metathesis mechanism to activate allylic C-H bonds. Finally, the dehydrogenation reactions of Sc{sup +} with n-butane and neopentane were revisited, and a new mechanism is proposed for such chemistry in light of the new results from this study. 34 refs., 5 figs., 2 tabs.

  4. 反相气相色谱法表征1-烯丙基-3-甲基氯代咪唑离子液体的表面性质%Characterization of surface properties of 1-allyl-3-methylimidazolium chloride ionic liquid by inverse gas chromatography

    Institute of Scientific and Technical Information of China (English)

    陈亚丽; 王强; 邓丽霜; 张正方; 唐军

    2013-01-01

    采用反相气相色谱(IGC)技术研究了不同温度下1-烯丙基-3-甲基氯代咪唑([AMIM]Cl)的表面性质.以正己烷、正庚烷、正辛烷和正壬烷作为非极性探针分子测定[AMIM] Cl在343.15、353.15、363.15和373.15 K温度下的表面色散自由能;以二氯甲烷、三氯甲烷、丙酮、乙酸乙酯、四氢呋喃作为极性探针分子测定离子液体Lewis酸碱性质,并测定了吸附自由能和吸附自由焓变等热动力学参数.实验结果表明,[AMIM]Cl的酸解离平衡常数Ka为0.34,碱解离平衡常数Kb为1.68,其表面呈Lewis两性偏碱性特点.在343.15、353.15、363.15和373.15 K温度下,[AMIM]Cl的表面色散自由能分别为52.26、50.82、46.08和42.05 mJ/m2.这一结果对研究离子液体的表面性质及应用有指导作用.%The determination of the dispersive component of surface free energies (γds) at different temperatures and Lewis acid-base parameters of 1-allyl-3-methylimidazolium chloride ionic liquid ([AMIM]C1) were investigated by means of inverse gas chromatography (IGC). Four n-alkanes, including n-hexane (C6), n-heptane (C7), re-octane (C8) and n.-nonane (C9), were chosen as the apolar probes to characterize the dispersive component of the surface free energies at 343. 15, 353.15, 363.15 and 373.15 K, respectively; and dichloromethane (DCM), trichlo-romethane (TCM), tetrahydrofuran (THF), ethyl acetate (EtAc), acetone (Acet) as the polar probes to estimate the Lewis acid-base parameters to judge the interactions between [ AMIM ] Cl and the solvents. The IGC characterizations encompassed the adsorption thermodynamic parameters to acid-base surface interactions, including the standard enthalpy (△Hsa) and the free energy change of adsorption (△Gsa) at different temperatures. The results showed that the Lewis acid parameter Ka of [ AMIM] Cl was 0.34, and the base parameter Kb was 1.68, which indicated it was Lewis amphoteric with predominantly basic character. Furthermore, the

  5. Synthesis of diversely substituted 2-(furan-3-yl)acetates from allenols through cascade carbonylations.

    Science.gov (United States)

    He, Yan; Zhang, Xinying; Fan, Xuesen

    2015-11-21

    Novel synthesis of diversely substituted 2-(furan-3-yl)acetates via palladium-catalyzed one-pot multi-component reactions of allenols, aryl iodides, alcohols, and carbon monoxide has been developed. Notably, the formation of the title compounds features a cascade process combining carbonylation of aryl iodide, alcohoxyl carbonylation of the in situ formed allyl palladium complex, and intramolecular condensation of the α-hydroxyl enone intermediate. Moreover, the 2-(furan-3-yl)acetates obtained herein were found to be ready intermediates for the construction of the biologically significant naphtho[1,2-b]furan-5-ol scaffold. PMID:26399394

  6. Zinc Acetate Immobilized on Mesoporous Materials by Acetate Ionic Liquids as Catalysts for Vinyl Acetate Synthesis

    Directory of Open Access Journals (Sweden)

    Hang Xu

    2015-01-01

    Full Text Available Ionic liquid containing active ingredient Zn(CH3COO2 was loaded in mesoporous silica gel to form supported ionic liquids catalyst (SILC which was used to synthesize vinyl acetate monomer (VAM. SILC was characterized by 1HNMR, FT-IR, TGA, BET, and N2 adsorption/desorption and the acetylene method was used to evaluate SILC catalytic activity and stability in fixed reactor. The result shows that 1-allyl-3-acetic ether imidazole acetate ionic liquid is successfully fixed within mesoporous channel of silica gel. The average thickness of ionic liquid catalyst layer is about 1.05 nm. When the catalytic temperature is 195°C, the acetic acid (HAc conversion is 10.9% with 1.1 g vinyl acetate yield and 98% vinyl acetate (VAc selectivity. The HAc conversion is increased by rise of catalytic temperature and molar ratio of C2H2 : HAc and decreased by mass space velocity (WHSV. The catalyst activity is not significantly reduced within 7 days and VAc selectivity has a slight decrease.

  7. 丙烯醇催化氨化合成3-甲基吡啶催化剂的制备及性能%Preparation and performance of Zn/H-ZSM-5 catalyst for catalytic amination of allyl alcohol to 3-picoline

    Institute of Scientific and Technical Information of China (English)

    马天奇; 魏天宇; 骈岩杰; 张月成; 赵继全

    2014-01-01

    采用浸渍法制备了一系列H-ZSM-5分子筛负载过渡金属锌催化剂,在固定床反应器上考察了这些催化剂对丙烯醇催化氨化合成3-甲基吡啶的催化性能。通过对 H-ZSM-5的硅铝比、锌负载量对催化剂催化性能影响的考察,发现硅铝比为80、锌负载量为12%时得到的催化剂Zn12/H-ZSM-5(80)的催化性能最佳。在常压、反应温度420℃、氨醇摩尔比3:1、空速300 h-1条件下,丙烯醇在该催化剂上的转化率和3-甲基吡啶的选择性分别达到97.8%和37.9%。利用X射线衍射(XRD)、X射线光电子能谱(XPS)以及吡啶吸附红外对催化剂进行了表征,结果表明,Zn12/H-ZSM-5(80)上负载的Zn2+为L酸;在丙烯醇生成3-甲基吡啶的反应过程中催化剂的脱氢活性物种为氧化锌,而加成和环合反应则主要是由催化剂中的L酸催化实现的。%H-ZSM-5 supported zinc catalysts were prepared by impregnation method, and their catalytic performances for amination of allyl alcohol to 3-picoline were evaluated in a fixed-bed reactor. It is found that the catalyst Zn12/H-ZSM-5(80) (H-ZSM-5 with 80 silicon/aluminum (Si/Al) ratio and zinc loading of 12%) shows the best performance among all the studied catalysts. 97.8%conversion of allyl alcohol and 37.9%selectivity toward 3-picoline are obtained on this catalyst using reaction conditions:atmospheric pressure, at 420℃, ammonia/allyl alcohol mole ratio 3:1 and gas hour space velocity 300 h-1. The characterization results, obtained by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and FT-IR of absorbed pyridine, indicate that zinc on Zn12/H-ZSM-5(80) is Zn2+, there is Lewis acid on HZSM-5. In 3-picoline formation, ZnO provides active sites of dehydrogenation reaction, and addition and cyclization reactions are mainly catalyzed by the Lewis acid.

  8. (2,4-二甲氧基苯基)烯丙基丙二酸二乙酯异构体的GC/MS研究%Study on Diethyl [3-(2,4-Dimethoxyphenyl) Allyl] Malonate Isomers by Gas Chromatography-Mass Spectrometry

    Institute of Scientific and Technical Information of China (English)

    王敏; 彭奇

    2012-01-01

    A method applying gas chromatography-ion trap mass spectrometry (GC/MS) for the simultaneous analysis of diethyl [3-(2,4-dimethoxyphenyl)allyl]malonate isomers is described. The diethyl [3-(2,4-dimethoxyph-enyl)allyl]malonate mixture of isomers was prepared by the decarboxylative Heck reaction of 2,4-dimethoxybenzoic acid with diethyl 2-al-lylmalonate firstly, and then was analyzed by GC/MS in Electron ionization (El) and Chemical ionization (CD full-scan mode. Two components were isolated by gas chromatography" and identified as isomers from the determination of the molecular ions. Next, the isomers were analyzed by tandem mass spectrometry (MS/MS) mode. Through the analysis of different cleavage fragments of the isomers in MS/MS mode, mass spectrometric fragmentation pathways of the isomers were discussed. The structures of two isomers were determined on the base of different mass characteristic fragmentation pathways. This new meth- od of identifying isomers is a time-saving, economical and effective method, which could provide reference for analysis and identification of this kind of compounds.%为了研究钯催化的2,4-二甲氧基苯甲酸与烯丙基丙二酸二乙酯的脱羧Heck反应的产物结构,建立了(2,4-二甲氧基苯基)烯丙基丙二酸二乙酯同分异构体的分离与鉴定的气相色谱-离子阱质谱方法.首先通过脱羧Heek反应制得(2,4-二甲氧基苯基)烯丙基丙二酸二乙酯异构体混合物,然后利用GC/MS联用技术对混合物进行分析,得到各组分的EI和CI全扫描模式质谱信息.通过对照各组分的分子离子峰确定互为异构体的组分,再对异构体组分采用MS/MS模式获取各自的裂解碎片.通过分析异构体的不同的裂解碎片,讨论质谱裂解方式,从而确定异构体的结构.该方法省时、经济、高效,可为此类化合物的分析与鉴别提供参考.

  9. Capillary electrochromatography enantiomeric separation of guaifenesin by allyl-β-cyclodextrin monolithic column%烯丙基-β-环糊精毛细管电色谱整体柱分离愈创甘油醚对映体

    Institute of Scientific and Technical Information of China (English)

    李英杰; 李芳; 张春雨; 高晴; 吕仁江

    2011-01-01

    Objective : To develop a method for enantiomeric separation of guaifenesin in capillary electrochromatography. Methods : Under capillary electrochromatography mode, guaifenesin enantiomers were separated by the prepared allyl -β - cyclodextrin chiral capillary monolithic column. The influences of mobile phase ratio , background buffer pH , temperature and applied voltage were investigated. Result : In the optimal conditions, guaifenesin enantiomers were separated by based - line. Conclusion : The capillary electrochromatography is simple, quick and suitable for the first separation of guaifenesin.%目的:建立一种用毛细管电色谱拆分愈创甘油醚对映体的方法.方法:采用制备的烯丙基-β-环糊精手性毛细管整体柱,在电色谱模式下,对愈创甘油醚对映体进行手性分离,考察了流动相配比、背景电解质溶液pH、柱温及分离电压等因素对分离的影响.结果:在优化的实验条件下,愈创甘油醚对映体达到基线分离.结论:毛细管电色谱首次分离愈创甘油醚对映体,该方法操作简单,分离效果好.

  10. Homogeneous preparation of cellulose acetate propionate (CAP) and cellulose acetate butyrate (CAB) from sugarcane bagasse cellulose in ionic liquid.

    Science.gov (United States)

    Huang, Kelin; Wang, Ben; Cao, Yan; Li, Huiquan; Wang, Jinshu; Lin, Weijiang; Mu, Chaoshi; Liao, Dankui

    2011-05-25

    Cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) were prepared homogeneously in a 1-allyl-3-methylimidazolium chloride (AmimCl) ionic liquid system from sugarcane bagasse (SB). The reaction temperature, reaction time, and molar ratio of butyric (propionic) anhydride/anhydroglucose units in the cellulose affect the butyryl (B) or propionyl (P) content of CAB or CAP samples. The (13)C NMR data revealed the distribution of the substituents of CAB and CAP. The thermal stability of sugar cane bagasse cellulose was found by thermogravimetric analysis to have decreased after chemical modification. After reaction, the ionic liquid was effectively recycled and reused. This study provides a new way for high-value-added utilization of SB and realizing the objective of turning waste into wealth. PMID:21452895

  11. Cobalt-catalyzed C-H olefination of aromatics with unactivated alkenes.

    Science.gov (United States)

    Manoharan, Ramasamy; Sivakumar, Ganesan; Jeganmohan, Masilamani

    2016-08-18

    A cobalt-catalyzed C-H olefination of aromatic and heteroaromatic amides with unactivated alkenes, allyl acetates and allyl alcohols is described. This method offers an efficient route for the synthesis of vinyl and allyl benzamides in a highly stereoselective manner. It is observed that the ortho substituent on the benzamide moiety is crucial for the observation of allylated products in unactivated alkenes.

  12. Allylation of Intraerythrocytic Hemoglobin by Raw Garlic Extracts

    OpenAIRE

    Bonaventura, Joseph; Rodriguez, Eva N.; Beyley, Veronica; Vega, Irving E.

    2010-01-01

    Recent studies have shown that deoxygenated human red blood cells (RBCs) converted garlic-derived polysulfides into hydrogen sulfide, which in turn produced vasorelaxation in aortic ring preparations. The vasoactivity was proposed to occur via glucose- and thiol-dependent acellular reactions. In the present study, we investigated the interaction of garlic extracts with human deoxygenated RBCs and its effect on intracellular hemoglobin molecules. The results showed that garlic extract covalent...

  13. 1-Allyl-3-phenylquinoxalin-2(1H-one

    Directory of Open Access Journals (Sweden)

    Hanane Benzeid

    2011-11-01

    Full Text Available The title compound, C17H14N2O, crystallizes with two molecules in the asymmetric unit. The dihedral angles between the mean planes of the quinoxaline ring system and the phenyl ring in the two molecules are 38.27 (10 and 37.14 (8°. In the crystal, π-stacking along the b axis contributes to the crystal cohesion with an average distance between quinoxaline units of 3.397 (3 Å. Weak C—H...O interactions also occur.

  14. Catalytic enantioselective reductions and allylations of prochiral ketones

    CERN Document Server

    Cunningham, A

    2002-01-01

    The use of LiGaH sub 4 in combination with the S,O-chelate 2-hydroxy-2'-mercapto-1,1'-binaphthyl (monothiobinaphthol, MTBH sub 2), forms an active catalyst (2 mol %) for the asymmetric reduction of prochiral ketones, when using catecholborane as the hydride source. This catalyst has successfully been applied to the enantioselective reduction of aryl/n-alkyl ketones, providing the chiral sec-alcohols in yields of 82 - 96% and with enantiomeric excess values of 59 - 93%. Alkyl/methyl ketones are reduced in yields of 72 - 93% and in 46 - 79% enantiomeric excess. Enantioface differentiation is on the basis of the steric requirements of the ketone substituents. The X-ray structure of the pre-catalyst, Li(THF) sub 3 Ga(MTB) sub 2 has been determined and in solution is in equilibrium with a dimeric species of constitution Li sub 2 Ga sub 2 (MTB) sub 4. An indium analogue whose X-ray structure was determined as Li sub 2 (THF) sub 5 lnCI(MTB) sub 2 has also been prepared. The indium- based catalyst does not form an en...

  15. Neutron response study using poly allyl diglycol carbonate

    Indian Academy of Sciences (India)

    Basma A El-Badry; M F Zaki; Tarek M Hegazy; A Ahmed Morsy

    2007-10-01

    The results of an experimental work aimed at improving the performance of the CR-39 nuclear track detector for neutron dosimetry applications are reported. A set of CR-39 plastic detectors was exposed to 252Cf neutron source, which has the emission rate of 0.68 × 108 s-1, and neutron dose equivalent rate 1 m apart from the source is equal to 3.8 mrem/h. The detection of fast neutrons performed with CR-39 detector foils, subsequent chemical etching and evaluation of the etched tracks by an automatic track counting system was studied. It is found that the track density increases with the increase of neutron dose and etching time. The track density in the detector is directly proportional to the neutron fluence producing the recoil tracks, provided the track density is in the countable range. This fact plays an important role in determining the equivalent dose in the field of neutron dosimetry. These results are compared with previous work. It is found that our results are in good agreement with their investigations.

  16. Synthesis of cubic Ia-3d mesoporous silica in anionic surfactant templating system with the aid of acetate.

    Science.gov (United States)

    Deng, Shao-Xin; Xu, Xue-Yan; He, Wen-Chao; Wang, Jin-Gui; Chen, Tie-Hong

    2014-08-01

    Mesoporous silica with three-dimensional (3D) bicontinuous cubic Ia-3d structure and fascinating caterpillar-like morphology was synthesized by using anionic surfactant N-lauroylsarcosine sodium (Sar-Na) as the template and 3-amionpropyltrimethoxysilane (APS) as the co-structure-directing agent (CSDA) with the aid of acetate. A phase transformation from high interfacial curvature 2D hexagonal to low interfacial curvature 3D cubic Ia-3d occurred in the presence of a proper amount of acetate. Other species of salts (excluding acetate) had the ability to induce the caterpillar-like morphology, but failed to induce the cubic Ia-3d mesostructure. Furthermore, [3-(2-aminoethyl)-aminopropyl]trimethoxysilane (DAPS) was also used as the CSDA to synthesize Ia-3d mesostructured silica under the aid of sodium acetate. After extraction of the anionic surfactants, amino and di-amine functionalized 3D bicontinuous cubic Ia-3d mesoporous silicas were obtained and used as supports to immobilize Pd nanoparticles for supported catalysts. The catalytic activity of the catalysts was tested by catalytic hydrogenation of allyl alcohol.

  17. Prophylactic Effects of Garlic Oil and Onion Oil Fractions as Compared to Vitamin E on Rats Orally Fed with Lead Acetate Solution.

    Science.gov (United States)

    Sajitha, G R; Augusti, K T; Jose, Regi

    2016-07-01

    Heavy metal pollution is a global public health challenge due to its stable and persistent environmental contamination. Of these lead is considered to be one of the most common ubiquitous and industrial pollutants and at low concentration it exerts extensive damages to the tissues. Daily feeding of lead acetate solution (Dose: 10 mg/kg/day) to normal rats for a month adversely altered the parameters of blood, serum and tissues, viz; RBC, WBC, Hb, ɗ- ALAD (Delta amino levulinic acid dehydratase), Pb content, lipids, oxidized lipids (TBARS), vitamins C and E and GSH levels and activities of AST, ALT and antioxidant enzymes viz; catalase, GR, Gpx and SOD. In order to study whether antioxidants have any effect to counteract the toxicity of lead we have selected comparatively better active allium fractions for the study viz: polar fraction of garlic (PFG) and polar fraction of onion (PFO). On feeding of these active fractions of garlic and onion oils i.e. their polar fractions and vitamin E (Dose 100 mg/kg/day) separately for a month along with or without lead acetate to rats each nutraceutical and vitamin E counteracted the adverse effects of Pb significantly (p ≤ 0.05). Their effects are in the order of PFG > PFO > Vitamin E. All these results point out that garlic and onion oils contain natural disulfoxide compounds which act as antioxidant and anti toxic to lead compounds. Their comparative differences in action may be due to the presence and position of double bonds and disulfide oxide bonds in their molecules. i.e., in PFG the allyl disulfide oxide group is present and in PFO saturated methyl and propyl groups and unsaturated propenyl group are present in place of allyl groups. The former group confers a better antioxidant activity on PFG, while the latter groups confer a lesser activity on PFO. PMID:27382196

  18. Integrated Process for Production of Galangal Acetate, the "Wasabi-Like" Spicy Compound, and Analysis of Essential Oils of Rhizoma Alpinia officinarum (Hance) Farw.

    Science.gov (United States)

    Lin, Li-Yun; Shen, Kun-Hung; Yeh, Xiang-Yü; Huang, Bou-Yü; Wang, Hui-Er; Chen, Kuan-Chou; Peng, Robert Y

    2016-06-01

    Rhizoma Alpinia officinarum (Hance) Farw, Zingiberaceae (AO), a ginger family herb exhibiting stimulant and a carminative bioactivity, is widely used in European and Asian countries as spicy condiment and medicinal uses. Allyl isothiocyanate (AITC) is the main pungent taste of native Wasabi (Wasabia japonica). The cytotoxicity of AITC has been implicated in thymus, adrenals, and white blood cells. Considering food safety, apparently a safer substitute for wasabi is worthy commercialized. Previously, we found AO crude paste to be rather feasible for use as a "Wasabi-substitute" in fresh meat and cold salads. A process linking cold ethyl acetate (EtAc) extraction with silica gel adsorption and reversed phase high-performance liquid chromatography (RP-HPLC) (mobile phase, 75% methanol) was used to isolate galangal acetate, the Wasabi-like taste constituent. AO contained abundant galangal acetate (3.84 ± 0.07%) compared to A. galangal (0.57 ± 0.16%), and as already confirmed by thin layer chromatography (TLC), gas chromatography (GC)/mass spectrometry (MS)/MS and Nuclear Magnetic Resonance Spectroscopy (NMR), galangal acetate was particularly thermally labile. The steam distilled essential oil (SDEO) of AO (0.14% on wet basis) contained 80 compounds (number of component, %): monoterpene hydrocarbon (21, 13.83%); oxygenated monoterpene (17, 27.08%); sesquiterpene hydrocarbon (20, 31.03%), and oxygenated sesquiterpene (20, 21.85%), respectively. However, no spicy wasabi-like constituent remained in SDEO. Alternatively, n-hexane, EtAc, and methanol extracts of AO all showed potent DPPH- and superoxide anion-scavenging activity. Conclusively, SDEO although contains 80 volatiles, galangal acetate is absent due to thermal instability. Galangal acetate exhibits pleasant "Wasabi-like taste" for which we have successively developed an integrated process for mass production. PMID:27166764

  19. Allyl vs ethyl substituted thioquinoline complexes with diiodine: Halogen bonds and iodocyclization

    Science.gov (United States)

    Matveychuk, Y. V.; Ilkaeva, M. V.; Vershinina, E. A.; Batalov, V. I.; Morozov, R. S.; Bartashevich, E. V.

    2016-09-01

    A comparative analysis of 2-allylthioquinoline and 2-ethylthioquinoline interactions with diiodine in solutions was performed using UV/Vis spectroscopy and molecular modelling with a TD-DFT approach. The named compounds exhibit different reactivity: 2-allylthioquinoline participates in the iodocyclization reaction and 2-ethylthioquinoline forms molecular complexes with diiodine only. The emergences of iodocyclization products and diiodine complexes of alkyl- and alkeny lsubstituted thioquinolines on spectra allow us to enable process control of interactions with diiodine.

  20. Bis(allyl)-ruthenium(iv) complexes with phosphinous acid ligands as catalysts for nitrile hydration reactions.

    Science.gov (United States)

    Tomás-Mendivil, Eder; Francos, Javier; González-Fernández, Rebeca; González-Liste, Pedro J; Borge, Javier; Cadierno, Victorio

    2016-09-14

    Several mononuclear ruthenium(iv) complexes with phosphinous acid ligands [RuCl2(η(3):η(3)-C10H16)(PR2OH)] have been synthesized (78-86% yield) by treatment of the dimeric precursor [{RuCl(μ-Cl)(η(3):η(3)-C10H16)}2] (C10H16 = 2,7-dimethylocta-2,6-diene-1,8-diyl) with 2 equivalents of different aromatic, heteroaromatic and aliphatic secondary phosphine oxides R2P([double bond, length as m-dash]O)H. The compounds [RuCl2(η(3):η(3)-C10H16)(PR2OH)] could also be prepared, in similar yields, by hydrolysis of the P-Cl bond in the corresponding chlorophosphine-Ru(iv) derivatives [RuCl2(η(3):η(3)-C10H16)(PR2Cl)]. In addition to NMR and IR data, the X-ray crystal structures of representative examples are discussed. Moreover, the catalytic behaviour of complexes [RuCl2(η(3):η(3)-C10H16)(PR2OH)] has been investigated for the selective hydration of organonitriles in water. The best results were achieved with the complex [RuCl2(η(3):η(3)-C10H16)(PMe2OH)], which proved to be active under mild conditions (60 °C), with low metal loadings (1 mol%), and showing good functional group tolerance. PMID:27510460

  1. 3-Allyl-2-hydroxy-5,6,8-trimethoxynaphthalene-1,4-dione

    Directory of Open Access Journals (Sweden)

    Margaret A. Brimble

    2008-10-01

    Full Text Available In the crystal structure of the title compound, C16H16O6, a pair of naphthoquinone rings are linked via O—H...O—C hydrogen bonds in a nearly orthogonal arrangement. This dimeric unit is linked to a neighbouring dimer by π–π stacking interactions between the naphthoquinone rings, where the distance between the mean plane of the naphtoquinone backbones is 3.468 Å, and O—H...O—C hydrogen bonds.

  2. The TRPA1 Activator Allyl Isothiocyanate (AITC) Contracts Human Jejunal Muscle: Pharmacological Analysis.

    Science.gov (United States)

    Sandor, Zsolt; Dekany, Andras; Kelemen, Dezsö; Bencsik, Timea; Papp, Robert; Bartho, Lorand

    2016-09-01

    The contractile effect of AITC (300 μM) on human jejunal longitudinal strips was inhibited by the TRPA1 antagonist HC 030031 and atropine or scopolamine, but was insensitive to tetrodotoxin, purinoceptor antagonists or capsaicin desensitization. It is concluded that TRPA1 activation stimulates a cholinergic mechanism in a tetrodotoxin-resistant manner. PMID:26928772

  3. Biomarkers derived from heterolytic and homolytic cleavage of allylic hydroperoxides resulting from alkenone autoxidation

    Digital Repository Service at National Institute of Oceanography (India)

    Rontania, J.F.; Harji, R.; Volkmanc, J.K.

    mixtures of n-alcohols, fatty acids, alkyldiols and hydroxyacids. Methyl alkenones produced saturated n-alkan-l-ols and fatty acids ranging from C sub(13) to C sub(16) and two series of C sub(13) - C sub(16) (w-1) hydroxyacids and (1,w-1)-diols. Ethyl...

  4. Chemically Modified Starch; Allyl- and Epoxy-Starch Derivatives: Their Synthesis and Characterization

    NARCIS (Netherlands)

    Franssen, M.C.R.; Boeriu, C.

    2014-01-01

    Both native and modified starches, such as starch that is pregelatinized, extruded, acid-converted, cross-linked, and substituted, are widely used in industry. This chapter describes a mild two-step process for the synthesis of novel, highly reactive granular epoxy-starch derivatives. Via this metho

  5. Perfluoro Allyl Fluorosulfate (FAFS: A Versatile Building Block for New Fluoroallylic Compounds

    Directory of Open Access Journals (Sweden)

    Giuseppe Marchionni

    2011-08-01

    Full Text Available In this study we will present and discuss both the synthesis of CF2=CFCF2OSO2F (perfluoroallyl fluorosulfate, FAFS, focusing in particular on the important role of C3F6/SO3 ratio, reaction temperature and boron catalyst/SO3 ratio on FAFS’ yield and selectivity, as well as a wide variety of ionic and radical reactions possible with FAFS. We focused our attention on reactions of FAFS with aliphatic and aromatic alcohols, acyl halides, halides, H2O2, ketones and radicals whose synthesis and reaction mechanisms will be presented and discussed. Particular attention will be devoted to the novel diallyl-fluoroalkyl peroxide obtained. Factors such as pKa and Lowry and Pearson’s Hard/Soft Acid-Base Theory which determine the selectivity between Addition/Elimination vs. Nucleophilic Substitution reaction mechanisms on FAFS will also be presented and discussed.

  6. Synthesis and Characterization of Novel Aliphatic Polycarbonates Bearing Pendant Allyl Ether Groups

    Institute of Scientific and Technical Information of China (English)

    Gang LIU; Feng HE; Yan Ping WANG; Jun FENG; Ren Xi ZHUO

    2006-01-01

    A new six-membered cyclic carbonate monomer, 5-allyloxytrimethylene carbonate (ATMC), was synthesized starting from glycerol, and the corresponding polycarbonates,poly(5-allyloxytrimethylene carbonate)(PATMC) were further synthesized by ring-opening polymerization in bulk at 150 ℃ using stannous octanoate as an initiator. The structures of the monomer and the polymers were confirmed by IR, 1H-NMR, 13C-NMR, and GPC analysis.

  7. Old yellow enzyme confers resistance of Hansenula polymorpha towards allyl alcohol

    NARCIS (Netherlands)

    Komduur, JA; Leao, AN; Monastyrska, [No Value; Veenhuis, M; Kiel, JAKW; Leão, Adriana N.; Monastyrska, Iryna

    2002-01-01

    In the methylotrophic yeast, Hansenula polymorpha, peroxisomes are formed during growth on methanol as sole carbon and energy source and contain the key enzymes for its metabolism, one of the major enzymes being alcohol oxidase (AO). Upon a shift of these cells to glucose-containing medium, peroxiso

  8. SYNTHESIS AND HALOCYCLIZATION OF ALLYL DERIVATIVES OF 4,5-DIHYDRO-1,3-THIAZOL-2-THIONE

    OpenAIRE

    Tarasova, N; Kim, D.

    2015-01-01

    2-Propenyl-(2-methyl-1-propenyl-, 2-butenylthioand (3-methylbutenyl-)thio4,5-dihydro-1,3-thiazoles are synthesized by alkylation of 4,5-dihydro-1,3-thiazol2-thione. These products were researched in halocyclization reactions with iodine and bromine.3-(halomethyl)-2,3,5,6-tetrahydrothiazolo[2,3-b]thiazolium and 6-halo-3,5,6,7-tetrahydro-2H-thiazolo[2,3-b]thiazinium halides were formed. The structure of all the synthesized compounds was confirmed by 1H NMR and gas chromatography-mass spectrometry.

  9. Physiological disposition and biotransformation of [allyl-1', 3' - 14C naloxone in the rat and some comparative observations on nalorphine.

    Science.gov (United States)

    Misra, A L; Pontani, R B; Vadlamani, N L; Mulé, S J

    1976-02-01

    A sensitive method is described for the estimation of [14C]naloxone in biological materials. After a 1 mg/kg s.c. dose of [14C]naloxone to male Wistar rats, mean peak levels of drug in brain (506 ng/g) and plasma (119 ng/ml) were attained within 15 minutes. No persistence of drug in brain was observed at this dose. After a 10 mg/kg s.c. dose, the peak levels of naloxone in brain and plasma were 4.31 mug/g and 1.27 mug/ml, respectively, and extensive localization of extractable free drug and its minor metabolite, naloxol, occurred in tissues with high levels in kidney, spleen, lung, heart, skeletal muscle and somewhat lower concentration in the liver. The T1/2 of naloxone and nalorphine in rat brain and plasma with 1 and 10 mg/kg s.c. doses was 0.4 hour. With a 10 mg/kg dose, significant amounts of radioactivity persisted in tissues but not in plasma 96 hours after injection. The brain/plasma ratios and degree of plasma-protein binding were significantly higher for naloxone as compared to nalorphine. The amounts of free naloxone excreted as a percentage of the dose in urine and feces 96 hours after injection of the 10 mg/kg s.c. dose were 4.1 and 3.9 (for nalorphine 4.7 and 8.3); conjugated drug 15.4 and 1.2 (for nalorphine 13 and 0.9); total radioactivity 43.3 and 20.9 (for nalorphine 34.8 and 19.2), respectively. Naloxone-3-glucuronide (major), 3-sulfate (minor), naloxol and conjugated naloxol (minor), 7,8-dihydro-14-hydroxynormorphine, 7,8-dihydro-14-hydroxynormorphine and their conjugates were shown to be the metabolites of naloxone. In addition, tentative evidence was obtained for two polar hydroxylated metabolites (with hydroxylation presumably in the 17-side chain or in position 2 of the aromatic nucleus). 7,8-Dihydro-14-hydroxynormorphinone and 2-polar metabolites were also observed in brain. Rapid metabolism of naloxone and rapid elimination are important factors in its short duration of action. Possible relevance of these observations on differential antagonistic properties of these two antagonists are discussed. PMID:1255476

  10. InCl{sub 3}/NaClO: a reagent for allylic chlorination of terminal olefins

    Energy Technology Data Exchange (ETDEWEB)

    Pisoni, Diego S.; Gamba, Douglas; Fonseca, Carlos V.; Costa, Jesse S. da; Petzhold, Cesar L.; Oliveira, Eduardo R. de; Ceschi, Marco A. [Rio Grande do Sul Univ., Porto Alegre, RS (Brazil). Inst. de Quimica]. E-mail: mceschi@iq.ufrgs.br

    2006-03-15

    Indium trichloride promotes the chlorination of terminal olefins in the presence of sodium hypochlorite with good results. Carvone was chosen as a model compound to examine some of the general features of this reaction, such as stoichiometry, temperature, reaction time and product conversion. Treatment of {beta}-pinene with sodium hypochlorite in the presence of indium trichloride resulted in a facile rearrangement to selectively yield perillyl chloride, which is an important precursor for C-7 oxygenated limonenes. (author)

  11. Direct asymmetric vinylogous aldol reaction of allyl ketones with isatins: Divergent synthesis of 3-hydroxy-2-oxindole derivatives

    KAUST Repository

    Zhu, Bo

    2013-05-03

    6 in 1: The highly enantioselective title reaction is mediated by a bifunctional catalyst and leads to E-configured vinylogous aldol products (see scheme). These products are used as common intermediates in the synthesis of six biologically active 3-hydroxy-2-oxindole derivatives (e.g., CPC-1). Computational studies indicated that the observed stereoselectivity is a result of favorable secondary π-π* and H-bonding interactions in the transition state. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Isolation of two independent allyl alcohol resistant Adh-1 null mutants following selection of pollen and seeds.

    NARCIS (Netherlands)

    Wisman, E.; Ramanna, M.S.; Zabel, P.

    1993-01-01

    The Adh-1 null mutant (B15-1-8) isolated previously was used to establish conditions that allow the selection of ADH-deficient pollen grains and seeds of tomato. New Adh-1 null mutants were then selected among the progenies derived from crosses between the genetically unstable tomato lines Yvms, Sul

  13. Synthesis of allyl amine on glass by continuous plasma; Sintesis de alilamina sobre vidrio por plasma continuo

    Energy Technology Data Exchange (ETDEWEB)

    Morales, J.; Olayo, R. [UAM-I, 09340 Mexico D.F. (Mexico); Vasquez, M.; OLayo, M.G.; Cruz, G. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico)

    2003-07-01

    In this work the synthesis by plasma of thin films of polyallyl amine under continuous plasma conditions for possible use in biomaterials is presented. It is shown that the thickness of the film depends so much of the time of synthesis like of the used power. The polymers were analyzed by X-ray photoelectron spectroscopy (XPS) and angle of contact before and after of being immersed in distilled water by 10 days. The allylamine shows lost of nitrogen and an increase in the content of oxygen with the immersion time due to the interaction among the water and the polymer. The angle of contact shows an increase of approximately 10 degrees, what indicates a change in the surface energy of the polymer. (Author)

  14. Polyhydroxyalkanoate (PHA) Synthesis by Activated Sludge Microbes Using Acetic Acid as Carbon Source%活性污泥微生物以乙酸为碳源合成聚羟基烷酸酯的研究

    Institute of Scientific and Technical Information of China (English)

    李伟; 陈银广

    2009-01-01

    聚羟基烷酸酯(polyhydroxyalkanoate,PHA)是一种生物可降解塑料,利用活性污泥合成PHA具有操作方便的优点.本研究对长期驯化的厌氧-好氧活性污泥工艺在厌氧条件下及好氧活性污泥工艺在好氧条件下利用乙酸合成PHA进行了比较分析,发现好氧活性污泥可以合成较多的PHA.在此基础上,研究了好氧条件下乙酸加入次数、乙酸浓度及硝化抑制剂(丙烯基硫脲,ATU)对PHA合成的影响,结果表明,将乙酸分3次加入到反应器、乙酸浓度为2 925 mg/L及加入6.74 mg/L ATU时,可以使污泥挥发性悬浮固体物中PHA的含量达到56.3%.%Polyhydroxyalkanoate (PHA) is a type of biodegradable plastics. The synthesis of PHA by activated sludge has the advantage of easy operation. With acetic acid as the carbon source, the anaerobic synthesis of PHA in the anaerobic-aerobic activated sludge system was compared with the aerobic one in the aerobic sludge system. It was observed that the aerobic PHA synthesis was greater than the anaerobic one. The influences of acetic acid addition frequency, acetic acid concentration and allyl thiourea (ATU) on aerobic PHA synthesis were further investigated. The results showed that the PHA content accounting for volatile suspended solids reached 56.3 % under conditions of acetic acid addition with frequency of 3, acetic acid concentration of 2 925 mg/L, and ATU concentration of 6.74 mg/L.

  15. Clostebol acetate

    Directory of Open Access Journals (Sweden)

    Elisabetta Maccaroni

    2011-08-01

    Full Text Available The title compound, C21H29ClO3 [systematic name (8R,9S,10R,13S,14S,17S-4-chloro-3-oxoandrost-4-en-17β-yl acetate], is a 4-chloro derivative of testosterone, used as an anabolic androgenic agent or applied topically in ophthalmological and dermatological treatments. The absolute configurations at positions 8, 9, 10, 13, 14 and 17 were established by refinement of the Flack parameter as R, S, R, S, S, and S, respectively. Rings B and C of the steroid ring system adopt chair conformations, ring A has a half-chair conformation, while ring D is in a C13 envelope conformation. Ring B and C, and C and D are trans fused. In the crystal, molecules are linked by a weak C—H...O interaction.

  16. Antioxidant capacity of eugenol derivatives

    Directory of Open Access Journals (Sweden)

    María E. Hidalgo

    2009-01-01

    Full Text Available Toxicity and antioxidant capacity of eugenol derivatives (E2 = 2-Methoxy-4-[1-propenylphenyl]acetate, E3 = 4-Allyl-2-methoxyphenylacetate, E4 = 4-Allyl-2-methoxy-4-nitrophenol, E5 = 5-Allyl-3-nitrobenzene-1,2-diol, E6 = 4-Allyl-2-methoxy-5-nitrophenyl acetate were evaluated in order to determine the influence of the sustituents. E2-E6 were synthesized from eugenol (E1. E1 was extracted from cloves oil, and E2-E6 were obtained through acetylation and nitration reactions. Antioxidant capacity evaluated by DPPH (1, 1-Diphenyl-2-picrylhydrazil and ORAC fluorescein demonstrated that E1 and E5 have a higher capacity and the minor toxicity evaluated by red blood cells haemolysis and the Artemia saline test. In accordance with our results, the compound's (E1-E5 use in the pharmaceutical, cosmetic and or food industries could be suggested.

  17. 基于乙酸为溶剂和催化剂的芳乙酮Mannich反应%Mannich Reaction of Aromatic Ketones Based on Acetic Acid as Solvent and Catalyst

    Institute of Scientific and Technical Information of China (English)

    卜辉娟; 张静; 穆博帅; 李媛

    2014-01-01

    Mannich reaction is one of the most important methods for preparation ofβ-amino ketones and alde-hydes and α,β-unsaturated carbonyl compounds, as well as one of the most important basic reaction types in organic chemistry and it is widely applied as a key step in the synthesis of numerous pharmaceuticals and natu-ral products. However, during the synthesis of 1-aryl acrylic ketone 2 by the Mannich reaction of aromatic ke-tones, formaldehyde and secondary amine using acetic acid as solvent and catalyst, the Mannich base and ex-pectedα,β-unsaturated ketones 2 were not obtained and another kind of compounds 3 , 2-aryl formyl allyl ace-tate were obtained in moderate to good yields(65%-73%) . The structure of compounds 3 was confirmed by 1 H NMR, 13 C NMR, HRMS and IR spectra. The reasons of producing compounds 3 were studied and the re-sults suggested that the special structure of aromatic ketones and excess acetic acid in reaction are responsible for the exceptional Mannich reaction. In addition, the reaction mechanism was postulated.%采用乙酸作溶剂和催化剂,将芳乙酮与甲醛和二级胺进行Mannich反应及热解反应,并未得到预期的Mannich碱或α,β-不饱和酮(2),而是以较高产率(65%~73%)生成了乙酸(2-芳甲酰基)烯丙酯(3a~3o)。通过核磁共振波谱、高分辨质谱和红外光谱表征了化合物3a~3o的结构,研究了此“异常”反应的发生条件,并提出了可能的反应机理。结果表明,芳乙酮的特殊结构及反应中过量的乙酸是产生化合物3a~3o的决定因素。

  18. Composition of the Essential Oil of Allium neapolitanum Cirillo Growing Wild in Sicily and its Activity on Microorganisms Affecting Historical Art Crafts.

    Science.gov (United States)

    Casiglia, Simona; Bruno, Maurizio; Senatore, Federica; Senatore, Felice

    2015-01-01

    Essential oil of the aerial parts of Allium neapolitanum Cirillo collected in Sicily were analyzed by gas-chromatography-flame-ionization detection and gas-chromatography-mass spectrometry. Nineteen compounds were identified in the oil and the main components were found to be (E)-chrysanthenyl acetate (28.1%), (Z)-chrysanthenyl acetate (23.8%), (E)-β-farnesene (9.6%), dimethyl trisulfide (9.6%), camphor (7.4%), methyl allyl disulfide (6.8%) and 1-methyl-3-allyl trisulfide (5.8%). The essential oil showed good antimicrobial activity against 11 strains of test microorganisms, including several species infesting historical material. PMID:26632947

  19. Computationally Designed Zirconium Organometallic Catalyst for Direct Epoxidation of Alkenes without Allylic H Atoms: Aromatic Linkage Eliminates Formation of Inert Octahedral Complexes

    CERN Document Server

    Yang, Bo

    2016-01-01

    We used density functional theory to computationally design a Zr organometallic catalyst for selectively oxidizing substrates using molecular oxygen as oxidant without coreductant. Each selective oxidation cycle involves four general steps: (a) a peroxo or weakly adsorbed O2 group releases an O atom to substrate to form substrate oxide and an oxo group, (b) an oxygen molecule adds to the oxo group to generate an eta2-ozone group, (c) the eta2-ozone group rearranges to form an eta3-ozone group, and (d) the eta3-ozone group releases an O atom to substrate to form substrate oxide and regenerate the peroxo or weakly adsorbed O2 group. This catalyst could potentially be synthesized via the condensation reaction Zr(N(R)R')4 + 2 C6H4-1,6-(N(C6H3-2',6'-(CH(CH3)2)2)OH)2 --> Zr(C6H4-1,6-(N(C6H3-2',6'-(CH(CH3)2)2)O)2)2 [aka Zr_Benzol catalyst] + 4 N(R)(R')H where R and R' are CH3, CH2CH3, or other alkyl groups. For direct ethylene epoxidation, the computed enthalpic energetic span (i.e., effective activation energy for ...

  20. Epoxidation of Allyl Alcohol over Ti-MWW Molecular Sieve Catalyst%烯丙醇在Ti-MWW催化剂上的环氧化反应

    Institute of Scientific and Technical Information of China (English)

    陈晓晖; 范志勇; 魏可镁

    2006-01-01

    以水热合成-酸处理法制得的Ti-MWW分子筛为催化剂,研究了烯丙醇(AAL)和H2O2在水中的环氧化反应,考察了反应条件对AAL的转化率和环氧丙醇(GLY)选择性的影响.实验结果表明,AAL的浓度较低时有利于反应的进行,高浓度的H2O2则降低GLY的选择性,n(AAL):n(H2O2)=1时,GLY的选择性最高;当反应温度高于333 K时,GLY的选择性随反应温度升高明显下降.当Ti-MWW催化剂用量为50 mg、AAL和H2O2的用量均为10mmol、水量为20 mL时,在333 K下反应30min,AAL的转化率达到96%,同时GLY的选择性可达98%以上.该反应的机理与TS-1催化剂催化烯烃环氧化反应类似,AAL和溶剂在活性位上存在竞争吸附.GLY的高选择性归因于Ti-MWW催化剂中Ti活性位与水、H2O2形成的五元环过渡态.

  1. Synthesis of Oxacyclic Scaffolds via Dual Ruthenium Hydride/Brønsted Acid‐Catalyzed Isomerization/Cyclization of Allylic Ethers

    DEFF Research Database (Denmark)

    Ascic, Erhad; Ohm, Ragnhild Gaard; Petersen, Rico;

    2014-01-01

    to enol ethers (Ru catalysis), then to oxocarbenium ions (Brønsted acid catalysis) amenable to endo cyclization with tethered nucleophiles. This methodology provides not only an attractive alternative to the traditional oxa‐Pictet–Spengler reaction for the synthesis of THPIs, but also convenient access...

  2. Titanocene Dichloride Complexes Bonded to Carbosilane Dendrimers Via a Spacer of Variable Length – Molecular Dynamics Calculations and Catalysis of Allylic Coupling Reactions

    OpenAIRE

    Strašák, T. (Tomáš); Jaroschik, F.; M. Malý; Čermák, J.; Sýkora, J.; Fajgar, R. (Radek); Karban, J.; Harakat, D.

    2014-01-01

    Carbosilane metallodendrimers of the first and second generation containing 4, 8 or 16 titanocene dichloride endgroups were prepared by the normal hydrosilylation method. Different chain lengths of the carbon spacer between the dendrimer and the Cp linkage were investigated. Computer atomistic models of the second generation metallodendrimers with the length of carbon spacer n = 1, 3 and 5 carbon atoms were created, parametrized, and consequently simulated in THF solvent using molecular dynam...

  3. Redox-active tetrathiafulvalene and dithiolene compounds derived from allylic 1,4-diol rearrangement products of disubstituted 1,3-dithiole derivatives

    OpenAIRE

    Filipe Vilela; Skabara, Peter J; Mason, Christopher R.; Thomas D. J. Westgate; Asun Luquin; Coles, Simon J.; Hursthouse, Michael B.

    2010-01-01

    We present a series of compounds by exploiting the unusual 1,4-aryl shift observed for electron-rich 1,3-dithiole-2-thione and tetrathiafulvalene (TTF) derivatives in the presence of perchloric acid. The mechanistic features of this rearrangement are discussed since this synthetic strategy provides an alternative route for the synthesis and functionalisation of sulfur rich compounds including redox active compounds of TTFs, and a Ni dithiolene.

  4. Synthesis of enantioenriched γ-quaternary cycloheptenones using a combined allylic alkylation/Stork–Danheiser approach: preparation of mono-, bi-, and tricyclic systems

    KAUST Repository

    Bennett, Nathan B.

    2012-01-01

    A general method for the synthesis of β-substituted and unsubstituted cycloheptenones bearing enantioenriched all-carbon γ-quaternary stereocenters is reported. Hydride or organometallic addition to a seven-membered ring vinylogous ester followed by finely tuned quenching parameters achieves elimination to the corresponding cycloheptenone. The resulting enones are elaborated to bi- and tricyclic compounds with potential for the preparation of non-natural analogs and whose structures are embedded in a number of cycloheptanoid natural products.

  5. Bis(allyl)ruthenium(IV) complexes containing water-soluble phosphane ligands: synthesis, structure, and application as catalysts in the selective hydration of organonitriles into amides.

    Science.gov (United States)

    Cadierno, Victorio; Díez, Josefina; Francos, Javier; Gimeno, José

    2010-08-23

    The novel mononuclear ruthenium(IV) complexes [RuCl(2)(eta(3):eta(3)-C(10)H(16))(L)] [L=(meta-sulfonatophenyl)diphenylphosphane sodium salt (TPPMS) (2a), 1,3,5-triaza-7-phosphatricyclo[3.3.1.1(3, 7)]decane (PTA) (2b), 1-benzyl-3,5-diaza-1-azonia-7-phosphatricyclo[3.3.1.1(3, 7)]decane chloride (PTA-Bn) (2c), 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane (DAPTA) (2d), and 2,4,10-trimethyl-1,2,4,5,7,10-hexaaza-3-phosphatricyclo[3.3.1.1(3, 7)]decane (THPA) (2e)] have been synthesized by treatment of the dimeric precursor [{RuCl(mu-Cl)(eta(3):eta(3)-C(10)H(16))}(2)] (C(10)H(16)=2,7-dimethylocta-2,6-diene-1,8-diyl) (1) with two equivalents of the corresponding water-soluble phosphane. Reaction of 1 with one equivalent of the cage-type diphosphane ligand 2,3,5,6,7,8-hexamethyl-2,3,5,6,7,8-hexaaza-1,4-diphosphabicyclo[2.2.2]octane (THDP) allowed also the high-yield preparation of the dinuclear derivative [{RuCl(2)(eta(3):eta(3)-C(10)H(16))}(2)(mu-THDP)] (2f). All these new complexes have been analytically and spectroscopically (IR and multinuclear NMR) characterized. In addition, the structure of 2b, 2c, 2d, and 2f was unequivocally confirmed by X-ray diffraction methods. Complexes 2a-f are active catalysts for the selective hydration of nitriles to amides in pure aqueous medium under neutral conditions. The wide scope of this catalytic transformation has been evaluated by using the most active catalysts [RuCl(2)(eta(3):eta(3)-C(10)H(16))(THPA)] (2e) and [{RuCl(2)(eta(3):eta(3)-C(10)H(16))}(2)(mu-THDP)] (2f). Advantages of using MW versus conventional thermal heating are also discussed. PMID:20586085

  6. The Effect of Allylic Sulfide-Mediated IrreversibleAddition-Fragment Chain Transfer on the EmulsionPolymerization Kinetics of Styrene

    Directory of Open Access Journals (Sweden)

    Li An

    2015-09-01

    Full Text Available The effect of the irreversible addition-fragment chain transfer agent, butyl(2-phenylallylsulfane (BPAS, on the course of the emulsion polymerization of styrene and on the product molecular weight was investigated. The emulsion polymerizations were performed using various amounts of sodium dodecyl sulfate (SDS as the surfactant and potassium peroxodisulfate (KPS as the initiator. The relationships between the rates of polymerization (\\(R_{p} \\ and the number of particles per volume (\\(N_{c} \\ with respect to the concentrations of KPS, SDS, and BPAS were found to be \\(R_{p} \\propto \\left\\lbrack KPS \\right\\rbrack^{0.29} \\, \\(N_{c} \\propto \\left\\lbrack KPS \\right\\rbrack^{0.26} \\,\\(R_{p} \\propto \\left\\lbrack SDS \\right\\rbrack^{0.68} \\, \\(N_{c} \\propto \\left\\lbrack SDS \\right\\rbrack^{0.72} \\, and \\(R_{p} \\propto \\left\\lbrack BPAS \\right\\rbrack^{- 0.73} \\ . The obtained relationships can be attributed to the exit of the leaving group radicals on BPAS from the polymer particles. The experimental values of the average number of radicals per particle (\\(\\overset{\\_}{n} \\ were strongly dependent on the BPAS concentration and were in good agreement with the theoretical values (\\({\\overset{\\_}{n}}_{theo} \\ from model calculations. The number-average molecular weight (\\(\\overset{\\_}{M_{n}} \\ can be controlled by BPAS over nearly the entire conversion range, which is also in agreement with the mathematical model. In addition, the transfer rate coefficient (\\(k_{tr} \\ of BPAS can be estimated as 326 L/mol/s at 70 \\(^\\circ\\C. Moreover, similar good results were found for the tested redox reactions at 30 \\(^\\circ\\C.

  7. A Novel Synthesis of 3-O-Allyl-4, 5, 6-tri-O-benzyl-1-O-(p-methoxybenzyl)-D-myo-inositol

    Institute of Scientific and Technical Information of China (English)

    Zhi Zhou YUE; Yuan Chao LI

    2005-01-01

    Highly efficient synthesis of the entitled compound was achieved from a readily available myo-inositol derivative. The key step involved a desymmetrization with (+)-camphor dimethyl ketal to give two diastereomers. The two diastereomers could be used to synthesize the same compound by changing the orders to introduce the protective groups.

  8. Adamantane-1-ammonium acetate

    Directory of Open Access Journals (Sweden)

    Elise J. C. de Vries

    2011-06-01

    Full Text Available In the title compound, C10H18N+·C2H3O2−, the ammonium H atoms of the cation are linked to three acetate anions via N—H...O hydrogen bonds, forming a chain structure extending along the b axis.

  9. Acetate Kinase Isozymes Confer Robustness in Acetate Metabolism

    DEFF Research Database (Denmark)

    Chan, Siu Hung Joshua; Nørregaard, Lasse; Solem, Christian;

    2014-01-01

    Acetate kinase (ACK) (EC no: 2.7.2.1) interconverts acetyl-phosphate and acetate to either catabolize or synthesize acetyl-CoA dependent on the metabolic requirement. Among all ACK entries available in UniProt, we found that around 45% are multiple ACKs in some organisms including more than 300...... physiological roles in L. lactis to maintain a robust acetate metabolism for fast growth at different extracellular acetate concentrations. The existence of ACK isozymes may reflect a common evolutionary strategy in bacteria in an environment with varying concentrations of acetate....

  10. Antibiofilm Properties of Acetic Acid

    DEFF Research Database (Denmark)

    Bjarnsholt, Thomas; Alhede, Morten; Jensen, Peter Østrup;

    2014-01-01

    -negative biofilms using acetic acid both as a liquid and as a dry salt. In addition, we present our clinical experience of acetic acid treatment of chronic wounds. In conclusion, we here present the first comprehensive in vitro and in vivo testing of acetic acid against bacterial biofilms....

  11. Preparing Process of Cerium Acetate and Rare Earth Acetate

    Institute of Scientific and Technical Information of China (English)

    Qiao Jun; Ma Ying; Xu Yanhui; Zhang Jun; Chang Shu; Hao Xianku

    2004-01-01

    Preparing process was presented and the influences of concentration of acetic acid, reaction temperature, the ratio of cerium carbonate and acetic acid, heat preservation time to the yield of cerium acetate were discussed.The crystalline cerium acetate and rare earth acetate such as ( La, Ce, Pr, Nd) (Ac) 3, ( Ce, Pr, Nd) (Ac) 3, ( Pr, Nd, Er,Y) (Ac) 3 and yttrium acetate were prepared under this condition.The shape, structure and composition of the crystals were determined by the methods of SEM, TG-DTA, X-ray diffraction and chemical analysis.The optimum prepared conditions of cerium acetate were described.This prepared process has characteristics such as simple process route, low cost, high yield, good quality, no pollution to environment, etc.

  12. Unexpected and Intriguing Reactivity of Imino Compounds

    Institute of Scientific and Technical Information of China (English)

    Makoto SHIMIZU

    2005-01-01

    @@ 1Introduction We have recently discovered a tandem N-alkylation-C-allylation reaction of α-imino esters with organoaluminum reagents and allyltributyltin[1]. In this reaction, iminium salts were readily prepared in situ by the oxidation of aluminum enolates, and the subsequent nucleophilic addition proceeded smoothly to afford N-alkylation-C-allylation products in good yields. During these studies, we focused on the generation of iminium species 2 by oxidizing a readily accessible and stable enol derivative with oxidants. A convenient method has been found for the generation of α-alkoxycarbonyl iminium salts 2 from ketene silyl acetals and the subsequent reaction with nucleophiles[2].

  13. Rhodium-catalyzed asymmetric hydroformylation with Taddol-based IndolPhos ligands

    NARCIS (Netherlands)

    J. Wassenaar; B. de Bruin; J.N.H. Reek

    2010-01-01

    A small library of Taddol-based IndolPhos ligands 2a−g and their use in asymmetric hydroformylation (AHF) reactions are reported. Moderate to good enantioselectivities are obtained for styrene, vinyl acetate, and allyl cyanide up to 72%, 74%, and 63% ee, respectively. High b/l ratios are obtained, w

  14. 4-Carbamoylpiperidinium acetate monohydrate

    Directory of Open Access Journals (Sweden)

    Urs D. Wermuth

    2010-12-01

    Full Text Available In the structure of the title compound, C6H13N2O+·C2H3O2−·H2O, the amide H atoms of the cations form centrosymmetric cyclic hydrogen-bonding associations incorporating two water molecules [graph set R42(8], which are conjoint with cyclic water-bridged amide–amide associations [R44(12] and larger R44(20 associations involving the water molecule and the acetate anions, which bridge through the piperidinium H-bond donors, giving an overall three-dimensional framework structure.

  15. ACETIC ACID AND A BUFFER

    DEFF Research Database (Denmark)

    2009-01-01

    The present invention relates to a composition comprising : a) 0.01-20% wt/wt acetic acid and b) a physiologically tolerable buffer capable of maintaining acetic acid at a pH in the range of 2-7; and use of such a composition as an antimicrobial agent.......The present invention relates to a composition comprising : a) 0.01-20% wt/wt acetic acid and b) a physiologically tolerable buffer capable of maintaining acetic acid at a pH in the range of 2-7; and use of such a composition as an antimicrobial agent....

  16. Acetate metabolism in Methanothrix soehngenii.

    NARCIS (Netherlands)

    Jetten, M.S.M.

    1991-01-01

    Acetate is quantitatively the most important intermediate in the anaerobic degradation of soluble organic matter. The conversion rate of acetate by methanogenic bacteria is proposed to be the rate limiting step in this degradation The study of acetoclastic methanogens, therefore is of relevance to o

  17. 75 FR 57945 - Atonik and Verbenone, Registration Review Proposed Decisions; Notice of Availability

    Science.gov (United States)

    2010-09-23

    ..., verbenone and 4-allyl anisole. Verbenone is a terpene that acts as an anti-aggregation pheromone in... southern pine beetle Dendroctonus frontalis. 4-allyl anisole is an alkenylbenzene compound that is...

  18. Tyrosine-selective protein alkylation using pi-allylpalladium complexes.

    Science.gov (United States)

    Tilley, S David; Francis, Matthew B

    2006-02-01

    A new protein modification reaction has been developed based on a palladium-catalyzed allylic alkylation of tyrosine residues. This technique employs electrophilic pi-allyl intermediates derived from allylic acetate and carbamate precursors and can be used to modify proteins in aqueous solution at room temperature. To facilitate the detection of modified proteins using SDS-PAGE analysis, a fluorescent allyl acetate was synthesized and coupled to chymotrypsinogen A and bacteriophage MS2. The tyrosine selectivity of the reaction was confirmed through trypsin digest analysis. The utility of the reaction was demonstrated by using taurine-derived carbamates as water solubilizing groups that are cleaved upon protein functionalization. This solubility switching technique was used to install hydrophobic farnesyl and C(17) chains on chymotrypsinogen A in water using little or no cosolvent. Following this, the C(17) alkylated proteins were found to associate with lipid vesicles. In addition to providing a new protein modification strategy targeting an under-utilized amino acid side chain, this method provides convenient access to synthetic lipoproteins. PMID:16433516

  19. Amidation reaction of eugenyl oxyacetate ethyl ester with 1,3 diaminopropane

    Science.gov (United States)

    Suryanti, V.; Wibowo, F. R.; Kusumaningsih, T.; Wibowo, A. H.; Khumaidah, S. A.; Wijayanti, L. A.

    2016-04-01

    Eugenol having various substituents on the aromatic ring (hydroxy, methoxy and allyl) are useful for starting material in synthesizing of its derivatives. Eugenol derivatives have shown wide future potential applications in many areas, especially as future drugs against many diseases. The aim of this work was to synthesize an amide of eugenol derivative. The starting material used was eugenol from clove oil and the reaction was conducted in 3 step reactions to give the final product. Firstly, eugenol was converted into eugenyl oxyacetate [2-(4-allyl-2-methoxyphenoxy) acetic acid] as a white crystal with 70.5% yield, which was then esterified with ethanol to have eugenyl oxyacetate ethyl ester [ethyl 2-(4-allyl-2-methoxyphenoxy) acetate] as brown liquid in 75.7%. The last step was the reaction between eugenyl oxyacetate ethyl ester and 1,3 diaminopropane to give 2-(4-allyl-2-methoxyphenoxy)-N-(3-aminopropyl) acetamide as a brown powder with 71.6% yield, where the amidation reaction was occurred.

  20. Acetate catabolism by Methanosarcina barkeri

    International Nuclear Information System (INIS)

    Cell suspensions of Methanosarcina barkeri convert the carboxyl and methyl group carbons of acetate to carbon dioxide and methane at pH 6 under an atmosphere of 100% CO2. The rate of loss of radioactivity from [1-14C]acetate was over three times greater than that from [2-14C]acetate under these conditions. Control experiments with both labeled substrates present showed that the rates were additive. Addition of a high level of 2-bromoethanesulfonate to selectively inhibit methane formation largely inhibited release of 14C from methyl-labeled acetate but only marginally decreased the rate of loss from [1-14C]acetate. Thus, in the absence of the inhibitor loss of 14C from [1-14C]acetate likely reflects an isotopic exchange reaction with CO2 superimposed on the overall conversion of acetate to CO2 and CH4. The exchange reaction was inhibited by uncouplers such as 2,4-dinitrophenol, CCCP, and FCCP. Cells permeabilized by treatment with nonionic detergents or disrupted by passage through a French pressure cell failed to catalyze the exchange reaction. Exchange activity was not restored by addition of ATP or by use of [1-14C]acetyl CoA as substrate. No evidence for involvement of carbon monoxide dehydrogenase in the exchange was found in these experiments when CO2 was replaced by CO. However, the soluble extracts retained the ability to convert acetate to methane in the presence of H2 and ATP

  1. LiOOt-Bu as a terminal oxidant in a titanium alkoxide-mediated [2+2+2] reaction cascade☆

    Science.gov (United States)

    Kim, Wan Shin; Aquino, Claudio; Mizoguchi, Haruki; Micalizio, Glenn C.

    2015-01-01

    LiOOt-Bu is an effective oxidant for converting the penultimate organometallic intermediate generated in a titanium alkoxide-mediated [2+2+2] reaction cascade to an allylic alcohol. Oxidation of the presumed allylic titanium species is highly regioselective, providing direct access to substituted hydroindanes containing a primary allylic alcohol. In addition to demonstrating the feasibility of this oxidation process, we document the ability to convert the primary allylic alcohol products to angularly substituted cis-fused hydroindanes. PMID:26097265

  2. 21 CFR 73.2396 - Lead acetate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 1 2010-04-01 2010-04-01 false Lead acetate. 73.2396 Section 73.2396 Food and... ADDITIVES EXEMPT FROM CERTIFICATION Cosmetics § 73.2396 Lead acetate. (a) Identity. The color additive lead acetate is the trihydrate of lead (2+) salt of acetic acid. The color additive has the chemical formula...

  3. 27 CFR 21.107 - Ethyl acetate.

    Science.gov (United States)

    2010-04-01

    ... 27 Alcohol, Tobacco Products and Firearms 1 2010-04-01 2010-04-01 false Ethyl acetate. 21.107....107 Ethyl acetate. (a) 85 percent ester: (1) Acidity (as acetic acid). Not more than 0.015 percent by...); for incorporation by reference, see § 21.6(b).) When 100 ml of ethyl acetate are distilled by...

  4. 21 CFR 173.228 - Ethyl acetate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethyl acetate. 173.228 Section 173.228 Food and..., Lubricants, Release Agents and Related Substances § 173.228 Ethyl acetate. Ethyl acetate (CAS Reg. No. 141-78... the specifications of the Food Chemicals Codex, 1 (Ethyl Acetate; p. 372, 3d Ed., 1981), which...

  5. 21 CFR 184.1185 - Calcium acetate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Calcium acetate. 184.1185 Section 184.1185 Food and... Substances Affirmed as GRAS § 184.1185 Calcium acetate. (a) Calcium acetate (Ca (C2H3O2)2, CAS Reg. No. 62-54-4), also known as acetate of lime or vinegar salts, is the calcium salt of acetic acid. It may...

  6. 40 CFR 721.10001 - 2-Ethoxyethanol, 2-ethoxyethanol acetate, 2-methoxyethanol, and 2-methoxyethanol acetate.

    Science.gov (United States)

    2010-07-01

    ... acetate, 2-methoxyethanol, and 2-methoxyethanol acetate. 721.10001 Section 721.10001 Protection of...-ethoxyethanol acetate, 2-methoxyethanol, and 2-methoxyethanol acetate. (a) Chemical substances and significant...-80-5), 2-ethoxyethanol acetate (CAS No. 111-15-9), 2-methoxyethanol (CAS No. 109-86-4), and...

  7. 5-(Chloromethylquinolin-8-yl acetate

    Directory of Open Access Journals (Sweden)

    Ling-Qian Kong

    2008-08-01

    Full Text Available The title compound, C12H10ClNO2, crystallizes with two independent molecules in the asymmetric unit; these are approximate mirror images of each other. In each molecule, the chloromethyl and acetate groups lie on the same side of the quinoline ring system, with dihedral angles between the ring plane and the plane of the acetate group of 82.0 (1 and −79.2 (1°. The C—C—C—Cl torsion angles for the chloromethyl groups of the two molecules are 80.9 (2 and −83.1 (2°.

  8. Trigeminal sensitization and desensitization in the nasal cavity: a study of cross interactions.

    Science.gov (United States)

    Jacquot, Laurence; Monnin, Julie; Lucarz, Annie; Brand, Gérard

    2005-06-01

    Chemical irritation in the human nasal cavity is poorly documented. In this field, an important issue concerns the differential responses produced by successive stimulation. Repeated identical chemical irritant stimuli can produce increases or decreases in responses (two phenomena known as self-sensitization or self-desensitization). In the same way, different molecules can interact and produce cross-sensitization or cross-desensitization. The aim of this study was to contribute to this question using two specific molecules, acetic acid (AA) and allyl isothiocyanate (AIC). As the self-sensitization and -desensitization for AIC is known, a first experiment in the present work investigated the response, acute effects and time course of sensitization or desensitization to acetic acid. A second experiment tested the responses of acetic acid after a previous stimulation with allyl isothiocyanate (mustard oil) and inversely with a short inter-stimulus interval (ISI of 45 s). A third experiment similar to the second used a long inter-stimulus interval (ISI of 3 min 30). Twelve healthy subjects participated in the study using psychophysical (intensity ratings) and psychophysiological (skin conductance response) measurements. Firstly, the results showed that repeated nasal stimulation with acetic acid produced a self-desensitization whatever the ISI. Secondly, the results showed a cross-desensitization of allyl isothiocyanate by previous acetic acid stimulation. In contrast, previous stimulation with allyl isothiocyanate had no effect on the following acetic acid response. These findings confirm that trigeminal sensitization and desensitization in the nasal cavity do not follow the same processes in relation to molecules used.

  9. Acetate reduces microglia inflammatory signaling in vitro

    OpenAIRE

    Soliman, Mahmoud L; Puig, Kendra L.; Combs, Colin K.; Rosenberger, Thad A.

    2012-01-01

    Acetate supplementation increases brain acetyl-CoA and histone acetylation and reduces lipopolysaccharide (LPS)-induced neuroglial activation and interleukin (IL)-1β expression in vivo. To determine how acetate imparts these properties, we tested the hypothesis that acetate metabolism reduces inflammatory signaling in microglia. To test this, we measured the effect acetate treatment had on cytokine expression, mitogen-activated protein kinase (MAPK) signaling, histone H3 at lysine 9 acetylati...

  10. 21 CFR 184.1721 - Sodium acetate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Sodium acetate. 184.1721 Section 184.1721 Food and... Substances Affirmed as GRAS § 184.1721 Sodium acetate. (a) Sodium acetate (C2H3O2Na, CAS Reg. No. 127-09-3 or... animal tissues. Sodium acetate may occur in either the anhydrous or trihydrated form. It is...

  11. 21 CFR 582.1005 - Acetic acid.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Acetic acid. 582.1005 Section 582.1005 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS....1005 Acetic acid. (a) Product. Acetic acid. (b) Conditions of use. This substance is...

  12. 21 CFR 522.533 - Deslorelin acetate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Deslorelin acetate. 522.533 Section 522.533 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Deslorelin acetate. (a) Specifications. Each implant contains 2.1 milligrams deslorelin acetate. (b)...

  13. 21 CFR 582.6185 - Calcium acetate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Calcium acetate. 582.6185 Section 582.6185 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Calcium acetate. (a) Product. Calcium acetate. (b) Conditions of use. This substance is...

  14. 21 CFR 582.1721 - Sodium acetate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Sodium acetate. 582.1721 Section 582.1721 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL DRUGS....1721 Sodium acetate. (a) Product. Sodium acetate. (b) Conditions of use. This substance is...

  15. 21 CFR 522.2476 - Trenbolone acetate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Trenbolone acetate. 522.2476 Section 522.2476 Food... Trenbolone acetate. (a) Sponsors. See sponsors in § 510.600(c) of this chapter for use as in paragraph (d) of... days. (A) 140 milligrams (mg) trenbolone acetate (one implant consisting of 7 pellets, each...

  16. 21 CFR 556.380 - Melengestrol acetate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Melengestrol acetate. 556.380 Section 556.380 Food... Tolerances for Residues of New Animal Drugs § 556.380 Melengestrol acetate. A tolerance of 25 parts per billion is established for residues of the parent compound, melengestrol acetate, in fat of cattle....

  17. Pallidol hexaacetate ethyl acetate monosolvate

    Directory of Open Access Journals (Sweden)

    Qinyong Mao

    2013-07-01

    Full Text Available The entire molecule of pallidol hexaacetate {systematic name: (±-(4bR,5R,9bR,10R-5,10-bis[4-(acetyloxyphenyl]-4b,5,9b,10-tetrahydroindeno[2,1-a]indene-1,3,6,8-tetrayl tetraacetate} is completed by the application of twofold rotational symmetry in the title ethyl acetate solvate, C40H34O12·C4H8O2. The ethyl acetate molecule was highly disordered and was treated with the SQUEEZE routine [Spek (2009. Acta Cryst. D65, 148–155]; the crystallographic data take into account the presence of the solvent. In pallidol hexaacetate, the dihedral angle between the fused five-membered rings (r.m.s. deviation = 0.100 Å is 54.73 (6°, indicating a significant fold in the molecule. Significant twists between residues are also evident as seen in the dihedral angle of 80.70 (5° between the five-membered ring and the pendent benzene ring to which it is attached. Similarly, the acetate residues are twisted with respect to the benzene ring to which they are attached [C—O(carboxy—C—C torsion angles = −70.24 (14, −114.43 (10 and −72.54 (13°]. In the crystal, a three-dimensional architecture is sustained by C—H...O interactions which encompass channels in which the disordered ethyl acetate molecules reside.

  18. 糖基含磷配体在不对称烯丙基取代反应中的应用%Application of Sugar-Based Phosphorus Ligands in Asymmetric Allylic Substitution

    Institute of Scientific and Technical Information of China (English)

    崔朋雷; 王彦恩; 果秀敏; 张冬暖; 李晓慧; 王春

    2014-01-01

    含磷的糖类衍生物作为配体已经广泛应用于不对称有机催化反应中,糖基含磷配体因具有特殊的空间结构而在一些不对称反应中表现出了很高的对映选择性.不对称烯丙基取代反应是一种重要的合成手性化合物的方法,综述了糖基含磷配体用于不对称烯丙基取代反应的最新研究进展.

  19. Maghemite decorated with ultra-small palladium nanoparticles (γ-Fe2O3–Pd): applications in the Heck–Mizoroki olefination, Suzuki reaction and allylic oxidation of alkenes

    Science.gov (United States)

    A nanocatalyst comprising ultra-small Pd/PdO nanoparticles (<5 nm) supported on maghemite was prepared by a co-precipitation protocol using inexpensive raw materials and was deployed successfully in various significant synthetic transformations, namely the Heck–Mizoroki olefinati...

  20. Effect of allyl-thiourea on the corrosive behaviour of bulk nanocrystalline ingot iron%丙烯基硫脲对纳米晶纯铁腐蚀行为影响研究

    Institute of Scientific and Technical Information of China (English)

    沈长斌; 丁志敏; 王颖

    2009-01-01

    在室温添加丙烯基硫脲(ATU)的稀盐酸溶液中,对块体纳米晶工业纯铁(BNII)和普通工业纯铁(CPII)的电化学腐蚀行为进行了对比研究.结果表明:在空白室温1mol.L~(-1) HCl中,BNII的抗腐蚀能力比CPII的强.当添加ATU,浸泡5min后,两种样品的EIS(电化学阻抗谱)均没有出现感抗弧.随着时间的延长,对于BNII,EIS谱图上出现-Warburg阻抗.在浓度为100mg.L~(-1),进行动电位极化测试时,两种样品均出现阳极脱附现象,脱附电位E_(des)有明显差异.与CPII相比,ATU对BNII的缓蚀作用非常有限,甚至有促进其腐蚀的趋势.

  1. (E)-3-Allyl­sulfanyl-N-(4-methoxy­benzyl­idene)-5-(3,4,5-trimethoxy­phen­yl)-4H-1,2,4-triazol-4-amine

    OpenAIRE

    Li, Qian-Zhu; Song, Bao-An; Yang, Song; Zheng, Yu-Guo; Guo, Qing-Qing

    2009-01-01

    The title compound, C22H24N4O4S, adopts a trans configuration with respect to the C=N double bond. A weak intra­molecular C—H⋯N hydrogen bond is observed between the N atom of the C=N double bond and its neighboring phenyl H atom. The crystal structure is stabilized by inter­molecular C—H⋯N hydrogen bonds and C—H⋯π inter­actions.

  2. Study on Fixed-Bed Process of Epoxidation of Allyl Chloride Catalyzed by Ti-MWW%Ti-MWW催化氯丙烯环氧化固定床工艺研究

    Institute of Scientific and Technical Information of China (English)

    姚明恺; 杨俊霞; 赵松; 刘月明; 吴海虹; 吴鹏

    2008-01-01

    以Ti-MWW分子筛为催化剂, H2O2为氧化剂,研究了氯丙烯环氧化制环氧氯丙烷固定床工艺过程的反应规律.结果表明, H2O2的空速对该反应过程起着非常重要的作用.优化的反应参数为: 以乙腈为溶剂, 氯丙烯/H2O2摩尔比为5, 反应温度为333 K, H2O2空速为0 44 h-1.在该条件下氯丙烯转化率、环氧氯丙烷选择性、 H2O2转化率及有效利用率分别达到19 0%, 99 9%, 98 0%和97 0%.

  3. Epoxidation of Allyl Alcohol to Glycidol on Ti-MWW Molecular Sieves%Ti-MWW分子筛上烯丙醇环氧化制环氧丙醇

    Institute of Scientific and Technical Information of China (English)

    陈晓晖; 范志勇; 权霞; 魏可镁

    2006-01-01

    以哌啶为模板剂, 硼酸为结构承载助剂,采用动态水热法成功地合成了Ti-MWW层状前体,经酸处理和煅烧后,得到Ti-MWW分子筛. 紫外-可见光谱表明, Ti-MWW层状前体中含有四面体和八面体配位的钛物种. 酸处理可以很容易地将非骨架的八面体钛脱除,煅烧后分子筛不含锐钛矿相;未经酸处理直接煅烧,部分八面体钛会聚集形成锐钛矿相. Ti-MWW层状前体的红外光谱在960 cm-1 处没有骨架钛的特征吸收谱带出现,经酸处理后,该特征吸收峰出现. 以H2O2为氧化剂,考察了Ti-MWW分子筛上的烯丙醇环氧化性能,发现凝胶Si/Ti=20, 15%HNO3处理12~16 h的情况下,制得的Ti-MWW的催化性能最好,在温度为333 K和反应时间为30 min, 转化率为88.7%, 选择性为99%;但酸处理时间过长可使部分Ti-MWW中的钛生成锐钛矿相,从而导致催化剂活性下降.

  4. Study on the kinetics of allyl alcohol epoxidition to glycidol over Ti-MWW catalyst%Ti-MWW催化烯丙醇环氧化制环氧丙醇的动力学研究

    Institute of Scientific and Technical Information of China (English)

    张文彬; 权霞; 墨玉欣; 陈晓晖; 魏可镁

    2006-01-01

    以水为溶剂,H2O2为氧化剂,Ti-MWW催化烯丙醇环氧化制备环氧丙醇的反应条件温和,产率高,对环境友好,并考察了反应温度、烯丙醇和H2O2的配比对环氧化反应的影响以及温度和pH值对副反应的影响.在此基础上提出了可能的反应机理,建立了主、副反应的动力学模型,确定了模型参数并对模型进行了检验.

  5. Highly Efficient Synthesis of Epichlorohydrin by Epoxidation of Allyl Chloride over Titanosilicate Ti-MWW%Ti-MWW催化烯丙基氯环氧化高效合成环氧氯丙烷

    Institute of Scientific and Technical Information of China (English)

    汪玲玲; 刘月明; 张海娇; 吴海虹; 蒋咏文; 吴鹏; 何鸣元

    2006-01-01

    研究了具有MWW结构的新一代钛硅分子筛Ti-MWW催化剂对烯丙基氯液相环氧化高效合成环氧氯丙烷的催化性能. 结果表明, Ti-MWW的催化活性以及产物选择性均优于传统的钛硅分子筛TS-1. 对于Ti-MWW,合适的溶剂为非质子性溶剂丙酮和乙腈,在该溶剂中环氧化物不易发生溶剂化开环反应;而对于TS-1,合适的溶剂是质子性溶剂甲醇,但甲醇可导致醇醚副产物的生成. 在Ti-MWW催化剂上烯丙基氯的转化率和环氧氯丙烷的选择性都能达到99%以上.

  6. Catalytic Synthesis of Allyl Hexanoate by nano-H4SiW12O40/SiO2%纳米复合钨硅杂多酸催化合成凤梨醛

    Institute of Scientific and Technical Information of China (English)

    张福捐; 王连广; 盛淑玲

    2010-01-01

    以纳米复合钨硅杂多酸为催化荆,己酸和丙烯醇为原料,通过酯化反应合成凤梨醛.结果表明,在醇酸物质的量比为1.8:1,催化剂用量5%,带水剂10 mL,反应时间2 h的条件下,酯化率可达97.2%.

  7. A Large Scale Formal Synthesis of CoQ{sub 10}: Highly Stereoselective Friedel-Crafts Allylation Reaction of Tetramethoxytoluene with (E)-4-Chloro-2-methyl-1-phenylsulfonyl-2-butene in the Presence of Montmorillonite K-10

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Sang Who; Lee, Hee Bong; Kim, Bong Chan; Sadaiah, Kadivendi; Lee, Kyuwoong; Shin, Hyunik [LG Life Sciences, Ltd., Daejeon (Korea, Republic of)

    2013-04-15

    We disclosed that MK-10 is a highly effective catalyst for the Friedel-Crafts reaction of 6 and 7 in terms of yield and of stereoselectivity. Although there are numerous applications of clays in Friedel-Crafts reaction, there is very limited example which demonstrated its effect on the stereoselectivity. In that context, our result is significant and further expansion in this direction is highly envisioned. Ubiquinone, as its name represents, exists ubiquitously in human body, particularly in the heart. It mediates the electron transfer process in mitochondria and also exerts strong antioxidant effect in its reduced form. In clinical trial, it showed beneficial effect on heart-related diseases such as myocardial infarction, angina, and other related symptoms to cause decreased mortality compared to the placebo group.

  8. Conversion to eslicarbazepine acetate monotherapy

    OpenAIRE

    Sperling, Michael R.; French, Jacqueline; Jacobson, Mercedes P.; Pazdera, Ladislav; Gough, Mallory; Cheng, Hailong; Grinnell, Todd; Blum, David

    2016-01-01

    Objective: To assess the efficacy and safety of eslicarbazepine acetate (ESL) monotherapy. Methods: This post hoc pooled analysis of 2 randomized double-blind studies (093-045 and -046) included adults with partial-onset seizures medically uncontrolled by 1 or 2 antiepileptic drugs (AEDs). Following the baseline period (8 weeks), eligible patients were randomized 2:1 to receive ESL 1,600 mg or 1,200 mg once daily for 18 weeks; the primary endpoint was study exit by meeting predefined exit cri...

  9. Impact of Substituents Attached to N-Heterocyclic Carbenes on the Catalytic Activity of Copper Complexes in the Reduction of Carbonyl Compounds with Triethoxysilane

    Institute of Scientific and Technical Information of China (English)

    PENG, Jiajian; CHEN, Lingzhen; XU, Zheng; HU, Yingqian; LI, Jiayun; BAI, Ying; QIU, Huayu; LAI, Guoqiao

    2009-01-01

    By using functionalized imidazolium salts such as 1-allyl-3-alkylimidazolium or 1-alkyi-3-vinylimidazolium salts as carbene ligand precursors, the reduction of aryl ketones with triethoxysilane may be catalyzed by copper salt/imidazolium salt/KO~tBu systems. The functional substituents attached to the N-heterocyclic carbene (NHC) serve to enhance the catalytic activity. Different copper salts also have an effect on the catalytic activity, with copper(Ⅱ) acetate monohydrate being superior to copper(I) chloride.

  10. Recent progress in lanthanide-catalyzed organic reactions in protic media

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Lanthanide triflates are stable in water. It is possible for lanthanides to undergo many organic reactions in environmentally friendly solvents. This makes lanthanides very promising in the field of green chemistry. This review describes the recent development of the lanthanidecatalyzed organic reactions in protic solvents. Those reactions include Diels-Alder, Aldol, Allylation, acetalization,pericyclization, radical reactions as well as some newly-developed lanthnides-based catalysts.

  11. Electrophysiology and behavior feedback of diamondback moth, Plutella xylostella, to volatile secondary metabolites emitted by Chinese cabbage

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    The volatiles, absorbed by Porapak Q and eluted by hexane, from Chinese cabbage, Brassica campestris chinesis (L.) Makino. var. communis Tsen et Lee, have been identified as allyl isothiocyanate, Z-3-hexenyl acetate, 3,7-dimethyl-1,3,6-octatriene, 2,5-hexanediol, Z-3-hexen-1-ol, nonanol, (-myrcene, (-pinene, E-2-hexen-1-ol, D-limonene, Z-3-hexenyl propanoate, linalool, geraniol, E-4-hexen-1-ol, Z-3-hexenyl isovalerate, (-terpinene, (-caryophyllene, 3-carene and (-caryophyllene, by their mass spectra and retention times in comparison with authentic samples. The first five chemicals are the main components. All components can elicite electroantennogram (EAG) responses of diamondback moth (DBM), Plutella xylostella, in which allyl isothiocyanate and C6 alcohols and esters, i.e. Z-3-hexen-1-ol, E-2-hexen-1-ol, E-4-hexen-1-ol, Z-3-hexenyl isovalerate and 2,5-hexanediol elicite stronger EAG responses than other components, and EAG responses of female moths to them are slightly larger than those of male moths. However, EAG responses elicited by terpenes are smaller, and EAG responses from females to terpenes are smaller than those from males, but ((myrcene can evoke stronger EAG responses from both females and males. Volatiles from intact Chinese cabbage, allyl isothiocyanate, 2,5-hexanediol and Z-3-hexenyl isovalerate intensely cause DBM directional flying and landing in wind tunnel, in which volatiles from intact Chinese cabbage have the strongest activity, and the next is allyl isothiocyanate. Allyl isothiocyanate is more attractive to females than to males a bit. As for (-terpinene and other subordinate components, EAG and wind tunnel test make sure they have weak activity.

  12. Simultaneous structure-activity studies and arming of natural products by C-H amination reveal cellular targets of eupalmerin acetate

    Science.gov (United States)

    Li, Jing; Cisar, Justin S.; Zhou, Cong-Ying; Vera, Brunilda; Williams, Howard; Rodríguez, Abimael D.; Cravatt, Benjamin F.; Romo, Daniel

    2013-06-01

    Natural products have a venerable history of, and enduring potential for the discovery of useful biological activity. To fully exploit this, the development of chemical methodology that can functionalize unique sites within these complex structures is highly desirable. Here, we describe the use of rhodium(II)-catalysed C-H amination reactions developed by Du Bois to carry out simultaneous structure-activity relationship studies and arming (alkynylation) of natural products at ‘unfunctionalized’ positions. Allylic and benzylic C-H bonds in the natural products undergo amination while olefins undergo aziridination, and tertiary amine-containing natural products are converted to amidines by a C-H amination-oxidation sequence or to hydrazine sulfamate zwitterions by an unusual N-amination. The alkynylated derivatives are ready for conversion into cellular probes that can be used for mechanism-of-action studies. Chemo- and site-selectivity was studied with a diverse library of natural products. For one of these—the marine-derived anticancer diterpene, eupalmerin acetate—quantitative proteome profiling led to the identification of several protein targets in HL-60 cells, suggesting a polypharmacological mode of action.

  13. Isobaric Vapor-Liquid Equilibrium of Binary Systems: p-Xylene + (Acetic Acid, Methyl Acetate and n-Propyl Acetate)and Methyl Acetate + n-Propyl Acetate in an Acetic Acid Dehydration Process

    Institute of Scientific and Technical Information of China (English)

    HUANG Xiuhui; ZHONG Weimin; PENG Changjun; QIAN Feng

    2013-01-01

    The vapor-liquid equilibrium data of four binary systems(acetic acid + p-xylene,methyl acetate + n-propyl acetate,n-propyl acetate + p-xylene and methyl acetate + p-xylene)are measured at 101.33 kPa with Ellis equilibrium still,and then both the NRTL and UNIQUAC models are used in combination with the HOC model for correlating and estimating the vapor-liquid equilibrium of these four binary systems.The estimated binary VLE results using correlated parameters agree well with the measured data except the methyl acetate + p-xylene system which easily causes bumping and liquid rushing out of the sampling tap due to their dramatically different boiling points.The correlation results by NRTL and UNIQUAC models have little difference on the average absolute deviations of temperature and composition of vapor phase,and the results by NRTL model are slightly better than those by UNIQUAC model except for the methyl acetate + n-propyl acetate system,for which the latter gives more accurate correlations.

  14. 21 CFR 184.1005 - Acetic acid.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Acetic acid. 184.1005 Section 184.1005 Food and... Substances Affirmed as GRAS § 184.1005 Acetic acid. (a) Acetic acid (C2H4O2, CAS Reg. No. 64-19-7) is known as ethanoic acid. It occurs naturally in plant and animal tissues. It is produced by fermentation...

  15. Solubilities of carbon dioxide in 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate and 3-methoxybutyl acetate

    International Nuclear Information System (INIS)

    Highlights: • Measured solubility data of CO2 in 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate and 3-methoxybutyl acetate. • Calculated Henry’s constant and thermodynamic properties of selected systems. • Concluded that selected absorbents have potential research value for CO2 capture. - Abstract: The solubilities of CO2 in 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, and 3-methoxybutyl acetate were measured by isothermal synthesis method under pressures up to 1.2 MPa and at temperatures ranging from (293.15 to 333.15) K. Henry’s constant was calculated based on experimental data regression. The solubilities of CO2 were found to increase with decreased temperature and increased the methyl group to the molecular structure of the absorbent. Henry’s constant and volumetric solubility of selected absorbents at T = 298.15 K were compared with those of commercial absorbents and common solvents. 3-Methoxybutyl acetate showed the best performance by mole fraction, and 2-methoxyethyl acetate behaved the best by volumetric fraction. Based on Henry’s constant, thermodynamic properties such as Gibbs free energy of solution, enthalpy of solution, and absorption entropy of solution were determined. These properties are very essential for designing an absorption process

  16. Optimization of coproduction of ethyl acetate and n-butyl acetate by reactive distillation☆

    Institute of Scientific and Technical Information of China (English)

    Hui Tian; Suying Zhao; Huidong Zheng; Zhixian Huang

    2015-01-01

    Based on a previous investigation, a simulation model was used for optimization of coproduction of ethyl acetate and n-butyl acetate by reactive distil ation. An experimental setup was established to verify the simulated results. The effects of various operating variables, such as ethanol feed location, acetic acid feed location, feed stage of reaction mixture of acetic acid and n-butanol, reflux ratio of ethyl acetate reactive distillation column, and distil-late to feed ratio of n-butyl acetate column, on the ethanol/n-butanol conversions, ethyl acetate/n-butyl acetate purity, and energy consumption were investigated. The optimal results in the simulation study are as follows:ethanol feed location, 15th stage;acetic acid feed location, eighth stage;feed location of reaction mixture of acetic acid and n-butanol, eighth stage;reflux ratio of ethyl acetate reactive distillation column, 2.0;and distillate to feed ratio of n-butyl acetate, 0.6.

  17. Direct Oxidation of Ethene to Acetic Acid

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Direct oxidation of ethene to acetic acid over Pd-SiW12/SiO2 catalysts prepared by several methods was studied. A better method for reducing palladium composition of the catalysts was found. Acetic acid was obtained with selectivity of 82.7% and once-through space time yield (STY) of 257.4 g/h×L.

  18. Desvenlafaxinium chloranilate ethyl acetate solvate

    Directory of Open Access Journals (Sweden)

    Manpreet Kaur

    2013-10-01

    Full Text Available In the cation of the title compound, C16H26NO2+·C6HCl2O4−·C4H8O2, the 1-hydroxy-cyclohexyl ring adopts a slightly distorted chair conformation. The dihedral angle between the mean planes of the 1-hydroxycyclohexyl and 4-hydroxyphenyl rings is 84.0 (8°. In the anion, the hydroxyl H atom is twisted slightly out of the ring plane with a C—C—O—H torsion angle of −171.9°. Disorder was modeled for the methyl group of the acetate group in the solvate with an occupancy ratio of 0.583 (15: 0.417 (15. In the crystal, O—H...O hydrogen bonds are observed between cations and between cations and anions, while bifuricated N—H...(O,O cation–anion hydrogen bonds are also present, forming chains along [010] and [100]. In addition weak cation–anion and cation–solvate C—H...O interactions occur.

  19. Conversion to eslicarbazepine acetate monotherapy

    Science.gov (United States)

    French, Jacqueline; Jacobson, Mercedes P.; Pazdera, Ladislav; Gough, Mallory; Cheng, Hailong; Grinnell, Todd; Blum, David

    2016-01-01

    Objective: To assess the efficacy and safety of eslicarbazepine acetate (ESL) monotherapy. Methods: This post hoc pooled analysis of 2 randomized double-blind studies (093-045 and -046) included adults with partial-onset seizures medically uncontrolled by 1 or 2 antiepileptic drugs (AEDs). Following the baseline period (8 weeks), eligible patients were randomized 2:1 to receive ESL 1,600 mg or 1,200 mg once daily for 18 weeks; the primary endpoint was study exit by meeting predefined exit criteria (signifying worsening seizure control). In each study, treatment was considered effective if the upper 95% confidence limit for exit rate was lower than the historical control threshold (65.3%). Results: Pooled exit rates were as follows: ESL 1,600 mg = 20.6% (95% confidence interval: 15.6%–26.8%); ESL 1,200 mg = 30.8% (23.0%–40.5%). Use of 2 baseline AEDs or rescue medication, US location, epilepsy duration ≥20 years, and higher maximum baseline seizure frequency were associated with higher exit risks. Median percent reductions in standardized seizure frequency between baseline and the 18-week double-blind period were as follows: ESL 1,600 mg = 43.2%; ESL 1,200 mg = 35.7%; baseline carbamazepine use was associated with smaller reductions. Safety profiles were similar between ESL doses. Conclusions: Exit rates for ESL monotherapy (1,600 mg and 1,200 mg once daily) were lower than the historical control threshold, irrespective of baseline AED use and region, with no additional safety concerns identified. Clinical factors and location clearly influence treatment responses in conversion-to-monotherapy trials. Classification of evidence: This pooled analysis provides Class IV evidence that for adults with medically uncontrolled partial-onset seizures, ESL monotherapy is well tolerated and effective. PMID:26911639

  20. Demand boom boosts ethyl, butyl acetate

    International Nuclear Information System (INIS)

    US ethyl and butyl acetate markets are being described as 'extremely tight.' One major domestic producer is 'in a sold-out position' and has 'gone on sales control' with respect to these two products. Producers say that sales of both ethyl and butyl acetate have increased during the past year, and industry observers say they expect to see an April 1 price initiative of 2 cts to 3 cts/lb, and possibly a second increase in October. While one producer suggests that this market strength could be 'a sign that the coatings industry is turning around,' most agree that reformulation is the principal driver of growth. Ethyl acetate is said to be replacing methyl ethyl ketone in many formulations, while butyl acetate and butyl acetate blends are substituting for methyl isobutyl ketone. In addition, both ethyl and butyl acetate work as substitutes for xylene and toluene in certain applications. In an effort to conform to the requirements of the Clean Air Act of 1990 and to cooperate with the Environmental Protection Agency's 33/50 voluntary emissions reduction program, coatings manufacturers are moving as quickly as possible to eliminate solvents from their products. And although solvents as a whole will eventually see a dramatic decline in consumption, the temporary beneficiaries of reformulation will be certain of the oxygenated solvents, says Jeff Back, business manager at Kline ampersand Co

  1. Synthesis of Phenyl Acetate from Phenol and Acetic Anhydride over Synthetic TS-1 Containing Template

    Institute of Scientific and Technical Information of China (English)

    Wu Guowen; Shi Chunfeng; Lin Min; Zhu Bin

    2014-01-01

    In this article, phenyl acetate was synthesized from phenol and acetic anhydride over titanium silicalite-1, in which the organic structure-directing agents were immobilized (TS-1-U). The reaction conditions were speciifed at a phenol to acetic anhydride molar ratio of 1:1.2, a catalyst dosage of 6 m%, and a reaction temperature of 70℃. A total of 96.5%of phenol was converted to phenyl acetate without producing any byproducts after 2.5 h of reaction. Besides, although the catalyst deactivation is inevitable, TS-1-U could be recycled for at least four times.

  2. Tested Demonstrations: Buffer Capacity of Various Acetic Acid-Sodium Acetate Systems: A Lecture Experiment.

    Science.gov (United States)

    Donahue, Craig J.; Panek, Mary G.

    1985-01-01

    Background information and procedures are provided for a lecture experiment which uses indicators to illustrate the concept of differing buffer capacities by titrating acetic acid/sodium acetate buffers with 1.0 molar hydrochloric acid and 1.0 molar sodium hydroxide. A table with data used to plot the titration curve is included. (JN)

  3. Acetic acid production from food wastes using yeast and acetic acid bacteria micro-aerobic fermentation.

    Science.gov (United States)

    Li, Yang; He, Dongwei; Niu, Dongjie; Zhao, Youcai

    2015-05-01

    In this study, yeast and acetic acid bacteria strains were adopted to enhance the ethanol-type fermentation resulting to a volatile fatty acids yield of 30.22 g/L, and improve acetic acid production to 25.88 g/L, with food wastes as substrate. In contrast, only 12.81 g/L acetic acid can be obtained in the absence of strains. The parameters such as pH, oxidation reduction potential and volatile fatty acids were tested and the microbial diversity of different strains and activity of hydrolytic ferment were investigated to reveal the mechanism. The optimum pH and oxidation reduction potential for the acetic acid production were determined to be at 3.0-3.5 and -500 mV, respectively. Yeast can convert organic matters into ethanol, which is used by acetic acid bacteria to convert the organic wastes into acetic acid. The acetic acid thus obtained from food wastes micro-aerobic fermentation liquid could be extracted by distillation to get high-pure acetic acid.

  4. Acetylation of Starch with Vinyl Acetate in Imidazolium Ionic Liquids and Characterization of Acetate Distribution

    Science.gov (United States)

    Starch was acetylated with vinyl acetate in different 1-butyl-3-methylimidazolium (BMIM) salts as solvent in effort to produce starches with different acetylation patterns. Overall degree of substitution was much higher for basic anions such as acetate and dicyanimide (dca) than for neutral anions ...

  5. Fierce Competition in China's Ethyl Acetate Market

    Institute of Scientific and Technical Information of China (English)

    Wang Zichang

    2007-01-01

    @@ Ethyl acetate is used extensively in the coatings, inks, pharmaceuticals,adhesives, cosmetics and organic synthesis sectors. With the sustained stable growth of China's national economy, the construction and automobile sectors are developing rapidly and environmental protection laws and regulations are becoming stricter.

  6. Formation of asymmetric cellulose acetate membranes

    NARCIS (Netherlands)

    Bokhorst, H.; Altena, F.W.; Smolders, C.A.

    1981-01-01

    Cellulose acetate membranes were prepared from casting solutions containing dioxane as a solvent and varying concentrations (up to 6%) of maleic acid as an additive. Coagulation took place in water at different temperatures. The effect of these variables on membrane structure and membrane properties

  7. Vinyl acetate polymerization by ionizing radiation

    International Nuclear Information System (INIS)

    The aim of this work is the synthesis and characterization of the poly(vinyl acetate) using the ionizing radiation. Six polymerizations of vinyl acetate were carried out using three techniques of polymerization: in bulk, emulsion and solution. In the technique of solution polymerization were used two solvents, the alcohol ethyl and the methylethylketone, in two proportions 1:0.5 and 1:1 related to the monomer. The solutions were irradiated with gamma rays from a 60Co source, with dose rate between 5.25 kGy/h and 6.26 kGy/h. The polymers obtained were characterized by Fourier Transform Infrared Spectroscopy (FTIR). The glass transition temperature (Tg) was investigated by Differential Scanning Calorimeter (DSC). The molecular weight was analyzed by the technique of Gel Permeation Chromatography (GPC). Tests of density, hardness and Vicat softening temperature were carried out. The infrared spectroscopy and others results confirmed that the polymers obtained by polymerization of vinyl acetate in bulk, emulsion and solution, using ionizing radiation, really correspond at poly(vinyl acetate). (author)

  8. Advanced Colloids Experiment (ACE-T1)

    Science.gov (United States)

    Meyer, William V.; Sicker, Ron; Brown, Dan; Eustace, John

    2015-01-01

    Increment 45 - 46 Science Symposium presentation of Advanced Colloids Experiment (ACE-T1) to RPO. The purpose of this event is for Principal Investigators to present their science objectives, testing approach, and measurement methods to agency scientists, managers, and other investigators.

  9. Acetate causes alcohol hangover headache in rats.

    Directory of Open Access Journals (Sweden)

    Christina R Maxwell

    Full Text Available BACKGROUND: The mechanism of veisalgia cephalgia or hangover headache is unknown. Despite a lack of mechanistic studies, there are a number of theories positing congeners, dehydration, or the ethanol metabolite acetaldehyde as causes of hangover headache. METHODS: We used a chronic headache model to examine how pure ethanol produces increased sensitivity for nociceptive behaviors in normally hydrated rats. RESULTS: Ethanol initially decreased sensitivity to mechanical stimuli on the face (analgesia, followed 4 to 6 hours later by inflammatory pain. Inhibiting alcohol dehydrogenase extended the analgesia whereas inhibiting aldehyde dehydrogenase decreased analgesia. Neither treatment had nociceptive effects. Direct administration of acetate increased nociceptive behaviors suggesting that acetate, not acetaldehyde, accumulation results in hangover-like hypersensitivity in our model. Since adenosine accumulation is a result of acetate formation, we administered an adenosine antagonist that blocked hypersensitivity. DISCUSSION: Our study shows that acetate contributes to hangover headache. These findings provide insight into the mechanism of hangover headache and the mechanism of headache induction.

  10. Phenyl Acetate Preparation from Phenol and Acetic Acid: Reassessment of a Common Textbook Misconception.

    Science.gov (United States)

    Hocking, M. B.

    1980-01-01

    Reassesses a common textbook misconception that "...phenols cannot be esterified directly." Results of experiments are discussed and data tables provided of an effective method for the direct preparation of phenyl acetate. (CS)

  11. The microwave spectrum of n-hexyl acetate and structural aspects of n-alkyl acetates

    Science.gov (United States)

    Attig, T.; Kannengießer, R.; Kleiner, I.; Stahl, W.

    2014-04-01

    The microwave spectrum of n-hexyl acetate was recorded in the range of 10-13.5 GHz using the Aachen MB-FTMW spectrometer. The rotational constants of the most abundant conformer were determined to be A = 3.3591100(32) GHz, B = 0.39596553(53) GHz, and C = 0.36999804(31) GHz. Quantum chemical calculations for specific conformers were carried out at the MP2/6-311++G(d,p) level. The programs XIAM and BELGI were used to analyze the internal rotation of the acetyl methyl group. The observed conformer of n-hexyl acetate was compared to the lowest energy conformers of n-butyl acetate and n-pentyl acetate.

  12. Expression of acetate permease-like (apl) genes in subsurface communities of Geobacter species under fluctuating acetate concentrations

    Energy Technology Data Exchange (ETDEWEB)

    Elifantz, H.; N' Guessan, L.A.; Mouser, P.J.; Williams, K H.; Wilkins, M J.; Risso, C.; Holmes, D.E.; Long, P.E.; Lovley, D.R.

    2010-03-01

    The addition of acetate to uranium-contaminated aquifers in order to stimulate the growth and activity of Geobacter species that reduce uranium is a promising in situ bioremediation option. Optimizing this bioremediation strategy requires that sufficient acetate be added to promote Geobacter species growth. We hypothesized that under acetate-limiting conditions, subsurface Geobacter species would increase the expression of either putative acetate symporters genes (aplI and aplII). Acetate was added to a uranium-contaminated aquifer (Rifle, CO) in two continuous amendments separated by 5 days of groundwater flush to create changing acetate concentrations. While the expression of aplI in monitoring well D04 (high acetate) weakly correlated with the acetate concentration over time, the transcript levels for this gene were relatively constant in well D08 (low acetate). At the lowest acetate concentrations during the groundwater flush, the transcript levels of aplII were the highest. The expression of aplII decreased 2-10-fold upon acetate reintroduction. However, the overall instability of acetate concentrations throughout the experiment could not support a robust conclusion regarding the role of apl genes in response to acetate limitation under field conditions, in contrast to previous chemostat studies, suggesting that the function of a microbial community cannot be inferred based on lab experiments alone.

  13. 21 CFR 582.5933 - Vitamin A acetate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Vitamin A acetate. 582.5933 Section 582.5933 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Supplements 1 § 582.5933 Vitamin A acetate. (a) Product. Vitamin A acetate. (b) Conditions of use....

  14. Microbial acetate oxidation in horizontal rotating tubular bioreactor

    Indian Academy of Sciences (India)

    A Slavica; B Šantek; S Novak; V Marić

    2004-06-01

    The aim of this work was to investigate the possibility of conducting a continuous aerobic bioprocess in a horizontal rotating tubular bioreactor (HRTB). Aerobic oxidation of acetate by the action of a mixed microbial culture was chosen as a model process. The microbial culture was not only grown in a suspension but also in the form of a biofilm on the interior surface of HRTB. Efficiency of the bioprocess was monitored by determination of the acetate concentration and chemical oxygen demand (COD). While acetate inlet concentration and feeding rate influenced efficiency of acetate oxidation, the bioreactor rotation speed did not influence the bioprocess dynamics significantly. Gradients of acetate concentration and pH along HRTB were more pronounced at lower feeding rates. Volumetric load of acetate was proved to be the most significant parameter. High volumetric loads (above 2 g acetate l–1 h–1) gave poor acetate oxidation efficiency (only 17 to 50%). When the volumetric load was in the range of 0.60–1.75 g acetate l–1 h–1, acetate oxidation efficiency was 50–75%. At lower volumetric loads (0.14–0.58 g acetate l–1 h–1), complete acetate consumption was achieved. On the basis of the obtained results, it can be concluded that HRTB is suitable for conducting aerobic continuous bioprocesses.

  15. Kinetics of Ethyl Acetate Synthesis Catalyzed by Acidic Resins

    Science.gov (United States)

    Antunes, Bruno M.; Cardoso, Simao P.; Silva, Carlos M.; Portugal, Ines

    2011-01-01

    A low-cost experiment to carry out the second-order reversible reaction of acetic acid esterification with ethanol to produce ethyl acetate is presented to illustrate concepts of kinetics and reactor modeling. The reaction is performed in a batch reactor, and the acetic acid concentration is measured by acid-base titration versus time. The…

  16. Acetic acid extraction from aqueous solutions using fatty acids

    NARCIS (Netherlands)

    IJmker, H.M.; Gramblicka, M.; Kersten, S.R.A.; Ham, van der A.G.J.; Schuur, B.

    2014-01-01

    A major challenge for production of acetic acid via bio-based routes is cost-effective concentration and purification of the acetic acid from the aqueous solutions, for which liquid–liquid extraction is a possible method. A main challenge in extraction of acetic acid from dilute aqueous solutions is

  17. Fermentation characteristics of Fusarium oxysporum grown on acetate

    DEFF Research Database (Denmark)

    Panagiotou, Gianni; Pachidou, Fotini; Petroutsos, Dimitris;

    2008-01-01

    In this study, the growth characteristics of Fusarium oxysporum were evaluated in minimal medium using acetate or different mixtures of acetate and glucose as carbon source. The minimum inhibitory concentration (MIC) of acetic acid that F oxysporum cells could tolerate was 0.8% w/v while glucose...

  18. 21 CFR 182.8892 - α-Tocopherol acetate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true α-Tocopherol acetate. 182.8892 Section 182.8892 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD...-Tocopherol acetate. (a) Product. α-Tocopherol acetate. (b) Conditions of use. This substance is...

  19. 21 CFR 582.5892 - a-Tocopherol acetate.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 6 2010-04-01 2010-04-01 false a-Tocopherol acetate. 582.5892 Section 582.5892 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) ANIMAL... Supplements 1 § 582.5892 a-Tocopherol acetate. (a) Product. a-Tocopherol acetate. (b) Conditions of use....

  20. 21 CFR 584.200 - Ethyl alcohol containing ethyl acetate.

    Science.gov (United States)

    2010-04-01

    ... Ethyl alcohol containing ethyl acetate. The feed additive ethyl alcohol containing ethyl acetate meets the requirement of 27 CFR 21.62, being not less than 92.5 percent ethyl alcohol, each 100 gallons... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Ethyl alcohol containing ethyl acetate....

  1. 40 CFR 721.3880 - Polyalkylene glycol substituted acetate.

    Science.gov (United States)

    2010-07-01

    ... acetate. 721.3880 Section 721.3880 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.3880 Polyalkylene glycol substituted acetate. (a) Chemical substance and... glycol substituted acetate (PMN P-91-1269) is subject to reporting under this section for the...

  2. Acetate in Oz: Some Strategic Moves

    Directory of Open Access Journals (Sweden)

    Colin Webb

    2005-08-01

    Full Text Available I would like to add my voice to the words of congratulations and thanks to the British Library for organising this forum, and for their generosity in making it possible for me to come across the world to be part of it. The issues we are discussing today have an importance extending beyond cellulose acetate, as they reflect our ability as custodians to deal with common threats to the documentary heritage we are charged with preserving. As I will argue later, we need to see this situation in the context of the full range of preservation management issues that face our institutions. While it imposes a burden and a challenge on us as preservation managers, it also presents opportunities to sort out some things that have needed attention for some time. I have been asked to talk about problems with cellulose acetate microfilm collections in Australia, and specifically the strategies – both national and local – that have been adopted or at least explored in response to those problems. In the time I have I will not be going into any of these in great detail, but I hope I can give you some sense of the situation down under, and perhaps draw out a few issues that might make this more than just an ‘us too’ session! One thing to emphasise from the start is that we have had a number of goes at dealing with acetate microfilm collections: it is not a newly discovered problem in Australia. One significant context in which we have been working is that of a national strategy for all kinds of cellulose acetate collection materials. Explaining this national strategy will form a major part of my presentation, with issues and approaches specific to microfilm discussed towards the end.

  3. PHOTOCOPOLYMERIZATION OF MALEIC ANHYDRIDE AND VINYL ACETATE

    Institute of Scientific and Technical Information of China (English)

    LI Xiaofang; LI Shanjun; QIN Anwei; YU Tongyin

    1990-01-01

    The charge-transfer complex of maleic anhydride and vinyl acetate was copolymerized under UV light. The chain composition and structure of the copolymer were analyzed with conductometry and NMR, and the chain sequence was determined as alternating. The copolymerization rates at different feed ratios, temperatures and in different solvents were investigated, giving evidence to the very active involvement of the CT complexes in the copolymerization. Terpolymerization with acrylonitrile also showed that the complex mechanism was a proper one for this system.

  4. Acetate supplementation attenuates lipopolysaccharide-induced neuroinflammation

    OpenAIRE

    Reisenauer, Chris J.; Bhatt, Dhaval P.; Mitteness, Dane J.; Slanczka, Evan R.; Gienger, Heidi M.; Watt, John A.; Rosenberger, Thad A

    2011-01-01

    Glyceryl triacetate (GTA), a compound effective at increasing circulating and tissue levels of acetate was used to treat rats subjected to a continual 28 day intra-ventricular infusion of bacterial lipopolysaccharide (LPS). This model produces a neuroinflammatory injury characterized by global neuroglial activation and a decrease in choline acetyltransferase immunoreactivity in the basal forebrain. During the LPS infusion, rats were given a daily treatment of either water or GTA at a dose of ...

  5. Co-fermentation of acetate and sugars facilitating microbial lipid production on acetate-rich biomass hydrolysates.

    Science.gov (United States)

    Gong, Zhiwei; Zhou, Wenting; Shen, Hongwei; Yang, Zhonghua; Wang, Guanghui; Zuo, Zhenyu; Hou, Yali; Zhao, Zongbao K

    2016-05-01

    The process of lignocellulosic biomass routinely produces a stream that contains sugars plus various amounts of acetic acid. As acetate is known to inhibit the culture of microorganisms including oleaginous yeasts, little attention has been paid to explore lipid production on mixtures of acetate and sugars. Here we demonstrated that the yeast Cryptococcus curvatus can effectively co-ferment acetate and sugars for lipid production. When mixtures of acetate and glucose were applied, C. curvatus consumed both substrates simultaneously. Similar phenomena were also observed for acetate and xylose mixtures, as well as acetate-rich corn stover hydrolysates. More interestingly, the replacement of sugar with equal amount of acetate as carbon source afforded higher lipid titre and lipid content. The lipid products had fatty acid compositional profiles similar to those of cocoa butter, suggesting their potential for high value-added fats and biodiesel production. This co-fermentation strategy should facilitate lipid production technology from lignocelluloses. PMID:26874438

  6. A NOVEL COPOLYMER-BOUND CIS- DICARBONYLRHODIUM COMPLEX FOR THE CARBONYLATION OF METHANOL TO ACETIC ACID AND ACETIC ANHYDRIDE

    Institute of Scientific and Technical Information of China (English)

    YUAN Guoqing; CHEN Yuying; CHEN Rongyao

    1989-01-01

    A series of porous microspheres of linear and ethylene diacrylate (M ') cross-linked copolymers of 2 - vinylpyridine (V) and methyl acrylate (M) reacted with tetracarbonyldichlorodirhodium to form a series of cis-dicarbonylrhodium chelate complex (MVRh and MVM 'Rh). They are thermally stable yet very reactive in the carbonylation of methanol to acetic acid, and of methanol - acetic acid mixture to acetic acid and acetic anhydride with a selectivity of 100% under relatively mild and anhydrous conditions.

  7. Overview on mechanisms of acetic acid resistance in acetic acid bacteria.

    Science.gov (United States)

    Wang, Bin; Shao, Yanchun; Chen, Fusheng

    2015-02-01

    Acetic acid bacteria (AAB) are a group of gram-negative or gram-variable bacteria which possess an obligate aerobic property with oxygen as the terminal electron acceptor, meanwhile transform ethanol and sugar to corresponding aldehydes, ketones and organic acids. Since the first genus Acetobacter of AAB was established in 1898, 16 AAB genera have been recorded so far. As the main producer of a world-wide condiment, vinegar, AAB have evolved an elegant adaptive system that enables them to survive and produce a high concentration of acetic acid. Some researches and reviews focused on mechanisms of acid resistance in enteric bacteria and made the mechanisms thoroughly understood, while a few investigations did in AAB. As the related technologies with proteome, transcriptome and genome were rapidly developed and applied to AAB research, some plausible mechanisms conferring acetic acid resistance in some AAB strains have been published. In this review, the related mechanisms of AAB against acetic acid with acetic acid assimilation, transportation systems, cell morphology and membrane compositions, adaptation response, and fermentation conditions will be described. Finally, a framework for future research for anti-acid AAB will be provided.

  8. Compound list: desmopressin acetate [Open TG-GATEs

    Lifescience Database Archive (English)

    Full Text Available desmopressin acetate DDAVP 00159 ftp://ftp.biosciencedbc.jp/archive/open-tggates/LA...TEST/Rat/in_vivo/Liver/Single/desmopressin_acetate.Rat.in_vivo.Liver.Single.zip ftp://ftp.biosciencedbc.jp/a...rchive/open-tggates/LATEST/Rat/in_vivo/Liver/Repeat/desmopressin_acetate.Rat.in_vivo.Liver.Repeat.zip ftp://...ftp.biosciencedbc.jp/archive/open-tggates/LATEST/Rat/in_vivo/Kidney/Single/desmopre...ssin_acetate.Rat.in_vivo.Kidney.Single.zip ftp://ftp.biosciencedbc.jp/archive/open-tggates/LATEST/Rat/in_vivo/Kidney/Repeat/desmopressin_acetate.Rat.in_vivo.Kidney.Repeat.zip ...

  9. [Degradation of oxytetracycline with ozonation in acetic acid solvent].

    Science.gov (United States)

    Li, Shi-Yin; Li, Xiao-Rong; Zhu, Yi-Ping; Zhu, Jiang-Peng; Wang, Guo-Xiang

    2012-12-01

    Use acetic acid as the media of ozone degradation of oxytetracycline (OTC), and effects of the initial dosing ratio of ozone/OTC, ozone flow, free radical scavenger, metal ions on the removal rate of OTC were investigated respectively. The results showed that acetic acid had a high ozone stability and solubility. OTC had a high removal rate and degradation rate in acetic acid solution. With the increase of OTC dosage, the removal rate of OTC decreased in acetic acid. Removal rate of OTC was increased distinctly when ozone flow increased properly. It was also observed that free radical scavenger had a significantly negative effect on OTC ozonation degradation in acetic acid. Furthermore the main reactions of OTC ozone oxidation were direct oxidation and indirect oxidation in acetic acid. When Fe3+ and Co2+ were existent in acetic acid, the degradation of OTC was inhibited significantly. PMID:23379161

  10. Acetic acid removal from corn stover hydrolysate using ethyl acetate and the impact on Saccharomyces cerevisiae bioethanol fermentation.

    Science.gov (United States)

    Aghazadeh, Mahdieh; Ladisch, Michael R; Engelberth, Abigail S

    2016-07-01

    Acetic acid is introduced into cellulose conversion processes as a consequence of composition of lignocellulose feedstocks, causing significant inhibition of adapted, genetically modified and wild-type S. cerevisiae in bioethanol fermentation. While adaptation or modification of yeast may reduce inhibition, the most effective approach is to remove the acetic acid prior to fermentation. This work addresses liquid-liquid extraction of acetic acid from biomass hydrolysate through a pathway that mitigates acetic acid inhibition while avoiding the negative effects of the extractant, which itself may exhibit inhibition. Candidate solvents were selected using simulation results from Aspen Plus™, based on their ability to extract acetic acid which was confirmed by experimentation. All solvents showed varying degrees of toxicity toward yeast, but the relative volatility of ethyl acetate enabled its use as simple vacuum evaporation could reduce small concentrations of aqueous ethyl acetate to minimally inhibitory levels. The toxicity threshold of ethyl acetate, in the presence of acetic acid, was found to be 10 g L(-1) . The fermentation was enhanced by extracting 90% of the acetic acid using ethyl acetate, followed by vacuum evaporation to remove 88% removal of residual ethyl acetate along with 10% of the broth. NRRL Y-1546 yeast was used to demonstrate a 13% increase in concentration, 14% in ethanol specific production rate, and 11% ethanol yield. This study demonstrated that extraction of acetic acid with ethyl acetate followed by evaporative removal of ethyl acetate from the raffinate phase has potential to significantly enhance ethanol fermentation in a corn stover bioethanol facility. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:929-937, 2016.

  11. Acetic acid removal from corn stover hydrolysate using ethyl acetate and the impact on Saccharomyces cerevisiae bioethanol fermentation.

    Science.gov (United States)

    Aghazadeh, Mahdieh; Ladisch, Michael R; Engelberth, Abigail S

    2016-07-01

    Acetic acid is introduced into cellulose conversion processes as a consequence of composition of lignocellulose feedstocks, causing significant inhibition of adapted, genetically modified and wild-type S. cerevisiae in bioethanol fermentation. While adaptation or modification of yeast may reduce inhibition, the most effective approach is to remove the acetic acid prior to fermentation. This work addresses liquid-liquid extraction of acetic acid from biomass hydrolysate through a pathway that mitigates acetic acid inhibition while avoiding the negative effects of the extractant, which itself may exhibit inhibition. Candidate solvents were selected using simulation results from Aspen Plus™, based on their ability to extract acetic acid which was confirmed by experimentation. All solvents showed varying degrees of toxicity toward yeast, but the relative volatility of ethyl acetate enabled its use as simple vacuum evaporation could reduce small concentrations of aqueous ethyl acetate to minimally inhibitory levels. The toxicity threshold of ethyl acetate, in the presence of acetic acid, was found to be 10 g L(-1) . The fermentation was enhanced by extracting 90% of the acetic acid using ethyl acetate, followed by vacuum evaporation to remove 88% removal of residual ethyl acetate along with 10% of the broth. NRRL Y-1546 yeast was used to demonstrate a 13% increase in concentration, 14% in ethanol specific production rate, and 11% ethanol yield. This study demonstrated that extraction of acetic acid with ethyl acetate followed by evaporative removal of ethyl acetate from the raffinate phase has potential to significantly enhance ethanol fermentation in a corn stover bioethanol facility. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:929-937, 2016. PMID:27090191

  12. Adaptation and tolerance of bacteria against acetic acid.

    Science.gov (United States)

    Trček, Janja; Mira, Nuno Pereira; Jarboe, Laura R

    2015-08-01

    Acetic acid is a weak organic acid exerting a toxic effect to most microorganisms at concentrations as low as 0.5 wt%. This toxic effect results mostly from acetic acid dissociation inside microbial cells, causing a decrease of intracellular pH and metabolic disturbance by the anion, among other deleterious effects. These microbial inhibition mechanisms enable acetic acid to be used as a preservative, although its usefulness is limited by the emergence of highly tolerant spoilage strains. Several biotechnological processes are also inhibited by the accumulation of acetic acid in the growth medium including production of bioethanol from lignocellulosics, wine making, and microbe-based production of acetic acid itself. To design better preservation strategies based on acetic acid and to improve the robustness of industrial biotechnological processes limited by this acid's toxicity, it is essential to deepen the understanding of the underlying toxicity mechanisms. In this sense, adaptive responses that improve tolerance to acetic acid have been well studied in Escherichia coli and Saccharomyces cerevisiae. Strains highly tolerant to acetic acid, either isolated from natural environments or specifically engineered for this effect, represent a unique reservoir of information that could increase our understanding of acetic acid tolerance and contribute to the design of additional tolerance mechanisms. In this article, the mechanisms underlying the acetic acid tolerance exhibited by several bacterial strains are reviewed, with emphasis on the knowledge gathered in acetic acid bacteria and E. coli. A comparison of how these bacterial adaptive responses to acetic acid stress fit to those described in the yeast Saccharomyces cerevisiae is also performed. A systematic comparison of the similarities and dissimilarities of the ways by which different microbial systems surpass the deleterious effects of acetic acid toxicity has not been performed so far, although such exchange

  13. Different cerebrovascular effects of medroxyprogesterone acetate and norethisterone acetate in the New Zealand White rabbit

    DEFF Research Database (Denmark)

    Pedersen, S H; Pedersen, N G; Dalsgaard, T;

    2004-01-01

    of different progestins on cerebrovascular reactivity in an animal model. METHODS: Fifty-six ovariectomized New Zealand White rabbits were randomized into seven groups receiving hormone treatment for 4 weeks: medroxyprogesterone acetate (MPA) (10 mg/day); norethisterone acetate (NETA) (3 mg/day); conjugated....... No overall differences were seen between CEE and E2. CONCLUSIONS: In rabbit cerebral arteries, MPA treatment causes a higher development in arterial tension compared with NETA, indicating that different progestins may display different cerebrovascular effects. However, when accompanied by estrogens...

  14. POLYMER—SUPPORTED RHODIUM CATALYSTS FOR CARBONYLATION OF METHYL ACETATE TO ACETIC ANHYDRIDE

    Institute of Scientific and Technical Information of China (English)

    CHENDean; HUANGShizhuan; 等

    1993-01-01

    Two kinds of rhodium catalysts supported on cross-linked styrene-divinylbenzene copolymers containing bipyridine or o-phenylene diamine have been prepared and found to display high activity for methyl acetate carbonylation to form acetic anhydride,the activities are even higher than their homogeneous counterparts. XPS analysis was used to characterize the synthetic catalysts.The apparent activation parameters were determined to be Eα=73.3KJ/mol,ΔH≠=66.3KJ/mol,ΔS≠=-28.6eu.These parameters are very close to those in methanol carbonylation and imply to have analogous mechanism in both cases.

  15. Temperature dependence of ion transport in dilute tetrabutylammonium triflate-acetate solutions and self-diffusion in pure acetate liquids.

    Science.gov (United States)

    Bopege, Dharshani N; Petrowsky, Matt; Fleshman, Allison M; Frech, Roger; Johnson, Matthew B

    2012-01-12

    Conductivities and static dielectric constants for 0.0055 M tetrabutylammonium trifluoromethanesulfonate in n-butyl acetate, n-pentyl acetate, n-hexyl acetate, n-octyl acetate, and n-decyl acetate have been collected over the temperature range of 0-80 °C. Self-diffusion coefficients and static dielectric constants of pure acetates were obtained over the same temperature range. Both temperature-dependent diffusion coefficients and ionic conductivities of these pure acetates and dilute acetate solutions can be accurately described by the compensated Arrhenius formalism. Activation energies were calculated from compensated Arrhenius plots for both conductivity and diffusion data. Activation energies are higher for conductivity data of 0.0055 M TbaTf-acetates compared to diffusion data of pure acetates. The plot of the exponential prefactor versus the dielectric constant yields a single master curve for both conductivity and diffusion data. These data support the argument that mass and charge transport are thermally activated processes in the acetates, as previously observed in alcohol-based electrolytes. PMID:22145961

  16. Acetate supplementation attenuates lipopolysaccharide-induced neuroinflammation.

    Science.gov (United States)

    Reisenauer, Chris J; Bhatt, Dhaval P; Mitteness, Dane J; Slanczka, Evan R; Gienger, Heidi M; Watt, John A; Rosenberger, Thad A

    2011-04-01

    Glyceryl triacetate (GTA), a compound effective at increasing circulating and tissue levels of acetate was used to treat rats subjected to a continual 28 day intra-ventricular infusion of bacterial lipopolysaccharide (LPS). This model produces a neuroinflammatory injury characterized by global neuroglial activation and a decrease in choline acetyltransferase immunoreactivity in the basal forebrain. During the LPS infusion, rats were given a daily treatment of either water or GTA at a dose of 6 g/kg by oral gavage. In parallel experiments, free-CoA and acetyl-CoA levels were measured in microwave fixed brains and flash frozen heart, liver, kidney and muscle following a single oral dose of GTA. We found that a single oral dose of GTA significantly increased plasma acetate levels by 15 min and remained elevated for up to 4 h. At 30 min the acetyl-CoA levels in microwave-fixed brain and flash frozen heart and liver were increased at least 2.2-fold. The concentrations of brain acetyl-CoA was significantly increased between 30 and 45 min following treatment and remained elevated for up to 4 h. The concentration of free-CoA in brain was significantly decreased compared to controls at 240 min. Immunohistochemical and morphological analysis demonstrated that a daily treatment with GTA significantly reduced the percentage of reactive glial fibrillary acidic protein-positive astrocytes and activated CD11b-positive microglia by 40-50% in rats subjected to LPS-induced neuroinflammation. Further, in rats subjected to neuroinflammation, GTA significantly increased the number of choline acetyltransferase (ChAT)-positive cells by 40% in the basal forebrain compared to untreated controls. These data suggest that acetate supplementation increases intermediary short chain acetyl-CoA metabolism and that treatment is potentially anti-inflammatory and neuroprotective with regards to attenuating neuroglial activation and increasing ChAT immunoreactivity in this model. PMID:21272004

  17. Aerobic oxidation of aqueous ethanol using heterogeneous gold catalysts: Efficient routes to acetic acid and ethyl acetate

    DEFF Research Database (Denmark)

    Jørgensen, Betina; Christiansen, Sofie Egholm; Thomsen, M.L.D.;

    2007-01-01

    The aerobic oxidation of aqueous ethanol to produce acetic acid and ethyl acetate was studied using heterogeneous gold catalysts. Comparing the performance of Au/MgAl2O4 and Au/TiO2 showed that these two catalysts exhibited similar performance in the reaction. By proper selection of the reaction...... conditions, yields of 90-95% of acetic acid could be achieved at moderate temperatures and pressures. Based on our findings, a reaction pathway for the catalytic oxidation of ethanol via acetaldehyde to acetic acid is proposed, and the rate-determining step (RDS) in the mechanism is found to be the (possibly......, the possibilities for producing ethyl acetate by the aerobic oxidation of ethanol is also studied. At low ethanol concentrations, the main product is acetic acid; at concentrations >60 wt%, it is ethyl acetate....

  18. Breast cancer and depot-medroxyprogesterone acetate

    OpenAIRE

    1985-01-01

    The preliminary results of a study of the incidence of breast cancer in relation to use of depot-medroxyprogesterone acetate (DMPA) are presented. The findings are based on data from three participating centres in Thailand, and one each in Kenya and Mexico. A relative risk for breast cancer of 0.7 was observed in women who had ever used DMPA; this was not statistically significant. Although no consistent decrease in risk with duration of use was observed, the lowest relative risk (0.5) was ob...

  19. Sphingolipids contribute to acetic acid resistance in Zygosaccharomyces bailii.

    Science.gov (United States)

    Lindahl, Lina; Genheden, Samuel; Eriksson, Leif A; Olsson, Lisbeth; Bettiga, Maurizio

    2016-04-01

    Lignocellulosic raw material plays a crucial role in the development of sustainable processes for the production of fuels and chemicals. Weak acids such as acetic acid and formic acid are troublesome inhibitors restricting efficient microbial conversion of the biomass to desired products. To improve our understanding of weak acid inhibition and to identify engineering strategies to reduce acetic acid toxicity, the highly acetic-acid-tolerant yeast Zygosaccharomyces bailii was studied. The impact of acetic acid membrane permeability on acetic acid tolerance in Z. bailii was investigated with particular focus on how the previously demonstrated high sphingolipid content in the plasma membrane influences acetic acid tolerance and membrane permeability. Through molecular dynamics simulations, we concluded that membranes with a high content of sphingolipids are thicker and more dense, increasing the free energy barrier for the permeation of acetic acid through the membrane. Z. bailii cultured with the drug myriocin, known to decrease cellular sphingo-lipid levels, exhibited significant growth inhibition in the presence of acetic acid, while growth in medium without acetic acid was unaffected by the myriocin addition. Furthermore, following an acetic acid pulse, the intracellular pH decreased more in myriocin-treated cells than in control cells. This indicates a higher inflow rate of acetic acid and confirms that the reduction in growth of cells cultured with myriocin in the medium with acetic acid was due to an increase in membrane permeability, thereby demonstrating the importance of a high fraction of sphingolipids in the membrane of Z. bailii to facilitate acetic acid resistance; a property potentially transferable to desired production organisms suffering from weak acid stress.

  20. Methylprednisolon acetate in the management of

    Directory of Open Access Journals (Sweden)

    N. Khaci, M.D.

    2008-01-01

    Full Text Available AbstractBackground and Purpose: Acute renal colic is a common complaint from patients entering the emergency departments. Although, urethral lithotripsy and extracorporeal shock wave lithotripsy are known to be effective, the role of medical-expulsive therapy for the treatment of this disease has not yet been established. This study assessed the clinical efficacy of addition methylprednisolon acetate in the medical-expulsive therapy of distal ureterolithiasis.Materials and Methods: Eighty five (85 consecutive patients with a symptomatic distal urethral stone were included in our study and randomized to one of two home treatment groups. Group A patients (n = 45 received tramadol (50mg bid and hydrochlorothiazide (50 mg daily for 21 days, and group B patients (n = 40 were treated with a corticosteroid drug (methylprednisolon acetate 40mg intra-muscular on 0, 7 and 14 days after treatment, in addition to tramadol and hydrochlorothiazide. The treatment duration was 21 days. All patients were re-evaluated after 21days with a clinical examination and KUB.Results: The mean stone size was 5.2mm and 5.8mm in groups A and B respectively (P value>0.05. Both groups had a significant difference in expulsion rate (20(44.4% for group A and 32 (88% for group B; (P value<0.001.Conclusion: Our results suggest that the use of a corticosteroid drug in association with tramadol and hydro-cholorothiazid appeared to induce an increase in the expulsion ra

  1. Immunotoxicity of trenbolone acetate in Japanese quail

    Science.gov (United States)

    Quinn, M.J.; McKernan, M.; Lavoie, E.T.; Ottinger, M.A.

    2007-01-01

    Trenbolone acetate is a synthetic androgen that is currently used as a growth promoter in many meat-exporting countries. Despite industry laboratories classifying trenbolone as nonteratogenic, data showed that embryonic exposure to this androgenic chemical altered development of the immune system in Japanese quail. Trenbolone is lipophilic, persistent, and released into the environment in manure used as soil fertilizer. This is the first study to date to assess this chemical's immunotoxic effects in an avian species. A one-time injection of trenbolone into yolks was administered to mimic maternal deposition, and subsequent effects on the development and function of the immune system were determined in chicks and adults. Development of the bursa of Fabricius, an organ responsible for development of the humoral arm of the immune system, was disrupted, as indicated by lower masse, and smaller and fewer follicles at day 1 of hatch. Morphological differences in the bursas persisted in adults, although no differences in either two measures of immune function were observed. Total numbers of circulating leukocytes were reduced and heterophil-lymphocyte ratios were elevated in chicks but not adults. This study shows that trenbolone acetate is teratogenic and immunotoxic in Japanese quail, and provides evidence that the quail immune system may be fairly resilient to embryonic endocrine-disrupting chemical-induced alterations following no further exposure posthatch.

  2. Zinc mediated domino elimination-alkylation of methyl 5-iodopentofuranosides

    DEFF Research Database (Denmark)

    Hyldtoft, Lene; Poulsen, Carina Storm; Madsen, Robert

    1999-01-01

    5-Iodopentofuranosides are converted with zinc and allyl/propargyl bromide into dienes/enynes which are further used in carbohydrate annulation reactions.......5-Iodopentofuranosides are converted with zinc and allyl/propargyl bromide into dienes/enynes which are further used in carbohydrate annulation reactions....

  3. Total synthesis of aeruginosin 98B.

    Science.gov (United States)

    Trost, Barry M; Kaneko, Toshiyuki; Andersen, Neil G; Tappertzhofen, Christoph; Fahr, Bruce

    2012-11-21

    The first total synthesis of aeruginosin 98B was accomplished. The key step is a highly diastereoselective Pd-catalyzed intramolecular asymmetric allylic alkylation reaction of a diastereomeric mixture of allylic carbonates that is enabled by the use of racemic phosphine ligand L1.

  4. Genetic dissection of acetic acid tolerance in Saccharomyces cerevisiae.

    Science.gov (United States)

    Geng, Peng; Xiao, Yin; Hu, Yun; Sun, Haiye; Xue, Wei; Zhang, Liang; Shi, Gui-Yang

    2016-09-01

    Dissection of the hereditary architecture underlying Saccharomyces cerevisiae tolerance to acetic acid is essential for ethanol fermentation. In this work, a genomics approach was used to dissect hereditary variations in acetic acid tolerance between two phenotypically different strains. A total of 160 segregants derived from these two strains were obtained. Phenotypic analysis indicated that the acetic acid tolerance displayed a normal distribution in these segregants, and suggested that the acetic acid tolerant traits were controlled by multiple quantitative trait loci (QTLs). Thus, 220 SSR markers covering the whole genome were used to detect QTLs of acetic acid tolerant traits. As a result, three QTLs were located on chromosomes 9, 12, and 16, respectively, which explained 38.8-65.9 % of the range of phenotypic variation. Furthermore, twelve genes of the candidates fell into the three QTL regions by integrating the QTL analysis with candidates of acetic acid tolerant genes. These results provided a novel avenue to obtain more robust strains.

  5. Effect of medroxyprogesterone acetate (Provera) on ovarian radiosensitivity

    Energy Technology Data Exchange (ETDEWEB)

    Jarrell, J.; YoungLai, E.V.; McMahon, A.; Barr, R.; O' Connell, G.; Belbec, L.

    1989-04-01

    Medroxyprogesterone acetate (Provera) is a drug that is commonly given to young women with cancer during chemotherapy and radiation to control heavy bleeding associated with anovulation. Because hypothalamic-pituitary-ovarian suppression has been associated with ovarian protection from the effects of chemotherapy and medroxyprogesterone acetate has been identified as a radiosensitizing agent, we explored the effects of medroxyprogesterone acetate on a rat model with known radiation injury characteristics. Sprague-Dawley rats were treated with medroxyprogesterone acetate or vehicle from day 22 to day 37 of life and were either irradiated or sham-irradiated on day 30 of life and then killed on day 44. Radiation with medroxyprogesterone acetate administration produced a greater loss in preantral and healthy control follicles than in control follicles. No suppression of luteinizing hormone or follicle-stimulating hormone had occurred by day 30 but ovarian glutathione content was reduced. These findings indicate that the administration of medroxyprogesterone acetate with radiotherapy may enhance ovarian injury.

  6. Methane-to-acetic acid synthesis matriculates at Penn State

    Energy Technology Data Exchange (ETDEWEB)

    Rotman, D.

    1994-04-20

    Direct conversion of methane to commercially valuable chemicals remains one of the grails of industrial chemistry. But scientists at Pennsylvania State University (University Park) appear to have made a significant step forward, reporting the direct catalytic conversion of methane into acetic acid under relatively mild conditions. Commercial acetic production involves a three-step process, including steam reforming of methane to synthesis gas (syngas) and the carbonylation of methanol of acetic acid.

  7. Analgesic principle from Abutilon indicum.

    Science.gov (United States)

    Ahmed, M; Amin, S; Islam, M; Takahashi, M; Okuyama, E; Hossain, C F

    2000-04-01

    Bioactivity guided isolation of Abutilon indicum yielded eugenol [4-allyl-2-methoxyphenol], which was found to possess significant analgesic activity. At doses of 10, 30, and 50 mg/kg body weight, eugenol exhibited 21.30 (p < 0.05), 42.25 (p < 0.01) and 92.96% (p < 0.001) inhibition of acetic acid induced writhing in mice. At a dose of 50 mg/kg body weight, eugenol showed 33.40% (p < 0.05) prolongation of tail flicking time determined by the radiant heat method. PMID:10798248

  8. Asymmetric C-C Bond-Formation Reaction with Pd: How to Favor Heterogeneous or Homogeneous Catalysis?

    DEFF Research Database (Denmark)

    Reimann, S.; Grunwaldt, Jan-Dierk; Mallat, T.;

    2010-01-01

    The enantioselective allylic alkylation of (E)-1,3-diphenylallyl acetate was studied to clarify the heterogeneous or homogeneous character of the Pd/Al2O3-(R)-BINAP catalyst system. A combined approach was applied: the catalytic tests were completed with in situ XANES measurements to follow...... is a clear deviation from the behavior of the corresponding homogeneous system. In contrast, halogenated solvents are easily dehalogenated on Pd/Al2O3 and thus they favor leaching of the metal and formation of soluble compounds, analogous to classical metal corrosion in the presence of halide ions...

  9. Fabrication and Characterization of Polysaccharide Ion Gels with Ionic Liquids and Their Further Conversion into Value-Added Sustainable Materials

    Directory of Open Access Journals (Sweden)

    Akihiko Takada

    2015-03-01

    Full Text Available A review of the fabrication of polysaccharide ion gels with ionic liquids is presented. From various polysaccharides, the corresponding ion gels were fabricated through the dissolution with ionic liquids. As ionic liquids, in the most cases, 1-butyl-3-methylimidazolium chloride has been used, whereas 1-allyl-3methylimidazolium acetate was specifically used for chitin. The resulting ion gels have been characterized by suitable analytical measurements. Characterization of a pregel state by viscoelastic measurement provided the molecular weight information. Furthermore, the polysaccharide ion gels have been converted into value-added sustainable materials by appropriate procedures, such as exchange with other disperse media and regeneration.

  10. Methyl vinyl glycolate as a diverse platform molecule

    DEFF Research Database (Denmark)

    Sølvhøj, Amanda Birgitte; Taarning, Esben; Madsen, Robert

    2016-01-01

    Methyl vinyl glycolate (methyl 2-hydroxybut-3-enoate, MVG) is available by zeolite catalyzed degradation of mono- and disaccharides and has the potential to become a renewable platform molecule for commercially relevant catalytic transformations. This is further illustrated here by the development...... and various long-chain terminal olefins give unsaturated α-hydroxy fatty acid methyl esters in good yields. [3,3]-Sigmatropic rearrangements of MVG also proceed in good yields to give unsaturated adipic acid derivatives. Finally, rearrangement of the allylic acetate of MVG proceeds in acceptable yield...

  11. Synthesis of allylamine in ethanol%乙醇中烯丙基胺的合成

    Institute of Scientific and Technical Information of China (English)

    唐炳涛; 张淑芬; 杨锦宗

    2005-01-01

    Allylamine was prepared from the ammonolysis of allyl chloride or the reaction of allyl chloride with hexamethylenetetramine in ethanol. The selectivity of allylamine was improved from 21.4% to 67.6% when the reaction was carried out in ethanol instead of liquid ammonia. At the same time, the selectivity of allylamine was increased from 13.3% to 67.6% when the molar ratio of NH3 to allyl chloride was increased from 4.5∶1 to 25∶1.However, the reaction of allyl chloride and hexamethylenetetramine in ethanol produced allylamine with high selectivity (100%) and high yield (87%).The synthesis of allylamine from the reaction of allyl chloride and hexamethylenetetramine in ethanol was more straightforward and convenient.

  12. AcEST: DK946718 [AcEST

    Lifescience Database Archive (English)

    Full Text Available 1Z0 Definition tr|Q9M1Z0|Q9M1Z0_ARATH Allyl alcohol dehydrogenase-like protein OS...roducing significant alignments: (bits) Value tr|Q9M1Z0|Q9M1Z0_ARATH Allyl alcoho...l dehydrogenase-like protein ... 74 7e-12 tr|Q8VZ93|Q8VZ93_ARATH Allyl alcohol dehydrogenase-like protein ..... OS=Oryza... 66 1e-09 tr|A2Y674|A2Y674_ORYSI Putative uncharacterized protein OS=Oryza... 66 1e-09 tr|B6T5A5|B6T5A5_MAIZE Allyl...rotein OSJNBa00... 33 9.8 >tr|Q9M1Z0|Q9M1Z0_ARATH Allyl alcohol dehydrogenase-lik

  13. Acetic orcein staining of prefixed tissue sections.

    Science.gov (United States)

    Reynolds, C; Lillie, R D

    1978-05-01

    Acetic orcein stains formol- and Carnoy-fixed tissues, coloring mast cells, nuclei, basophilic cytoplasm, cerebral corpora amylacea, and cartilage strongly; keratin and erythrocytes moderately; muscle and collagen weakly. Guinea pig Brunner gland and rat colonic goblet cell mucins did not stain. The red nuclear stain contrasts well with the Prussian blue reaction of hemosiderin and the ferric ferricyanide (Turnbull's blue) reaction of enterochromaffin. A weak (0.01%) fast-green FCF stain changes collagen and sometimes smooth muscle to green, without impairing nucleic acid or mast cell staining. Picroindigocarmine gives blue collagen, yellow muscle, and red elastin, nucleic acids and mast cells. Picro-methyl blue tends to override the red nuclear stain. Carnoy fixation is somewhat better for nuclei, formol for basophil cytoplasms.

  14. Unsuccessful treatment of acromegaly with medroxyprogesterone acetate.

    Science.gov (United States)

    Atkinson, R L; Dimond, R C; Howard, W J; Earll, J M

    1974-09-01

    6 patients with active acromegaly were treated with 10 mg of medroxyprogesterone acetate (MPA) every 6 hours daily for 2 weeks to 6 months. Oral glucose tolerance tests, growth hormone (GH) levels, and insulin tolerance tests (ITT) were done before and during MPA treatment. Basal GH levels varied widely during control and therapy periods; no significant lowering of GH levels occurred during treatment. Carbohydrate tolerance was not significantly affected by MPA therapy, although 5 out of 6 patients had deterioration at least once during treatment. Blood glucose response to ITT was unchanged by MPA. MPA did not affect the clinical features of acromegaly. There was no consistent effect of MPA on insulin-induced or arginine-induced GH secretion. It is concluded that MPA is not an effective agent for treating acromegaly.

  15. A radioimmunoassay for serum medroxyprogesterone acetate.

    Science.gov (United States)

    Shrimanker, K; Saxena, B N; Fotherby, K

    1978-04-01

    When injected intramuscularly in a dose of 150 mg, Depo Provera, a microcrystalline suspension of medroxyprogesterone acetate (MPA), will provide a contraceptive effect for at least 3 months. This paper describes a sensitive radioimmunoassay for MPA which has been used in the author's laboratory for the past 2 years. MPA was converted to MPA-3-CMO and the oxime was conjugated with bovine serum albumin (BSA) by the mixed anahydride method. 4 rabbits were immunized with the antiserum. A high titre of MPA antibodies was detected 6 months after immunization. Serum from the rabbit with the highest titre of antibodies to MPA was subjected to radioimmunoassay. 7 days after the intramuscular injection of 150 mg Depo-Provera, serum levels of MPA were found in the range of 1750 to 9000 pg/ml. By 75 days, the levels had decreased to 680-2600 pg/ml. The method was found to have adequate accuracy, precision and sensitivity. PMID:661315

  16. Oxidation of indole-3-acetic acid to oxindole-3-acetic acid by an enzyme preparation from Zea mays

    Science.gov (United States)

    Reinecke, D. M.; Bandurski, R. S.

    1988-01-01

    Indole-3-acetic acid is oxidized to oxindole-3-acetic acid by Zea mays tissue extracts. Shoot, root, and endosperm tissues have enzyme activities of 1 to 10 picomoles per hour per milligram protein. The enzyme is heat labile, is soluble, and requires oxygen for activity. Cofactors of mixed function oxygenase, peroxidase, and intermolecular dioxygenase are not stimulatory to enzymic activity. A heat-stable, detergent-extractable component from corn enhances enzyme activity 6- to 10-fold. This is the first demonstration of the in vitro enzymic oxidation of indole-3-acetic acid to oxindole-3-acetic acid in higher plants.

  17. Liquid-Liquid equilibria of the water-acetic acid-butyl acetate system

    Directory of Open Access Journals (Sweden)

    E. Ince

    2002-04-01

    Full Text Available Experimental liquid-liquid equilibria of the water-acetic acid-butyl acetate system were studied at temperatures of 298.15± 0.20, 303.15± 0.20 and 308.15± 0.20 K. Complete phase diagrams were obtained by determining solubility and tie-line data. The reliability of the experimental tie-line data was ascertained by using the Othmer and Tobias correlation. The UNIFAC group contribution method was used to predict the observed ternary liquid-liquid equilibrium (LLE data. It was found that UNIFAC group interaction parameters used for LLE did not provide a good prediction. Distribution coefficients and separation factors were evaluated for the immiscibility region.

  18. Different cerebrovascular effects of medroxyprogesterone acetate and norethisterone acetate in the New Zealand White rabbit

    DEFF Research Database (Denmark)

    Pedersen, S H; Pedersen, N G; Dalsgaard, T;

    2004-01-01

    of different progestins on cerebrovascular reactivity in an animal model. METHODS: Fifty-six ovariectomized New Zealand White rabbits were randomized into seven groups receiving hormone treatment for 4 weeks: medroxyprogesterone acetate (MPA) (10 mg/day); norethisterone acetate (NETA) (3 mg/day); conjugated......, acetylcholine, sodium nitroprusside, L-NAME (N(omega)-nitro-L-arginine methyl ester), calcium and endothelin-1 were established. RESULTS: Treatment with MPA caused a significant increase in vasoconstriction, expressed as E(max) (mN/mm, mean +/- SEM; p ....47 +/- 0.19) and calcium (4.00 +/- 0.22 vs. 3.34 +/- 0.14) in the posterior cerebral artery, and to endothelin-1 (6.88 +/- 0.69 vs. 5.22 +/- 0.30) in the basilar artery, when compared with NETA. This difference was neutralized in the groups receiving the combined treatment of MPA + CEE and NETA + E2...

  19. Chemistry of Ketene N,S-Acetals: An Overview.

    Science.gov (United States)

    Zhang, Lin; Dong, Jinhuan; Xu, Xianxiu; Liu, Qun

    2016-01-27

    Push-pull alkenes, which bear electron-donating and -accepting group(s) at both termini of a C═C double bond, respectively, are of interest not only for their unique electronic properties but also for their importance as versatile building blocks in organic synthesis. In the world of ketene acetals having the push-pull alkene skeleton, ketene N,S-acetal is most likely the biggest family according to the number and types of these compounds. The first ketene N,S-acetal compound was reported in 1956. As a cyclic ketene N,S-acetal compound, nithiazine, the first lead structure of neonicotinoid insecticides, was reported in 1978. The characteristics of ketene N,S-acetals, which have the structural feature of ketene S,S-acetals and enaminones, make them versatile and easy to use, especially in cyclization and multicomponent reactions for the synthesis of various heterocyclic systems and related natural products. There has been an increasing wealth of information about the synthesis and synthetic applications of ketene N,S-acetals, especially, in recent years. This review provides comprehensive knowledge on the chemistry of ketene N,S-acetals. PMID:26760899

  20. Trehalose accumulation enhances tolerance of Saccharomyces cerevisiae to acetic acid.

    Science.gov (United States)

    Yoshiyama, Yoko; Tanaka, Koichi; Yoshiyama, Kohei; Hibi, Makoto; Ogawa, Jun; Shima, Jun

    2015-02-01

    Trehalose confers protection against various environmental stresses on yeast cells. In this study, trehalase gene deletion mutants that accumulate trehalose at high levels showed significant stress tolerance to acetic acid. The enhancement of trehalose accumulation can thus be considered a target in the breeding of acetic acid-tolerant yeast strains.

  1. Acetic acid assisted cobalt methanesulfonate catalysed chemoselective diacetylation of aldehydes

    Institute of Scientific and Technical Information of China (English)

    Min Wang; Zhi Guo Song; Hong Gong; Heng Jiang

    2008-01-01

    Cobalt methanesulfonate in combination with acetic acid catalysed the chemoselective diacetylation of aldehyde with acetic anhydride at room temperature under solvent free conditions. After reaction, cobalt methanesulfonate can be easily recovered and mused many times. The reaction was mild and efficient with good to high yields.

  2. Acetalization of furfural with zeolites under benign reaction conditions

    DEFF Research Database (Denmark)

    Rubio-Caballeroa, Juan Miguel; Shunmugavel, Saravanamurugan; Maireles-Torres, Pedro;

    2014-01-01

    Acetalization is a viable method to protect carbonyl functionalities in organic compounds and offers apotential synthetic strategy for synthesizing derived chemicals. In this work, several families of commer-cial zeolites have been employed as solid acid catalysts in the acetalization of furfural...

  3. Pharmacokinetics of depot medroxyprogesterone acetate contraception.

    Science.gov (United States)

    Mishell, D R

    1996-05-01

    Depot medroxyprogesterone acetate (DMPA) is an aqueous suspension of 17-acetoxy 6-methyl progestin administered by intramuscular injection for long-term contraception. This highly effective injectable formulation of medroxyprogesterone acetate (MPA) has a prolonged duration of action since the progestin is released slowly from the muscle. MPA is detected in the serum within 30 minutes after an injection of 150 mg. Serum concentrations vary between individual women but generally plateau at about 1.0 ng/mL for about three months, after which there is a gradual decline. In some women, MPA can be detected in the serum for as long as nine months after a single injection of 150 mg. The circulating MPA initially inhibits the midcycle leutinizing hormone (LH) peak, but LH and follicle stimulating hormone (FSH) levels remain in the range of those for the luteal phase of a pretreatment control cycle. Since ovulation is inhibited, serum progesterone levels remain low (< 0.4 ng/mL) for several months following an injection of DMPA. When MPA levels fall below 0.1 ng/mL, ovulation resumes. Thus, return to fertility is delayed for several months if a woman wishes to conceive after receiving one or more injections of DMPA. Following an injection of DMPA, serum estradiol levels initially are in the early to midfollicular phase range (mean approximately 50 pg/nL). Serum estradiol levels begin to rise about four months after a single injection when MPA levels fall below 0.5 ng/mL. For women who have used DMPA for several years, serum estradiol levels range between 10 and 92 pg/mL, with mean levels of about 40 pg/mL. Despite these low levels of estradiol, hot flushes are a rare event, and the vaginal epithelium remains moist and well rugated. Women using DMPA for several years do not observe a change in breast size. DMPA causes the endometrium to become atrophic, with small, straight endometrial glands and decidualized stroma. The cervical mucus remains thick and viscid. DMPA is a

  4. Fermentation of lignocellulosic sugars to acetic acid by Moorella thermoacetica.

    Science.gov (United States)

    Ehsanipour, Mandana; Suko, Azra Vajzovic; Bura, Renata

    2016-06-01

    A systematic study of bioconversion of lignocellulosic sugars to acetic acid by Moorella thermoacetica (strain ATCC 39073) was conducted. Four different water-soluble fractions (hydrolysates) obtained after steam pretreatment of lignocellulosic biomass were selected and fermented to acetic acid in batch fermentations. M. thermoacetica can effectively ferment xylose and glucose in hydrolysates from wheat straw, forest residues, switchgrass, and sugarcane straw to acetic acid. Xylose and glucose were completely utilized, with xylose being consumed first. M. thermoacetica consumed up to 62 % of arabinose, 49 % galactose and 66 % of mannose within 72 h of fermentation in the mixture of lignocellulosic sugars. The highest acetic acid yield was obtained from sugarcane straw hydrolysate, with 71 % of theoretical yield based on total sugars (17 g/L acetic acid from 24 g/L total sugars). The lowest acetic acid yield was observed in forest residues hydrolysate, with 39 % of theoretical yield based on total sugars (18 g/L acetic acid from 49 g/L total sugars). Process derived compounds from steam explosion pretreatment, including 5-hydroxymethylfurfural (0.4 g/L), furfural (0.1 g/L) and total phenolics (3 g/L), did not inhibit microbial growth and acetic acid production yield. This research identified two major factors that adversely affected acetic acid yield in all hydrolysates, especially in forest residues: (i) glucose to xylose ratio and (ii) incomplete consumption of arabinose, galactose and mannose. For efficient bioconversion of lignocellulosic sugars to acetic acid, it is imperative to have an appropriate balance of sugars in a hydrolysate. Hence, the choice of lignocellulosic biomass and steam pretreatment design are fundamental steps for the industrial application of this process. PMID:26992903

  5. Fermentation of lignocellulosic sugars to acetic acid by Moorella thermoacetica.

    Science.gov (United States)

    Ehsanipour, Mandana; Suko, Azra Vajzovic; Bura, Renata

    2016-06-01

    A systematic study of bioconversion of lignocellulosic sugars to acetic acid by Moorella thermoacetica (strain ATCC 39073) was conducted. Four different water-soluble fractions (hydrolysates) obtained after steam pretreatment of lignocellulosic biomass were selected and fermented to acetic acid in batch fermentations. M. thermoacetica can effectively ferment xylose and glucose in hydrolysates from wheat straw, forest residues, switchgrass, and sugarcane straw to acetic acid. Xylose and glucose were completely utilized, with xylose being consumed first. M. thermoacetica consumed up to 62 % of arabinose, 49 % galactose and 66 % of mannose within 72 h of fermentation in the mixture of lignocellulosic sugars. The highest acetic acid yield was obtained from sugarcane straw hydrolysate, with 71 % of theoretical yield based on total sugars (17 g/L acetic acid from 24 g/L total sugars). The lowest acetic acid yield was observed in forest residues hydrolysate, with 39 % of theoretical yield based on total sugars (18 g/L acetic acid from 49 g/L total sugars). Process derived compounds from steam explosion pretreatment, including 5-hydroxymethylfurfural (0.4 g/L), furfural (0.1 g/L) and total phenolics (3 g/L), did not inhibit microbial growth and acetic acid production yield. This research identified two major factors that adversely affected acetic acid yield in all hydrolysates, especially in forest residues: (i) glucose to xylose ratio and (ii) incomplete consumption of arabinose, galactose and mannose. For efficient bioconversion of lignocellulosic sugars to acetic acid, it is imperative to have an appropriate balance of sugars in a hydrolysate. Hence, the choice of lignocellulosic biomass and steam pretreatment design are fundamental steps for the industrial application of this process.

  6. Hydrolyses of alpha-naphthyl acetate, beta-naphthyl acetate, and acetyl-DL-phenylalanine beta-naphthyl ester

    DEFF Research Database (Denmark)

    Kirkeby, S; Moe, D

    1983-01-01

    Using simultaneous coupling azo dye techniques kidney enzymes active against alpha-naphthyl acetate, beta-naphthyl acetate, and acetyl-DL-phenylalanine beta-naphthyl ester are characterized. The enzymes show identical distribution in the section. The banding patterns in zymograms are the same after...

  7. Biological Function of Acetic Acid-Improvement in Obesity and Glucose Tolerance by Acetic Acid in Type 2 Diabetic Rats.

    Science.gov (United States)

    Yamashita, Hiromi

    2016-07-29

    Fatty acids derived from adipose tissue are oxidized by β-oxidation to form ketone bodies as final products under the starving condition. Previously, we found that free acetic acid was formed concomitantly with the production of ketone bodies in isolated rat liver perfusion, and mitochondrial acetyl CoA hydrolase was appeared to be involved with the acetic acid production. It was revealed that acetic acid was formed as a final product of enhanced β-oxidation of fatty acids and utilized as a fuel in extrahepatic tissues under the starving condition. Under the fed condition, β-oxidation is suppressed and acetic acid production is decreased. When acetic acid was taken daily by obesity-linked type 2 diabetic Otsuka Long-Evans Tokushima Fatty (OLETF) rats under the fed condition, it protected OLETF rats against obesity. Furthermore, acetic acid contributed to protect from the accumulation of lipid in the liver as well as abdominal fat in OLETF rats. Transcripts of lipogenic genes in the liver were decreased, while transcripts of myoglobin and Glut4 genes in abdominal muscles were increased in the acetic acid-administered OLETF rats. It is indicated that exogenously administered acetic acid would have effects on lipid metabolism in both the liver and the skeletal muscles, and have function that works against obesity and obesity-linked type 2 diabetes.

  8. Morphological diversity of Blastocystis hominis in sodium acetate-acetic acid-formalin-preserved stool samples stained with iron hematoxylin.

    OpenAIRE

    Macpherson, D. W.; MacQueen, W M

    1994-01-01

    The objective of this investigation was to study the morphological characteristics of Blastocystis hominis in sodium acetate-acetic acid-Formalin-preserved stool samples. Routinely processed samples were examined for morphological detail, including size, shape, nuclear detail, and central body characteristics. Morphological findings revealing the importance of recognizing B. hominis in the diagnostic laboratory are described.

  9. Morphological diversity of Blastocystis hominis in sodium acetate-acetic acid-formalin-preserved stool samples stained with iron hematoxylin.

    Science.gov (United States)

    MacPherson, D W; MacQueen, W M

    1994-01-01

    The objective of this investigation was to study the morphological characteristics of Blastocystis hominis in sodium acetate-acetic acid-Formalin-preserved stool samples. Routinely processed samples were examined for morphological detail, including size, shape, nuclear detail, and central body characteristics. Morphological findings revealing the importance of recognizing B. hominis in the diagnostic laboratory are described. PMID:7510311

  10. The effect of oral sodium acetate administration on plasma acetate concentration and acid-base state in horses

    Directory of Open Access Journals (Sweden)

    Lindinger Michael I

    2007-12-01

    Full Text Available Abstract Aim Sodium acetate (NaAcetate has received some attention as an alkalinizing agent and possible alternative energy source for the horse, however the effects of oral administration remain largely unknown. The present study used the physicochemical approach to characterize the changes in acid-base status occurring after oral NaAcetate/acetic acid (NAA administration in horses. Methods Jugular venous blood was sampled from 9 exercise-conditioned horses on 2 separate occasions, at rest and for 24 h following a competition exercise test (CET designed to simulate the speed and endurance test of 3-day event. Immediately after the CETs horses were allowed water ad libitum and either: 1 8 L of a hypertonic NaAcetate/acetic acid solution via nasogastric tube followed by a typical hay/grain meal (NAA trial; or 2 a hay/grain meal alone (Control trial. Results Oral NAA resulted in a profound plasma alkalosis marked by decreased plasma [H+] and increased plasma [TCO2] and [HCO3-] compared to Control. The primary contributor to the plasma alkalosis was an increased [SID], as a result of increased plasma [Na+] and decreased plasma [Cl-]. An increased [Atot], due to increased [PP] and a sustained increase in plasma [acetate], contributed a minor acidifying effect. Conclusion It is concluded that oral NaAcetate could be used as both an alkalinizing agent and an alternative energy source in the horse.

  11. Measurement of the rates of oxindole-3-acetic acid turnover, and indole-3-acetic acid oxidation in Zea mays seedlings

    Science.gov (United States)

    Nonhebel, H. M.; Bandurski, R. S. (Principal Investigator)

    1986-01-01

    Oxindole-3-acetic acid is the principal catabolite of indole-3-acetic acid in Zea mays seedlings. In this paper measurements of the turnover of oxindole-3-acetic acid are presented and used to calculate the rate of indole-3-acetic acid oxidation. [3H]Oxindole-3-acetic acid was applied to the endosperm of Zea mays seedlings and allowed to equilibrate for 24 h before the start of the experiment. The subsequent decrease in its specific activity was used to calculate the turnover rate. The average half-life of oxindole-3-acetic acid in the shoots was found to be 30 h while that in the kernels had an average half-life of 35h. Using previously published values of the pool sizes of oxindole-3-acetic acid in shoots and kernels from seedlings of the same age and variety, and grown under the same conditions, the rate of indole-3-acetic acid oxidation was calculated to be 1.1 pmol plant-1 h-1 in the shoots and 7.1 pmol plant-1 h-1 in the kernels.

  12. Oxidation of indole-3-acetic acid and oxindole-3-acetic acid to 2,3-dihydro-7-hydroxy-2-oxo-1H indole-3-acetic acid-7'-O-beta-D-glucopyranoside in Zea mays seedlings

    Science.gov (United States)

    Nonhebel, H. M.; Bandurski, R. S.

    1984-01-01

    Radiolabeled oxindole-3-acetic acid was metabolized by roots, shoots, and caryopses of dark grown Zea mays seedlings to 2,3-dihydro-7-hydroxy-2-oxo-1H indole-3-acetic acid-7'-O-beta-D-glycopyranoside with the simpler name of 7-hydroxyoxindole-3-acetic acid-glucoside. This compound was also formed from labeled indole-3-acetic acid supplied to intact seedlings and root segments. The glucoside of 7-hydroxyoxindole-3-acetic acid was also isolated as an endogenous compound in the caryopses and shoots of 4-day-old seedlings. It accumulates to a level of 4.8 nanomoles per plant in the kernel, more than 10 times the amount of oxindole-3-acetic acid. In the shoot it is present at levels comparable to that of oxindole-3-acetic acid and indole-3-acetic acid (62 picomoles per shoot). We conclude that 7-hydroxyoxindole-3-acetic acid-glucoside is a natural metabolite of indole-3-acetic acid in Z. mays seedlings. From the data presented in this paper and in previous work, we propose the following route as the principal catabolic pathway for indole-3-acetic acid in Zea seedlings: Indole-3-acetic acid --> Oxindole-3-acetic acid --> 7-Hydroxyoxindole-3-acetic acid --> 7-Hydroxyoxindole-3-acetic acid-glucoside.

  13. Eslicarbazepine acetate for partial-onset seizures.

    Science.gov (United States)

    Rauchenzauner, Markus; Luef, Gerhard

    2011-12-01

    Eslicarbazepine acetate (ESL), a new voltage-gated sodium channel blocker that is chemically related to carbamazepine and partially metabolized to oxcarbazepine, has attracted attention as results of previous Phase II and III studies demonstrated and confirmed efficacy and tolerability of ESL 800 and 1200 mg once daily as add-on therapy for adult patients with drug-resistant partial-onset seizures. In children, efficacy data point towards a dose-dependent decrease in seizure frequency and tolerability analyses showed a low incidence of mild drug-related adverse effects at 5 and 15 mg/kg/day. The most frequently reported adverse effects were dizziness, somnolence, headache, diplopia, nausea and vomiting. The convenience of once-daily dosing and a short/simple titration regimen in combination with a comparative efficacy and tolerability profile might promote ESL as a valid alternative to the current adjunctive antiepileptic drug therapy armamentarium for drug-resistant partial seizures in adults. Since clinical trials in children and adolescents on ESL efficacy and safety are ongoing and data already published are far from conclusive, the therapeutic value of ESL in this special population has to be established in the near future. PMID:22091592

  14. Pharmacokinetics and drug interactions of eslicarbazepine acetate.

    Science.gov (United States)

    Bialer, Meir; Soares-da-Silva, Patricio

    2012-06-01

    Eslicarbazepine acetate (ESL) is a novel once-daily antiepileptic drug (AED) approved in Europe since 2009 that was found to be efficacious and well tolerated in a phase III clinical program in adult patients with partial onset seizures previously not controlled with treatment with one to three AEDs, including carbamazepine (CBZ). ESL shares with CBZ and oxcarbazepine (OXC) the dibenzazepine nucleus bearing the 5-carboxamide substitute, but is structurally different at the 10,11 position. This molecular variation results in differences in metabolism, preventing the formation of toxic epoxide metabolites such as carbamazepine-10,11-epoxide. Unlike OXC, which is metabolized to both eslicarbazepine and (R)-licarbazepine, ESL is extensively converted to eslicarbazepine. The systemic exposure to eslicarbazepine after ESL oral administration is approximately 94% of the parent dose, with minimal exposure to (R)-licarbazepine and OXC. After ESL oral administration, the effective half-life (t(1/2,eff) ) of eslicarbazepine was 20-24 h, which is approximately two times longer than its terminal half-life (t(1/2)). At clinically relevant doses (400-1,600 mg/day) ESL has linear pharmacokinetics (PK) with no effects of gender or moderate liver impairment. However, because eslicarbazepine is eliminated primarily (66%) by renal excretion, dose adjustment is recommended for patients with renal impairment. Eslicarbazepine clearance is induced by phenobarbital, phenytoin, and CBZ and it dose-dependently decreases plasma exposure of oral contraceptive and simvastatin. PMID:22612290

  15. Simultaneous production of acetic and gluconic acids by a thermotolerant Acetobacter strain during acetous fermentation in a bioreactor.

    Science.gov (United States)

    Mounir, Majid; Shafiei, Rasoul; Zarmehrkhorshid, Raziyeh; Hamouda, Allal; Ismaili Alaoui, Mustapha; Thonart, Philippe

    2016-02-01

    The activity of bacterial strains significantly influences the quality and the taste of vinegar. Previous studies of acetic acid bacteria have primarily focused on the ability of bacterial strains to produce high amounts of acetic acid. However, few studies have examined the production of gluconic acid during acetous fermentation at high temperatures. The production of vinegar at high temperatures by two strains of acetic acid bacteria isolated from apple and cactus fruits, namely AF01 and CV01, respectively, was evaluated in this study. The simultaneous production of gluconic and acetic acids was also examined in this study. Biochemical and molecular identification based on a 16s rDNA sequence analysis confirmed that these strains can be classified as Acetobacter pasteurianus. To assess the ability of the isolated strains to grow and produce acetic acid and gluconic acid at high temperatures, a semi-continuous fermentation was performed in a 20-L bioreactor. The two strains abundantly grew at a high temperature (41°C). At the end of the fermentation, the AF01 and CV01 strains yielded acetic acid concentrations of 7.64% (w/v) and 10.08% (w/v), respectively. Interestingly, CV01 was able to simultaneously produce acetic and gluconic acids during acetic fermentation, whereas AF01 mainly produced acetic acid. In addition, CV01 was less sensitive to ethanol depletion during semi-continuous fermentation. Finally, the enzymatic study showed that the two strains exhibited high ADH and ALDH enzyme activity at 38°C compared with the mesophilic reference strain LMG 1632, which was significantly susceptible to thermal inactivation.

  16. Biogas Production through the Syntrophic Acetate-Oxidising Pathway. Characterisation and Detection of Syntrophic Acetate- Oxidising Bacteria

    Energy Technology Data Exchange (ETDEWEB)

    Westerholm, Maria [Faculty of Natural Resources and Agricultural Sciences, Dept. of Microbiology, Swedish Univ. of Agricultural Sciences, Uppsala (Sweden)

    2012-11-01

    Biogas produced from wastes, residues and energy crops has promising potential to reduce greenhouse gas emissions and to secure future energy supply. Methane is the energy-rich component of biogas, and is formed as the end product during degradation of organic material without oxygen (anaerobic). Acetate is an important intermediate in anaerobic degradation and can be converted to methane through two pathways: aceticlastic methanogenesis and syntrophic acetate oxidation (SAO). SAO is a two-step reaction, consisting of acetate oxidation to hydrogen and carbon dioxide by syntrophic acetate-oxidising bacteria (SAOB), followed by conversion of these products to methane by hydrogenotrophic methanogens. Ammonia and acetate concentration, hydraulic retention time, temperature and methanogenic population structure are operational parameters considered to influence the acetate conversion pathway. This thesis sought to increase understanding of SAO by examining syntrophic acetate oxidisers in pure culture, co-culture and methanogenic reactors. Two novel species of SAOB, Syntrophaceticus schinkii and Tepidanaerobacter acetatoxydans, were isolated and their phenotypic and phylogenetic traits were characterised. Quantitative molecular approaches were developed and applied to determine structural dynamics in the methane-producing population in a mesophilic biogas reactor during an ammonia-induced shift from aceticlastic to syntrophic acetate degradation. The abundance of SAOB increased, with a simultaneous decrease in aceticlastic methanogens. The majority of known SAOB are considered acetogens, and gradually increased ammonia concentration was shown to cause distinct shifts in the putative acetogenic population structure in mesophilic biogas reactors. However, the acetogenic bacterial abundance remained relatively stable. Bioaugmentation of syntrophic acetate-oxidising cultures did not improve process performance or support establishment of SAO as the dominant acetate

  17. Effect of Acetate Group Content in Ethylene-Vinyl Acetate Copolymer on Properties of Composite Based on Low Density Polyethylene and Polyamide-6

    OpenAIRE

    Nhi Dinh Bui; Ngo Dinh Vu; Thao Thi Minh; Huong Thi Thanh Dam; Regina Romanovna Spiridonova; Semenovich Alexandr Sirotkin

    2016-01-01

    The effect of the content of vinyl acetate groups in ethylene-vinyl acetate copolymer on the properties of polymer composite based on low density polyethylene and polyamide-6 was studied. Ethylene-vinyl acetate copolymer containing less vinyl acetate groups (10–14 wt.%) has a positive compatibility effect on polymer composite than ethylene-vinyl acetate copolymer containing 21–30 wt.% vinyl acetate groups. The polymer composites of LDPE, PA-6, and EVA containing 10–14 wt.% vinyl acetate group...

  18. SAGA complex components and acetate repression in Aspergillus nidulans.

    Science.gov (United States)

    Georgakopoulos, Paraskevi; Lockington, Robin A; Kelly, Joan M

    2012-11-01

    Alongside the well-established carbon catabolite repression by glucose and other sugars, acetate causes repression in Aspergillus nidulans. Mutations in creA, encoding the transcriptional repressor involved in glucose repression, also affect acetate repression, but mutations in creB or creC, encoding components of a deubiquitination system, do not. To understand the effects of acetate, we used a mutational screen that was similar to screens that uncovered mutations in creA, creB, and creC, except that glucose was replaced by acetate to identify mutations that were affected for repression by acetate but not by glucose. We uncovered mutations in acdX, homologous to the yeast SAGA component gene SPT8, which in growth tests showed derepression for acetate repression but not for glucose repression. We also made mutations in sptC, homologous to the yeast SAGA component gene SPT3, which showed a similar phenotype. We found that acetate repression is complex, and analysis of facA mutations (lacking acetyl CoA synthetase) indicates that acetate metabolism is required for repression of some systems (proline metabolism) but not for others (acetamide metabolism). Although plate tests indicated that acdX- and sptC-null mutations led to derepressed alcohol dehydrogenase activity, reverse-transcription quantitative real-time polymerase chain reaction showed no derepression of alcA or aldA but rather elevated induced levels. Our results indicate that acetate repression is due to repression via CreA together with metabolic changes rather than due to an independent regulatory control mechanism.

  19. Uranyl complexes of n-alkanediaminotetra-acetic acids

    International Nuclear Information System (INIS)

    The uranyl complexes of n-propanediaminetetra-acetic acid, n-butanediaminetetra-acetic acid and n-hexanediaminetetra-acetic acid have been studied by potentiometry, with computer evaluation of the titration data by the MINIQUAD program. Stability constants of the 1:1 and 2:1 metal:ligand chelates have been determined as well as the respective hydrolysis and polymerization constants at 25 deg in 0.10M and 1.00M KNO3. The influence of the length of the alkane chain of the ligands on the complexes formed is discussed. (author)

  20. Leuprolide acetate suppresses pedophilic urges and arousability.

    Science.gov (United States)

    Schober, Justine M; Kuhn, Phyllis J; Kovacs, Paul G; Earle, James H; Byrne, Peter M; Fries, Ruth A

    2005-12-01

    Cognitive-behavioral psychotherapy was compared with cognitive-behavioral psychotherapy augmented by leuprolide acetate (LA) for suppression of pedophilic behavior. Five male pedophiles (M age, 50 years; range, 36-58) were administered LA by Depo injection for 12 months, followed by saline placebo for 12 months. Testosterone levels, sexual interest preference by visual reaction time (Abel Assessment), penile tumescence (Monarch Penile Plethysmography, PPG), as well as strong sexual urges toward children and masturbatory frequency involving thoughts of children (polygraph), were measured every 3 months. On LA, testosterone decreased to castrate levels. Penile tumescence was significantly suppressed compared with baseline, but sufficient response remained to detect pedophilic interest. Pedophilic interest was also detected by visual reaction times. When asked about having pedophilic urges and masturbating to thoughts of children, all subjects self-reported a decrease. Polygraph responses indicated subjects were not deceptive. On placebo, testosterone and physiologic arousal eventually rose to baseline. As noted by polygraph, at baseline and on placebo, subjects were deceptive regarding increased pedophilic urges and masturbatory frequency. Interest preference, as measured by Abel Assessment and Monarch PPG, was generally unchanged throughout the study. Cognitive-behavioral psychotherapy augmented with LA significantly reduced pedophilic fantasies, urges, and masturbation; however, pedophilic interest did not change during 1 year of therapy. Deceptive responses by polygraph suggested that self-report was unreliable. Follow-up utilizing objective measures is essential for monitoring efficacy of treatment in pedophilia. Our study supports the premise that suppression of pedophilic behavior is possible. LA may augment cognitive-behavioral psychotherapy and help break the sequence leading to a re-offense. PMID:16362253

  1. Comparison of growth, acetate production, and acetate inhibition of Escherichia coli strains in batch and fed-batch fermentations.

    Science.gov (United States)

    Luli, G W; Strohl, W R

    1990-04-01

    The growth characteristics and acetate production of several Escherichia coli strains were compared by using shake flasks, batch fermentations, and glucose-feedback-controlled fed-batch fermentations to assess the potential of each strain to grow at high cell densities. Of the E. coli strains tested, including JM105, B, W3110, W3100, HB101, DH1, CSH50, MC1060, JRG1046, and JRG1061, strains JM105 and B were found to have the greatest relative biomass accumulation, strain MC1060 accumulated the highest concentrations of acetic acid, and strain B had the highest growth rates under the conditions tested. In glucose-feedback-controlled fed-batch fermentations, strains B and JM105 produced only 2 g of acetate.liter-1 while accumulating up to 30 g of biomass.liter-1. Under identical conditions, strains HB101 and MC1060 accumulated less than 10 g of biomass.liter-1 and strain MC1060 produced 8 g of acetate.liter-1. The addition of various concentrations of sodium acetate to the growth medium resulted in a logarithmic decrease, with respect to acetate concentration, in the growth rates of E. coli JM105, JM105(pOS4201), and JRG1061. These data indicated that the growth of the E. coli strains was likely to be inhibited by the acetate they produced when grown on media containing glucose. A model for the inhibition of growth of E. coli by acetate was derived from these experiments to explain the inhibition of acetate on E. coli strains at neutral pH. PMID:2187400

  2. Inhibition of ice growth and recrystallization by zirconium acetate and zirconium acetate hydroxide.

    Science.gov (United States)

    Mizrahy, Ortal; Bar-Dolev, Maya; Guy, Shlomit; Braslavsky, Ido

    2013-01-01

    The control over ice crystal growth, melting, and shaping is important in a variety of fields, including cell and food preservation and ice templating for the production of composite materials. Control over ice growth remains a challenge in industry, and the demand for new cryoprotectants is high. Naturally occurring cryoprotectants, such as antifreeze proteins (AFPs), present one solution for modulating ice crystal growth; however, the production of AFPs is expensive and inefficient. These obstacles can be overcome by identifying synthetic substitutes with similar AFP properties. Zirconium acetate (ZRA) was recently found to induce the formation of hexagonal cavities in materials prepared by ice templating. Here, we continue this line of study and examine the effects of ZRA and a related compound, zirconium acetate hydroxide (ZRAH), on ice growth, shaping, and recrystallization. We found that the growth rate of ice crystals was significantly reduced in the presence of ZRA and ZRAH, and that solutions containing these compounds display a small degree of thermal hysteresis, depending on the solution pH. The compounds were found to inhibit recrystallization in a manner similar to that observed in the presence of AFPs. The favorable properties of ZRA and ZRAH suggest tremendous potential utility in industrial applications.

  3. Inhibition of ice growth and recrystallization by zirconium acetate and zirconium acetate hydroxide.

    Directory of Open Access Journals (Sweden)

    Ortal Mizrahy

    Full Text Available The control over ice crystal growth, melting, and shaping is important in a variety of fields, including cell and food preservation and ice templating for the production of composite materials. Control over ice growth remains a challenge in industry, and the demand for new cryoprotectants is high. Naturally occurring cryoprotectants, such as antifreeze proteins (AFPs, present one solution for modulating ice crystal growth; however, the production of AFPs is expensive and inefficient. These obstacles can be overcome by identifying synthetic substitutes with similar AFP properties. Zirconium acetate (ZRA was recently found to induce the formation of hexagonal cavities in materials prepared by ice templating. Here, we continue this line of study and examine the effects of ZRA and a related compound, zirconium acetate hydroxide (ZRAH, on ice growth, shaping, and recrystallization. We found that the growth rate of ice crystals was significantly reduced in the presence of ZRA and ZRAH, and that solutions containing these compounds display a small degree of thermal hysteresis, depending on the solution pH. The compounds were found to inhibit recrystallization in a manner similar to that observed in the presence of AFPs. The favorable properties of ZRA and ZRAH suggest tremendous potential utility in industrial applications.

  4. KINETIC STUDY OF CARBONYLATION OF METHANOL TO ACETIC ACID AND ACETIC ANHYDRIDE OVER A NOVEL COPOLYMER- BOUND CIS- DICARBONYLRHODIUM COMPLEX

    Institute of Scientific and Technical Information of China (English)

    CHEN Yuying; YUAN Guoqing; CHEN Rongyao

    1989-01-01

    The kinetic study of carbonylation of methanol-acetic acid mixture to acetic acid and acetic anhydride over a cis-dicarbonylrhodium complex (MVM' Rh)coordinated with the ethylene diacrylate (M')crosslinked copolymer of methyl acrylate (M) and 2 - vinylpyridine (V) shows that the rate of reaction is zero order with respect to both reactants methanol and carbon monoxide, but first order in the concentrations of promoter methyl iodide and rhodium in the complex . Polar solvents can accelerate the reaction .Activation parameters were calculated from the experimental results, being comparable to that of the homogeneous system . A mechanism similar to that of soluble rhodium catalyst was proposed .

  5. Measurement and modelization of VLE of binary mixtures of propyl acetate, butyl acetate or isobutyl acetate with methanol at pressure of 0.6 MPa

    Institute of Scientific and Technical Information of China (English)

    P Susial; D Garca; R Susial; YC Clavijo; A Martn

    2016-01-01

    The vapor–liquid equilibrium of binary mixtures of propyl acetate, butyl acetate and isobutyl acetate with meth-anol has been determined at a constant pressure of 0.6 MPa. Results have been modeled with the Peng–Robinson equation, a traditional cubic equation of state widely employed in chemical industries, as well as with the perturbed-chain statistical associating fluid PC-SAFT theory of Gross–Sadowski. By correlation of the binary inter-action parameters of these equations, the measured vapor–liquid equilibrium data can be accurately predicted. Thus, this work shows that these models are able to represent the experimental data for systems with associating compounds via hydrogen bonding.

  6. Densities, speeds of sound, and refractive indices of the ternary mixtures (toluene + methyl acetate + butyl acetate) and (toluene + methyl acetate + methyl heptanoate) at 298.15 K

    Energy Technology Data Exchange (ETDEWEB)

    Mariano, Alejandra [Departamento de Quimica, Facultad de Ingenieria, Universidad Nacional del Comahue, Buenos Aires 1400 (8300) Neuquen (Argentina); Postigo, Miguel [Departamento de Quimica, Facultad de Ingenieria, Universidad Nacional del Comahue, Buenos Aires 1400 (8300) Neuquen (Argentina)]. E-mail: postigo@uncoma.edu.ar; Gonzalez-Salgado, Diego [Departamento de Fisica Aplicada, Universidad de Vigo, Facultad de Ciencias del Campus de Ourense, E 32004 Ourense (Spain); Romani, Luis [Departamento de Fisica Aplicada, Universidad de Vigo, Facultad de Ciencias del Campus de Ourense, E 32004 Ourense (Spain)

    2007-02-15

    Density, {rho}, speed of sound, u, and refractive index, n {sub D}, at 298.15 K and atmospheric pressure have been measured over the entire composition range for (toluene + methyl acetate + butyl acetate) and (toluene + methyl acetate + methyl heptanoate) systems. Excess molar volumes, V {sup E}, isentropic compressibility, {kappa} {sub s}, isentropic compressibility deviations, {delta}{kappa} {sub s}, and changes of refractive index on mixing, {delta}n {sub D}, for the above systems, have been calculated from experimental data and fitted to Cibulka, Singh et al., and Nagata and Sakura equations, standard deviations from the regression lines are shown. Geometrical solution models, Tsao and Smith, Kholer, Jacob and Fitzner, Rastogi et al. were also applied to predict ternary properties from binary contributions.

  7. Ammonia effect on hydrogenotrophic methanogens and syntrophic acetate oxidizing bacteria

    DEFF Research Database (Denmark)

    Wang, Han; Fotidis, Ioannis; Angelidaki, Irini

    2015-01-01

    Ammonia-rich substrates can cause inhibition on anaerobic digestion process. Syntrophic acetate oxidizing bacteria (SAOB) and hydrogenotrophic methanogens are important for the ammonia inhibitory mechanism on anaerobic digestion. The roles and interactions of SAOB and hydrogenotrophic methanogens...

  8. Effect of lead acetate toxicity on experimental male albino rat

    Directory of Open Access Journals (Sweden)

    Nabil M Ibrahim

    2012-01-01

    Conclusions: It can be concluded that lead acetate has harmful effect on experimental male albino rats. Therefore, the present work advises people to prevent exposure to the lead compound to avoid injurious hazard risk.

  9. Catalytic Esterification of Methyl Alcohol with Acetic Acid

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Esterification of methyl alcohol with acetic acid catalysed by Amberlyst-15 (cation-exchange resin) was carried out in a batch reactor in the temperature ranging between 318-338 K, at atmospheric pressure. The reaction rate increased with increase in catalyst concentration and reaction temperature, but decreased with an increase in water concentration. Stirrer speed had virtually no effect on the rate under the experimental conditions. The rate data were correlated with a second-order kinetic model based on homogeneous reaction. The apparent activation energy was found to be 22.9kJ.mo1-1 for the formation of methyl acetate. The methyl acetate production was carried out aa batch and continuous in a packed bed restive distillation column with high purity methyl acetate produced.

  10. Chemistry and electrochemistry in trifluoroacetic acid. Comparison with acetic acid

    International Nuclear Information System (INIS)

    As the trifluoroacetic acid is, with the acetic acid, one of most often used carboxylic acids as solvent, notably in organic chemistry, this research thesis addresses some relatively simple complexing and redox reactions to highlight the peculiar feature of this acid, and to explain its very much different behaviour with respect to acetic acid. The author develops the notion of acidity level in solvents of low dielectric constant. The second part addresses a specific solvent: BF3(CH3COOH)2. The boron trifluoride strengthens the acidity of acetic acid and modifies its chemical and physical-chemical properties. In the third part, the author compares solvent properties of CF3COOH and CH3COOH. Noticed differences explain why the trifluoroacetic acid is a more interesting reaction environment than acetic acid for reactions such as electrophilic substitutions or protein solubilisation

  11. Biosynthesis of the halogenated auxin, 4-chloroindole-3-acetic acid.

    Science.gov (United States)

    Tivendale, Nathan D; Davidson, Sandra E; Davies, Noel W; Smith, Jason A; Dalmais, Marion; Bendahmane, Abdelhafid I; Quittenden, Laura J; Sutton, Lily; Bala, Raj K; Le Signor, Christine; Thompson, Richard; Horne, James; Reid, James B; Ross, John J

    2012-07-01

    Seeds of several agriculturally important legumes are rich sources of the only halogenated plant hormone, 4-chloroindole-3-acetic acid. However, the biosynthesis of this auxin is poorly understood. Here, we show that in pea (Pisum sativum) seeds, 4-chloroindole-3-acetic acid is synthesized via the novel intermediate 4-chloroindole-3-pyruvic acid, which is produced from 4-chlorotryptophan by two aminotransferases, TRYPTOPHAN AMINOTRANSFERASE RELATED1 and TRYPTOPHAN AMINOTRANSFERASE RELATED2. We characterize a tar2 mutant, obtained by Targeting Induced Local Lesions in Genomes, the seeds of which contain dramatically reduced 4-chloroindole-3-acetic acid levels as they mature. We also show that the widespread auxin, indole-3-acetic acid, is synthesized by a parallel pathway in pea. PMID:22573801

  12. CHARACTERIZATION OF REGENERATED CELLULOSE MEMBRANES HYDROLYZED FROM CELLULOSE ACETATE

    Institute of Scientific and Technical Information of China (English)

    Yun Chen; Xiao-peng Xiong; Guang Yang; Li-na Zhang; Sen-lin Lei; Hui Lianga

    2002-01-01

    A series of cellulose acetate membranes were prepared by using formamide as additive, and then were hydrolyzedin 4 wt% aqueous NaOH solution for 8 h to obtain regenerated cellulose membranes. The dependence of degree ofsubstitution, structure, porous properties, solubility and thermal stability on hydrolysis time was studied by chemical titration,Fourier transform infrared spectroscopy, scanning electron microscopy, wide-angle X-ray diffraction, and differentialscanning calorimetry, respectively. The results indicated that the pore size of the regenerated cellulose membranes wasslightly smaller than that of cellulose acetate membrane, while solvent-resistance, crystallinity and thermostability weresignificantly improved. This work provides a simple way to prepare the porous cellulose membranes, which not only kept thegood pore characteristics of cellulose acetate membranes, but also possessed solvent-resistance, high crystallinity andthermostability. Therefore, the application range of cellulose acetate membranes can be expanded.

  13. New reactions of cyclic oxygen, nitrogen and sulfur acetal derivatives

    OpenAIRE

    Mann, S. E.

    2011-01-01

    This thesis describes the development of new reactions of cyclic oxygen, nitrogen and sulfur acetal derivatives and their applications in a diverse range of synthetic organic and organometallic chemistry. Detailed herein are advances in three main areas of acetal chemistry, namely: studies towards a new methodology for the synthesis of medium ring heterocycles; the use of thioacetals as directing groups for the palladium-mediated oxidation of olefins; and multi-component reactions for the syn...

  14. Probiotic and Acetic Acid Effect on Broiler Chickens Performance

    OpenAIRE

    Martin Král; Mária Angelovičová; Ľubica Mrázová; Jana Tkáčová; Martin Kliment

    2011-01-01

    Probiotics and organic acids are widely accepted as an alternative to in-feed antibiotics in poultry production. We carried the experiment with broiler chickens. In experiment we research effect of probiotic and acetic acids on the performance of broiler chickens. A total number of 200 one day old broiler chickens were distributed to two dietary groups. Broiler chickens in control group were fed with standard feed mixture and experimental group 1% vinegar contained 5% acetic acid used in drin...

  15. Protection of historical lead against acetic acid vapour

    OpenAIRE

    Pecenová Z.; Kouřil M.

    2016-01-01

    Historical lead artefacts (small figurines, appliques, bull (metal seal) can be stored in depository and archives in inconvenient storage conditions. The wooden show-case or paper packagings release volatile organic compound to the air during their degradation. These acids, mainly acetic acid are very corrosive for lead. The thin layer of corrosion products which slows atmospheric corrosion is formed on lead surface in atmospheric condition. In presence of acetic acid vapour the voluminous co...

  16. Influence of calcium acetate on rye bread volume

    Directory of Open Access Journals (Sweden)

    Katharina FUCKERER

    2016-01-01

    Full Text Available Abstract The positive accepted savoury taste of rye bread is dependent on acetate concentration in the dough of such breads. In order to study how calcium acetate influences rye bread properties, the pH of rye doughs fortified with calcium acetate and the resulting volume of the breads were measured. Furthermore, CO2 formation of yeast with added calcium acetate and yeast with different pH levels (4, 7, 9 were measured. Thereby, it was determined that the addition of calcium acetate increased the pH of dough from 4.42 to 5.29 and significantly reduced the volume of the breads from 1235.19 mL to 885.52 mL. It could be proven that bread volume was affected by a 30.9% lower CO2 amount production of yeast, although bread volume was not affected by changing pH levels. Due to reduced bread volume, high concentrations of calcium acetate additions are not recommended for improving rye bread taste.

  17. Genetic dissection of acetic acid tolerance in Saccharomyces cerevisiae.

    Science.gov (United States)

    Geng, Peng; Xiao, Yin; Hu, Yun; Sun, Haiye; Xue, Wei; Zhang, Liang; Shi, Gui-Yang

    2016-09-01

    Dissection of the hereditary architecture underlying Saccharomyces cerevisiae tolerance to acetic acid is essential for ethanol fermentation. In this work, a genomics approach was used to dissect hereditary variations in acetic acid tolerance between two phenotypically different strains. A total of 160 segregants derived from these two strains were obtained. Phenotypic analysis indicated that the acetic acid tolerance displayed a normal distribution in these segregants, and suggested that the acetic acid tolerant traits were controlled by multiple quantitative trait loci (QTLs). Thus, 220 SSR markers covering the whole genome were used to detect QTLs of acetic acid tolerant traits. As a result, three QTLs were located on chromosomes 9, 12, and 16, respectively, which explained 38.8-65.9 % of the range of phenotypic variation. Furthermore, twelve genes of the candidates fell into the three QTL regions by integrating the QTL analysis with candidates of acetic acid tolerant genes. These results provided a novel avenue to obtain more robust strains. PMID:27430512

  18. AcEST: DK947004 [AcEST

    Lifescience Database Archive (English)

    Full Text Available : 427 R 427 TrEMBL (release 39.9) Link to BlastX Result : TrEMBL tr_hit_id Q9M1Z0 Definition tr|Q9M1Z0|Q9M1Z0_ARATH Allyl...s: (bits) Value tr|Q9M1Z0|Q9M1Z0_ARATH Allyl alcohol dehydrogenase-like protein ... 74 5e-12 tr|Q8VZ93|Q8VZ93_ARATH Allyl...haracterized protein OS=Oryza... 66 8e-10 tr|B6T5A5|B6T5A5_MAIZE Allyl alcohol de...d protein (Putativ... 33 8.0 tr|B7ZXT7|B7ZXT7_MAIZE Putative uncharacterized protein OS=Zea m... 33 8.0 >tr|Q9M1Z0|Q9M1Z0_ARATH Allyl... >tr|Q8VZ93|Q8VZ93_ARATH Allyl alcohol dehydrogenase-like protein (Putative uncharacterized protein At3g5983

  19. Pulmonary and percutaneous absorption of 2-propoxyethyl acetate and 2-ethoxyethyl acetate in beagle dogs

    International Nuclear Information System (INIS)

    A comparison was made of the absorption and elimination rates of 2-propoxyethyl acetate (PEA) and 2-ethoxyethyl acetate (EEA) following inhalation, dermal application of IV administration. Male beagle dogs were exposed to 50 ppm PEA or EEA for 5 hr, and breath samples were collected during the exposure and a 3-hr recovery period. Both compounds were rapidly absorbed through the lungs. After 10 min of exposure, the concentrations of the parent compounds in the expired breath were 5 to 10 ppm (80-90% absorption) and reached plateau values at about 3 hr of 13 ppm for PEA (74% absorption) and 16 ppm for EEA (68% absorption). Post-exposure breath samples declined exponentially to 0.5 ppm and 2 ppm after 3 hr for PEA and EEA, respectively. Expired concentrations of PEA were slightly, but significantly (p 14C]PEA, the urine contained 61% and 88% of the dose in 4 and 24 hr, respectively. [14C]EEA was eliminated more slowly, with 20% and 61% of the dose appearing in the urine in 4 and 24 hr, respectively. Blood elimination half-lives were 1.6 hr for [14C]PEA and 7.9 hr for [14C]EEA. Only trace amounts of 14CO2 (14C]PEA or [14C]EEA was added to undiluted compounds and applied in a glass cell to a shaved area on a dog's thorax for 30 or 60 min. Blood and expired air were collected for 8 hr and urine for 24 hr. The pattern of urinary elimination for each compound was similar to that seen after IV dosing with [14C]PEA being excreted more rapidly than [14C]EEA. 15 references, 4 figures, 4 tables

  20. Tetrazole acetic acid: Tautomers, conformers, and isomerization

    Energy Technology Data Exchange (ETDEWEB)

    Araujo-Andrade, C. [Unidad Académica de Física de la Universidad Autónoma de Zacatecas, Zacatecas (Mexico); Department of Chemistry, University of Coimbra, 3004-535 Coimbra (Portugal); Reva, I., E-mail: reva@qui.uc.pt; Fausto, R. [Department of Chemistry, University of Coimbra, 3004-535 Coimbra (Portugal)

    2014-02-14

    Monomers of (tetrazol-5-yl)-acetic acid (TAA) were obtained by sublimation of the crystalline compound and the resulting vapors were isolated in cryogenic nitrogen matrices at 13 K. The conformational and tautomeric composition of TAA in the matrix was characterized by infrared spectroscopy and vibrational calculations carried out at the B3LYP/6-311++G(d,p) level. TAA may adopt two tautomeric modifications, 1H- and 2H-, depending on the position of the annular hydrogen atom. Two-dimensional potential energy surfaces (PESs) of TAA were theoretically calculated at the MP2/6-311++G(d,p) level, for each tautomer. Four and six symmetry-unique minima were located on these PESs, for 1H- and 2H-TAA, respectively. The energetics of the detected minima was subsequently refined by calculations at the QCISD level. Two 1H- and three 2H-conformers fall within the 0–8 kJ mol{sup −1} energy range and should be appreciably populated at the sublimation temperature (∼330 K). Observation of only one conformer for each tautomer (1ccc and 2pcc) is explained in terms of calculated barriers to conformational rearrangements. All conformers with the cis O=COH moiety are separated by low barriers (less than 10 kJ mol{sup −1}) and collapse to the most stable 1ccc (1H-) and 2pcc (2H-) forms during deposition of the matrix. On the trans O=COH surfaces, the relative energies are very high (between 12 and 27 kJ mol{sup −1}). The trans forms are not thermally populated at the sublimation conditions and were not detected in matrices. One high-energy form in each tautomer, 1cct (1H-) and 2pct (2H-), was found to differ from the most stable form only by rotation of the OH group and separated from other forms by high barriers. This opened a perspective for their stabilization in a matrix. 1cct and 2pct were generated in the matrices selectively by means of narrow-band near-infrared (NIR) irradiations of the samples at 6920 and 6937 cm{sup −1}, where the first OH stretching overtone

  1. Additive effects of acetic acid upon hydrothermal reaction of amylopectin

    International Nuclear Information System (INIS)

    It is well known that over 0.8 kg kg−1 of starch is consisted of amylopectin (AP). In this study, production of glucose for raw material of ethanol by hydrothermal reaction of AP as one of the model compound of food is discussed. Further, additive effects of acetic acid upon hydrothermal reactions of AP are also investigated. During hydrothermal reaction of AP, production of glucose occurred above 453 K, and the glucose yield increased to 0.48 kg kg−1 at 473 K. Upon hydrothermal reaction of AP at 473 K, prolongation of the holding time was not effective for the increase of the glucose yield. Upon hydrothermal reaction of AP at 473 K for 0 s, the glucose yield increased significantly by addition between 0.26 mol L−1 and 0.52 mol L−1 of acetic acid. However, the glucose yield decreased and the yield of the other constituents increased with the increases of concentration of acetic acid from 0.65 mol L−1 to 3.33 mol L−1. It was considered that hydrolysis of AP to yield glucose was enhanced due to the increase of the amount of proton derived from acetic acid during hydrothermal reaction with 0.52 mol L−1 of acetic acid. -- Highlights: ► Glucose production by hydrothermal reaction of amylopectin (AP) at 473 K. ► Glucose yield increased to 0.48 kg kg-1 at 473 K. ► Prolongation of holding time was not effective for glucose yield. ► Glucose yield increased significantly by acetic acid (0.26–0.52 mol L-1) addition. ► Hydrolysis of AP to glucose was enhanced due to increase of proton from acetic acid.

  2. Kureha-sodium acetate gypsum method, flue gas desulfurization

    Energy Technology Data Exchange (ETDEWEB)

    Kaminaga, T.; Noguchi, K.

    1975-01-01

    The Kureha Chemical Co. previously developed two flue gas desulfurization techniques, the sodium sulfite method and sodium sulfite-gypsum method, which after being installed at various factories have given good desulfurization results. However, the previous methods had disadvantages either of costly operation or of being non-closed systems. A third method has been developed and is now under experimental operation. The new method utilizes sodium acetate to absorb sulfur dioxide and its reaction products are acetic acid and sodium sulfite. The former product is reacted with calcium carbonate to produce calcium acetate which is further reacted with sodium sulfate to produce gypsum and sodium acetate. Sodium sulfate is produced by air oxidation and sodium sulfite, therefore the desulfurization process is made in a closed system and the only chemical consumed is inexpensive calcium carbonate. Since the sodium acetate aqueous solution is a weak alkali, the SO/sub 2/ absorption is of high efficiency. When the pH of the absorbing solution was greater than 5.0, the desulfurization efficiency was nearly 100 percent, and the SO/sub 2/ level in the treated flue gas was less than 10 ppM when an initial SO/sub 2/ concentration of 1200 to 1300 ppM was used. The acetic acid concentration in the treated flue gas was less than 5 ppM. The 100 percent reaction between sodium sulfate and calcium acetate proceeded within 4 to 5 hr. No special heating step in the desulfurization process was necessary, and the above results could be obtained under reaction temperatures between 50 and 60/sup 0/C.

  3. Continuous production of palm biofuel under supercritical ethyl acetate

    International Nuclear Information System (INIS)

    Highlights: • Continuous synthesized biofuel from palm oil in supercritical ethyl acetate was examined. • Mass flow rate of palm oil and ethyl acetate mixture influent to biofuel production in continuous system. • Water addition to reacting mixture improves the production of fatty acid ethyl esters and triacetin. • The generated acetic acid from ETA hydrolysis can protect the products from thermal decomposition. - Abstract: The interesterification of palm oil in supercritical ethyl acetate (ETA) to produce fatty acid ethyl ester (FAEEs) or biofuel was conducted in a continuous tubular reactor. The density of the mixtures in the system was estimated using the Peng–Robinson equation of state process simulator, and the residence time was calculated. The effects of the reaction conditions, including the molar ratios of palm oil to ethyl acetate, the temperature, and the pressure, were investigated under various mass flow rates of the mixtures and optimized. The results showed that reaction temperatures above 653 K and long residence times affected the content of FAEEs and triacetin, a valuable by-product. The addition of water to the mixture in a 1:30:10 M ratio of palm oil to ethyl acetate to water at 653 K, 16 MPa, and a mixture mass flow rate of 1.5 g/min increased the total production of FAEEs and triacetin from 90.9 to 101.5 wt% in 42.4 min. The main finding of the present study is that triglyceride associated with ETA hydrolysis used to form acetic acid protected the products from decomposition at high temperatures and long residence times. The results will aid the selection of an efficient and economical process for alternative biofuel production from palm oil in supercritical ETA

  4. 21 CFR 862.1390 - 5-Hydroxyindole acetic acid/serotonin test system.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false 5-Hydroxyindole acetic acid/serotonin test system... Test Systems § 862.1390 5-Hydroxyindole acetic acid/serotonin test system. (a) Identification. A 5-hydroxyindole acetic acid/serotonin test system is a device intended to measure 5-hydroxyindole acetic...

  5. The sensitizing potential of primary amyl acetate in the guinea pig.

    Science.gov (United States)

    Ballantyne, B; Tyler, T R; Auletta, C S

    1986-06-01

    Primary amyl acetate is a liquid mixture of the isomeric forms of pentyl acetate, which is used as a volatile organic solvent. Because of the possibility for skin contact, primary amyl acetate was investigated for its potential to cause allergic contact dermatitis. Using a guinea pig maximization procedure, primary amyl acetate was found to be a possible marginal skin sensitizer. PMID:3727350

  6. 含硫Schiff碱型配体的合成研究--芳醛缩-4-烯丙基-3-硫代氨基脲的合成与表征%Synthetic study of Schiff base type ligands containing thiocar bamide group--synthesis and characterization of aro-matic-4-allyl-3-thiosemicarbazone

    Institute of Scientific and Technical Information of China (English)

    赵明根; 范建凤; 李志英; 刘成琪

    2003-01-01

    @@ 1合成方法 在100mL反应器中,加入1.31g(0.01mol)4-烯丙基-3-硫代氨基脲,20mL无水乙醇,加热搅拌溶解,然后加入0.01mol醛及1~2滴催化剂浓盐酸,电磁搅拌,回流反应2h,趁热将反应液转移到小烧杯中,冷却,溶剂自然挥发到一定量后有晶体析出.将所得粗品用醇-水重结晶即得纯品.

  7. Colour Reaction of N-Allyl-N′-(sodium-p-benzenesulfonate)thiourea with Palladium? and Its Application%N-烯丙基-N′-(对苯磺酸钠)硫脲与钯的显色反应及其应用

    Institute of Scientific and Technical Information of China (English)

    马万山; 许春萱; 张玉霞; 杨海申

    2001-01-01

    @@ 1 引言 N-烯丙基-N′-(对苯磺酸钠)硫脲(以下简写为NaNTU)是我们合成的一种新的硫脲类衍生物,性质稳定,易溶于水,无毒,具有很好的分析特性.从我们研究的36种离子与NaNTU 的反应情况看,在1.7~4.2 mol/L的HNO3溶液中,只有钯?能与NaNTU生成黄色络合物 .据此,我们成功地将其用于钯?的鉴定,取得了很好的效果.在此基础上,将该试剂首次应用于钯?的光度分析,从而建立了光度法测定微量钯?的新方法.研究表明,在1.7~4 .2 mol/L的HNO3溶液中,Pd2+和NaNTU形成一种稳定的摩尔比为1∶2的黄色水溶性络合物.络合物的最大吸收波长位于402 nm处;表观摩尔吸光系数ε402=3 .7×104L*mol-1*cm-1.钯?的浓度在0~4.8 mg/L范围内服从比尔定律,相关系数r=0.9996,灵敏度高于硫脲试剂法.该法试验条件容易控制,显色稳定 ,操作简便.研究了36种离子对钯?的干扰情况,在一定倍量的范围内均不干扰钯?的测定 .与有关文献报道的其它一些硫脲类衍生物作为显色剂分光光度测钯?的方法相比,该法具有线性范围宽,Cu2+不干扰等特点.因此,NaNTU是光度法测钯?的选择性很高的试剂.将其用于合成试样、催化剂中钯?的测定,均得到满意结果.

  8. 新显色剂N-烯丙基-N'-(对苯磺酸钠)硫脲与钌的显色反应及其应用%Colour Reaction of N-Allyl-N'-(Sodium-p-benzenesulfonate) thiourea with Ruthenium(Ⅲ) and Its Application

    Institute of Scientific and Technical Information of China (English)

    马万山; 甄西合; 马东兰

    2000-01-01

    研究了显色剂N-烯丙基-N'-(对苯磺酸钠)硫脲与钌(Ⅲ)的显色反应.在4.5~6.0 mol/L的HCl溶液中,钌(Ⅲ)与N-烯丙基-N'-(对苯磺酸钠)硫脲形成稳定的1:3蓝色水溶性络合物.最大吸收波长在630 nm,表观摩尔吸光系数为2.30×104L.mol-1.cm-1;钌(Ⅲ)的浓度在0.4~3.2 mg/L范围内服从比尔定律.此法具有显色稳定,选择性好,操作简便等优点.用于测定二次合金管理样和合成试样中钌,结果满意.

  9. Synthesis of Allyl Hexanoate Catalyzed by Activated Carbon Supported SnCl4·5H2O under Microwave Irradiation%微波促进活性炭负载四氯化锡催化合成己酸烯丙酯

    Institute of Scientific and Technical Information of China (English)

    袁霖

    2007-01-01

    在微波辐射下,以活性炭负载四氯化锡(SnCl4·5H2O/C)为催化剂,不用溶剂,合成了己酸烯丙酯.其优化条件是:负载量为20%的SnCl4·5H2O/C催化剂0.1g,己酸1mgL,烯丙醇2mL,微波功率600W,反应时间8min,酯化率达85.5%.产物经过红外光谱表征.该催化剂亦能用于乙醇、异丙醇、正丁醇、正戊醇与己酸的酯化反应.

  10. 稀土固体超强酸SO42-/TiO2/La3+催化合成己酸烯丙酯%The Catalytic Synthesis of Allyl Hexanoate by SO42-/TiO2/La3+ Rare Earth Solid Superacid

    Institute of Scientific and Technical Information of China (English)

    韩敬华

    2001-01-01

    研究了以稀土固体超强酸SO42-/TiO:/La3+为催化剂,己酸和烯丙醇为原料合成己酸烯丙酯,并考察了影响反应的因素.结果表明,醇酸比为2.0:1,催化剂用量为0.8 g(己酸为0.2mol的情况下),带水剂甲苯为20mL,反应时问为2.0 h是最适宜的反应条件,酯化率达96.2%.

  11. Microwave assisted modification of allyl alcohol polyethylene oxide ether on methane hydrogen siloxane and the performance of its defoamer%微波辅助烯丙醇聚氧烷基醚改性甲基含氢硅氧烷及其消泡剂性能

    Institute of Scientific and Technical Information of China (English)

    刘停; 蒋柏泉; 邹友琴

    2015-01-01

    采用微波辅助技术进行了烯丙醇聚氧烷基醚改性甲基含氢硅氧烷的合成.通过单因素实验考察了主要操作参数对Si-H转化率的影响并确定了最适宜的工艺条件.结果表明,在最适宜的微波功率280 W,原料醚/烷摩尔比1.2∶1.0、催化剂用量2.0×10-4%和微波辐射时间25 min的条件下,转化率达到99.80%.傅里叶红外表征显示原料聚醚中的C=C键与硅氧烷中的Si-H键均已发生反应生成了目标产物.用合成产物制备的复配消泡剂具有优良的稳定和水分散性能,其消泡和抑泡性能明显好于国产消泡剂,高温下消泡性能优于国外奥地利产品.微波辅助加热比常规加热大大节省了时间,降低了能耗.

  12. 罗丹明B试法鉴定UO2+2用N-烯丙基-N′-(对苯磺钠)硫脲掩蔽Fe3+的干扰%Eliminating the interference of Fe3+ with the N-allyl-N′-(sodium-p-benzenesulfonate) thiourea in the indentification of UO2+2 using Rodamine B

    Institute of Scientific and Technical Information of China (English)

    马万山; 许春萱; 钟瑞琴; 张秀兰

    2002-01-01

    以实验为基础,提出了用罗丹明B试法鉴定UO2+2时,用N-烯丙基-N′-(对苯磺酸钠)硫脲掩蔽Fe3+离子的干扰.与传统的消除干扰的方法相比,具有条件容易控制,操作简便等优点.

  13. Eslicarbazepine acetate: an update on efficacy and safety in epilepsy.

    Science.gov (United States)

    Verrotti, Alberto; Loiacono, Giulia; Rossi, Alessandra; Zaccara, Gaetano

    2014-01-01

    Epilepsy is a common neurological disorder. Despite a broad range of commonly used antiepileptic drugs, approximately 30% of patients with epilepsy have drug resistance or encounter significant adverse effects. Eslicarbazepine acetate is a new central nervous system-active compound with anticonvulsant activity whose mechanism of action is by blocking the voltage-gated sodium channel. Eslicarbazepine acetate was approved by the European Medicines Agency and launched onto the European market in 2009 for adjunctive treatment in adult subjects of partial-onset seizures, with or without secondary generalization. This article provides an overview on the recent studies on eslicarbazepine acetate in the treatment of drug-resistant partial epilepsy. Efficacy and safety of this drug for partial-onset seizures were assessed in four randomized clinical trials with responder rates ranged between 17% and 43%. Adverse events were usually mild to moderate in intensity and the most common were dizziness, somnolence, nausea, diplopia, headache, vomiting, abnormal coordination, blurred vision, vertigo and fatigue. Eslicarbazepine acetate is not recommended below 18 years, but a published phase II trial had the main goal to evaluate the pharmacokinetics, efficacy and safety of this drug in pediatric population. Eslicarbazepine acetate appears to be a safe and effective drug with a linear pharmacokinetics, very low potential for drug-drug interactions and therefore it can offer a valid alternative to current antiepileptic drugs. Additionally, it is undergoing investigation for monotherapy in subjects with partial epilepsy, and other neurological and psychiatric disorders. PMID:24225327

  14. Self-Relay Gold(I)-Catalyzed Pictet-Spengler/Cyclization Cascade Reaction for the Rapid Elaboration of Pentacyclic Indole Derivatives.

    Science.gov (United States)

    Gobé, Valérian; Retailleau, Pascal; Guinchard, Xavier

    2015-12-01

    Gold-catalyzed cascade reactions allow the rapid elaboration of pentacyclic indolo[2,3-a]quinolizidines from N-allyl tryptamines and ortho-alkynylarylaldehydes. The tandem process combines a gold-catalyzed Pictet-Spengler reaction and a cyclization occurring concomitantly with an allyl transfer from the nitrogen atom to the stilbene function. Various substituted allyls were successfully transferred, furnishing the products in yields typically ranging from 60-98 % in high diastereoselectivity. Tryptamines bearing a butenol chain undergo an additional cyclization to chiral hemiaminals in high diastereoselectivities. PMID:26443069

  15. Rotameric transformations in the photochemistry of TpM(CO)2(η(3)-C3H4R), where Tp = tris(pyrazolyl)borate, M = Mo or W, and R = H or Me.

    Science.gov (United States)

    Thornley, Wyatt A; Bitterwolf, Thomas E

    2015-05-01

    Low energy photolysis of TpM(CO)2(η(3)-C3H4R), where Tp = tris(pyrazolyl)borate, M = Mo or W, and R = 2-H or 2-Me in PVC matrices at 85 K results in exo/gauche isomerism of the allyl ligand. This transformation comes in contrast to the behaviour observed in cyclopentadienyl analogues which undergo exo/endo isomerism. DFT computations reveal an η(3) → η(1)* → η(3) mechanism for the allyl rotameric interconversion where the η(1)*-allyl intermediate is generated upon MLCT excitation.

  16. Characterization of differently sized granule fractions of yellow pea, cowpea and chickpea starches after modification with acetic anhydride and vinyl acetate

    NARCIS (Netherlands)

    Huang, J.; Schols, H.A.; Jin, Z.; Sulmann, E.; Voragen, A.G.J.

    2007-01-01

    The effect of reagent type on the properties of acetylated starches was studied for yellow pea, cowpea and chickpea starches after modification with acetic anhydride and vinyl acetate. Samples modified with vinyl acetate showed higher swelling volume and peak viscosity than those acetylated with ace

  17. Syntrophic acetate oxidation in industrial CSTR biogas digesters.

    Science.gov (United States)

    Sun, Li; Müller, Bettina; Westerholm, Maria; Schnürer, Anna

    2014-02-10

    The extent of syntrophic acetate oxidation (SAO) and the levels of known SAO bacteria and acetate- and hydrogen-consuming methanogens were determined in sludge from 13 commercial biogas production plants. Results from these measurements were statistically related to the prevailing operating conditions, through partial least squares (PLS) analysis. This revealed that high abundance of microorganisms involved in SAO was positively correlated with relatively low abundance of aceticlastic methanogens and high concentrations of free ammonia (>160 mg/L) and volatile fatty acids (VFA). Temperature was identified as another influencing factor for the population structure of the syntrophic acetate oxidising bacteria (SAOB). Overall, there was a high abundance of SAOB in the different digesters despite differences in their operating parameters, indicating that SAOB are an enduring and important component of biogas-producing consortia.

  18. Crystal structure of febuxostat–acetic acid (1/1

    Directory of Open Access Journals (Sweden)

    Min Wu

    2015-05-01

    Full Text Available The asymmetric unit of the title compound [systematic name: 2-(3-cyano-4-isobutyloxyphenyl-4-methylthiazole-5-carboxylic acid–acetic acid (1/1], C16H16N2O3S·CH3COOH, contains a febuxostat molecule and an acetic acid molecule. In the febuxostat molecule, the thiazole ring is nearly coplanar with the benzene ring [dihedral angle = 3.24 (2°]. In the crystal, the febuxostat and acetic acid molecules are linked by O—H...O, O—H...N hydrogen bonds and weak C—H...O hydrogen bonds, forming supramolecular chains propagating along the b-axis direction. π–π stacking is observed between nearly parallel thiazole and benzene rings of adjacent molecules; the centroid-to-centroid distances are 3.8064 (17 and 3.9296 (17 Å.

  19. Cellulose acetate as solid phase in ELISA for plague

    Directory of Open Access Journals (Sweden)

    Barbosa AD

    2000-01-01

    Full Text Available Antigen from Yersinia pestis was adsorbed on cellulose acetate discs (0.5 cm of diameter which were obtained from dialysis membrane by using a paper punch. ELISA for human plague diagnosis was carried out employing this matrix and was capable to detect amount of 1.3 µg of antigen, 3,200 times diluted positive serum using human anti-IgG conjugate diluted 1:4,000. No relevant antigen lixiviation from the cellulose acetate was observed even after washing the discs 15 times. The discs were impregnated by the coloured products from the ELISA development allowing its use in dot-ELISA. Furthermore, cellulose acetate showed a better performance than the conventional PVC plates.

  20. Lipid extraction and iontophoretic transport of leuprolide acetate through porcine epidermis.

    Science.gov (United States)

    Rastogi, S K; Singh, J

    2001-03-14

    The purpose of this study was to explore the effect of lipid extraction by the simple alkyl acetates of increasing carbon chain lengths (e.g. methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl acetates) and iontophoresis on the in-vitro transport of leuprolide acetate through porcine epidermis. The extent of lipid extraction from the stratum corneum (SC) by alkyl acetates was studied by Fourier transform infrared (FT-IR) spectroscopy. Ethyl, propyl, pentyl, hexyl, and octyl acetates significantly increased (P acetate through the epidermis in comparison to the control (epidermis without alkyl acetate treatment). Iontophoresis further increased (P acetate for all the alkyl acetates studied, when compared to their corresponding passive permeability. Ethyl acetate produced the maximum passive (13.47 microg/cm(2)/h) and iontophoretic (89.79 microg/cm(2)/h) flux among all the alkyl acetates studied. The SC treated with alkyl acetates showed a decrease in peak heights and areas of asymmetric and symmetric C--H stretching absorbances in comparison to untreated SC. A greater percentage decrease in peak heights and areas was obtained by ethyl acetate. Chloroform:methanol(2:1) [C:M(2:1)] was used as a positive control for lipid extraction. Our findings provide evidence that alkyl acetates cause lipid extraction, which leads to an enhancement in the passive and iontophoretic permeability of leuprolide acetate. PMID:11250109

  1. High purity neodymium acetate from mixed rare earth carbonates

    Energy Technology Data Exchange (ETDEWEB)

    Queiroz, Carlos A. da Silva; Rocha, Soraya M. Rizzo da; Vasconcellos, Mari E. de; Lobo, Raquel M.; Seneda, Jose A., E-mail: cqueiroz@ipen.b, E-mail: smrrocha@ipen.b, E-mail: mstela@ipen.b, E-mail: rmlobo@ipen.b, E-mail: jaseneda@ipen.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Pedreira, Walter dos R., E-mail: walter.pedreira@fundacentro.gov.b [Fundacao Jorge Duprat Figueiredo de Seguranca e Medicina do Trabalho (FUNDACENTRO), Sao Paulo, SP (Brazil)

    2011-07-01

    A simple and economical chemical process for obtaining high purity neodymium acetate is discussed. The raw material in the form rare earth carbonate is produced industrially from the chemical treatment of Brazilian monazite. Ion exchange chromatography technique with a strong cationic resin, proper to water treatment, and without the use of retention ions was used for the fractionating of the rare earth elements (REE). In this way, it was possible to obtain 99.9% pure Nd{sub 2}O{sub 3} in yields greater than or equal 80%, with the elution of the REE using ammonium salt of ethylenediaminetetraacetic acid (EDTA) solution in pH controlled. The complex of EDTA-neodymium was transformed into neodymium oxide, which was subsequently dissolved in acetic acid to obtain the neodymium acetates. Molecular absorption spectrophotometry was used to monitor the neodymium content during the process and sector field inductively coupled plasma mass spectrometry was used to certify the purity of the neodymium acetates. The typical neodymium acetates obtained contain the followings contaminants in {mu}g g{sup -1}: Sc(5.1); Y (0.9); La (1.0); Ce (6.1); Pr (34,4); Sm (12.8); Eu (1.1); Gd (15.4); Tb (29.3); Dy (5.2), Ho(7.4); Er (14.6); Tm (0.3); Yb (2.5); Lu (1.0). The high purity neodymium acetates obtained from this procedure have been applied, replacing the imported product, in research and development area on rare earth catalysts. (author)

  2. Search for Deuterated methyl acetate in the ISM

    Science.gov (United States)

    Gorai, Prasanta; Chakrabarti, Sandip Kumar; Das, Ankan; Majumdar, Liton; Sahu, Dipen; Sivaraman, Bhalamurugan

    2016-07-01

    Methyl acetate (CH_3COOCH_3 ) has been recently observed by IRAM 30 m radio telescope in Orion. But the existence of its deuterated form are yet to be confirmed. Here, we study the properties of methyl acetate and its singly deuterated forms (CH_3COOCH_3, CH_2DCOOCH_3 and CH_3COOCH_2D). Our simulation results reveal that deuterated forms of methyl acetate could efficiently be produced both in gas as well as in ice phase. Production of methyl acetate could follow radical-radical reaction between acetyl (CH_3CO) and methoxy (CH_3O) radicals. To predict abundances of CH_3COOCH_3 along with its two singly deuterated isotopomers and its two isomers (ethyl formate and hydroxy acetone), we prepare a large gas-grain chemical network to study chemical evolution of these molecules. Since gas phase rate coefficients of our newly adopted network for methyl acetate and its related species were unknown, in our simulation, either we consider similar rate coefficients for similar types of reactions (by following existing data bases) or we carry out quantum chemical calculations to estimate the unknown rate coefficients. For the surface reactions, we use adsorption energies of reactants from some earlier studies. Moreover, we perform quantum chemical calculations to find out various spectral properties of various forms of methyl acetate in infrared, ultraviolet and sub-millimeter regions. We prepare two catalog files for the rotational transitions of CH_2DCOOCH_3 and CH_3COOCH_2D in JPL format, which might be useful for its detection in regions of interstellar media where CH_3COOCH_3 has already been observed.

  3. Eugenol and its synthetic analogues inhibit cell growth of human cancer cells (Part I)

    Energy Technology Data Exchange (ETDEWEB)

    Carrasco A, H.; Cardona, W. [Universidad Andres Bello, Vina del Mar (Chile). Dept. de Ciencias Quimicas]. E-mail: hcarrasco@unab.cl; Espinoza C, L.; Gallardo, C.; Catalan M, K. [Universidad Tecnica Federico Santa Maria, Valparaiso (Chile). Dept. de Quimica; Cardile, V.; Lombardo, L. [University of Catania (Italy). Dept. of Physiological Sciences; Cuellar F, M. [Universidad de Valparaiso (Chile). Facultad de Farmacia; Russo, A. [University of Catania (Italy). Dept. of Biological Chemistry, Medical Chemistry and Molecular Biology

    2008-07-01

    Eugenol (4-allyl-2-methoxyphenol) (1) has been reported to possess antioxidant and anticancer properties. In an attempt to enhance intrinsic activity of this natural compound, some derivatives were synthesized. Eugenol was extracted from cloves oil and further, the eugenol analogues (2-6) were obtained through acetylation and nitration reactions. Eugenol (1) and its analogues (2-6) were examined by in vitro model of cancer using two human cancer cell lines: DU-145 (androgeninsensitive prostate cancer cells) and KB (oral squamous carcinoma cells). Cell viability, by tetrazolium salts assay, was measured. Lactic dehydrogenase (LDH) release was also investigated to evaluate the presence of cell toxicity as a result of cell disruption, subsequent to membrane rupture. In the examined cancer cells, all compounds showed cell-growth inhibition activity. The obtained results demonstrate that the compounds 5-allyl-3-nitrobenzene-1,2-diol (3) and 4-allyl- 2-methoxy-5-nitrophenyl acetate (5) were significantly (p < 0,001) more active than eugenol, with IC{sub 50} values in DU-145 cells of 19.02 x 10{sup -6} and 21.5 x 10{sup -6} mol L{sup -1}, respectively, and in KB cells of 18.11 x 10{sup -6} and 21.26 x 10{sup -6} mol L{sup -1}, respectively, suggesting that the presence of nitro and hydroxyl groups could be important in the activity of these compounds. In addition, our results seem to indicate that apoptotic cell demise appears to be induced in KB and DU-145 cells. In fact, in our experimental conditions, no statistically significant increase in LDH release was observed in cancer cells treated with eugenol and its analogues. (author)

  4. Unimolecular Gas-Phase Thermolysis of Ethyl Acetate

    DEFF Research Database (Denmark)

    Egsgaard, Helge; Carlsen, Lars

    1983-01-01

    The unimolecular gas-phase thermolysis of ethyl acetate has been investigated by the Flash-Vacuum-Thermolysis/Field-Ionization Mass Spectrometry (FVT/FI-MS) method in combination with Collision Activation (CA) mass spectrometry at 1253K. Two predominant reactions are observed: elimination...... of ethylene affording acetic acid, the latter to some extent consecutively yielding ketene, and intramolecular oxygen to oxygen ethyl group migration. Additionally minor amounts of acetaldehyde is formed. The mechanistic aspects are discussed based on 18O and 18O/ 13C labelling....

  5. Migration of 2-butoxyethyl acetate from polycarbonate infant feeding bottles

    DEFF Research Database (Denmark)

    Petersen, Jens Højslev; Lund, K.H.

    2003-01-01

    An enforcement campaign was carried out to assess the migration of 2-butoxyethyl acetate (2-BEA) from polycarbonate infant feeding bottles intended for repeated use. Migration was measured by three successive migration tests into two of the European Union official food simulants: distilled water...... and 3% acetic acid testing at 40degrees C for 10 days. The Danish Veterinary and Food Administration (DVFA) has assessed that a migration above 0.33 mg for 2-BEA and a group of eight related substances kg(-1) foodstuff from plastics articles used exclusively for infants is unacceptable. Migration of 2...

  6. Abiraterone Acetate and Castration Resistant Ductal Adenocarcinoma of the Prostate

    Directory of Open Access Journals (Sweden)

    Edgar Linden-Castro

    2014-01-01

    Full Text Available Ductal adenocarcinoma of the prostate is a rare histological variant that only represents <1% of prostate tumors. This histological variant has several important clinical implications with respect to their evolution, clinical prognosis, and treatment. We report the case of a 64-year-old patient with ductal adenocarcinoma of the prostate, which progresses to castration-resistant prostate cancer, that was treated with abiraterone acetate with good clinical response, to our knowledge, the first case of ductal adenocarcinoma of the prostate in treatment with abiraterone acetate.

  7. Fate and residues of trenbolone acetate in edible tissues from sheep amd calves implanted with tritium-labeled trenbolone acetate

    Energy Technology Data Exchange (ETDEWEB)

    Evrard, P.; Maghuin-Rogister, G.; Rico, A.G. (Univ. of Liege (Belgium))

    1989-06-01

    In order to study the fate and residues of trenbolone acetate in edible tissues, two groups of six animals from two ruminant species (ewes and calves) were implanted with (3H)trenbolone acetate. The distribution of extractable radioactive residues was measured in liver, kidney and muscle. We found that the largest proportion of residues was not extractable and thus was considered as covalently bound residues. The proportion of the main extractable metabolites (17 alpha-trenbolone, trendione, 17 beta-trenbolone) was measured. The evaluation of the distribution of trenbolone acetate metabolites directly soluble in water showed that unknown metabolite(s) were predominant. The covalent binding to nucleic acids was measured. It was so low that it was not detectable. The results are discussed in light of the data presented in the scientific report on anabolic agents in animal production from the European scientific working group.

  8. MORPHOLOGY, IN VITRO - DEGRADATION AND DRUG RELEASE PROFILE OF POLY (ETHYLENE-CO-VINYL ACETATE / MICROCRYSTALLINE CELLULOSE ACETATE

    Directory of Open Access Journals (Sweden)

    K. Lakshmi Narayana

    2011-06-01

    Full Text Available Microcrystalline cellulose acetate (MCC was incorporated in poly (ethylene-co-vinyl acetate (EVA at different loading. The morphology, swelling properties and drug release profile were studied with respect to MCC loading to study its potential application as ocular inserts. The XRD patterns showed a good compatibility between the components. However swelling ratio and in-vitro degradation of EVA increase with MCC loading. This has been explained in terms of the hygroscopic nature of cellulose acetate. The study shows that EVA/MCC system can be tuned in terms of important parameters such as swelling behavior, in vitro release and degradation by varying blend composition, thus fulfilling specific biomedical requirements.

  9. Experimental Measurements and Correlations Isobaric Vapor-Liquid Equilibria for Water + Acetic Acid + Sec-butyl Acetate at 101.3 kPa

    Institute of Scientific and Technical Information of China (English)

    LI Ling; HE Yong; WU Yanxiang; ZOU Wenhu

    2013-01-01

    Isobaric vapor-liquid equilibrium(VLE) data for acetic acid + sec-butyl acetate and water + acetic acid + sec-butyl acetate systems were determined at 101.3 kPa using a modified Rose type.The nonideality of the vapor phase caused by the association of the acetic acid was corrected by the chemical theory and Hayden-O'Connell method.Thermodynamic consistency was tested for the binary VLE data.The experimental data were correlated successfully with the Non-Random Two Liquids (NRTL) model.The Root Mean Square Deviation (RMSD) of the ternary system was 0.0038.The saturation vapor pressure of sec-butyl acetate at 329 to 385 K was measured by means of two connected equilibrium cells.The vapor pressures of water and sec-butyl acetate were correlated with the Antoine equation.The binary interaction parameters and the ternary VLE data were obtained from this work.

  10. Effect of Acetate Group Content in Ethylene-Vinyl Acetate Copolymer on Properties of Composite Based on Low Density Polyethylene and Polyamide-6

    Directory of Open Access Journals (Sweden)

    Nhi Dinh Bui

    2016-01-01

    Full Text Available The effect of the content of vinyl acetate groups in ethylene-vinyl acetate copolymer on the properties of polymer composite based on low density polyethylene and polyamide-6 was studied. Ethylene-vinyl acetate copolymer containing less vinyl acetate groups (10–14 wt.% has a positive compatibility effect on polymer composite than ethylene-vinyl acetate copolymer containing 21–30 wt.% vinyl acetate groups. The polymer composites of LDPE, PA-6, and EVA containing 10–14 wt.% vinyl acetate groups possess the ability of biodegradation. The physical-mechanical properties of sample and molecular mass reduce after 28 days of incubation.

  11. Acetate stimulates secretion in the rabbit mandibular gland

    DEFF Research Database (Denmark)

    Novak, I; Young, J A

    1989-01-01

    In isolated perfused rabbit mandibular glands undergoing stimulation with 0.8 microM acetylcholine, replacement of HCO3- with acetate (25 mM) increased fluid secretion by more than 100%. Other short-chain fatty acids, except for propionate, had a similar effect. We focused our further studies...

  12. Photocatalytic decomposition of cortisone acetate in aqueous solution

    NARCIS (Netherlands)

    Sobral Romao, Joana; Hamdy, Mohamed S.; Mul, Guido; Baltrusaitis, Jonas

    2015-01-01

    The photocatalytic decomposition of cortisone 21-acetate (CA), a model compound for the commonly used steroid, cortisone, was studied. CA was photocatalytically decomposed in a slurry reactor with the initial rates between 0.11 and 0.46 mg L−1 min−1 at 10 mg L−1 concentration, using the following he

  13. 21 CFR 522.960b - Flumethasone acetate injection.

    Science.gov (United States)

    2010-04-01

    ... alcohol (as preservative); 8 milligrams of sodium chloride; 1 milligram of polysorbate 80; 0.1 milligram... 21 Food and Drugs 6 2010-04-01 2010-04-01 false Flumethasone acetate injection. 522.960b Section 522.960b Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN...

  14. First Acetic Acid Survey with CARMA in Hot Molecular Cores

    CERN Document Server

    Shiao, Y -S Jerry; Remijan, Anthony J; Snyder, Lewis E; Friedel, Douglas N

    2010-01-01

    Acetic acid (CH$_3$COOH) has been detected mainly in hot molecular cores where the distribution between oxygen (O) and nitrogen (N) containing molecular species is co-spatial within the telescope beam. Previous work has presumed that similar cores with co-spatial O and N species may be an indicator for detecting acetic acid. However, does this presumption hold as higher spatial resolution observations become available of large O and N-containing molecules? As the number of detected acetic acid sources is still low, more observations are needed to support this postulate. In this paper, we report the first acetic acid survey conducted with the Combined Array for Research in Millimeter-wave Astronomy (CARMA) at 3 mm wavelengths towards G19.61-0.23, G29.96-0.02 and IRAS 16293-2422. We have successfully detected CH$_3$COOH via two transitions toward G19.61-0.23 and tentatively confirmed the detection toward IRAS 16293-2422 A. The determined column density of CH$_3$COOH is 2.0(1.0)$\\times 10^{16}$ cm$^{-2}$ and the...

  15. Demixing and gelation behavior of ternary cellulose acetate solutions

    NARCIS (Netherlands)

    Reuvers, A.J.; Altena, F.W.; Smolders, C.A.

    1986-01-01

    The demixing behavior on cooling of ternary systems of cellulose acetate/solvent/water has been examined for CA concentrations up to 40 wt% CA in several solvents. Cloud points have been measured as a function of cooling rate. The rapid process of liquid - liquid demixing can be discriminated from t

  16. Megestrol acetate in the treatment of metastatic breast cancer

    NARCIS (Netherlands)

    J. Alexieva-Figusch (Jana)

    1984-01-01

    textabstractThere are many non-elucidated questions concerning cancer, especially of the breast, in which hormones are involved. The scope of this particular study is to bring more clarity on the role of the progestin megestrol acetate in the hormonal treatment of breast cancer. It should be kept in

  17. Eslicarbazepine acetate in the management of refractory bipolar disorder.

    Science.gov (United States)

    Nath, Kamal; Bhattacharya, Arnab; Praharaj, Samir Kumar

    2012-01-01

    Eslicarbazepine acetate is a novel third-generation antiepileptic related to carbamazepine and oxcarbazepine with a benign adverse effect profile. We report a patient with bipolar mania with intolerance to multiple antimanic drugs, responding to eslicarbazepine without any serious adverse effect. PMID:23151469

  18. Transformation of Schizosaccharomyces pombe: Lithium Acetate/ Dimethyl Sulfoxide Procedure.

    Science.gov (United States)

    Murray, Johanne M; Watson, Adam T; Carr, Antony M

    2016-04-01

    Transformation ofSchizosaccharomyces pombewith DNA requires the conditioning of cells to promote DNA uptake followed by cell growth under conditions that select and maintain the plasmid or integration event. The three main methodologies are electroporation, treatment with lithium cations, and transformation of protoplasts. The lithium acetate method described here is widely used because it is simple and reliable. PMID:27037075

  19. Preparation and properties of polyvinyl acetal sponge modified by chitosan

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    The polyvinyl acetal sponge modified by chitosan was prepared by adding chitosan/polyvinyl alcohol (PVA) solution during the acetalation reaction of PVA and formaldehyde.The effect of vesicant and chitosan to the pore morphology,water absorption ratio,water absorption rate,expansion time and mechanical properties were studied.The polyvinyl acetal sponge modified by chitosan was used as a hemostatic packing material for the injured rabbit nasal tissue.The hemostatic effect and the healing effect of the modified sponge on the nasal mucosa after nasal surgery were studied.The results indicated that the polyvinyl acetal sponge modified by chitosan has an interconnected pore structure and the wall between large pores also has small pores.The chitosan adhered on the inner surface of the pores.The increased content of vesicant led to an increase in pore diameter,in the water absorption ratio and in expansion time.However,there was only a small change in the water absorption rate and a decrease in tensile strength and compression strength were noted.With an increase in chitosan content,the pore diameter and interconnection of the sponge was reduced.Water absorption ratio,expansion time and water absorption rate decreased,but tensile strength and compression strength improved.Observation of the rabbit nasal tissue after surgical operation suggested that polyvinyl acetal sponge modified by chitosan has an anti-inflammatory,hemostatic and antiadherent characteristic and could promote the healing and functional recovery of rabbit nasal mucosa.

  20. Quantitative analysis and purity evaluation of medroxyprogesterone acetate by HPLC.

    Science.gov (United States)

    Cavina, G; Valvo, L; Alimenti, R

    1985-01-01

    A reversed-phase high-performance liquid chromatographic method was developed for the assay of medroxyprogesterone acetate and for the detection and determination of related steroids present as impurities in the drug. The method was compared with the normal-phase technique of the USP XX and was also applied to the analysis of tablets and injectable suspensions. PMID:16867645