Sample records for z-trisubstituted allylic alcohols

  1. Palladium-catalyzed amination of allyl alcohols.

    Ghosh, Raju; Sarkar, Amitabha


    An efficient catalytic amination of aryl-substituted allylic alcohols has been developed. The complex [(η(3)-allyl)PdCl](2) modified by a bis phosphine ligand, L, has been used as catalyst in the reaction that afforded a wide range of allyl amines in good to excellent yield under mild conditions.

  2. Enantioselective Synthesis of All-Carbon Quaternary Stereogenic Centers via Copper-Catalyzed Asymmetric Allylic Alkylation of (Z)-Allyl Bromides with Organolithium Reagents

    Fananas-Mastral, Martin; Vitale, Romina; Perez, Manuel; Feringa, Ben L.


    A copper/phosphoramidite catalyzed asymmetric allylic alkylation of Z trisubstituted allyl bromides with organolithium reagents is reported. The reaction affords all-carbon quaternary stereogenic centers in high yields and very good regio- and enantioselectivity. This systematic study illustrates

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

    Full Text Available allyl alcohol AA 00010 ftp:/.../ ...

  4. Synthesis of insect pheromones belonging to the group of (Z)-trisubstituted alkenes

    Grigorieva, Natalia Ya; Tsiklauri, Paata G [N.D.Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow (Russian Federation)


    Stereo- and regiocontrolled methods for the construction of a (Z)-trisubstituted C=C bond and for the regiospecific introduction of a chiral fragment are exemplified in total syntheses of insect pheromones belonging to (Z)-trisubstituted alkenes. The bibliography includes 113 references.

  5. Synthesis of insect pheromones belonging to the group of (Z)-trisubstituted alkenes

    Grigorieva, Natalia Ya; Tsiklauri, Paata G.


    Stereo- and regiocontrolled methods for the construction of a (Z)-trisubstituted C=C bond and for the regiospecific introduction of a chiral fragment are exemplified in total syntheses of insect pheromones belonging to (Z)-trisubstituted alkenes. The bibliography includes 113 references.

  6. Catalytic Asymmetric Generation of (Z)-Disubstituted Allylic Alcohols

    Salvi, Luca; Jeon, Sang-Jin; Fisher, Ethan L.; Carroll, Patrick J.; Walsh, Patrick J.


    A one-pot method for the direct preparation of enantioenriched (Z)-disubstituted allylic alcohols is introduced. Hydroboration of 1-halo-1-alkynes with dicyclohexylborane, reaction with t-BuLi, and transmetallation with dialkylzinc reagents generates (Z)-disubstituted vinylzinc intermediates. In situ reaction of these reagents with aldehydes in the presence of a catalyst derived from (−)-MIB generates (Z)-disubstituted allylic alcohols. It was found that the resulting allylic alcohols were ra...

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

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


    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.

  8. Regio- and Stereospecific Formation of Protected Allylic Alcohols via Zirconium-Mediated SN2' Substitution of Allylic Chlorides

    Fox, Richard J; Lalic, Gojko; Bergman, Robert G.


    A new, highly regio- and stereospecific SN2' substitution reaction between a zirconium oxo complex and allylic chloride has been achieved. The resulting allylic alcohol or TBS-protected allylic ether products were isolated in good to excellent yields with a wide range of E-allylic chlorides. A mechanism for the SN2' allylic substitution consistent with kinetic, stereochemical and secondary isotope effect studies was proposed.

  9. Amination of allylic alcohols in water at room temperature.

    Nishikata, Takashi; Lipshutz, Bruce H


    The "trick" to carrying out regiocontrolled aminations of allylic alcohols in water as the only medium is use of a nanomicelle's interior as the organic reaction solvent. When HCO(2)Me is present, along with the proper base and source of catalytic Pd, allylic amines are cleanly formed at room temperature.

  10. Catalytic asymmetric generation of (Z)-disubstituted allylic alcohols.

    Salvi, Luca; Jeon, Sang-Jin; Fisher, Ethan L; Carroll, Patrick J; Walsh, Patrick J


    A one-pot method for the direct preparation of enantioenriched (Z)-disubstituted allylic alcohols is introduced. Hydroboration of 1-halo-1-alkynes with dicyclohexylborane, reaction with t-BuLi, and transmetalation with dialkylzinc reagents generate (Z)-disubstituted vinylzinc intermediates. In situ reaction of these reagents with aldehydes in the presence of a catalyst derived from (-)-MIB generates (Z)-disubstituted allylic alcohols. It was found that the resulting allylic alcohols were racemic, most likely due to a rapid addition reaction promoted by LiX (X = Br and Cl). To suppress the LiX-promoted reaction, a series of inhibitors were screened. It was found that 20-30 mol % tetraethylethylenediamine inhibited LiCl without inhibiting the chiral zinc-based Lewis acid. In this fashion, (Z)-disubstituted allylic alcohols were obtained with up to 98% ee. The asymmetric (Z)-vinylation could be coupled with tandem diastereoselective epoxidation reactions to provide epoxy alcohols and allylic epoxy alcohols with up to three contiguous stereogenic centers, enabling the rapid construction of complex building blocks with high levels of enantio- and diastereoselectivity.

  11. Direct activation of allylic alcohols in palladium catalyzed coupling reactions

    Gümrükçü, Y.


    The direct use of allylic alcohols in substitution reactions without pre-activation of the hydroxyl-group into a better leaving group or the use of additional stoichiometric in situ activators remains challenging due to the poor leaving group ability of the hydroxyl-group. Hence, it is important to develop new methods to activate (bio-mass derived) allyl-alcohols, which allow ‘green’ chemical processes for a broad substrate range. This may have a considerable impact on the methodology for fin...

  12. Direct activation of allylic alcohols in palladium catalyzed coupling reactions

    Gümrükçü, Y.


    The direct use of allylic alcohols in substitution reactions without pre-activation of the hydroxyl-group into a better leaving group or the use of additional stoichiometric in situ activators remains challenging due to the poor leaving group ability of the hydroxyl-group. Hence, it is important to

  13. Radiation initiated copolymerization of allyl alcohol with acrylonitrile

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


    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).

  14. Radiation initiated copolymerization of allyl alcohol with acrylonitrile

    Şolpan, Dilek; Güven, Olgun


    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.

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

    H Surya Prakash Rao; S P Senthilkumar


    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.

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

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


    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.

  17. A Mechanistic Study of Direct Activation of Allylic Alcohols in Palladium Catalyzed Amination Reactions

    Yasemin Gumrukcu; Bas de Bruin; Reek, Joost N. H.


    We here report a computational approach on the mechanism of allylicamination reactions using allyl-alcohols and amines as the substrates and phosphoramidite palladium catalyst 1a, which operates in the presence of catalytic amount of 1,3-diethylurea as a co-catalyst. DFT calculations showed a cooperative hydrogen-bonding array between the urea moiety and the hydroxyl group of the allyl alcohol, which strengthens the hydrogen bond between the O-H moiety of the coordinated allyl-alcohol and th...

  18. Direct use of allylic alcohols for platinum-catalyzed monoallylation of amines.

    Utsunomiya, Masaru; Miyamoto, Yoshiki; Ipposhi, Junji; Ohshima, Takashi; Mashima, Kazushi


    A new direct catalytic amination of allylic alcohols promoted by the combination of platinum and a large bite-angle ligand DPEphos was developed in which the allylic alcohol was effectively converted to a pi-allylplatinum intermediate without the use of an activating reagent. The use of the DPEphos ligand was essential for obtaining high catalyst activity and high monoallylation selectivity of primary amines, allowing the formation of a variety of monoallylation products in good to excellent yield.

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

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


    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. Preparation of Stereodefined Homoallylic Amines from the Reductive Cross-Coupling of Allylic Alcohols with Imines

    Chen, Ming Z.; McLaughlin, Martin; Takahashi, Masayuki; Tarselli, Michael A.; Yang, Dexi; Umemura, Shuhei; Micalizio, Glenn C.


    Regio-, diastereo-, and enantioselective coupling reactions between imines and allylic alcohols have been developed. These coupling reactions deliver complex homoallylic amine products through a convergent C–C bond forming process that does not proceed through intermediate allylic organometallic reagents. In general, convergent coupling, by exposure of an allylic alkoxide to a preformed Ti–imine complex, occurs with allylic transposition in a predictable and stereocontrolled manner. While simple diastereoselection in these reactions is high, delivering anti-products with ≥ 20:1 selectivity, the organometallic transformation described is compatible with a diverse range of functionality and substrates (including: aliphatic and aromatic imines, allylic silanes, trisubstituted alkenes, vinyl- and aryl halides, trifluoromethyl groups, thioethers, and aromatic heterocycles). Alkene geometry of the products is a complex function of the allylic alcohol structure, and is consistent with a mechanistic proposal based on syn-carbometalation followed by syn-elimination by way of a boat-like transition state geometry. Single asymmetric coupling reactions provide a means to translate the stereochemical information of the allylic alcohol to the homoallylic amine with very high levels of fidelity, or to control diastereoselection in the coupling reactions of achiral allylic alcohols with chiral imines. Double asymmetric coupling reactions are also described that afford a unique means to control stereoselection in these complex convergent coupling processes. Finally, empirical models are proposed that are consistent with the observed stereochemical course of these coupling reactions en route to chiral homoallylic amines possessing di- or trisubstituted alkenes, and anti- or syn- relative stereochemistry at the allylic and homoallylic positions. Overall, the bond construction enabled by this Ti-mediated reductive cross-coupling is unmatched by available methods in organic

  1. A Mechanistic Study of Direct Activation of Allylic Alcohols in Palladium Catalyzed Amination Reactions

    Yasemin Gumrukcu


    Full Text Available We here report a computational approach on the mechanism of allylicamination reactions using allyl-alcohols and amines as the substrates and phosphoramidite palladium catalyst 1a, which operates in the presence of catalytic amount of 1,3-diethylurea as a co-catalyst. DFT calculations showed a cooperative hydrogen-bonding array between the urea moiety and the hydroxyl group of the allyl alcohol, which strengthens the hydrogen bond between the O-H moiety of the coordinated allyl-alcohol and the carbonyl-moiety of the ligand. This hydrogen bond pattern facilitates the (rate-limiting C-O oxidative addition step and leads to lower energy isomers throughout the catalytic cycle, clarifying the role of the urea-moiety.

  2. Transient overexpression of adh8a increases allyl alcohol toxicity in zebrafish embryos.

    Nils Klüver

    Full Text Available Fish embryos are widely used as an alternative model to study toxicity in vertebrates. Due to their complexity, embryos are believed to more resemble an adult organism than in vitro cellular models. However, concerns have been raised with respect to the embryo's metabolic capacity. We recently identified allyl alcohol, an industrial chemical, to be several orders of magnitude less toxic to zebrafish embryo than to adult zebrafish (embryo LC50 = 478 mg/L vs. fish LC50 = 0.28 mg/L. Reports on mammals have indicated that allyl alcohol requires activation by alcohol dehydrogenases (Adh to form the highly reactive and toxic metabolite acrolein, which shows similar toxicity in zebrafish embryos and adults. To identify if a limited metabolic capacity of embryos indeed can explain the low allyl alcohol sensitivity of zebrafish embryos, we compared the mRNA expression levels of Adh isoenzymes (adh5, adh8a, adh8b and adhfe1 during embryo development to that in adult fish. The greatest difference between embryo and adult fish was found for adh8a and adh8b expression. Therefore, we hypothesized that these genes might be required for allyl alcohol activation. Microinjection of adh8a, but not adh8b mRNA led to a significant increase of allyl alcohol toxicity in embryos similar to levels reported for adults (LC50 = 0.42 mg/L in adh8a mRNA-injected embryos. Furthermore, GC/MS analysis of adh8a-injected embryos indicated a significant decline of internal allyl alcohol concentrations from 0.23-58 ng/embryo to levels below the limit of detection (< 4.6 µg/L. Injection of neither adh8b nor gfp mRNA had an impact on internal allyl alcohol levels supporting that the increased allyl alcohol toxicity was mediated by an increase in its metabolization. These results underline the necessity to critically consider metabolic activation in the zebrafish embryo. As demonstrated here, mRNA injection is one useful approach to study the role of candidate enzymes

  3. Synthesis of (Z)-trisubstituted olefins by decarboxylative grob-type fragmentations: epothilone D, discodermolide, and peloruside A.

    Prantz, Kathrin; Mulzer, Johann


    Methyl-branched (Z)-trisubstituted olefins are found in many polyketides with interesting biological activity, such as epothilone D (1), discodermolide (3), and peloruside A (2). Despite the employment of numerous different strategies, this motif has often been the weak point in total synthesis. Thus, we present a novel hydroxide- induced Grob-type fragmentation as an easy access to trisubstituted olefins. In our case, beta-mesyloxy delta-lactones with three stereogenic centers were chosen whose fragmentation underlies a high stereoelectronic control. Major challenges in the syntheses were the installation of quaternary stereocenters, achieved by enzymatic desymmetrization of meso-diesters and by aluminium-promoted stereoselective rearrangement of chiral epoxides, respectively. Different aldol strategies were developed for the formation of the fragmentation precursors. Additionally a short survey about nucleophilic additions to aldehydes with quaternary alpha-centers is presented.

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

    Manzini, Simone


    [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. A Mechanistic Study of Direct Activation of Allylic Alcohols in Palladium Catalyzed Amination Reactions

    Gumrukcu, Y.; de Bruin, B.; Reek, J.N.H.


    We here report a computational approach on the mechanism of allylicamination reactions using allyl-alcohols and amines as the substrates and phosphoramidite palladium catalyst 1a, which operates in the presence of catalytic amount of 1,3-diethylurea as a co-catalyst. DFT calculations showed a cooper

  6. Cooperative catalysis by palladium and a chiral phosphoric acid: enantioselective amination of racemic allylic alcohols.

    Banerjee, Debasis; Junge, Kathrin; Beller, Matthias


    Cooperative catalysis by [Pd(dba)2] and the chiral phosphoric acid BA1 in combination with the phosphoramidite ligand L8 enabled the efficient enantioselective amination of racemic allylic alcohols with a variety of functionalized amines. This catalytic protocol is highly regio- and stereoselective (up to e.r. 96:4) and furnishes valuable chiral amines in almost quantitative yield.

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

    Wei Ming XU; You Chu ZHANG; Xian HUANG


    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.

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

    Imandi, Venkataramana; Nair, Nisanth N.


    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.

  9. Chemoenzymatic one-pot synthesis in an aqueous medium: combination of metal-catalysed allylic alcohol isomerisation-asymmetric bioamination.

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


    The ruthenium-catalysed isomerisation of allylic alcohols was coupled, for the first time, with asymmetric bioamination in a one-pot process in an aqueous medium. In the cases involving prochiral ketones, the ω-TA exhibited excellent enantioselectivity, identical to that observed in the single step. As a result, amines were obtained from allylic alcohols with high overall yields and excellent enantiomeric excesses.

  10. Epoxidation of allyl alcohol to glycidol over the microporous TS-1 catalyst.

    Wróblewska, Agnieszka; Fajdek, Anna


    The results of the epoxidation of allyl alcohol with 30% hydrogen peroxide over the TS-1 catalyst have been presented. The studies were carried out under the atmospheric pressure and at the presence of methanol as a solvent. The influence of the following technological parameters on the course of epoxidation was examined: the temperature of 20-60 degrees C, the molar ratio of AA/H(2)O(2) 1:1-5:1, the methanol concentration of 5-90 wt%, the catalyst content of 0.1-5.0 wt% and the reaction time 5-300 min. The main functions describing the process were the selectivity to glycidol in relation to allyl alcohol consumed, the conversion of substrates, and the selectivity of transformation to organic compounds in relation to hydrogen peroxide consumed. The parameters at which the functions describing the process reached the highest values were determined.

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

    Mita, Tsuyoshi; Higuchi, Yuki; Sato, Yoshihiro


    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.

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

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


    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)

  13. Synthesis of functionalized epoxides by copper-catalyzed alkylative epoxidation of allylic alcohols with alkyl nitriles.

    Bunescu, Ala; Wang, Qian; Zhu, Jieping


    A copper-catalyzed oxyalkylation of allylic alcohols using nonactivated alkyl nitriles as reaction partners was developed. A sequence involving generation of an alkyl nitrile radical followed by its addition to a double bond and a copper-mediated formation of C(sp(3))-O bond was proposed to account for the reaction outcome. The protocol provided an efficient route to functionalized tri- and tetrasubstituted epoxides via formation of a C(sp(3))-C(sp(3)) and a C(sp(3))-O bond with moderate to excellent diastereoselectivity.

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

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


    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.

  15. Chirality Transfer in Gold(I)-Catalysed Direct Allylic Etherifications of Unactivated Alcohols: Experimental and Computational Study.

    Barker, Graeme; Johnson, David G; Young, Paul C; Macgregor, Stuart A; Lee, Ai-Lan


    Gold(I)-catalysed direct allylic etherifications have been successfully carried out with chirality transfer to yield enantioenriched, γ-substituted secondary allylic ethers. Our investigations include a full substrate-scope screen to ascertain substituent effects on the regioselectivity, stereoselectivity and efficiency of chirality transfer, as well as control experiments to elucidate the mechanistic subtleties of the chirality-transfer process. Crucially, addition of molecular sieves was found to be necessary to ensure efficient and general chirality transfer. Computational studies suggest that the efficiency of chirality transfer is linked to the aggregation of the alcohol nucleophile around the reactive π-bound Au-allylic ether complex. With a single alcohol nucleophile, a high degree of chirality transfer is predicted. However, if three alcohols are present, alternative proton transfer chain mechanisms that erode the efficiency of chirality transfer become competitive.

  16. Characterization of an allylic/benzyl alcohol dehydrogenase from Yokenella sp. strain WZY002, an organism potentially useful for the synthesis of α,β-unsaturated alcohols from allylic aldehydes and ketones.

    Ying, Xiangxian; Wang, Yifang; Xiong, Bin; Wu, Tingting; Xie, Liping; Yu, Meilan; Wang, Zhao


    A novel whole-cell biocatalyst with high allylic alcohol-oxidizing activities was screened and identified as Yokenella sp. WZY002, which chemoselectively reduced the C=O bond of allylic aldehydes/ketones to the corresponding α,β-unsaturated alcohols at 30°C and pH 8.0. The strain also had the capacity of stereoselectively reducing aromatic ketones to (S)-enantioselective alcohols. The enzyme responsible for the predominant allylic/benzyl alcohol dehydrogenase activity was purified to homogeneity and designated YsADH (alcohol dehydrogenase from Yokenella sp.), which had a calculated subunit molecular mass of 36,411 Da. The gene encoding YsADH was subsequently expressed in Escherichia coli, and the purified recombinant YsADH protein was characterized. The enzyme strictly required NADP(H) as a coenzyme and was putatively zinc dependent. The optimal pH and temperature for crotonaldehyde reduction were pH 6.5 and 65°C, whereas those for crotyl alcohol oxidation were pH 8.0 and 55°C. The enzyme showed moderate thermostability, with a half-life of 6.2 h at 55°C. It was robust in the presence of organic solvents and retained 87.5% of the initial activity after 24 h of incubation with 20% (vol/vol) dimethyl sulfoxide. The enzyme preferentially catalyzed allylic/benzyl aldehydes as the substrate in the reduction of aldehydes/ketones and yielded the highest activity of 427 U mg(-1) for benzaldehyde reduction, while the alcohol oxidation reaction demonstrated the maximum activity of 79.9 U mg(-1) using crotyl alcohol as the substrate. Moreover, kinetic parameters of the enzyme showed lower Km values and higher catalytic efficiency for crotonaldehyde/benzaldehyde and NADPH than for crotyl alcohol/benzyl alcohol and NADP(+), suggesting the nature of being an aldehyde reductase.

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


    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.

  18. Direct Nucleophilic Substitution of Free Allylic Alcohols in Water Catalyzed by FeCl3⋅6 H2O: Which is the Real Catalyst?

    Trillo Alarcón, María Paz; Baeza, Alejandro; Nájera Domingo, Carmen


    The allylic substitution reaction, and particularly the direct allylic amination reaction, of free allylic alcohols in water catalyzed by FeCl3⋅6 H2O is described. This novel environmentally-friendly methodology allows the use of a wide variety of nitrogenated nucleophiles such as sulfonamides, carbamates, benzamides, anilines, benzotriazoles, and azides, generally giving good yields of the corresponding substitution products. The synthetic applicability of the process is also demonstrated be...

  19. Efficient, regioselective palladium-catalyzed tandem Heck-isomerization reaction of aryl bromides and non-allylic benzyl alcohols.

    Crawley, Matthew L; Phipps, Kristin M; Goljer, Igor; Mehlmann, John F; Lundquist, Joseph T; Ullrich, John W; Yang, Cuijian; Mahaney, Paige E


    An efficient and mild method to couple aryl bromides and activated non-allylic alcohols in a Heck reaction with tandem isomerization to selectively afford high yields of 1,5-diarylalkan-1-ones has been developed. Mechanistic insight was gained through NMR studies of products derived from deuterium-labeled intermediates.

  20. Epoxidation of olefins and allylic alcohols with hydrogen peroxide catalyzed by heteropoly acids in the presence of cetylpyridinium chloride

    Okabayashi, Takuji; Yamawaki, Kazumasa; Nishihara, Hideki; Yamada, Hiroshi; Ura, Toshikazu; Ishii, Yasutaka; Ogawa, Masaya


    The epoxidation of olefins and allylic alcohols with aqueous hydrogen peroxide could be achieved in good yield when 12-tungustophosphoric acid(WPA) was used with two phase condition using chloroform as the solvent. From the epoxidation result by 12-molybdophosphoric acid(MPA) and WPA catalysts, epoxidation activity of WPA catalyst was found to be remarkably higher than that of MPA. The rate of epoxidation by heteropoly acids catalyst depended markedly upon the activity of the reaction medium. Epoxidation of allylic alcohols with hydrogen peroxide proceeded under mild conditions, resulting good yield of epoxi-alcohols. Epoxidation of olefins by WPA/cetylpyridium chloride was confirmed to be promoted selectively with cheap and pure hydrogen peroxide, resulting good yield. (3 figs, 2 tabs, 18 refs)

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

    Trillo, Paz; Baeza, Alejandro; Nájera, Carmen


    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.

  2. Platinum-catalyzed direct amination of allylic alcohols under mild conditions: ligand and microwave effects, substrate scope, and mechanistic study.

    Ohshima, Takashi; Miyamoto, Yoshiki; Ipposhi, Junji; Nakahara, Yasuhito; Utsunomiya, Masaru; Mashima, Kazushi


    Transition metal-catalyzed amination of allylic compounds via a pi-allylmetal intermediate is a powerful and useful method for synthesizing allylamines. Direct catalytic substitution of allylic alcohols, which forms water as the sole coproduct, has recently attracted attention for its environmental and economical advantages. Here, we describe the development of a versatile direct catalytic amination of both aryl- and alkyl-substituted allylic alcohols with various amines using Pt-Xantphos and Pt-DPEphos catalyst systems, which allows for the selective synthesis of various monoallylamines, such as the biologically active compounds Naftifine and Flunarizine, in good to high yield without need for an activator. The choice of the ligand was crucial toward achieving high catalytic activity, and we demonstrated that not only the large bite-angle but also the linker oxygen atom of the Xantphos and DPEphos ligands was highly important. In addition, microwave heating dramatically affected the catalyst activity and considerably decreased the reaction time compared with conventional heating. Furthermore, several mechanistic investigations, including (1)H and (31)P{(1)H} NMR studies; isolation and characterization of several catalytic intermediates, Pt(xantphos)Cl(2), Pt(eta(2)-C(3)H(5)OH)(xantphos), etc; confirmation of the structure of [Pt(eta(3)-allyl)(xantphos)]OTf by X-ray crystallographic analysis; and crossover experiments, suggested that formation of the pi-allylplatinum complex through the elimination of water is an irreversible rate-determining step and that the other processes in the catalytic cycle are reversible, even at room temperature.

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

    Felipe Augusto Moro Loureiro


    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.

  4. Tandem SN2' nucleophilic substitution/oxidative radical cyclization of aryl substituted allylic alcohols with 1,3-dicarbonyl compounds.

    Zhang, Zhen; Li, Cheng; Wang, Shao-Hua; Zhang, Fu-Min; Han, Xue; Tu, Yong-Qiang; Zhang, Xiao-Ming


    A novel and efficient tandem SN2' nucleophilic substitution/oxidative radical cyclization reaction of aryl substituted allylic alcohols with 1,3-dicarbonyl compounds has been developed by using Mn(OAc)3 as an oxidant, which enables the expeditious synthesis of polysubstituted dihydrofuran (DHF) derivatives in moderate to high yields. The use of weakly acidic hexafluoroisopropanol (HFIP) as the solvent rather than AcOH has successfully improved the yields and expanded the substrate scope of this type of radical cyclization reactions. Mechanistic studies confirmed the cascade reaction process involving a final radical cyclization.

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

    Wróblewska Agnieszka


    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.

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

    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


    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.

  7. Allylation of Aromatic Aldehyde under Microwave Irradiation

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


    @@ 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.

  8. Exciton Coupling in Circular Dichroic Spectroscopy as a Tool for Establishing the Absolute Configuration of alpha,beta-Unsaturated Esters of Allylic Alcohols

    Lauridsen, A.; Cornett, Claus; Christensen, S. B.


    alpha-beta-Unsaturated esters of allylic alcohols have been shown to exhibit exciton coupling by circular dichroic spectroscopy. This coupling permits the establishment of the absolute configuration. The method was used to prove the absolute configuration at C-2 of archangelolide. Detailed NMR sp...

  9. Stereochemistry of Pd(II)-Catalyzed THF Ring Formation of ε-Hydroxy Allylic Alcohols and Synthesis of 2,3,5-Trisubstituted and 2,3,4,5-Tetrasubstituted Tetrahydrofurans.

    Murata, Yuki; Uenishi, Jun'ichi


    Pd(II)-catalyzed ring formation of 2,3,5-trisubstituted and 2,3,4,5-tetrasubstituted tetrahydrofurans is described. Oxypalladation of a chiral ε-hydroxy allylic alcohol provides a 5-alkenyltetrahydrofuran ring in excellent yields via a 5-exo-trigonal process. Nine substrates including six secondary allylic alcohols and three primary allylic alcohols with or without an additional secondary hydroxy substituent at the γ-position have been examined. Their structures are restricted by a 2,2,4,4-tetraisopropyl-1,3,5,2,4-trioxadisilocane ring. The stereochemistry of the resulting tetrahydrofuran products was determined by chemical transformation. The reaction mechanism is discussed on the basis of the stereochemical results. The steps in the chiral allylic alcohol directed or the nucleophilic alcohol directed facial selection for the formation of the alkene-Pd(II)-π-complex, the cis-oxypalladation, and a syn-elimination mechanism account for the observed stereochemistry of the reaction.

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

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


    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".

  11. Facile coupling of propargylic, allylic and benzylic alcohols with allylsilane and alkynylsilane, and their deoxygenation with Et3SiH, catalyzed by Bi(OTf)3 in [BMIM][BF4] ionic liquid (IL), with recycling and reuse of the IL.

    Kumar, G G K S Narayana; Laali, Kenneth K


    Allyltrimethylsilane (allyl-TMS) reacts with propargylic alcohols 1a-1d in the presence of 10% Bi(OTf)(3) in [BMIM][BF(4)] solvent to furnish the corresponding 1,5-enynes in respectable isolated yields (87-93%) at room temperature. The utility of Bi(OTf)(3) as a superior catalyst was demonstrated in a survey study on coupling of allyl-TMS with employing several metallic triflates (Bi, Ln, Al, Yb) as well as, B(C(6)F(5))(3), Zn(NTf(2))(2) and Bi(NO(3))(3)·5H(2)O. Coupling of cyclopropyl substituted propargylic alcohol with allyl-TMS gave the skeletally intact 1,5-enyne and a ring opened derivative as a mixture. Coupling of propargylic/allylic alcohol with allyl-TMS resulted in allylation at both benzylic (2 isomers) and propargylic positions, as major and minor products respectively. The scope of this methodology for allylation of a series of allylic and benzylic alcohols was explored. Chemoselective reduction of a host of propargylic, propagylic/allylic, bis-allylic, allylic, and benzylic alcohols with Et(3)SiH was achieved in high yields with short reaction times. The same approach was successfully applied to couple representative propargylic and allylic alcohols with 1-phenyl-2-trimethylsilylacetylene. The recovery and reuse of the ionic liquid (IL) was gauged in a case study with minimal decrease in isolated yields after six cycles.

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

    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.


    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.

  13. Structure and stability of acrolein and allyl alcohol networks on Ag(111) from density functional theory based calculations with dispersion corrections

    Ferullo, Ricardo M.; Branda, Maria Marta; Illas, Francesc


    The interaction of acrolein and allyl alcohol with the Ag(111) surface has been studied by means of periodic density functional theory based calculations including explicitly dispersion terms. Different coverage values have been explored going from isolated adsorbed molecules to isolated dimers, interacting dimers or ordered overlayers. The inclusion of the dispersion terms largely affects the calculated values of the adsorption energy and also the distance between adsorbed molecule and the metallic surface but much less the adsorbate-adsorbate interactions. Owing to the large dipole moment of acrolein, the present calculations predict that at high coverage this molecule forms a stable extensive two-dimensional network on the surface, caused by the alignment of the adsorbate dipoles. For the case of allyl alcohol, dimers and complex networks exhibit similar stability.

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

    Amankait Asanov


    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.

  15. Enantiodivergent Fluorination of Allylic Alcohols: Data Set Design Reveals Structural Interplay between Achiral Directing Group and Chiral Anion.

    Neel, Andrew J; Milo, Anat; Sigman, Matthew S; Toste, F Dean


    Enantioselectivity values represent relative rate measurements that are sensitive to the structural features of the substrates and catalysts interacting to produce them. Therefore, well-designed enantioselectivity data sets are information rich and can provide key insights regarding specific molecular interactions. However, if the mechanism for enantioselection varies throughout a data set, these values cannot be easily compared. This premise, which is the crux of free energy relationships, exposes a challenging issue of identifying mechanistic breaks within multivariate correlations. Herein, we describe an approach to addressing this problem in the context of a chiral phosphoric acid catalyzed fluorination of allylic alcohols using aryl boronic acids as transient directing groups. By designing a data set in which both the phosphoric and boronic acid structures were systematically varied, key enantioselectivity outliers were identified and analyzed. A mechanistic study was executed to reveal the structural origins of these outliers, which was consistent with the presence of several mechanistic regimes within the data set. While 2- and 4-substituted aryl boronic acids favored the (R)-enantiomer with most of the studied catalysts, meta-alkoxy substituted aryl boronic acids resulted in the (S)-enantiomer when used in combination with certain (R)-phosphoric acids. We propose that this selectivity reversal is the result of a lone pair-π interaction between the substrate ligated boronic acid and the phosphate. On the basis of this proposal, a catalyst system was identified, capable of producing either enantiomer in high enantioselectivity (77% (R)-2 to 92% (S)-2) using the same chiral catalyst by subtly changing the structure of the achiral boronic acid.

  16. Adsorption of acrolein, propanal, and allyl alcohol on Pd(111): a combined infrared reflection-absorption spectroscopy and temperature programmed desorption study.

    Dostert, Karl-Heinz; O'Brien, Casey P; Mirabella, Francesca; Ivars-Barceló, Francisco; Schauermann, Swetlana


    Atomistic-level understanding of the interaction of α,β-unsaturated aldehydes and their derivatives with late transition metals is of fundamental importance for the rational design of new catalytic materials with the desired selectivity towards C[double bond, length as m-dash]C vs. C[double bond, length as m-dash]O bond partial hydrogenation. In this study, we investigate the interaction of acrolein, and its partial hydrogenation products propanal and allyl alcohol, with Pd(111) as a prototypical system. A combination of infrared reflection-absorption spectroscopy (IRAS) and temperature programmed desorption (TPD) experiments was applied under well-defined ultrahigh vacuum (UHV) conditions to obtain detailed information on the adsorption geometries of acrolein, propanal, and allyl alcohol as a function of coverage. We compare the IR spectra obtained for multilayer coverages, reflecting the molecular structure of unperturbed molecules, with the spectra acquired for sub-monolayer coverages, at which the chemical bonds of the molecules are strongly distorted. Coverage-dependent IR spectra of acrolein on Pd(111) point to the strong changes in the adsorption geometry with increasing acrolein coverage. Acrolein adsorbs with the C[double bond, length as m-dash]C and C[double bond, length as m-dash]O bonds lying parallel to the surface in the low coverage regime and changes its geometry to a more upright orientation with increasing coverage. TPD studies indicate decomposition of the species adsorbed in the sub-monolayer regime upon heating. Similar strong coverage dependence of the IR spectra were found for propanal and allyl alcohol. For all investigated molecules a detailed assignment of vibrational bands is reported.

  17. Expression of liver functions following sub-lethal and non-lethal doses of allyl alcohol and acetaminophen in the rat

    Tygstrup, N; Jensen, S A; Krog, B


    , doses producing no and about 30% mortality, respectively, within 2 days. In the morning 2, 6, 12, 24, and 36 h after intoxication, RNA was extracted from liver tissue. By slot blot hybridization mRNA levels were determined for acute phase proteins, enzymes involved in ammonia elimination and urea...... synthesis, and for proteins related to liver regeneration. RESULTS: After allyl alcohol, mRNA of "positive" acute phase proteins was higher than after acetaminophen and increased with the dose, whereas after acetaminophen it decreased with the dose. The mRNA of the urea cycle enzymes and glutamine...

  18. Highly efficient redox isomerisation of allylic alcohols catalysed by pyrazole-based ruthenium(IV) complexes in water: mechanisms of bifunctional catalysis in water.

    Bellarosa, Luca; Díez, Josefina; Gimeno, José; Lledós, Agustí; Suárez, Francisco J; Ujaque, Gregori; Vicent, Cristian


    The catalytic activity of ruthenium(IV) ([Ru(η(3):η(3)-C(10)H(16))Cl(2)L]; C(10)H(16) = 2,7-dimethylocta-2,6-diene-1,8-diyl, L = pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole, 3-methyl-5-phenylpyrazole, 2-(1H-pyrazol-3-yl)phenol or indazole) and ruthenium(II) complexes ([Ru(η(6)-arene)Cl(2)(3,5-dimethylpyrazole)]; arene = C(6)H(6), p-cymene or C(6)Me(6)) in the redox isomerisation of allylic alcohols into carbonyl compounds in water is reported. The former show much higher catalytic activity than ruthenium(II) complexes. In particular, a variety of allylic alcohols have been quantitatively isomerised by using [Ru(η(3):η(3)-C(10)H(16))Cl(2)(pyrazole)] as a catalyst; the reactions proceeded faster in water than in THF, and in the absence of base. The isomerisations of monosubstituted alcohols take place rapidly (10-60 min, turn-over frequency = 750-3000 h(-1)) and, in some cases, at 35 °C in 60 min. The nature of the aqueous species formed in water by this complex has been analysed by ESI-MS. To analyse how an aqueous medium can influence the mechanism of the bifunctional catalytic process, DFT calculations (B3LYP) including one or two explicit water molecules and using the polarisable continuum model have been carried out and provide a valuable insight into the role of water on the activity of the bifunctional catalyst. Several mechanisms have been considered and imply the formation of aqua complexes and their deprotonated species generated from [Ru(η(3):η(3)-C(10)H(16))Cl(2)(pyrazole)]. Different competitive pathways based on outer-sphere mechanisms, which imply hydrogen-transfer processes, have been analysed. The overall isomerisation implies two hydrogen-transfer steps from the substrate to the catalyst and subsequent transfer back to the substrate. In addition to the conventional Noyori outer-sphere mechanism, which involves the pyrazolide ligand, a new mechanism with a hydroxopyrazole complex as the active species can be at work in water. The

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

    Pradipta Sinha; Moloy Banerjee; Abhijit Kundu; Sujit Roy


    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.

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

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


    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

  1. Polymer-incarcerated gold-palladium nanoclusters with boron on carbon: a mild and efficient catalyst for the sequential aerobic oxidation-Michael addition of 1,3-dicarbonyl compounds to allylic alcohols.

    Yoo, Woo-Jin; Miyamura, Hiroyuki; Kobayashi, Shuū


    We have developed a polymer-incarcerated bimetallic Au-Pd nanocluster and boron as a catalyst for the sequential oxidation-addition reaction of 1,3-dicarbonyl compounds with allylic alcohols. The desired tandem reaction products were obtained in good to excellent yields under mild conditions with broad substrate scope. In the course of our studies, we discovered that the excess reducing agent, sodium borohydride, reacts with the polymer backbone to generate an immobilized tetravalent boron catalyst for the Michael reaction. In addition, we found bimetallic Au-Pd nanoclusters to be particularly effective for the aerobic oxidation of allylic alcohols under base- and water-free conditions. The ability to conduct the reaction under relatively neutral and anhydrous conditions proved to be key in maintaining good catalyst activity during recovery and reuse of the catalyst. Structural characterization (STEM, EDS, SEM, and N(2) absorption/desorption isotherm) of the newly prepared PI/CB-Au/Pd/B was performed and compared to PI/CB-Au/Pd. We found that while boron was important for the Michael addition reaction, it was found to alter the structural profile of the polymer-carbon black composite material to negatively affect the allylic oxidation reaction.

  2. Iridium-Catalyzed Allylic Substitution

    Hartwig, John F.; Pouy, Mark J.

    Iridium-catalyzed asymmetric allylic substitution has become a valuable method to prepare products from the addition of nucleophiles at the more substituted carbon of an allyl unit. The most active and selective catalysts contain a phosphoramidite ligand possessing at least one arylethyl substituent on the nitrogen atom of the ligand. In these systems, the active catalyst is generated by a base-induced cyclometalation at the methyl group of this substituent to generate an iridium metalacycle bound by the COD ligand of the [Ir(COD)Cl]2 precursor and one additional labile dative ligand. Such complexes catalyze the reactions of linear allylic esters with alkylamines, arylamines, phenols, alcohols, imides, carbamates, ammonia, enolates and enolate equivalents, as well as typical stabilized carbon nucleophiles generated from malonates and cyanoesters. Iridium catalysts for enantioselective allylic substitution have also been generated from phosphorus ligands with substituents bound by heteroatoms, and an account of the studies of such systems, along with a description of the development of iridium catalysts is included.

  3. An investigation of the Lewis acid mediated 1,3-dipolar cycloaddition between N-benzyl-C-(2-pyridyl)nitrone and allylic alcohol. Direct entry to isoxazolidinyl C-nucleosides.

    Merino, Pedro; Tejero, Tomas; Laguna, Mariano; Cerrada, Elena; Moreno, Ana; Lopez, Jose A


    The cycloaddition reaction of N-benzyl C-(2-pyridyl) nitrone with allylic alcohol has been carried out to obtain the corresponding 2-benzyl-3-(2-pyridyl)-5-hydroxymethylisoxazolidine. The influence of Lewis acids in the reaction has been studied and a complete 3,5-regioselectivity and cis diastereoselectivity was observed when the reaction was carried out with 1.0 equiv of AgOTf, [Ag(OClO3)(PPh2Me)] or Zn(OTf)2. Insight into the mechanism of the reaction has been obtained by isolating and characterizing (X-ray) the intermediate complexes. Also, a model based on both experimental and theoretical results is proposed.


    Rispens, Minze T.; Zondervan, Charon; Feringa, Bernard


    Several chiral Cu(II)-complexes of cyclic amino acids catalyse the enantioselective allylic oxidation of cyclohexene to cyclohexenyl esters. Cyclohexenyl propionate was obtained in 86% yield with e.e.'s up to 61%.

  5. Fe(Ⅲ)催化的烯丙醇的Friedel-Crafts环化反应合成多取代茚%Synthesis of Multisubstituted Indenes by Fe(Ⅲ)-Catalyzed Friedel-Crafts Cyclization of Allylic Alcohols

    张继坦; 张金花; 方旷; 束官莹; 谢美华


    在FeCl3·6H2O催化下,多取代的烯丙醇可以顺利进行分子内Friedel-Crafts环化反应,以中等到优良的产率得到一系列多取代茚化合物,该反应操作简单、反应条件温和.产物结构经IR,1H NMR,13C NMR,HR MS及X射线单晶衍射分析确证.%FeCl3·6H2O-catalyzed intramolecular Friedel-Crafts cyclization of multisubstituted allylic alcohols proceeded smoothly and a series of multisubstituted indenes were synthesized in moderate to high yields. The reaction has the advantages of simple manipulation and mild reaction conditions. The products were characterized by IR, 'H NMR, 13C NMR, HR MS and X-ray diffraction analysis.

  6. Regiospecific decarboxylative allylation of nitriles

    Recio, Antonio; Tunge, Jon A.


    Palladium-catalyzed decarboxylative α-allylation of nitriles readily occurs using Pd2(dba)3 and rac-BINAP. This catalyst mixture also allows the highly regiospecific α-allylation of nitriles in the presence of much more acidic α-protons. Thus, the reported method provides access to compounds that are not readily available via base-mediated allylation chemistries. Lastly, mechanistic investigations indicate that there is a competition between C- and N-allylation of an intermediate nitrile-stabilized anion and that N-allylation is followed by a rapid [3,3]-sigmatropic rearrangement. PMID:19921827

  7. Allyl 4-hydroxyphenyl carbonate

    Víctor Hugo Flores Ahuactzin


    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. Highly selective allylborations of aldehydes using α,α-disubstituted allylic pinacol boronic esters.

    Hesse, Matthew J; Essafi, Stéphanie; Watson, Charlotte G; Harvey, Jeremy N; Hirst, David; Willis, Christine L; Aggarwal, Varinder K


    α,α-Disubstituted allylic pinacol boronic esters undergo highly selective allylborations of aldehydes to give tetrasubstituted homoallylic alcohols with exceptional levels of anti-Z-selectivity (>20:1). The scope of the reaction includes both acyclic and cyclic allylic boronic esters which lead to acyclic and exocyclic tetrasubstituted homoallylic alcohols. The use of β-borylated allylic boronic esters gave fully substituted alkenes bearing a boronic ester which underwent further cross-coupling enabling a highly modular and stereoselective approach to the synthesis of diaryl tetrasubstituted alkenes. Computational analysis revealed the origin of the remarkable selectivity observed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Copper-Catalyzed Enantioselective Allyl-Allyl Cross-Coupling

    Hornillos, Valentin; Perez, Manuel; Fananas-Mastral, Martin; Feringa, Ben L.


    A Cu(I)-phosphoramidite-based catalytic system that allows asymmetric allyl-allyl cross-coupling with high enantioselectivity is reported. This transformation tolerates a large variety of functionalized substrates. The versatility of this new reaction is illustrated in the catalytic asymmetric

  10. Nanoscaled copper metal-organic framework (MOF) based on carboxylate ligands as an efficient heterogeneous catalyst for aerobic epoxidation of olefins and oxidation of benzylic and allylic alcohols.

    Qi, Yue; Luan, Yi; Yu, Jie; Peng, Xiong; Wang, Ge


    Aerobic epoxidation of olefins at a mild reaction temperature has been carried out by using nanomorphology of [Cu3(BTC)2] (BTC = 1,3,5-benzenetricarboxylate) as a high-performance catalyst through a simple synthetic strategy. An aromatic carboxylate ligand was employed to furnish a heterogeneous copper catalyst and also serves as the ligand for enhanced catalytic activities in the catalytic reaction. The utilization of a copper metal-organic framework catalyst was further extended to the aerobic oxidation of aromatic alcohols. The shape and size selectivity of the catalyst in olefin epoxidation and alcohol oxidation was investigated. Furthermore, the as-synthesized copper catalyst can be easily recovered and reused several times without leaching of active species or significant loss of activity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Preconditioning with subneurotoxic allyl nitrile: protection against allyl nitrile neurotoxicity.

    Tanii, H; Higashi, T; Saijoh, K


    High-dose cruciferous allyl nitrile can induce behavioral abnormalities in rodents, while repeated exposure to allyl nitrile at subneurotoxic levels can increase phase 2 detoxification enzymes in many tissues, although the brain has not been investigated yet. In the present study, we examined the effect of 5 days repeated exposure to subneurotoxic allyl nitrile (0-400 micromol/kg/day) on the brain. Elevated glutathione S-transferase activity was recorded in the striatum, hippocampus, medulla oblongata plus pons, and cortex. Enhancement of quinone reductase activity was observed in the medulla oblongata plus pons, hippocampus, and cortex. In the medulla oblongata plus pons, elevated glutathione levels were recorded. Following repeated subneurotoxic allyl nitrile exposure (0-400 micromol/kg/day), mice were administered a high-dose allyl nitrile (1.2 mmol/kg) which alone led to appearance of behavioral abnormalities. Compared with the 0 micromol/kg/day group, animals in the 200 and 400 micromol/kg/day pre-treatment groups exhibited decreased behavioral abnormalities and elevated GABA-positive cell counts in the substantia nigra pars reticulata and the interpeduncular nucleus. These data suggest that repeated exposure to subneurotoxic levels of allyl nitrile can induce phase 2 enzymes in the brain, which together with induction in other tissues, may contribute to protection against allyl nitrile neurotoxicity. Copyright 2009 Elsevier Ltd. All rights reserved.


    ZHANG Zhenfeng; HU Xingzhou; YAN Qing


    Photoinduced grafting of acrylic and allyl monomers on polyethylene surface was generally studied by using benzophenone (BP) as a photoinitiator. The grafting process was carried out either in vapor-phase or in solution of the monomers. In the vapor-phase reaction with a filter used to cut off the short wavelength UV light, allyl amine is the most reactive of the four monomers used and acrylic amide is comparatively more reactive than acrylic acid and allyl alcohol. Acetone, as a solvent and carrier for initiator and monomers, however, shows its reactivity to participate the reaction. The solution grafting with a filter is much faster than the corresponding vapor-phase reaction, and a fully covered surface by the grafted polymer can be achieved in this way.

  13. Catalyst-Free Imidation of Allyl Sulfides with Chloramine-T and Subsequent [2,3]-Sigmatropic Rearrangement

    江玉波; 莫凡洋; 邱迪; 匡春香; 张艳; 王剑波


    A facile synthesis of various allyl sulfonamides based on imidation of allyl sulfides with chloramine-T and sub- sequent [2,3]-sigmatropic rearrangement has been achieved without metal catalysts. The reaction completes smoothly within 10 min, providing excellent yields in environment friendly solvent of alcohol. Functional groups such as bromine, hydroxyl, protected amido and aldehyde are tolerant under this condition.

  14. Scalable and sustainable electrochemical allylic C-H oxidation

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


    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.

  15. Tsuji-Trost N-allylation with allylic acetates using cellulose-Pd catalyst

    Allylic amines are synthesized using heterogeneous cellulose-Pd catalyst via N-allylation of amines; aliphatic and benzyl amines undergo facile reaction with substituted and unsubstituted allyl acetates in high yields.

  16. Formation and reaction of allylic species on silver surfaces: bond-order conservation Morse-potential analysis

    Shustorovich, Evgeny


    The reaction energetics, particularly the intrinsic activation barriers for possible reactions involving allylic species C 3H 5X, X = H, OH, O, Cl on clean and oxygen-preadsorbed Ag surfaces, have been calculated by using the bond-order conservation Morse-potential (BOC-MP) method. The calculations were made for low coverages of C 3H 5X with qualitative corrections for higher coverages. On clean Ag surfaces, propylene C 3H 6 and allyl alcohol C 3H 5OH are projected to desorb without dissociation, in contrast to allyl chloride C 3H 5C1, which is projected to desorb only at high coverages but to dissociate at low coverages forming a stable π-allyl (and atomic chlorine). It is found that the intrinsic activation barrier for dimerization of π-allyl into 1,5-hexadiene is very small and the apparent barrier should be mainly of diffusional character. In the presence of preadsorbed hydroxyl OH s, π-allyl is projected to undergo various transformations producing allyl alcohol, allyl alkoxide, acrolein, and propylene, when most recombination and disproportionation reactions have low intrinsic activation barriers. The BOC-MP model projections are in good agreement with experiment, particularly with the recent HREEL and TPD studies of C 3H 5C1.

  17. Allylic alcohol transposition by ortho ester-initiated carbonate extension. synthesis of the vasodilator 11(R),12(S),15(S)-trihydroxyeicosa- 5(Z),8(Z),13(E)-trienoic acid.

    Conrow, Raymond E


    [reaction: see text] The title compound 1 was obtained via methyl ester 2, which was synthesized in four steps from an isomeric 11,14,15-triol ester 5. In the key step, Boc orthoformate 9 was treated with TMS triflate to initiate intramolecular nucleophilic substitution with allylic transposition, forming cyclic carbonates 10 and 11.

  18. [3,3]-sigmatropic rearrangements of fluorinated allyl (Thio)cyanates - a tool for the synthesis of fluorinated (Thio)ureas.

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


    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.

  19. Oxidation of tertiary homoallylic alcohols by thallium trinitrate: fragmentation versus ring contraction

    Silva Junior, Luiz F.; Quintiliano, Samir A.P.; Ferraz, Helena M.C. [Sao Paulo Univ., SP (Brazil). Inst. de Quimica. Dept. de Quimica Fundamental]. E-mail:; Santos, Leonardo S.; Eberlin, Marcos N. [Universidade Estadual de Campinas, SP (Brazil). Inst. de Quimica


    The oxidation of tertiary homoallylic alcohols with thallium trinitrate (TTN) was investigated. The alcohols bearing an allylic methyl group lose a molecule of acetone via a fragmentation reaction that leads to isomeric secondary allylic alcohols as major products, together with their corresponding acetylated derivatives. On the other hand, treating analogous tertiary alcohols without the allylic methyl group with TTN gives indans, through a ring contraction reaction. (author)

  20. Chiral Phosphoric Acid Catalyzed Enantioselective Allylation of Aldehydes with Allyltrichlorosilane%Chiral Phosphoric Acid Catalyzed Enantioselective Allylation of Aldehydes with Allyltrichlorosilane

    程柯; 范甜甜; 孙健


    Easily accessible chiral phosphoric acid lb has been applied as efficient organocatalyst for the asymmetric al- lylation of aldehydes with allyltrichlorosilane. In the presence of 20 mol% of lb, the allylation of a broad range of aldehydes proceeded smoothly to give the corresponding homoallylic alcohol with up to 87% ee and 97% yield.

  1. Allyl nitrile: Toxicity and health effects.

    Tanii, Hideji


    Allyl nitrile (3-butenenitrile) occurs naturally in the environment, in particular, in cruciferous vegetables, indicating a possible daily intake of the compound. There is no report on actual health effects of allyl nitrile in humans, although it is possible that individuals in the environment are at a risk of exposure to allyl nitrile. However, little is known about its quantitative assessment for the environment and bioactivity in the body. This study provides a review of previous accumulated studies on allyl nitrile. Published literature on allyl nitrile was examined for findings on toxicity, metabolism, risk of various cancers, generation, intake estimates, and low-dose effects in the body. High doses of allyl nitrile produce toxicity characterized by behavioral abnormalities, which are considered to be produced by an active metabolite, 3,4-epoxybutyronitrile. Cruciferous vegetables have been shown to have a potential role in reducing various cancers. Hydrolysis of the glucosinolate sinigrin, rich in cruciferous vegetables, results in the generation of allyl nitrile. An intake of allyl nitrile is estimated at 0.12 μmol/kg body weight in Japan. Repeated exposure to low doses of allyl nitrile upregulates antioxidant/phase II enzymes in various tissues; this may contribute to a reduction in neurotoxicity and skin inflammation. These high and low doses are far more than the intake estimate. Allyl nitrile in the environment is a compound with diverse bioactivities in the body, characterized by inducing behavioral abnormalities at high doses and some antioxidant/phase II enzymes at low doses.

  2. The allylic chalcogen effect in olefin metathesis

    Yuya A. Lin


    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.

  3. The allylic chalcogen effect in olefin metathesis

    Lin, Yuya A


    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

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

    John, Kevin D [Los Alamos National Laboratory; Martin, Richard L [Los Alamos National Laboratory; Obrey, Steven J [Los Alamos National Laboratory; Scott, Brian L [Los Alamos National Laboratory


    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{sup -}}{eta}{sup 1}, {eta}{sup 3} bonding mode; theoretical studies elucidate the role sof the {sigma}- and {pi}-donor ligands in the interplay of metal-allyl and metal-metal bonding.

  5. Efficient synthesis of α,β-unsaturated alkylimines performed with allyl cations and azides: application to the synthesis of an ant venom alkaloid.

    Hayashi, Kyohei; Tanimoto, Hiroki; Zhang, Huan; Morimoto, Tsumoru; Nishiyama, Yasuhiro; Kakiuchi, Kiyomi


    An efficient synthesis of α,β-unsaturated alkylimines at low temperature using azides has been developed. Carbocations generated from allyl alcohols helped achieve a rapid conversion under mild conditions with azides to afford reactive α,β-unsaturated imines. Hydroxy or alkoxy groups are essential for these transformations, and utilizing readily accessible allyl alcohols gave a wide extension of substrates. The efficiency of this novel method is demonstrated in the total synthesis of an iminium ant venom alkaloid.

  6. Allylation of Functionalized Aldehydes by Potassium Allyltrifluoroborate Catalyzed by 18-Crown-6 in Aqueous Media

    Roberta A. Oliveira


    Full Text Available An efficient method for the allylation of aldehydes containing a broad range of functional groups using potassium allyltrifluoroborate is described. The reaction utilizes a catalytic amount of 18-C-6 in biphasic media under open atmosphere and room temperature to provide the corresponding homoallylic alcohols in high yields and without the necessity of any subsequent purification.

  7. Alcohol

    ... that's how many accidents occur. continue What Is Alcoholism? What can be confusing about alcohol is that ... develop a problem with it. Sometimes, that's called alcoholism (say: al-kuh-HOL - ism) or being an ...

  8. Alcohol

    If you are like many Americans, you drink alcohol at least occasionally. For many people, moderate drinking ... risky. Heavy drinking can lead to alcoholism and alcohol abuse, as well as injuries, liver disease, heart ...

  9. Process for the synthesis of unsaturated alcohols

    Maughon, Bob R.; Burdett, Kenneth A.; Lysenko, Zenon


    A process of preparing an unsaturated alcohol (olefin alcohol), such as, a homo-allylic mono-alcohol or homo-allylic polyol, involving protecting a hydroxy-substituted unsaturated fatty acid or fatty acid ester, such as methyl ricinoleate, derived from a seed oil, to form a hydroxy-protected unsaturated fatty acid or fatty acid ester; homo-metathesizing or cross-metathesizing the hydroxy-protected unsaturated fatty acid or fatty acid ester to produce a product mixture containing a hydroxy-protected unsaturated metathesis product; and deprotecting the hydroxy-protected unsaturated metathesis product under conditions sufficient to prepare the unsaturated alcohol. Preferably, methyl ricinoleate is converted by cross-metathesis or homo-metathesis into the homo-allylic mono-alcohol 1-decene-4-ol or the homo-allylic polyol 9-octadecene-7,12-diol, respectively.

  10. A Green Approach for Allylations of Aldehydes and Ketones: Combining Allylborate, Mechanochemistry and Lanthanide Catalyst

    Viviane P. de Souza


    Full Text Available Secondary and tertiary alcohols synthesized via allylation of aldehydes and ketones are important compounds in bioactive natural products and industry, including pharmaceuticals. Development of a mechanochemical method using potassium allyltrifluoroborate salt and water, to successfully perform the allylation of aromatic and aliphatic carbonyl compounds is reported for the first time. By controlling the grinding parameters, the methodology can be selective, namely, very efficient for aldehydes and ineffective for ketones, but by employing lanthanide catalysts, the reactions with ketones can become practically quantitative. The catalyzed reactions can also be performed under mild aqueous stirring conditions. Considering the allylation agent and its by-products, aqueous media, energy efficiency and use of catalyst, the methodology meets most of the green chemistry principles.

  11. 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

    马天奇; 魏天宇; 骈岩杰; 张月成; 赵继全


    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.

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

    Tong, Guanghu


    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.

  13. Alcohol

    Hendriks, H.F.; Tol, A. van


    Alcohol consumption affects overall mortality. Light to moderate alcohol consumption reduces the risk of coronary heart disease; epidemiological, physiological and genetic data show a causal relationship. Light to moderate drinking is also associated with a reduced risk of other vascular diseases an

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

    Zhu, Bo


    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.

  15. Alcohol

    ... changes that come from drinking alcohol can make people do stupid or embarrassing things, like throwing up or peeing on themselves. Drinking also gives people bad breath, and no one enjoys a hangover. ...

  16. Asymmetric Catalysis with CO2 : The Direct α-Allylation of Ketones.

    Pupo, Gabriele; Properzi, Roberta; List, Benjamin


    Quaternary stereocenters are found in numerous bioactive molecules. The Tsuji-Trost reaction has proven to be a powerful C-C bond forming process, and, at least in principle, should be well suited to access quaternary stereocenters via the α-allylation of ketones. However, while indirect approaches are known, the direct, catalytic asymmetric α-allylation of branched ketones has been elusive until today. By combining "enol catalysis" with the use of CO2 as a formal catalyst for asymmetric catalysis, we have now developed a solution to this problem: we report a direct, highly enantioselective and highly atom-economic Tsuji-Trost allylation of branched ketones with allylic alcohol. Our reaction delivers products bearing quaternary stereocenters with high enantioselectivity and water as the sole by-product. We expect our methodology to be of utility in asymmetric catalysis and inspire the design of other highly atom-economic transformations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. [N-allyl-Dmt1]-endomorphins are micro-opioid receptor antagonists lacking inverse agonist properties.

    Marczak, Ewa D; Jinsmaa, Yunden; Li, Tingyou; Bryant, Sharon D; Tsuda, Yuko; Okada, Yoshio; Lazarus, Lawrence H


    [N-allyl-Dmt1]-endomorphin-1 and -2 ([N-allyl-Dmt1]-EM-1 and -2) are new selective micro-opioid receptor antagonists obtained by N-alkylation with an allyl group on the amino terminus of 2',6'-dimethyl-L-tyrosine (Dmt) derivatives. To further characterize properties of these compounds, their intrinsic activities were assessed by functional guanosine 5'-O-(3-[35S]thiotriphosphate) binding assays and forskolin-stimulated cyclic AMP accumulation in cell membranes obtained from vehicle, morphine, and ethanol-treated SK-N-SH cells and brain membranes isolated from naive and morphine-dependent mice; their mode of action was compared with naloxone or naltrexone, which both are standard nonspecific opioid-receptor antagonists. [N-allyl-Dmt1]-EM-1 and -2 were neutral antagonists under all of the experimental conditions examined, in contrast to naloxone and naltrexone, which behave as neutral antagonists only in membranes from vehicle-treated cells and mice but act as inverse agonists in membranes from morphine- and ethanol-treated cells as well as morphine-treated mice. Both endomorphin analogs inhibited the naloxone- and naltrexone-elicited withdrawal syndromes from acute morphine dependence in mice. This suggests their potential therapeutic application in the treatment of drug addiction and alcohol abuse without the adverse effects observed with inverse agonist alkaloid-derived compounds that produce severe withdrawal symptoms.

  18. Synthesis of allyl esters of fatty acids and their ovicidal effect on Cydia pomonella (L.).

    Escribà, Marc; Barbut, Montserrat; Eras, Jordi; Canela, Ramon; Avilla, Jesús; Balcells, Mercè


    Eight allyl esters of fatty acids were synthesized in moderate to high yields with a novel two-step procedure using glycerol as a starting material. The two-step methodology avoids the use of allyl alcohol. The first step consisted of heating at 80 degrees C for 48 h a 2:1:5 mmol mixture of glycerol, a fatty acid, and chlorotrimethylsilane in a solvent-free medium. The crude compound was then dissolved in butanone and heated at 115 degrees C in the presence of NaI. A tandem Finkelstein rearrangement-elimination reaction occurs, producing the corresponding allyl ester. The activity of these esters against Cydia pomonella (L.) (Lepidoptera: Tortricidae) eggs was tested in the laboratory by topical application of one 0.1 microL drop. All of the compounds showed a concentration-mortality response and caused 100% mortality at the highest concentration tested (10 mg/mL). There was an inverse relationship between the alkyl chain length and the ovicidal activity of the allyl ester; the LC(50) and the LC(90) of the two compounds that have the longer alkyl chains were significantly higher than those of the rest of the compounds. The ovicidal and IGR activities of this kind of compound appear to be unprecedented.

  19. Synthesis of 3-Allyl-4-phosphachromones by Cyclized Coupling of Ethyl o-Hydroxyphenyl(ethynyl)phosphinate with Allyl Bromide


    3-Allyl-4-phosphachromones as the phosphorus analogues of chromone were firstly prepared in good yields and high regioselectivity by the palladium(Ⅱ)-catalyzed cyclized coupling reaction of ethyl o-hydroxyphenyl(ethynyl)-phosphinate with allyl bromide.

  20. Rh-Catalyzed Chemo- and Enantioselective Hydrogenation of Allylic Hydrazones.

    Hu, Qiupeng; Hu, Yanhua; Liu, Yang; Zhang, Zhenfeng; Liu, Yangang; Zhang, Wanbin


    A highly efficient P-stereogenic diphosphine-rhodium complex was applied to the chemo- and enantioselective hydrogenation of allylic hydrazones for the synthesis of chiral allylic hydrazines in 89-96 % yields and with 82-99 % ee values. This methodology was successfully applied to the preparation of versatile chiral allylic amine derivatives.

  1. The Allyl Intermediate in Regioselective and Enantioselective Iridium-Catalyzed Asymmetric Allylic Substitution Reactions

    Madrahimov, Sherzod T.; Markovic, Dean; Hartwig, John F.


    The isolation and structural characterization of metallacyclic allyl (2a) and crotyl (2b) iridium complexes are reported. Complexes 2a and 2b are rare examples of iriduim allyl complexes that undergo nucleophilic attack at terminal position, rather than the central position, of the allyl unit. Structures of 2a and 2b were obtained by X-ray diffraction. Nucleophilic attack was observed at the carbon that is bound to iridium trans to phosphorus through a longer Ir-C bond. However, the effect of...

  2. Elementary reaction allyl radical with oxygen

    DONG Feng; KONG Fanao


    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.

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

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


    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.

  4. Palladacyclic imidazoline-naphthalene complexes: synthesis and catalytic performance in Pd(II)-catalyzed enantioselective reactions of allylic trichloroacetimidates.

    Cannon, Jeffrey S; Frederich, James H; Overman, Larry E


    A new family of air- and moisture-stable enantiopure C,N-palladacycles (PIN-acac complexes) were prepared in good overall yield in three steps from 2-iodo-1-naphthoic acid and enantiopure β-amino alcohols. Three of these PIN complexes were characterized by single-crystal X-ray analysis. As anticipated, the naphthalene and imidazoline rings of PIN-acac complexes 18a and 18b were canted significantly from planarity and projected the imidazoline substituents R(1) and R(2) on opposite faces of the palladium square plane. Fifteen PIN complexes were evaluated as catalysts for the rearrangement of prochiral (E)-allylic trichloroacetimidate 19 (eq 2) and the S(N)2' allylic substitution of acetic acid with prochiral (Z)-allylic trichloroacetimidate 23. Although these complexes were kinetically poor catalysts for the Overman rearrangement, they were good catalysts for the allylic substitution reaction, providing branched allylic esters in high yield. However, enantioselectivities were low to moderate and significantly less than that realized with palladacyclic complexes of the COP family. Computational studies support an anti-acetoxypalladation/syn-deoxypalladation mechanism analogous to that observed with COP catalysts. The computational study further suggests that optimizing steric influence in the vicinity of the carbon ligand of a chiral C,N-palladacycle, rather than near the nitrogen heterocycle, is the direction to pursue in future development of improved enantioselective catalysts of this motif.

  5. The allyl intermediate in regioselective and enantioselective iridium-catalyzed asymmetric allylic substitution reactions.

    Madrahimov, Sherzod T; Markovic, Dean; Hartwig, John F


    The isolation and structural characterization of metallacyclic allyl (2a) and crotyl (2b) iridium complexes are reported. Complexes 2a and 2b are rare examples of iriduim allyl complexes that undergo nucleophilic attack at terminal position, rather than the central position, of the allyl unit. Structures of 2a and 2b were obtained by X-ray diffraction. Nucleophilic attack was observed at the carbon that is bound to iridium trans to phosphorus through a longer Ir-C bond. However, the effect of the trans phosphine ligand on the Ir-C bond lengths was smaller than the effect of the substituent on the allyl group in 2b. The competence of complexes 2a and 2b to be intermediates in the catalytic asymmetric allylic substitutions was evaluated by studying their reactivity toward stabilized carbon and heteroatom nucleophiles and comparing the rates and selectivities to those of the catalytic reactions. The stereoselectivity and regioselectivity of stoichiometric reactions of 2b were similar to those of reactions catalyzed by the previously reported iridium catalysts, supporting their intermediacy in the catalytic reactions. On the basis of the structural data, a model is proposed for the origin of stereoselectivity in iridium-catalyzed asymmetric allylic substitution reactions.

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

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


    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.

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

    Thomas Zeuch


    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.


    Gagik Torosyan


    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.

  9. Escherichia coli mutants with a temperature-sensitive alcohol dehydrogenase.

    Lorowitz, W; Clark, D.


    Mutants of Escherichia coli resistant to allyl alcohol were selected. Such mutants were found to lack alcohol dehydrogenase. In addition, mutants with temperature-sensitive alcohol dehydrogenase activity were obtained. These mutations, designated adhE, are all located at the previously described adh regulatory locus. Most adhE mutants were also defective in acetaldehyde dehydrogenase activity.

  10. Direct Conversion of Aldehydes and Ketones to Allylic Halides by a NbX(5-)[3,3] Rearrangement.

    Fleming, Fraser F; Ravikumar, P C; Yao, Lihua


    Sequential addition of vinylmagnesium bromide and NbCl(5), or NbBr(5), to a series of aldehydes and ketones directly provides homologated, allylic halides. Transposition of the intermediate vinyl alkoxide is envisaged through a metalla-halo-[3,3] rearrangement with concomitant delivery of the halogen to the terminal carbon. The [3,3] rearrangement is equally effective for the conversion of a propargyllic alcohol to the corresponding allenyl bromide.

  11. Direct Conversion of Aldehydes and Ketones to Allylic Halides by a NbX5-[3,3] Rearrangement

    Fleming, Fraser F.; Ravikumar, P. C.; Yao, Lihua


    Sequential addition of vinylmagnesium bromide and NbCl5, or NbBr5, to a series of aldehydes and ketones directly provides homologated, allylic halides. Transposition of the intermediate vinyl alkoxide is envisaged through a metalla-halo-[3,3] rearrangement with concomitant delivery of the halogen to the terminal carbon. The [3,3] rearrangement is equally effective for the conversion of a propargyllic alcohol to the corresponding allenyl bromide. PMID:20046989

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

    YUAN Shi-Zhen; LIU Jin


    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.

  13. Use of Cyclic Allylic Bromides in the Zinc–Mediated Aqueous Barbier–Grignard Reaction

    Suzanne M. Perala


    Full Text Available The zinc–mediated aqueous Barbier–Grignard reaction of cyclic allylic bromide substrates with various aldehydes and ketones to afford homoallylic alcohols was investigated. Aromatic aldehydes and ketones afforded adducts in good yields (66–90% and with good diastereoselectivities. Non–aromatic aldehydes also reacted well under these conditions, but only poor yields were obtained with non–aromatic ketones. Regioselectivity was high when some substituted cyclic allylic bromides were investigated.

  14. Green synthesis of allyl isobornyl ether%烯丙基异冰片基醚绿色合成研究

    王士康; 徐徐; 兰蓝; 樊媛媛; 王石发


    以莰烯和烯丙醇为原料,研究了烯丙基异冰片基醚的绿色合成工艺,探讨了催化剂种类及用量、反应温度、反应时间,以及烯丙醇与莰烯物质的量之比对莰烯醚化反应选择性及烯丙基异冰片基醚产物得率的影响.采用正交试验方法确定了烯丙基异冰片基醚的最适工艺条件:A-15型阳离子树脂为催化剂,催化剂用量为烯丙醇和莰烯原料总质量的5%,烯丙醇与莰烯物质的量之比为1.5:1,反应温度75℃,反应时间7h.在此条件下工业莰烯转化率为85.5%,反应选择性为97.5%,烯丙基异冰片基醚得率为83.4%.最后采用GC-MS、IR等分析技术对合成所得产物的结构进行了分析测定.%Green synthetic method of allyl isobornyl ether was investigated by using camphene and allyl alcohol as the raw materials in this paper. Influence of catalysts and their usages, reaction temperature, reaction time, and the molar ratio of allyl alcohol to camphene on the selectivity of etherification and the yield of allyl isobornyl ether were examined, and the optimum synthesis conditions were determined based on the orthogonal test results as follows: A-15 resin was used as the catalyst for etherification, and the amount of A-15 cationic exchange resin was 5 % (based on the total weight of camphene and allyl alcohol) ; molar ratio of allyl alcohol to camphene was 1. 5-1; reaction temperature and reaction time were 75 ℃ and 7 h, respectively. The conversion ratio of camphene and the reaction selectivity reached 85. 5 % and 97. 5 % respectively, and the yield of allyl isobornyl ether also reached 83. 4 %. The structure of allyl isobornyl ether was identified by GC-MS and IR spectra.

  15. Allyl borates: a novel class of polyhomologation initiators

    Wang, De


    Allyl borates, a new class of monofunctional polyhomologation initiators, are reported. These monofunctional initiators are less sensitive and more effective towards polymethylene-based architectures. As an example, the synthesis of α-vinyl-ω-hydroxypolymethylenes is given. By designing/synthesizing different allylic borate initiators, and using 1H and 11B NMR spectroscopy, the initiation mechanism was elucidated.

  16. Radiation and thermal polymerization of allyl(p-allylcarbonate) benzoate

    Lopez-V, D., E-mail: dlopez@siu.buap.m [Facultad de Ciencias Quimicas, Benemerita Universidad Autonoma de Puebla, Antiguo Edificio de la Fac. de Cs., Quimica. Av. San Claudio y Boulevard de la 14 sur, Col. San Manuel, Puebla, Pue., CP 72500 (Mexico); Herrera-G, A.M., E-mail: mherrera@uaeh.reduaeh.m [Centro de Inv. en Materiales y Metalurgia, UAEH. Km 4.5, C.U., CP 42184, Pachuca de S. Hidalgo (Mexico); Castillo-Rojas, S., E-mail: castillo@nucleares.unam.m [Instituto de Ciencias Nucleares, Universidad Nacional Autonoma de Mexico, Circuito Exterior, Ciudad Universitaria, 04510 DF (Mexico)


    Bulk polymerization of novel allyl(p-allylcarbonate) benzoate was investigated using different sources of energy, such as gamma rays, ultraviolet rays as well as thermal polymerization. The poly(allyl(p-allylcarbonate) benzoate) obtained is a cross-linking, transparent, thermoset polycarbonate. Compositions of the monomer and the polycarbonate were analyzed by infrared spectroscopy, elemental analysis, and {sup 1}H NMR spectroscopy.

  17. Screening of allyl alcohol resistant mutant of Rhizopus oryzae and ...



    Jan 19, 2009 ... acidulant, flavour and preservative in the food, pharma- ceutical, leather .... determining the ADH and LDH specific activities, and the others were dried to ... using HPLC by a reversed-phase C18 column as previously reported.

  18. Palladium Catalyzed Allylic C-H Alkylation

    Engelin, Casper Junker; Fristrup, Peter


    -H alkylation reaction which is the topic of the current review. Particular emphasis is put on current mechanistic proposals for the three reaction types comprising the overall transformation: C-H activation, nucleophillic addition, and re-oxidation of the active catalyst. Recent advances in C-H bond activation...... an acetate ion coordinated to Pd. Several of the reported systems rely on benzoquinone for re-oxidation of the active catalyst. The scope for nucleophilic addition in allylic C-H alkylation is currently limited, due to demands on pKa of the nucleophile. This limitation could be due to the pH dependence...

  19. Direct, intermolecular, enantioselective, iridium-catalyzed allylation of carbamates to form carbamate-protected, branched allylic amines.

    Weix, Daniel J; Marković, Dean; Ueda, Mitsuhiro; Hartwig, John F


    The direct reaction between carbamates and achiral allylic carbonates to form branched, conveniently protected primary allylic amines with high regioselectivity and enantioselectivity is reported. This process occurs without base or with 0.5 equiv K(3)PO(4) in the presence of a metalacyclic iridium catalyst containing a labile ethylene ligand. The reactions of aryl-, heteroaryl-, and alkyl-substituted allylic carbonates with BocNH(2), FmocNH(2), CbzNH(2), TrocNH(2), TeocNH(2), and 2-oxazolidinone occur in good yields, with high selectivity for the branched isomer and high enantioselectivities (98% average ee).

  20. Chiral allylic and allenic metal reagents for organic synthesis.

    Marshall, James A


    This account traces the evolution of our work on the synthesis of chiral allylic and allenic organometal compounds of tin, silicon, zinc, and indium and their application to natural product synthesis over the past quarter century.

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

    Hyldtoft, Lene; Madsen, Robert


    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....

  2. Direct aerobic oxidation of primary alcohols to methyl esters catalyzed by a heterogeneous gold catalyst

    Nielsen, Inger Staunstrup; Taarning, Esben; Egeblad, Kresten


    Methyl esters can be produced in high yield by oxidising methanolic solutions of primary alcohols with dioxygen over a heterogeneous gold catalyst. The versatility of this new methodology is demonstrated by the fact that alkylic, benzylic and allylic alcohols, as well as alcohols containing...

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

    Hyldtoft, Lene; Madsen, Robert


    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....

  4. Copper-catalyzed regioselective allylic substitution reactions with indium organometallics.

    Rodríguez, David; Sestelo, José Pérez; Sarandeses, Luis A


    The first nucleophilic allylic substitution reactions of triorganoindium compounds with allylic halides and phosphates are reported. The reactions of trialkyl- and triarylindium reagents with cinnamyl and geranyl halides and phosphates, with the aid of copper catalysis [Cu(OTf)(2)/P(OEt)(3)], are described. In general, the reaction proceeds efficiently to give good yields and regioselectively to afford the S(N)2' product.

  5. Molecular Mechanics and Quantum Chemistry Based Study of Nickel-N-Allyl Urea and N-Allyl Thiourea Complexes

    P. D. Sharma


    Full Text Available Eigenvalue, eigenvector and overlap matrix of nickel halide complex of N-allyl urea and N-allyl thiourea have been evaluated. Our results indicate that ligand field parameters (Dq, B’ and β evaluated earlier by electronic spectra are very close to values evaluated with the help of eigenvalues and eigenvectors. Eigenvector analysis and population analysis shows that in bonding 4s, 4p, and 3dx2-y2, 3dyz orbitals of nickel are involved but the coefficient values differ in different complexes. Out of 4px, 4py, 4pz the involvement of either 4pz or 4py, is noticeable. The theoretically evaluated positions of infrared bands indicate that N-allyl urea is coordinated to nickel through its oxygen and N-allyl thiourea is coordinated to nickel through its sulphur which is in conformity with the experimental results.

  6. Alcoholism and Alcohol Abuse

    ... their drinking causes distress and harm. It includes alcoholism and alcohol abuse. Alcoholism, or alcohol dependence, is a disease that causes ... groups. NIH: National Institute on Alcohol Abuse and Alcoholism

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

    Lichtenberg, Crispin; Okuda, Jun


    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.

  8. A convenient method for lactonization of α-allyl esters using iodine ...

    A convenient method for lactonization of α-allyl esters using iodine in dimethyl- sulphoxide. ... KEY WORDS: γ-Butyrolactones, α-Allyl esters, Iodine, Dimethyl sulphoxide. Bull. Chem. Soc. Ethiop. 2014, 28(3) ... Article Metrics. Metrics Loading .

  9. SnCl2/Cu-Mediated Carbonyl Allylation Reaction in Water:Scope,Selectivity and Mechanism

    TAN,Xiang-Hui(谭翔晖); HOU,Yong-Quan(侯永泉); LIU,Lei(刘磊); GUO,Qing-Xiang(郭庆祥)


    Copper was found to be able to promote the SnC12-mediated carbonyl allylation reactions in water,giving the corresponding homoallylic alcohol products in very high yields.Detailed studies showed that the reaction could be applied to a variety of carbonyl compounds including those with hydroxyl,amino and nitro groups.It was also found that this reaction showed good regioselectivities for some substrates.Furthermore,carefully controled experiments and in situ NMR measurements provided important insights into the mechanism of the newly developed reaction.

  10. Catalytic Enantioselective Allylic Amination of Olefins for the Synthesis of ent-Sitagliptin.

    Bao, Hongli; Bayeh, Liela; Tambar, Uttam K


    The presence of nitrogen atoms in most chiral pharmaceutical drugs has motivated the development of numerous strategies for the synthesis of enantioenriched amines. Current methods are based on the multi-step transformation of pre-functionalized allylic electrophiles into chiral allylic amines. The enantioselective allylic amination of unactivated olefins represents a more direct and attractive strategy. We report the enantioselective synthesis of ent-sitagliptin via an allylic amination of an unactivated terminal olefin.

  11. Redox-Neutral Rh(III)-Catalyzed Olefination of Carboxamides with Trifluoromethyl Allylic Carbonate.

    Park, Jihye; Han, Sangil; Jeon, Mijin; Mishra, Neeraj Kumar; Lee, Seok-Yong; Lee, Jong Suk; Kwak, Jong Hwan; Um, Sung Hee; Kim, In Su


    The rhodium(III)-catalyzed olefination of various carboxamides with α-CF3-substituted allylic carbonate is described. This reaction provides direct access to linear CF3-allyl frameworks with complete trans-selectivity. In particular, a rhodium catalyst provided Heck-type γ-CF3-allylation products via the β-O-elimination of rhodacycle intermediate and subsequent olefin migration process.

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


    ... 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 (P-91...

  13. Titanium-promoted Allyl Transfer to Carbon Monoxide and Other Unsaturated Molecules

    Klei, Bert; Teuben, Jan H.; Liefde Meijer, Henk J. de


    Carbonylation of Cp2Ti-(π-allyl) yields Cp2Ti(CO)2 and triallylmethanol; reactions of Cp2Ti-(π-allyl) and Cp2Ti-(π-1-methylallyl) with other ligands proceed via insertion or allyl-elimination pathways.

  14. Tribromoisocyanuric acid/triphenylphosphine: a new system for conversion of alcohols into alkyl bromides

    Andrade, Vitor S.C. de; Mattos, Marcio C.S. de, E-mail: [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Instituto de Quimica. Departamento de Quimica Organica


    An efficient and facile method has been developed for the conversion of alcohols into alkyl bromides under neutral conditions using tribromoisocyanuric acid and triphenylphosphine (molar ratio 1.0:0.7:2.0, alcohol/tribromoisocyanuric acid/triphenylphosphine) in dichloromethane at room temperature. This method can be applied for the conversion of primary, secondary, benzilic and allylic alcohols, and their corresponding bromides are obtained in 67-82 % yield. Tertiary alcohols do not react under these conditions. (author)

  15. Selective bromochlorination of a homoallylic alcohol for the total synthesis of (−)-anverene

    Seidl, Frederick J


    Summary The scope of a recently reported method for the catalytic enantioselective bromochlorination of allylic alcohols is expanded to include a specific homoallylic alcohol. Critical factors for optimization of this reaction are highlighted. The utility of the product bromochloride is demonstrated by the first total synthesis of an antibacterial polyhalogenated monoterpene, (−)-anverene. PMID:27559385

  16. Sulfonium-based Ionic Liquids Incorporating the Allyl Functionality

    Paul J. Dyson


    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.

  17. Single pulse shock tube study of allyl radical recombination.

    Fridlyand, Aleksandr; Lynch, Patrick T; Tranter, Robert S; Brezinsky, Kenneth


    The recombination and disproportionation of allyl radicals has been studied in a single pulse shock tube with gas chromatographic measurements at 1-10 bar, 650-1300 K, and 1.4-2 ms reaction times. 1,5-Hexadiene and allyl iodide were used as precursors. Simulation of the results using derived rate expressions from a complementary diaphragmless shock tube/laser schlieren densitometry study provided excellent agreement with precursor consumption and formation of all major stable intermediates. No significant pressure dependence was observed at the present conditions. It was found that under the conditions of these experiments, reactions of allyl radicals in the cooling wave had to be accounted for to accurately simulate the experimental results, and this unusual situation is discussed. In the allyl iodide experiments, higher amounts of allene, propene, and benzene were found at lower temperatures than expected. Possible mechanisms are discussed and suggest that iodine containing species are responsible for the low temperature formation of allene, propene, and benzene.

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

    Waldvogel, Siegfried R; Selt, Maximilian


    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.

  19. 1-Allyl-5-chloroindoline-2,3-dione

    Zineb Tribak


    Full Text Available In the title compound, C11H8ClNO2, the allyl side chain is almost perpendicular to the 5-chloroindoline-2,3-dione ring system, with a dihedral angle of 88.0 (3°. In the crystal, C—H...O interactions link the molecules into layers lying parallel to the bc plane.


    Kennedy, J.


    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.

  1. Rh2(esp)2-catalyzed allylic and benzylic oxidations.

    Wang, Yi; Kuang, Yi; Wang, Yuanhua


    The dirhodium(II) catalyst Rh2(esp)2 allows direct solvent-free allylic and benzylic oxidations by T-HYDRO with a remarkably low catalyst loading. This method is operationally simple and scalable at ambient temperature without the use of any additives. The high catalyst stability in these reactions may be attributed to a dirhodium(II,II) catalyst resting state, which is less prone to decomposition.

  2. An Unexpected Reaction of Allylic Propynoate under Palladium(Ⅱ) Catalysis

    ZHANG,Zhao-Guo(张兆国); LU,Xi-Yan(陆熙炎); LANG,Shen-Hui(郎深慧)


    Palladium (Ⅱ) catalyzed reactions of allyl propynoate in the presence of excess halide ions with or without allyl halide or acrolein were studied, yielding (E)-3-halo-2-allyl-acrylic acid as the sole product. A mechanism involving halopalladation, carbopalladation, ring opening and β-heteroatom elimination was prioposed and was further justified by the reaction with deuterated substrate.keywords palladium, enyne, halopalladation, carbopalladation,β-heteroatom elimination was proposed and was further justified by the reaction with deuterated substrate.

  3. Silver-Catalyzed Decarboxylative Allylation of Aliphatic Carboxylic Acids in Aqueous Solution.

    Cui, Lei; Chen, He; Liu, Chao; Li, Chaozhong


    Direct decarboxylative radical allylation of aliphatic carboxylic acids is described. With K2S2O8 as the oxidant and AgNO3 as the catalyst, the reactions of aliphatic carboxylic acids with allyl sulfones in aqueous CH3CN solution gave the corresponding alkenes in satisfactory yields under mild conditions. This site-specific allylation method is applicable to all primary, secondary, and tertiary alkyl acids and exhibits wide functional group compatibility.

  4. Allyl strontium compounds: synthesis, molecular structure and properties.

    Jochmann, Phillip; Davin, Julien P; Maslek, Stefanie; Spaniol, Thomas P; Sarazin, Yann; Carpentier, Jean-Francois; Okuda, Jun


    The synthesis and attempted isolation of neutral bis(allyl)strontium [Sr(C(3)H(5))(2)] (1) resulted in the isolation of potassium tris(allyl)strontiate K[Sr(C(3)H(5))(3)] (2). In situ generated 1 shows a pronounced Brønsted basicity, inducing polymerisation of THF. Ate complex 2 crystallises as [K(THF)(2){Sr(C(3)H(5))(3)}(THF)](∞) (2·(THF)(3)). The salt-like solid state structure of 2·(THF)(3) comprises a two-dimensional network of (μ(2)-η(3):η(3)-C(3)H(5))(-) bridged potassium and strontium centres. Synthesis of allyl complexes 1 and 2 utilised SrI(2), [Sr(TMDS)(2)] (3) (TMDS = tetramethyldisilazanide), and [Sr(HMDS)(2)] (HMDS = hexamethyldisilazanide) as strontium precursors. The solid state structure of previously reported [Sr(TMDS)(2)] (3) was established by X-ray single crystal analysis as a dissymmetric dimer of [Sr(2)(TMDS)(4)(THF)(3)] (3·(THF)(3)) with multiple Si-HSr agostic interactions. The presence of ether ligands (THF, 18-crown-6) influenced the Si-HSr resonances in the NMR spectra of the amido complex 3.

  5. Mechanism of the Suzuki–Miyaura Cross-Coupling Reaction Mediated by [Pd(NHC)(allyl)Cl] Precatalysts

    Meconi, Giulia Magi


    Density functional theory calculations have been used to investigate the activation mechanism for the precatalyst series [Pd]-X-1–4 derived from [Pd(IPr)(R-allyl)X] species by substitutions at the terminal position of the allyl moiety ([Pd] = Pd(IPr); R = H (1), Me (2), gem-Me2 (3), Ph (4), X = Cl, Br). Next, we have investigated the Suzuki–Miyaura cross-coupling reaction for the active catalyst species IPr-Pd(0) using 4-chlorotoluene and phenylboronic acid as substrates and isopropyl alcohol as a solvent. Our theoretical findings predict an upper barrier trend, corresponding to the activation mechanism for the [Pd]-Cl-1–4 series, in good agreement with the experiments. They indeed provide a quantitative explanation of the low yield (12%) displayed by [Pd]-Cl-1 species (ΔG⧧ ≈ 30.0 kcal/mol) and of the high yields (≈90%) observed in the case of [Pd]-Cl-2–4 complexes (ΔG⧧ ≈ 20.0 kcal/mol). Additionally, the studied Suzuki–Miyaura reaction involving the IPr-Pd(0) species is calculated to be thermodynamically favorable and kinetically facile. Similar investigations for the [Pd]-Br-1–4 series, derived from [Pd(IPr)(R-allyl)Br], indicate that the oxidative addition step for IPr-Pd(0)-mediated catalysis with 4-bromotoluene is kinetically more favored than that with 4-chlorotoluene. Finally, we have explored the potential of Ni-based complexes [Ni((IPr)(R-allyl)X] (X = Cl, Br) as Suzuki–Miyaura reaction catalysts. Apart from a less endergonic reaction energy profile for both precatalyst activation and catalytic cycle, a steep increase in the predicted upper energy barriers (by 2.0–15.0 kcal/mol) is calculated in the activation mechanism for the [Ni]-X-1–4 series compared to the [Pd]-X-1–4 series. Overall, these results suggest that Ni-based precatalysts are expected to be less active than the Pd-based precatalysts for the studied Suzuki–Miyaura reaction.

  6. Catalyst-free synthesis of skipped dienes from phosphorus ylides, allylic carbonates, and aldehydes via a one-pot SN2' allylation-Wittig strategy.

    Xu, Silong; Zhu, Shaoying; Shang, Jian; Zhang, Junjie; Tang, Yuhai; Dou, Jianwei


    A catalyst-free allylic alkylation of stabilized phosphorus ylides with allylic carbonates via a regioselective SN2' process is presented. Subsequent one-pot Wittig reaction with both aliphatic and aromatic aldehydes as well as ketenes provides structurally diverse skipped dienes (1,4-dienes) in generally high yields and moderate to excellent stereoselectivity with flexible substituent patterns. This one-pot SN2' allylation-Wittig strategy constitutes a convenient and efficient synthetic method for highly functionalized skipped dienes from readily available starting materials.

  7. Direct Substitution of the Hydroxy Group at the Allylic/propargylic Position with Carbon-and Heteroatomcentered Nucleophiles Catalyzed by Yb(OTf)3

    HUANG Wen; SHEN Quan-Sheng; WANG Jia-Liang; ZHOU Xi-Geng


    An efficient and highly selective Yb(OTf)3-catalyzed direct substitution of the hydroxy group at the allylic and propargylic positions with a variety of heteroatom- and carbon-centered nucleophiles, such as alcohols, thiols,amines, amides and active methylene compounds has been developed. The advantages of the present catalytic system are wide availability of the starting materials, especially for tolerance to thiols, no need for dried solvents and additives, mild conditions, short time of reaction, simple manipulation and environmentally friendly catalyst that can be recovered and reused at least ten times without significant reduction of activity.

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

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


    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...

  9. Corn oil and milk enhance the absorption of orally administered allyl isothiocyanate in rats.

    Ippoushi, Katsunari; Ueda, Hiroshi; Takeuchi, Atsuko


    Allyl isothiocyanate, a chief component of mustard oil, exhibits anticancer effects in both cultured cancer cells and animal models. The accumulation of the N-acetylcysteine conjugate of allyl isothiocyanate, the final metabolite of allyl isothiocyanate, in urine was evaluated in rats that were orally coadministered allyl isothiocyanate with fluids (e.g., water, green tea, milk, and 10% ethanol) or corn oil. The N-acetylcysteine conjugate of allyl isothiocyanate content in urine when allyl isothiocyanate (2 or 4μmol) was coadministered with corn oil or milk showed a greater increase (1.4±0.22 or 2.7±0.34μmol or 1.2±0.32 or 2.5±0.36μmol, 1.6- to 1.8-fold or 1.5-fold, respectively) than when allyl isothiocyanate (2 or 4μmol) was coadministered with water (0.78±0.10 or 1.7±0.17μmol). This result demonstrates that corn oil and milk enhance the absorption of allyl isothiocyanate in rats.

  10. Catalytic membrane-installed microchannel reactors for one-second allylic arylation.

    Yamada, Yoichi M A; Watanabe, Toshihiro; Torii, Kaoru; Uozumi, Yasuhiro


    A variety of catalytic membranes of palladium-complexes with linear polymer ligands were prepared inside a microchannel reactor via coordinative and ionic molecular convolution to provide catalytic membrane-installed microdevices, which were applied to the instantaneous allylic arylation reaction of allylic esters and aryl boron reagents under microflow conditions to afford the corresponding coupling products within 1 second of residence time.

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

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


    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.

  12. P ' CP '-Pincer palladium complex-catalyzed allylation of N,N-dimethylsulfamoyl-protected aldimines

    Li, Jie; Minnaard, Adriaan J.; Gebbink, Robertus J. M. Klein; van Koten, Gerard


    The P'CP'-pincer palladium complex-catalyzed allylation of N,N-dimethylsulfamoyl-protected aldimines with allyl(tributyl)stannane is investigated for the preparation of N-homoallylic sulfamides. The desired N,N-dimethylsulfamoyl-protected products are obtained in moderate to high yields in DMF under

  13. Reactivity of Phenol Allylation Using Phase-Transfer Catalysis in Ion-Exchange Membrane Reactor

    Ho Shing Wu


    Full Text Available This study investigates the reactivity of phenol allylation using quaternary ammonium salt as a phase-transfer catalyst in three types of membrane reactors. Optimum reactivity and turnover of phenol allylation were obtained using a respond surface methodology. The contact angle, water content, and degree of crosslinkage were measured to understand the microenvironment in the ion exchange membrane.

  14. Copper-Catalyzed SN2'-Selective Allylic Substitution Reaction of gem-Diborylalkanes.

    Zhang, Zhen-Qi; Zhang, Ben; Lu, Xi; Liu, Jing-Hui; Lu, Xiao-Yu; Xiao, Bin; Fu, Yao


    A Cu/(NHC)-catalyzed SN2'-selective substitution reaction of allylic electrophiles with gem-diborylalkanes is reported. Different substituted gem-diborylalkanes and allylic electrophiles can be employed in this reaction, and various synthetic valuable functional groups can be tolerated. The asymmetric version of this reaction was initially researched with chiral N-heterocyclic carbene (NHC) ligands.

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

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


    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.

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

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


    @@ 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.

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

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


    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.

  18. Release and antibacterial activity of allyl isothiocyanate/β-cyclodextrin complex encapsulated in electrospun nanofibers.

    Aytac, Zeynep; Dogan, Sema Y; Tekinay, Turgay; Uyar, Tamer


    Allyl isothiocyanate (AITC) is known as an efficient antibacterial agent but it has a very high volatility. Herein, AITC and AITC/β-cyclodextrin (CD)-inclusion complex (IC) incorporated in polyvinyl alcohol (PVA) nanofibers were produced via electrospinning. SEM images elucidated that incorporation of AITC and AITC/β-CD-IC into polymer matrix did not affect the bead-free fiber morphology of PVA nanofibers. (1)H-NMR and headspace GC-MS analyses revealed that very low amount of AITC was remained in PVA/AITC-NF because of the rapid evaporation of AITC during the electrospinning process. Nevertheless, much higher amount of AITC was preserved in the PVA/AITC/β-CD-IC-NF due to the CD inclusion complexation. The sustained release of AITC from nanofibers was evaluated at 30°C, 50°C and 75°C via headspace GC-MS. When compared to PVA/AITC-NF, PVA/AITC/β-CD-IC-NF has shown higher antibacterial activity against Escherichia coli and Staphylococcus aureus due to the presence of higher amount of AITC in this sample which was preserved by CD-IC.

  19. Palladium Catalyzed Allylic C-H Alkylation: A Mechanistic Perspective

    Casper Junker Engelin


    Full Text Available 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-H alkylation reaction which is the topic of the current review. Particular emphasis is put on current mechanistic proposals for the three reaction types comprising the overall transformation: C-H activation, nucleophillic addition, and re-oxidation of the active catalyst. Recent advances in C-H bond activation are highlighted with emphasis on those leading to C-C bond formation, but where it was deemed necessary for the general understanding of the process closely related C-H oxidations and aminations are also included. It is found that C-H cleavage is most likely achieved by ligand participation which could involve an acetate ion coordinated to Pd. Several of the reported systems rely on benzoquinone for re-oxidation of the active catalyst. The scope for nucleophilic addition in allylic C-H alkylation is currently limited, due to demands on pKa of the nucleophile. This limitation could be due to the pH dependence of the benzoquinone/hydroquinone redox couple. Alternative methods for re-oxidation that does not rely on benzoquinone could be able to alleviate this limitation.

  20. Allylation of intraerythrocytic hemoglobin by raw garlic extracts.

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


    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 covalently modified intraerythrocytic deoxygenated hemoglobin. The modification identified consisted of an addition of 71 atomic mass units, suggesting allylation of the cysteine residues. Consistently, purified human deoxyhemoglobin reacted with chemically pure diallyl disulfide, showing the same modification as garlic extracts. Tandem mass spectrometry analysis demonstrated that garlic extract and diallyl disulfide modified hemoglobin's beta-chain at cysteine-93 (beta-93C) or cysteine-112 (beta-112C). These results indicate that garlic-derived organic disulfides as well as pure diallyl disulfide must permeate the RBC membrane and modified deoxyhemoglobin at beta-93C or beta-112C. Although the physiological role of the reported garlic extract-induced allyl modification on human hemoglobin warrants further study, the results indicate that constituents of natural products, such as those from garlic extract, modify intracellular proteins.

  1. Do garlic-derived allyl sulfides scavenge peroxyl radicals?

    Amorati, Riccardo; Pedulli, Gian Franco


    The chain-breaking antioxidant activities of two garlic-derived allyl sulfides, i.e. diallyl disulfide (1), the main component of steam-distilled garlic oil, and allyl methyl sulfide (3) were evaluated by studying the thermally initiated autoxidation of cumene or styrene in their presence. Although the rate of cumene oxidation was reduced by addition of both 1 and 3, the dependence on the concentration of the two sulfides could not be explained on the basis of the classic antioxidant mechanism as with phenolic antioxidants. The rate of oxidation of styrene, on the other hand, did not show significant changes upon addition of either 1 or 3. This unusual behaviour was explained in terms of the co-oxidant effect, consisting in the decrease of the autoxidation rate of a substrate forming tertiary peroxyl radicals (i.e. cumene) upon addition of little amounts of a second oxidizable substrate giving rise instead to secondary peroxyl radicals. The relevant rate constants for the reaction of ROO(.) with 1 and 3 were measured as 1.6 and 1.0 M(-1) s(-1), respectively, fully consistent with the H-atom abstraction from substituted sulfides. It is therefore concluded that sulfides 1 and 3 do not scavenge peroxyl radicals and therefore cannot be considered chain-breaking antioxidants.

  2. Tungstosilicic Acid: An Efficient and Ecofriendly Catalyst for the Conversion of Alcohols to Alkyl Iodides

    Masoud Mokhtary


    Full Text Available Treatment of a range of benzylic, allylic, and secondary aliphatic alcohols with potassium iodides in the presence of H4SiW12O40 affords the corresponding alkyl iodides in good to excellent yield with straightforward purification at room temperature in CH3CN.

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  4. Highly stereoselective synthesis of functionalized 1,3-dienes from a new allyl bromide

    Asma Fray


    Full Text Available New and highly functionalized 1,3-dienes 3 and 4 have been synthesized via two different pathways starting from allyl bromide 1. Firstly, the reaction of allyl bromide 1 with triethylphosphite leads to an allylphosphonate 2, which undergoes the Wittig-Horner reaction with a range of saturated and unsaturated aldehydes gives rise to the corresponding 1,3-dienes 3. Secondly, a highly stereoselective reaction between allyl bromide 1 and nitroalkane salts, offers the possibility to obtaining functionalized (E-1,3-dienes 4.

  5. Chemoselective allylation of ketones in ionic liquids containing sulfonate anions.

    Galletti, Paola; Moretti, Fabio; Samorì, Chiara; Tagliavini, Emilio


    The chemoselective addition of tetraallyltin to dialkyl, alkenyl-alkyl, and alkynyl-alkyl ketones can be performed with high yields in N-methyl-N-butylpyrrolidinium trifuoromethansulfonate (MBP-Tf). Other room temperature ionic liquids (RTILs) can also be successfully employed if some sulfonic acid is added. The reaction is very sensitive to the electronic properties of the substrate. Aryl alkyl ketones bearing electron-withdrawing substituents behave like dialkyl ketones and react promptly; on the contrary, electron-rich aryl alkyl ketones react sluggishly, which allows selective competitive allylation of dialkyl substrates to occur. The ionic liquid solvent can be easily recycled, which meets the green chemistry principles of selectivity and reuse of chemicals. NMR spectroscopic data support the formation of tin-triflate catalysts in situ.

  6. Sequence-defined polymers via orthogonal allyl acrylamide building blocks.

    Porel, Mintu; Alabi, Christopher A


    Biological systems have long recognized the importance of macromolecular diversity and have evolved efficient processes for the rapid synthesis of sequence-defined biopolymers. However, achieving sequence control via synthetic methods has proven to be a difficult challenge. Herein we describe efforts to circumvent this difficulty via the use of orthogonal allyl acrylamide building blocks and a liquid-phase fluorous support for the de novo design and synthesis of sequence-specific polymers. We demonstrate proof-of-concept via synthesis and characterization of two sequence-isomeric 10-mer polymers. (1)H NMR and LCMS were used to confirm their chemical structure while tandem MS was used to confirm sequence identity. Further validation of this methodology was provided via the successful synthesis of a sequence-specific 16-mer polymer incorporating nine different monomers. This strategy thus shows promise as an efficient approach for the assembly of sequence-specific functional polymers.

  7. Aerobic Linear Allylic C-H Amination: Overcoming Benzoquinone Inhibition.

    Pattillo, Christopher C; Strambeanu, Iulia I; Calleja, Pilar; Vermeulen, Nicolaas A; Mizuno, Tomokazu; White, M Christina


    An efficient aerobic linear allylic C-H amination reaction is reported under palladium(II)/bis-sulfoxide/Brønsted base catalysis. The reaction operates under preparative, operationally simple conditions (1 equiv of olefin, 1 atm O2 or air) with reduced Pd(II)/bis-sulfoxide catalyst loadings while providing higher turnovers and product yields than systems employing stoichiometric benzoquinone (BQ) as the terminal oxidant. Pd(II)/BQ π-acidic interactions have been invoked in various catalytic processes and are often considered beneficial in promoting reductive functionalizations. When such electrophilic activation for functionalization is not needed, however, BQ at high concentrations may compete with crucial ligand (bis-sulfoxide) binding and inhibit catalysis. Kinetic studies reveal an inverse relationship between the reaction rate and the concentration of BQ, suggesting that BQ is acting as a ligand for Pd(II) which results in an inhibitory effect on catalysis.

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

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


    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.

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

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


    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.

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

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

    Laboratory incubation of alkenone mixtures with tert-butyl hydroperoxide and di-tert-butyl nitroxide (radical initiator) in hexane, as a means to simulate alkenone autoxidation processes, rapidly led to the formation of allylic hydroperoxides, whose...

  11. Origins of Enantioselectivity during Allylic Substitution Reactions Catalyzed by Metallacyclic Iridium Complexes

    Madrahimov, Sherzod T.; Hartwig, John F.


    In depth mechanistic studies of iridium catalyzed regioselective and enantioselective allylic substitution reactions are presented. A series of cyclometallated allyliridium complexes that are kinetically and chemically competent to be intermediates in the allylic substitution reactions was prepared and characterized by 1D and 2D NMR spectroscopies and solid state structural analysis. The rates of epimerization of the less thermodynamically stable diastereomeric allyliridium complexes to the t...

  12. Diene-ligated iridium catalyst for allylation reactions of ketones and imines.

    Barker, Timothy J; Jarvo, Elizabeth R


    [Ir(cod)Cl](2) is a highly reactive catalyst for allylation reactions of ketones using allylboronic ester. Mechanistic experiments are consistent with formation of a nucleophilic allyliridium(I) complex that is activated by the diene ligand toward attack of a ketone. Aryl and alkyl ketones react smoothly at room temperature. Aldimines also undergo allylation under these reaction conditions, requiring increased reaction times relative to the corresponding ketones.

  13. A Concomitant Allylic Azide Rearrangement/Intramolecular Azide–Alkyne Cycloaddition Sequence


    An intramolecular Huisgen cycloaddition of an interconverting set of isomeric allylic azides with alkynes affords substituted triazoles in high yield. The stereoisomeric vinyl-substituted triazoloxazines formed depend on the rate of cycloaddition of the different allylic azide precursors when the reaction is carried out under thermal conditions. In contrast, dimerized macrocyclic products were obtained when the reaction was done using copper(I)-catalyzed conditions, demonstrating the ability to control the reaction products through changing conditions. PMID:24635056

  14. A concomitant allylic azide rearrangement/intramolecular azide-alkyne cycloaddition sequence.

    Vekariya, Rakesh H; Liu, Ruzhang; Aubé, Jeffrey


    An intramolecular Huisgen cycloaddition of an interconverting set of isomeric allylic azides with alkynes affords substituted triazoles in high yield. The stereoisomeric vinyl-substituted triazoloxazines formed depend on the rate of cycloaddition of the different allylic azide precursors when the reaction is carried out under thermal conditions. In contrast, dimerized macrocyclic products were obtained when the reaction was done using copper(I)-catalyzed conditions, demonstrating the ability to control the reaction products through changing conditions.

  15. Catalytic allylic oxidation of internal alkenes to a multifunctional chiral building block

    Bayeh, Liela; Le, Phong Q.; Tambar, Uttam K.


    The stereoselective oxidation of hydrocarbons is one of the most notable advances in synthetic chemistry over the past fifty years. Inspired by nature, enantioselective dihydroxylations, epoxidations and other oxidations of unsaturated hydrocarbons have been developed. More recently, the catalytic enantioselective allylic carbon-hydrogen oxidation of alkenes has streamlined the production of pharmaceuticals, natural products, fine chemicals and other functional materials. Allylic functionalization provides a direct path to chiral building blocks with a newly formed stereocentre from petrochemical feedstocks while preserving the olefin functionality as a handle for further chemical elaboration. Various metal-based catalysts have been discovered for the enantioselective allylic carbon-hydrogen oxidation of simple alkenes with cyclic or terminal double bonds. However, a general and selective allylic oxidation using the more common internal alkenes remains elusive. Here we report the enantioselective, regioselective and E/Z-selective allylic oxidation of unactivated internal alkenes via a catalytic hetero-ene reaction with a chalcogen-based oxidant. Our method enables non-symmetric internal alkenes to be selectively converted into allylic functionalized products with high stereoselectivity and regioselectivity. Stereospecific transformations of the resulting multifunctional chiral building blocks highlight the potential for rapidly converting internal alkenes into a broad range of enantioenriched structures that can be used in the synthesis of complex target molecules.

  16. Effect of allyl isothiocyanate on developmental toxicity in exposed Xenopus laevis embryos

    John Russell Williams


    Full Text Available The pungent natural compound allyl isothiocyanate isolated from the seeds of Cruciferous (Brassica plants such as mustard is reported to exhibit numerous beneficial health-promoting antimicrobial, antifungal, anticarcinogenic, cardioprotective, and neuroprotective properties. Because it is also reported to damage DNA and is toxic to aquatic organisms, the objective of the present study was to determine whether it possesses teratogenic properties. The frog embryo teratogenesis assay-Xenopus (FETAX was used to determine the following measures of developmental toxicity of the allyl isothiocyanate: (a 96-h LC50, defined as the median concentration causing 50% embryo lethality; (b 96-h EC50, defined as the median concentration causing 50% malformations of the surviving embryos; and (c teratogenic malformation index (TI, equal to 96-h LC50/96-h EC50. The quantitative results and the photographs of embryos before and after exposure suggest that allyl isothiocyanate seems to exhibit moderate teratogenic properties. The results also indicate differences in the toxicity of allyl isothiocyanate toward exposed embryos observed in the present study compared to reported adverse effects of allyl isothiocyanate in fish, rodents, and humans. The significance of the results for food safety and possible approaches to protect against adverse effects of allyl isothiocyanate are discussed.

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  18. Cp*Rh(III)-Catalyzed Low Temperature C-H Allylation of N-Aryl-trichloro Acetimidamide.

    Debbarma, Suvankar; Bera, Sourav Sekhar; Maji, Modhu Sudan


    The readily synthesized trichloro acetimidamide was found to be an excellent directing group for the directed C-H-allylation reactions. Depending on the allylating agent used, selectively either mono- or diallylated products were readily synthesized. Moreover, the trichloro acetimidamide directing group was found to be highly efficient even at lower temperature for the C-H-allylation reaction. Due to mildness of the reaction conditions, double bond isomerization or cyclization to indole side product was not observed.

  19. Gold-catalyzed intermolecular coupling of sulfonylacetylene with allyl ethers: [3,3]- and [1,3]-rearrangements

    Jungho Jun


    Full Text Available Gold-catalyzed intermolecular couplings of sulfonylacetylenes with allyl ethers are reported. A cooperative polarization of alkynes both by a gold catalyst and a sulfonyl substituent resulted in an efficient intermolecular tandem carboalkoxylation. Reactions of linear allyl ethers are consistent with the [3,3]-sigmatropic rearrangement mechanism, while those of branched allyl ethers provided [3,3]- and [1,3]-rearrangement products through the formation of a tight ion–dipole pair.

  20. Origins of Regioselectivity in Iridium Catalyzed Allylic Substitution.

    Madrahimov, Sherzod T; Li, Qian; Sharma, Ankit; Hartwig, John F


    Detailed studies on the origin of the regioselectivity for formation of branched products over linear products have been conducted with complexes containing the achiral triphenylphosphite ligand. The combination of iridium and P(OPh)3 was the first catalytic system shown to give high regioselectivity for the branched product with iridium and among the most selective for forming branched products among any combination of metal and ligand. We have shown the active catalyst to be generated from [Ir(COD)Cl]2 and P(OPh)3 by cyclometalation of the phenyl group on the ligand and have shown such species to be the resting state of the catalyst. A series of allyliridium complexes ligated by the resulting P,C ligand have been generated and shown to be competent intermediates in the catalytic system. We have assessed the potential impact of charge, metal-iridium bond length, and stability of terminal vs internal alkenes generated by attack at the branched and terminal positions of the allyl ligand, respectively. These factors do not distinguish the regioselectivity for attack on allyliridium complexes from that for attack on allylpalladium complexes. Instead, detailed computational studies suggest that a series of weak, attractive, noncovalent interactions, including interactions of H-bond acceptors with a vinyl C-H bond of the alkene ligand, favor formation of the branched product with the iridium catalyst. This conclusion underscores the importance of considering attractive interactions, as well as repulsive steric interactions, when seeking to rationalize selectivities.

  1. Allyl isothiocyanate induced stress response in Caenorhabditis elegans

    Saini AkalRachna K


    Full Text Available 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 seed was improved to allow the measurement of AITC release in the first minutes after exposure of ground mustard seed to water. Using this assay, we determined that temperatures above 67°C decreased sinigrin conversion to AITC in hydrated ground B. juncea seed. A pH near 6.0 was found to be necessary for AITC release. RT-qPCR revealed no significant change in HSP70A mRNA expression at low concentrations of AITC ( 1.0 μM resulted in a four- to five-fold increase in expression. A HSP70 ELISA showed that AITC toxicity in C. elegans was ameliorated by the presence of ground seed from low sinigrin B. juncea cv. Arrid. Conclusions • AITC induced toxicity in C. elegans, as measured by HSP70 expression. • Conditions required for the conversion of sinigrin to AITC in ground B. juncea seed were determined. • The use of C. elegans as a bioassay to test AITC or mustard biopesticide efficacy is discussed.

  2. SN2 reactions with allylic substrates--Trends in reactivity

    Ochran, Richard A.; Uggerud, Einar


    The gas-phase identity SN2 reactions of allylic substrates has been studied by systematic altering of the nucleophile/nucleofuge X, the remote substituent Y, and the number of methyl substituents at the reaction centre: X- + YCHCHCZ2X --> YCHCHCZ2X + X- (X = H, CH3, NH2, F, Cl; Y = F, OH, H, CHO, BH2; Z = H, CH3). Key regions of the potential energy surfaces have been explored by MP2, B3LYP, G3B3 and G3 calculations; the latter two methods providing accurate estimates of the reaction barrier. The calculations show that irrespective of theoretical level, for the second row of the periodic table (X = CH3, NH2, OH, and F), the tendency is that the barrier height decreases in going from left to right in agreement with the previously observed trend for identity SN2 reactions at methyl. The barrier height decreases by introduction a [pi] electron withdrawing substituents, Y, remote 6rom the reaction centre. The barrier height increases by introducing methyl groups (Z = CH3) next to the reaction centre, but the effect is less than half of that of changing the remote substituent from Y = CHO to Y = OH. The trends cannot be explained by simplified valence bond theory and are discussed in light of a simple electrostatic bonding model of the transition structure.

  3. Allyl isothiocyanate enhances shelf life of minimally processed shredded cabbage.

    Banerjee, Aparajita; Penna, Suprasanna; Variyar, Prasad S


    The effect of allyl isothiocyanate (AITC), in combination with low temperature (10°C) storage on post harvest quality of minimally processed shredded cabbage was investigated. An optimum concentration of 0.05μL/mL AITC was found to be effective in maintaining the microbial and sensory quality of the product for a period of 12days. Inhibition of browning was shown to result from a down-regulation (1.4-fold) of phenylalanine ammonia lyase (PAL) gene expression and a consequent decrease in PAL enzyme activity and o-quinone content. In the untreated control samples, PAL activity increased following up-regulation in PAL gene expression that could be linearly correlated with enhanced o-quinone formation and browning. The efficacy of AITC in extending the shelf life of minimally processed shredded cabbage and its role in down-regulation of PAL gene expression resulting in browning inhibition in the product is reported here for the first time. Copyright © 2015 Elsevier Ltd. All rights reserved.

  4. Mesoporous Metal Complex–Silica Aerogels for Environmentally Friendly Amination of Allylic Alcohols

    Grau Atienza, Aida; Baeza, Alejandro; Serrano, Elena; Garcia-Martinez, Javier; Nájera Domingo, Carmen


    Two series of mesoporous hybrid iron(III) complex–silica aerogels were prepared in one-pot synthesis by using the sol–gel coordination chemistry approach. The use of the ligands 3-(2-aminoethylamino)propyltrimethoxysilane and 2-(diphenylphosphino)ethyltriethoxysilane, both with terminal triethoxysilyl groups, were used to incorporate metal complexes in situ into the framework of silica, through their co-condensation with a silicon alkoxide during the aerogel formation. This methodology yielde...


    I Made Sudarma


    Full Text Available The aim of this preliminary research was to synthesize derivatives of eugenol such as 4-allyl-2-methoxy-6-nitrophenol (2 and 4-allyl-2-methoxy-6-aminophenol (3. The result could be used as a reference on the transformation of eugenol to its derivatives. Theoriticaly nitration of eugenol (1 by nitric acid could produced 4-allyl-2-methoxy-6-nitrophenol (2 and followed by reduction could achieved 4-allyl-2-mehtoxy-6-aminophenol (3. The formation of this product was analyzed by analytical thin layer chromatography (TLC and GC-MS. These analysis showed the formation of product (2 and (3 were visible. TLC showed product (1 less polar than eugenol and gave orange colour, and supported by GC-MS which showed molecular ion at m/z 209 due to the presence of -NO2 by replacing one H at 6 position of eugenol. Product (3 was afforded by reduction of (2 with Sn/HCl and tlc analysis showed compound (3 more polar than eugenol (1 and (2 and supported by GC-MS which showed molecular ion at m/z 179 due to the presence of -NH2.   Keywords: Synthesis, 4-allyl-2-methoxy-6-aminophenol, Eugenol

  6. Bis(μ-N,N-di-allyl-dithio-carbamato)bis[(N,N-di-allyl-dithio-carbamato)cadmium].

    Onwudiwe, Damian C; Hrubaru, Madalina; Hosten, Eric C; Arderne, Charmaine


    The title compound, [Cd2(C7H10NS2)4], is a neutral dinuclear cadmium(II) complex bearing four bis N,N-di-allyl-di-thio-carbamate ligands coordinating to two Cd(II) cations. In each of the monomeric subunits, there are four S atoms of two di-thio-carbamate ligands [Cd-S = 2.5558 (3), 2.8016 (3), 2.6050 (3) and 2.5709 (3) Å] that coordinate to one Cd(II) atom in a bidentate mode. The dimers are located over an inversion centre bridged by two additional bridging Cd-S bonds [2.6021 (3) Å], leading to a substantial distortion of the geometry of the monomeric subunit from the expected square-planar geometry. The five-coordinate environment around each of the Cd(II) ions in the dimer is best described as substanti-ally tetra-gonally distorted square pyramidal. The di-thio-carbamate groups are themselves planar and are also coplanar with the Cd(II) ions. The negative charge on these groups is delocalized by resonance across the S atoms bound to the Cd(II) cation. This delocalization of the π electrons in the di-thio-carbamate groups also extends to the C-N bonds as they reveal significant double bond character [C-N = 1.3213 (16) and 1.3333 (15) Å].

  7. An Efficient Synthesis of de novo Imidates via Aza-Claisen Rearrangements of N-Allyl Ynamides.

    Dekorver, Kyle A; North, Troy D; Hsung, Richard P


    A novel thermal 3-aza-Claisen rearrangement of N-allyl ynamides for the synthesis of α-allyl imidates is described. Also, a sequential aza-Claisen, Pd-catalyzed Overman rearrangement is described for the synthesis of azapine-2-ones.

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

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


    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...... reactions with carbon, nitrogen, and oxygen nucleophiles. In this latter step, the respective (E) and (Z) alkene substrate isomers were observed to react with opposite stereospecificity: the (E) alkene reacted with retention and the (Z) alkene with inversion of stereochemistry with respect to both...... the allylic stereocenter and the alkene geometry. Thus, a single $gamma@-substituted ester was obtained as the overall product, in high isomeric purity. The method was applied to a synthesis of a subunit of the iejimalides, a group of cytotoxic macrolides....

  9. Allyl isothiocyanate sensitizes TRPV1 to heat stimulation.

    Alpizar, Yeranddy A; Boonen, Brett; Gees, Maarten; Sanchez, Alicia; Nilius, Bernd; Voets, Thomas; Talavera, Karel


    The powerful plant-derived irritant allyl isothiocyanate (AITC, aka mustard oil) induces hyperalgesia to heat in rodents and humans through mechanisms that are not yet fully understood. It is generally believed that AITC activates the broadly tuned chemosensory cation channel transient receptor potential cation channel subfamily A member 1 (TRPA1), triggering an inflammatory response that sensitizes the heat sensor transient receptor potential cation channel subfamily V member 1 (TRPV1). In the view of recent data demonstrating that AITC can directly activate TRPV1, we here explored the possibility that this compound sensitizes TRPV1 to heat stimulation in a TRPA1-independent manner. Patch-clamp recordings and intracellular Ca(2+) imaging experiments in HEK293T cells over-expressing mouse TRPV1 revealed that the increase in channel activation induced by heating is larger in the presence of AITC than in control conditions. The analysis of the effects of AITC and heat on the current-voltage relationship of TRPV1 indicates that the mechanism of sensitization is based on additive shifts of the voltage dependence of activation towards negative voltages. Finally, intracellular Ca(2+) imaging experiments in mouse sensory neurons isolated from Trpa1 KO mice yielded that AITC enhances the response to heat, specifically in the subpopulation expressing TRPV1. Furthermore, this effect was strongly reduced by the TRPV1 inhibitor capsazepine and virtually absent in neurons isolated from double Trpa1/Trpv1 KO mice. Taken together, these findings demonstrate that TRPV1 is a locus for cross sensitization between AITC and heat in sensory neurons and may help explaining, at least in part, the role of this channel in AITC-induced hyperalgesia to heat.

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

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


    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.

  11. Biphilic Organophosphorus Catalysis: Regioselective Reductive Transposition of Allylic Bromides via PIII/PV Redox Cycling

    Reichl, Kyle D.; Dunn, Nicole L.; Fastuca, Nicholas J.; Radosevich, Alexander T.


    We report that a regioselective reductive transposition of primary allylic bromides is catalyzed by a biphilic organophosphorus (phosphetane) catalyst. Spectroscopic evidence supports the formation of a pentacoordinate (σ5-P) hydridophosphorane as a key reactive intermediate. Kinetics experiments and computational modeling are consistent with a unimolecular decomposition of the σ5-P hydridophosphorane via a concerted cyclic transition structure that delivers the observed allylic transposition and completes a novel PIII/PV redox catalytic cycle. These results broaden the growing repertoire of reactions catalyzed within the PIII/PV redox couple and suggest additional opportunities for organophosphorus catalysis in a biphilic mode. PMID:25874950

  12. Origins of enantioselectivity during allylic substitution reactions catalyzed by metallacyclic iridium complexes.

    Madrahimov, Sherzod T; Hartwig, John F


    In depth mechanistic studies of iridium catalyzed regioselective and enantioselective allylic substitution reactions are presented. A series of cyclometalated allyliridium complexes that are kinetically and chemically competent to be intermediates in the allylic substitution reactions was prepared and characterized by 1D and 2D NMR spectroscopies and single-crystal X-ray difraction. The rates of epimerization of the less thermodynamically stable diastereomeric allyliridium complexes to the thermodynamically more stable allyliridium stereoisomers were measured. The rates of nucleophilic attack by aniline and by N-methylaniline on the isolated allyliridium complexes were also measured. Attack on the thermodynamically less stable allyliridium complex was found to be orders of magnitude faster than attack on the thermodynamically more stable complex, yet the major enantiomer of the catalytic reaction is formed from the more stable diastereomer. Comparison of the rates of nucleophilic attack to the rates of epimerization of the diastereomeric allyliridium complexes containing a weakly coordinating counterion showed that nucleophilic attack on the less stable allyliridium species is much faster than conversion of the less stable isomer to the more stable isomer. These observations imply that Curtin-Hammett conditions are not met during iridium catalyzed allylic substitution reactions by η(3)-η(1)-η(3) interconversion. Rather, these data imply that when these conditions exist for this reaction, they are created by reversible oxidative addition, and the high selectivity of this oxidative addition step to form the more stable diastereomeric allyl complex leads to the high enantioselectivity. The stereochemical outcome of the individual steps of allylic substitution was assessed by reactions of deuterium-labeled substrates. The allylic substitution was shown to occur by oxidative addition with inversion of configuration, followed by an outer sphere nucleophilic attack

  13. Additive-Free Pd-Catalyzed α-Allylation of Imine-Containing Heterocycles.

    Kljajic, Marko; Puschnig, Johannes G; Weber, Hansjörg; Breinbauer, Rolf


    An additive-free Pd-catalyzed α-allylation of different imino-group-ontaining heterocycles is reported. The activation of α-CH pronucleophiles (pKa (DMSO) > 25) occurs without the addition of strong bases or Lewis acids using only the Pd/Xantphos catalyst system. The reaction scope has been studied for various 5- and 6-membered nitrogen-containing heterocycles (yields up to 96%). Mechanistic investigations suggest an initial allylation of the imine-N followed by a Pd-catalyzed formal aza-Claisen rearrangement.

  14. FeCl3 catalysed regioselective allylation of phenolic substrates with (-hydroxy)allylphosphonates

    Mandala Anitha; Ramesh Kotikalapudi; K C Kumara Swamy


    Electrophilic allylation of phenolic substrates including salicylaldehydes with (-hydroxy) allylphosphonates is presented. It is observed that catalytic FeCl3 is sufficient to accomplish the allylation. Interestingly, the reaction led to the formation of allylphosphonates in addition to vinylphosphonates, depending upon the substituent. The vinylphosphonates obtained here are -isomers. More importantly, the reaction occurred regioselectively with respect to the phenolic substrates. Substituted allylphosphonates are formed when salicylaldehyde or (2-hydroxy-phenyl)arylmethanones are used. Conclusive proof for the formation of allylphosphontates as well as vinylphosphonates has been provided by single crystal X-ray crystallography.

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

    Antonio Monopoli


    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.

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

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


    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...

  17. A Novel, One-Step Palladium and Phenylsilane Activated Amidation from Allyl Ester on Solid Support

    Zheming Ruan


    Full Text Available The direct conversion of solid-supported carboxylic acid allyl esters to carboxamides through the use of phenylsilane and catalytic Pd(PPh34 under mild reaction conditions is reported. The use of this methodology for the generation of a 48 compound solid-phase array is described herein.

  18. Reductive coupling reaction of benzyl, allyl and alkyl halides in aqueous medium promoted by zinc

    Sá Ana C. P. F. de


    Full Text Available Organic halides undergo reductive dimerization (Wurtz-type coupling promoted by zinc at room temperature in aqueous medium. The reaction yields are strongly enhanced by copper catalysis. This coupling procedure provides an efficient and simple method for the homocoupling of benzylic and allylic bromides and primary alkyl iodides.

  19. Asymmetric synthesis of N,O-heterocycles via enantioselective iridium-catalysed intramolecular allylic amidation

    Zhao, Depeng; Fananas-Mastral, Martin; Chang, Mu-Chieh; Otten, Edwin; Feringa, Ben L.


    Chiral N,O-heterocycles were synthesized in high yields and excellent enantioselectivity up to 97% ee via iridium-catalysed intramolecular allylic substitution with nucleophilic attack by the amide oxygen atom. The resulting benzoxazine derivatives were further transformed into challenging chiral

  20. Catalytic allylation of phenols : chloride-free route towards epoxy resins

    Rijn, Jimmy Antonius van


    An industrially applicable process was developed for the synthesis of epoxy resin components. A catalytic reaction was explored towards allyl phenyl ethers that prevents the use of chloride-containing starting materials and thus formation of chloride-containing side products. The preferred allylatin

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

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


    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) indi...

  2. A convenient method for lactonization of α-allyl esters using iodine in dimethyl- sulphoxide

    B. R. Nawghare


    Full Text Available A simple method for the synthesis of α-γ-disubstituted-γ-butyrolactones by cyclization of α-allyl esters using iodine in dimethylsulphoxide is reported. This method is efficient and operationally simple in comparison to methods using transition metal complexes. DOI:

  3. Method of preparing water purification membranes. [polymerization of allyl amine as thin films in plasma discharge

    Hollahan, J. R.; Wydeven, T. J., Jr. (Inventor)


    Allyl amine and chemically related compounds are polymerized as thin films in the presence of a plasma discharge. The monomer compound can be polymerized by itself or in the presence of an additive gas to promote polymerization and act as a carrier. The polymerized films thus produced show outstanding advantages when used as reverse osmosis membranes.

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

    Hang Zhang


    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%.

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

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


    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.

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

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


    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.

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

    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: [Department of Chemistry, National Cheng Kung University, Tainan 701, Taiwan (China)


    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.

  8. Palladium-catalyzed cross-coupling reactions of allylic halides and acetates with indium organometallics.

    Rodríguez, David; Pérez Sestelo, José; Sarandeses, Luis A


    The palladium(0)-catalyzed cross-coupling reaction of allylic halides and acetates with indium organometallics is reported. In this synthetic transformation, triorganoindium compounds and tetraorganoindates (aryl, alkenyl, and methyl) react with cinnamyl and geranyl halides and acetates to afford the S(N)2 product regioselectively and in good yield. The reaction proceeds with net inversion of the stereochemical configuration.

  9. Facile Formation of Ytterbium Diiodide and Its Use in the Synthesis of Allyl Selenides

    SU,Wei-Ke(苏为科); ZHANG,Yong-Min(张永敏); ZHENG,Yun-Fa(郑云法); LI,Yong-Shu(李永曙)


    Ytterbium metal reacts with iodine to generate ytterbium diiodide directly, which can react with diselenides to form ytterbium selenolates (RSeYbI2). These species reacted smoothly with allyl bromide to give allylselenides in moderate to good yields under neutral conditions.

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

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


    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...

  11. Copper-catalyzed asymmetric allylic substitution reactions with organozinc and Grignard reagents

    Geurts, Koen; Fletcher, Stephen P.; van Zijl, Anthoni W.; Minnaard, Adriaan J.; Feringa, Ben L.; Bignall, H. E.; Jauncey, D. L.; Lovell, J. E. J.; Tzioumis, A. K.; Kedziora-Chudczer, L. L.; MacQuart, J. P.; Tingay, S. J.; Rayner, D. P.; Clay, R. W.


    Asymmetric allylic alkylations (AAAs) are among the most powerful C-C bond-forming reactions. We present a brief overview of copper-catalyzed AAAs with organometallic reagents and discuss our own contributions to this field. Work with zinc reagents and phosphoramidite ligands provided a framework fo

  12. National Institute on Alcohol Abuse and Alcoholism

    Skip to main content National Institute on Alcohol Abuse and Alcoholism (NIAAA) Main Menu Search Search form Search Alcohol & Your Health Overview of Alcohol Consumption Alcohol's Effects on the Body Alcohol Use ...

  13. Synthesis, Characterization, and Some Properties of Cp*W(NO)(H)(η(3)-allyl) Complexes.

    Baillie, Rhett A; Holmes, Aaron S; Lefèvre, Guillaume P; Patrick, Brian O; Shree, Monica V; Wakeham, Russell J; Legzdins, Peter; Rosenfeld, Devon C


    Sequential treatment at low temperatures of Cp*W(NO)Cl2 in THF with 1 equiv of a binary magnesium allyl reagent, followed by an excess of LiBH4, affords three new Cp*W(NO)(H)(η(3)-allyl) complexes, namely, Cp*W(NO)(H)(η(3)-CH2CHCMe2) (1), Cp*W(NO)(H)(η(3)-CH2CHCHPh) (2), and Cp*W(NO)(H)(η(3)-CH2CHCHMe) (3). Complexes 1-3 are isolable as air-stable, analytically pure yellow solids in good to moderate yields by chromatography or fractional crystallization. In solutions, complex 1 exists as two coordination isomers in an 83:17 ratio differing with respect to the endo/exo orientation of the allyl ligand. In contrast, complexes 2 and 3 each exist as four coordination isomers, all differing by the orientation of their allyl ligands which can have either an endo or an exo orientation with the phenyl or methyl groups being either proximal or distal to the nitrosyl ligand. A DFT computational analysis using the major isomer of Cp*W(NO)(H)(η(3)-CH2CHCHMe) (3a) as the model complex has revealed that its lowest-energy thermal-decomposition pathway involves the intramolecular isomerization of 3a to the 16e η(2)-alkene complex, Cp*W(NO)(η(2)-CH2═CHCH2Me). Such η(2)-alkene complexes are isolable as their 18e PMe3 adducts when compounds 1-3 are thermolyzed in neat PMe3, the other organometallic products formed during these thermolyses being Cp*W(NO)(PMe3)2 (5) and, occasionally, Cp*W(NO)(H)(η(1)-allyl)(PMe3). All new complexes have been characterized by conventional spectroscopic and analytical methods, and the solid-state molecular structures of most of them have been established by single-crystal X-ray crystallographic analyses.

  14. Highly enantio- and diastereoselective synthesis of β-methyl-γ- monofluoromethyl-substituted alcohols

    Yang, Wenguo


    Enanatiopure β-methyl-γ-monofluoromethyl alcohols were prepared from the allylic alkylation between fluorobis(phenylsulfonyl)methane with Morita-Baylis-Hillman carbonates. The reaction was catalyzed by using the Cinchona alkaloid derivative, (DHQD)2AQN. The origin of the stereoselectivity was verified by DFT methods. Calculated geometries and relative energies of various transition states strongly support the observed stereoselectivity. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. The magnesium-ene cyclization stereochemically directed by an allylic oxyanionic group and its application to a highly stereoselective synthesis of (+/-)-matatabiether. Allylmagnesium compounds by reductive magnesiation of allyl phenyl sulfides.

    Cheng, D; Zhu, S; Yu, Z; Cohen, T


    The first example of a magnesium-ene cyclization stereochemically directed by an allylic oxyanionic group is demonstrated by a highly stereoselective synthesis of the bicyclic terpene matatabiether 10. The synthetic method is particularly valuable, not only because of the stereochemical control and the utility of the versatile hydroxyl group introduced into the product, but also because the precursor of the allylmagnesium is an allyl phenyl sulfide, which is more stable and more easily prepared in a connective fashion than the usual allyl halide precursor. Since the presence of lithium ions encourages undesirable proton transfer to the cyclized organometallic and is detrimental to the stereochemical control, the conversion of the allylic thioether to the allylmagnesium utilizes a lithium-free method involving direct reductive magnesiation in the presence of the magnesium-anthracene complex.

  16. From the tunneling dimer to the onset of microsolvation: Infrared spectroscopy of allyl radical water aggregates in helium nanodroplets

    Leicht, Daniel; Kaufmann, Matin; Pal, Nitish; Schwaab, Gerhard; Havenith, Martina


    The infrared spectrum of allyl:water clusters embedded in helium nanodroplets was recorded. Allyl radicals were produced by flash vacuum pyrolysis and trapped in helium droplets. Deuterated water was added to the doped droplets, and the infrared spectrum of the radical water aggregates was recorded in the frequency range 2570-2820 cm-1. Several absorption bands are observed and assigned to 1:1 and 1:2 allyl:D2O clusters, based on pressure dependent measurements and accompanying quantum chemical calculations. The analysis of the 1:1 cluster spectrum revealed a tunneling splitting as well as a combination band. For the 1:2 cluster, we observe a water dimer-like motif that is bound by one π-hydrogen bond to the allyl radical.

  17. Alcohol Abuse

    ... even small amounts of alcohol may hurt an unborn child)Drink alcohol while you are looking after ... shakes, being very suspicious), and can even include death. This is why you need your doctor’s care ...

  18. Alcohol Test


    The recent alcohol tax increase poses a challenge to China’s white spirits makers Alcohol, rather than wine, is an in-dispensable component to Chinese table culture. The financial crisis has failed to affect white spirits sales, but an alcohol tax increase might.

  19. Alcohol Poisoning

    ... t be awakened is at risk of dying. Alcohol poisoning is an emergency If you suspect that someone has alcohol poisoning — even if you don't see the ... immediately. Never assume the person will sleep off alcohol poisoning. Be prepared to provide information. If you ...

  20. [Surface modification of poly methyl methacrylate intraocular lens by alpha-allyl glucoside].

    Qu, Chao; Yao, Ke; Kou, Ruiqiang; Xu, Zhikang


    A method for improving the biocompatibility of the intraocular lens (IOL) and reducing the cell attachment was adopted in this study. The alpha-Allyl glucoside was used for the surface modification of the poly methyl methacrylate (PMMA) IOL by way of plasma-induced in situ polymerization. The surfaces of the control and treatment IOLs were characterized by contact angle estimation and ESCA techniques. The resolution, diopter and anti-fatigue of loops were determined by physical and optical methods. Cell attachment on the surfaces was examined by light microscopy. The results indicated that all of the treatment groups had excellent physical and optical properties. The modification with the use of alpha-Allyl glucoside could improve the hydrophilicity of the anterior surface of the PMMA IOLs and reduce the cell attachment.

  1. Iron complexes of tetramine ligands catalyse allylic hydroxyamination via a nitroso-ene mechanism.

    Porter, David; Poon, Belinda M-L; Rutledge, Peter J


    Iron(II) complexes of the tetradentate amines tris(2-pyridylmethyl)amine (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(hydroxy)carbamate) 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).

  2. Synthesis, characterization and evaluation of antioxidant and anticancer activities of novel benzisoxazole-substituted-allyl derivatives

    Anand, Mohanam [Kingston Engineering College, Vellore (India); Selvaraj, Vaithialingam [University College of Engineering-Villupuram, Villupuram (India); Alagar, Muthukaruppan [Anna University, Chennai (India)


    A novel series of various 2-allylbenzo[d]isoxazol-3(2H)-ones were synthesized using benzo[d]isoxazol-3(2H)-one treated with different allyl bromides/chlorides in the presence of water-mediated cesium carbonate as a new catalyst 3(a-h). The structures of the newly synthesized Benzisoxazole-substituted-allyl derivatives were characterized by spectroscopic methods and mass spectrometry. These synthesized compounds were evaluated for their in vitro antioxidant and anticancer activity. Compounds 3b, d, f, h were identified as the best hit against HT-29 Human colon cancer cells. Similarly, compounds like 3b, d, f, h showed significant antioxidant activity compared to the standard drug butylated hydroxy toluene (BHT)

  3. Recent Advances in the Application of Chiral Phosphine Ligands in Pd-Catalysed Asymmetric Allylic Alkylation

    Erika Martin


    Full Text Available One of the most powerful approaches for the formation of simple and complex chiral molecules is the metal-catalysed asymmetric allylic alkylation. This reaction has been broadly studied with a great variety of substrates and nucleophiles under different reaction conditions and it has promoted the synthesis of new chiral ligands to be evaluated as asymmetric inductors. Although the mechanism as well as the active species equilibria are known, the performance of the catalytic system depends on the fine tuning of factors such as type of substrate, nucleophile nature, reaction medium, catalytic precursor and type of ligand used. Particularly interesting are chiral phosphines which have proved to be effective asymmetric inductors in several such reactions. The present review covers the application of phosphine-donor ligands in Pd-catalysed asymmetric allylic alkylation in the last decade.

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

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


    The Barbier allylation of a series of para-substituted benzaldehydes with allylbromide in the presence of Zn, In, Sn, Sb, Bi, and Mg was investigated using competition experiments. In all cases, the slope of the Hammett plots indicated a build-up of negative charge in the selectivity-determining ......The Barbier allylation of a series of para-substituted benzaldehydes with allylbromide in the presence of Zn, In, Sn, Sb, Bi, and Mg was investigated using competition experiments. In all cases, the slope of the Hammett plots indicated a build-up of negative charge in the selectivity......-up of negative charge along with a small positive secondary kinetic isotope effect (k(H)/k(D) = 1.06) indicated that the selectivity-determining step was the generation of the radical anion of benzaldehyde. The reaction through a six-membered transition state was modeled using density functional theory...

  5. Crystal structure of (E-3-allyl-2-sulfanylidene-5-[(thiophen-2-ylmethylidene]thiazolidin-4-one

    Rahhal El Ajlaoui


    Full Text Available Molecules of the title compound, C11H9NOS3, are built up by one thiophene and one 2-thioxathiazolidin-4-one ring which are connected by a methylene bridge. In addition, there is an allyl substituent attached to nitrogen. The two rings are almost coplanar, making a dihedral angle between them of 0.76 (11°. The allyl group is oriented perpendicular to the mean plane through both ring systems. The crystal structure exhibits inversion dimers in which molecules are linked by pairs of C—H...O hydrogen bonds. Additional π–π interactions between neighboring thiophene and 2-thioxathiazolidin-4-one rings [intercentroid distance = 3.694 (2 Å] lead to the formation of a three-dimensional network.

  6. Synthetic Applications of Chiral Unsaturated Epoxy Alcohols Prepared by Sharpless Asymmetric Epoxidation

    María Moreno


    Full Text Available An overview of the synthesis and applications of chiral 2,3-epoxy alcohols containing unsaturated chains is presented. One of the fundamental synthetic routes to these compounds is Sharpless asymmetric epoxidation, which is reliable, highly chemoselective and enables easy prediction of the product enantioselectivity. Thus, unsaturated epoxy alcohols are readily obtained by selective oxidation of the allylic double bond in the presence of other carbon-carbon double or triple bonds. The wide availability of epoxy alcohols with unsaturated chains, the versatility of the epoxy alcohol functionality (e.g. regio- and stereo-selective ring opening; oxidation; and reduction, and the arsenal of established alkene chemistries, make unsaturated epoxy alcohols powerful starting materials for the synthesis of complex targets such as biologically active molecules. The popularization of ring-closing metathesis has further increased their value, making them excellent precursors to cyclic compounds.

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

    Rakesh Kumar Sharma; Ashoka G Samuelson


    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.

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

    Cox Liam R


    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.

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

    Hemelaere, Rémy; Carreaux, François; Carboni, Bertrand


    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.

  10. Facts about Alcohol and Alcoholism.

    Hall, Leonard C.

    Recognition of alcoholism as a treatable illness is a result of public education based on scientific facts. This publication, a digest of a more detailed survey of research about drinking and alcoholism, presents information about alcohol and its effects on individuals and society. It provides facts about the short-term and long-term effects of…

  11. Nonradical Zinc-Barbier Reaction for Diastereoselective Synthesis of Vicinal Amino Alcohols

    Keinicke, Lise Edelmann; Fristrup, Peter; Norrby, Per-Ola


    A new protocol for the synthesis of vicinal amino alcohols is described. The method employs a Barbier-type reaction between an imine and 3-benzoyloxyallyl bromide in the presence of zinc metal. The addition products are debenzoylated to afford amino alcohols in good yields and with diastereomeric...... ratios greater than 85:15 in favor of the anti isomer. A Hammett study has been performed which strongly indicates that the allylation does not follow a radical mechanism, but instead an organometallic reagent is formed which subsequently reacts with the imine. A computational study based...

  12. Alcoholic cardiomyopathy

    Gonzalo; Guzzo-Merello; Marta; Cobo-Marcos; Maria; Gallego-Delgado; Pablo; Garcia-Pavia


    Alcohol is the most frequently consumed toxic substance in the world. Low to moderate daily intake of alcohol has been shown to have beneficial effects on the cardiovascular system. In contrast, exposure to high levels of alcohol for a long period could lead to progressive cardiac dysfunction and heart failure. Cardiac dysfunction associated with chronic and excessive alcohol intake is a specific cardiac disease known as alcoholic cardiomyopathy(ACM). In spite of its clinical importance, data on ACM and how alcohol damages the heart are limited. In this review, we evaluate available evidence linking excessive alcohol consumption with heart failure and dilated cardiomyopathy. Additionally, we discuss the clinical presentation, prognosis and treatment of ACM.

  13. Study of effective atomic numbers and electron densities, kerma of alcohols, phantom and human organs, and tissues substitutes

    Singh Vishwanath P.


    Full Text Available Effective atomic numbers (ZPIeff and electron densities of eighteen alcohols such as wood alcohol, CH3OH; grain alcohol, C2H5OH; rubbing alcohol, C3H7OH; butanol, C4H9OH; amyl alcohol, C5H11OH; cetyl alcohol, C16H33OH; ethylene glycol, C2H4(OH2; glycerin, C3H5(OH3; PVA, C2H4O; erythritol, C4H6(OH4; xylitol, C5H7(OH5; sorbitol, C6H8(OH6; volemitol, C7H9(OH7; allyl alcohol, C3H5OH; geraniol, C10H17OH; propargyl alcohol, C3H3OH; inositol, C6H6(OH6, and menthol, C10H19OH have been calculated in the photon energy region of 1 keV-100 GeV. The estimated values have been compared with experimental values wherever possible. The comparison of ZPIeff of the alcohols with water phantom and PMMA phantom indicate that the ethylene glycol, glycerin, and PVA are substitute for PMMA phantom and PVA is substitute of water phantom. ZPIeff of alcohols have also been compared with human organs and tissues. Ethylene glycol, glycerin and PVA, allyl alcohol, and wood alcohols are found tissue substitutes for most of human organs. Kerma which is the product of the energy fluence and mass energy-absorption coefficient, have been calculated in the energy region from 1 keV to 20 MeV for the alcohols. The results show the kerma is more or less independent of energy above 100 keV.

  14. Lanthanide-surfactant-combined catalysts for the allylation of benzaldehyde with tetraallyltin in aqueous solutions

    Deleersnyder, Karen; Shi Danzhao; Binnemans, Koen [Katholieke Universiteit Leuven, Department of Chemistry, Laboratory of Coordination Chemistry, Celestijnenlaan 200F, B-3001 Leuven (Belgium); Parac-Vogt, Tatjana N. [Katholieke Universiteit Leuven, Department of Chemistry, Laboratory of Coordination Chemistry, Celestijnenlaan 200F, B-3001 Leuven (Belgium)], E-mail:


    Metal-surfactant-combined catalysts having the general formula M(DOS){sub x} (DOS = dodecylsulfate), x = 1-3, can be used for the efficient allylation of benzaldehyde with tetraallyltin in water. Due to the formation of micelles the reaction proceeds in the absence of organic solvents. Examination of a series of lanthanide(III) and divalent transition-metal dodecylsulfates as catalysts for the reaction between benzaldehyde and tetraallyltin revealed that the highest yields can be obtained when lanthanide(III) and copper(II) salts are used. Within 6 h at room temperature nearly quantitative conversion of benzaldehyde to 1-phenyl-3-buten-1-ol was achieved in the presence of 10 mol% of Cu(DOS){sub 2} or Yb(DOS){sub 3}. The influence of the amount of catalyst and tetraallyltin on the reaction yield was investigated. Different alkylsulfates, alkylsulfonates and arylsulfonates metal salts were prepared and tested as catalysts in the allylation reaction. The highest yields were obtained with ytterbium(III) alkylsulfates and ytterbium(III) arylsulfonates, while ytterbium(III) alkylsulfonates were found to be poor allylation catalysts. The results show that both the nature of the metal cation as well as the length and the nature of anionic surfactant chain are crucial for the activity of the metal-surfactant-combined catalysts in water.

  15. Catalytic enantioselective reductions and allylations of prochiral ketones

    Cunningham, A


    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...

  16. Naltrexone for Alcoholism

    ... Prescription Medicines, Your Health ResourcesTags: alcohol abuse, alcohol addiction, alcohol dependence, alcoholism, craving, Depade, drunk, hepatoxicity, intoxication, naltrexone, narcotic antagonist, opiate ...

  17. Impact of allyl disulfide on oxidative damage and liver regeneration in an experimental hepatectomy model.

    Battal, M; Kartal, A; Citgez, B; Yilmaz, B; Akcakaya, A; Karatepe, O


    We investigated the effects of allyl disulfide (agarlic extract) on tissue damage, regeneration, proliferation and oxidative damage in an experimental liver resection model. In the study, 24 female Wistar albinorats weighing approximately 200-250 g were used. Group 1:The rats in the experimental group all received a 70%hepatectomy and were fed an Allyl disulfide (30 μg kg day,Allyl disulfide, Sigma-Aldrich, formula: C6H10S2, CASNumber: 2179-57-9, formula weight: 146.27 g mol) in supplement to a regular diet for 1 week both preoperatively and postoperatively. Group 2: The rats in the control group also underwent a 70% hepatectomy and were given regular food and water for 1 week both preop and postop. Group 3: In the sham group, all rats were sacrificed 7 days after surgery. Forbiochemical evaluation, SGOT, SGPT, bilirubin, CRP and MDA were studied. In a histopathological examination, the fattening of the liver tissue, existence of (macro-micro vesicular),fibrosis, pleomorphism at hepatocyte nuclei, portal inflammation, existence of intralobular inflammatory cells,dilation at sinusoids, congestion, congestion at the central vein, regeneration, existence of Kupffer cells in the sinu soidallumen and ki-67 proliferation index at hepatocytes were examined. A significant difference between group 1 and group2 was observed regarding the existence of regeneration,(p:0.06), the occurrence of nuclear pleomorphisms (p:0,001)and the fibroblast activity status (p:0.001). Significant differences were found between the experimental groups in regard to Kupffer cell increase and dilation and the hyperemiastatus in the sinusoid lumens (p:0.013 and p:0.001,respectively). In the Allyl disulfide group, the proliferation index was significantly higher than that of the other groups(p:0,001), while the average plasma MDA value was lower than that of the other groups (p: 0,042). No significant differences were found among the groups with respect to tissue MDA values (p:0,720). No

  18. Chemical Kinetics of Hydrogen Atom Abstraction from Allylic Sites by (3)O2; Implications for Combustion Modeling and Simulation.

    Zhou, Chong-Wen; Simmie, John M; Somers, Kieran P; Goldsmith, C Franklin; Curran, Henry J


    Hydrogen atom abstraction from allylic C-H bonds by molecular oxygen plays a very important role in determining the reactivity of fuel molecules having allylic hydrogen atoms. Rate constants for hydrogen atom abstraction by molecular oxygen from molecules with allylic sites have been calculated. A series of molecules with primary, secondary, tertiary, and super secondary allylic hydrogen atoms of alkene, furan, and alkylbenzene families are taken into consideration. Those molecules include propene, 2-butene, isobutene, 2-methylfuran, and toluene containing the primary allylic hydrogen atom; 1-butene, 1-pentene, 2-ethylfuran, ethylbenzene, and n-propylbenzene containing the secondary allylic hydrogen atom; 3-methyl-1-butene, 2-isopropylfuran, and isopropylbenzene containing tertiary allylic hydrogen atom; and 1-4-pentadiene containing super allylic secondary hydrogen atoms. The M06-2X/6-311++G(d,p) level of theory was used to optimize the geometries of all of the reactants, transition states, products and also the hinder rotation treatments for lower frequency modes. The G4 level of theory was used to calculate the electronic single point energies for those species to determine the 0 K barriers to reaction. Conventional transition state theory with Eckart tunnelling corrections was used to calculate the rate constants. The comparison between our calculated rate constants with the available experimental results from the literature shows good agreement for the reactions of propene and isobutene with molecular oxygen. The rate constant for toluene with O2 is about an order magnitude slower than that experimentally derived from a comprehensive model proposed by Oehlschlaeger and coauthors. The results clearly indicate the need for a more detailed investigation of the combustion kinetics of toluene oxidation and its key pyrolysis and oxidation intermediates. Despite this, our computed barriers and rate constants retain an important internal consistency. Rate constants

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

    Marta Francisco


    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.

  20. Resonance energies of the allyl cation and allyl anion: contribution by resonance and inductive effects toward the acidity and hydride abstraction enthalpy of propene.

    Barbour, Josiah B; Karty, Joel M


    Density functional theory was employed to calculate the acidities and hydride abstraction enthalpies of propene (3) and propane (4), along with their vinylogues (5 and 6, respectively). The same reaction enthalpies were calculated for the propene vinylogues in which the terminal vinyl group was rotated perpendicular to the rest of the conjugated system (7). The contribution by resonance and inductive effects toward the acidity and hydride abstraction enthalpy of each vinylogue of 5 (n = 1-3) was computed and extrapolated to n = 0 (the parent propene system). The resonance energies of the allyl cation and anion were determined to be about 20-22 and 17-18 kcal/mol, respectively. Comparisons are made to resonance energies calculated using other methodologies.

  1. S-Allyl cysteine improves nonalcoholic fatty liver disease in type 2 diabetes Otsuka Long-Evans Tokushima Fatty rats via regulation of hepatic lipogenesis and glucose metabolism.

    Takemura, Shigekazu; Minamiyama, Yukiko; Kodai, Shintaro; Shinkawa, Hiroji; Tsukioka, Takuma; Okada, Shigeru; Azuma, Hideki; Kubo, Shoji


    It is important to prevent and improve diabetes mellitus and its complications in a safe and low-cost manner. S-Allyl cysteine, an aged garlic extract with antioxidant activity, was investigated to determine whether S-allyl cysteine can improve type 2 diabetes in Otsuka Long-Evans Tokushima Fatty rats with nonalcoholic fatty liver disease. Male Otsuka Long-Evans Tokushima Fatty rats and age-matched Long-Evans Tokushima Otsuka rats were used and were divided into two groups at 29 weeks of age. S-Allyl cysteine (0.45% diet) was administered to rats for 13 weeks. Rats were killed at 43 weeks of age, and detailed analyses were performed. S-Allyl cysteine improved hemoglobinA1c, blood glucose, triglyceride, and low-density lipoprotein cholesterol levels. Furthermore, S-allyl cysteine normalized plasma insulin levels. S-Allyl cysteine activated the mRNA and protein expression of both peroxisome proliferator-activated receptor α and γ, as well as inhibiting pyruvate dehydrogenase kinase 4 in Otsuka Long-Evans Tokushima Fatty rat liver. Sterol regulatory element-binding protein 1c and forkhead box O1 proteins were normalized by S-allyl cysteine in Otsuka Long-Evans Tokushima Fatty rat liver. In conclusions, these findings support the hypothesis that S-allyl cysteine has diabetic and nonalcoholic fatty liver disease therapeutic potential as a potent regulating agent against lipogenesis and glucose metabolism.

  2. Substitution controlled functionalization of ortho-bromobenzylic alcohols via palladium catalysis: synthesis of chromenes and indenols.

    Mahendar, Lodi; Satyanarayana, Gedu


    An efficient domino Pd-catalyzed transformation of simple ortho-bromobenzyl tertiary alcohols to chromenes is presented. Their formation is believed to proceed via the formation of a five-membered palladacycle, which, in turn, involves in an intermolecular homocoupling with the second ortho-bromobenzyltertiary alcohol to yield the homo-biaryl bond followed by intramolecular C-O bond formation. Interestingly, when there is an allylic substituent on the benzylic carbon atom, a chemoselective switch was observed, which preferred intramolecular Heck coupling and gave indenols. Further, it has been confirmed that the tertiary alcohol functionality is indispensible to give the coupled products, whereas the use of primary/secondary benzylic alcohols furnished the simple carbonyl products via a possible reductive debromination followed by oxidation due to the availability of β-hydrogen(s).

  3. Thermosetting composite matrix materials based on allyl and/or propargyl substituted cyclopentadiene, indene and fluorene

    Tregre, Gregory Jude

    A series of all-hydrocarbon thermoset composite matrix resins was synthesized via electrophilic substitution of cyclopentadiene, indene, and fluorene ring systems with allyl and/or propargyl halides under phase transfer conditions. Reaction of cyclopentadiene with allyl chloride (ACP resin), propargyl bromide (PCP resin) or various feed ratios of allyl chloride and propargyl bromide (APCP resins) yielded mixtures of products with 2-6 substituents per cyclopentadiene ring. Reaction of indene with allyl chloride (Al resins) or propargyl bromide (PI resins) yielded mixtures of products with 2-4 substituents per indene. In both sets of resins the allyl functionality obtained a greater average degree of substitution than the analogous propargyl species. Differential scanning calorimetric (DSC) analysis of the multifunctional resins showed broad, high-energy thermal cures in all cases. The enthalpies of cure for ACP and PCP were 750 J/g and 805 J/g, respectively, with peak cure energies occurring at 310 and 248sp°C. The enthalpy of cure for APCP resins ranged from 750 J/g to 800 J/g with higher propargyl-functional resins yielding higher enthalpies of cure. Physically mixed ACP/PCP resin systems gave peak cure temperatures and energy values comparable to APCP resins. The enthalpies of cure for Al and PI-resins were 480 J/g and 630 J/g, respectively. Peak cure temperature for Al resin was 320sp°C, while the peak cure for PI resin occurred at 282sp°C. Infrared spectroscopy (IR) and nuclear magnetic resonance spectroscopy (NMR) were used to evaluate mechanisms of cure in the experimental resins. The allyl functional resins cured through a combination of ene reactions and polyaddition reactions. The propargyl functional resins cured through ene reactions and polyadditions but also underwent some cyclotrimerization of the propargyl functionalities. A small amount of autoxidation was seen in all of the resins. Thermal stability and carbon yields of the cured resins were

  4. Alcohol and pregnancy

    Drinking alcohol during pregnancy; Fetal alcohol syndrome - pregnancy; FAS - fetal alcohol syndrome ... lead to lifelong damage. DANGERS OF ALCOHOL DURING PREGNANCY Drinking a lot of alcohol during pregnancy can ...

  5. Alcohol Energy Drinks

    ... Home / About Addiction / Alcohol / Alcohol Energy Drinks Alcohol Energy Drinks Read 28133 times font size decrease font size increase font size Print Email Alcohol energy drinks (AEDs) or Caffeinated alcoholic beverages (CABs) are premixed ...

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

    Yang, Wenguo


    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.

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

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


    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

  8. Stereodivergent Allylic Substitutions with Aryl Acetic Acid Esters by Synergistic Iridium and Lewis Base Catalysis.

    Jiang, Xingyu; Beiger, Jason J; Hartwig, John F


    The preparation of all possible stereoisomers of a given chiral molecule bearing multiple stereocenters by a simple and unified method is a significant challenge in asymmetric catalysis. We report stereodivergent allylic substitutions with aryl acetic acid esters catalyzed synergistically by a metallacyclic iridium complex and benzotetramisole. Through permutations of the enantiomers of the two chiral catalysts, all four stereoisomers of the products bearing two adjacent stereocenters are accessible with high diastereoselectivity and enantioselectivity. The resulting chiral activated ester products can be converted readily to enantioenriched amides, unactivated esters, and carboxylic acids in a one-pot manner.

  9. N-(2-Allyl-4-ethoxy-2H-indazol-5-yl-4-methylbenzenesulfonamide

    Hakima Chicha


    Full Text Available The indazole ring system of the title compound, C19H21N3O3S, is almost planar (r.m.s. deviation = 0.0192 Å and forms dihedral angles of 77.99 (15 and 83.9 (3° with the benzene ring and allyl group, respectively. In the crystal, centrosymmetrically related molecules are connected by pairs of N—H...O hydrogen bonds into dimers, which are further linked by C—H...O hydrogen bonds, forming columns parallel to the b axis.

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

    Elmaghraby, Elsayed K.; Seddik, Usama


    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.

  11. Catalytic enantioselective 1,6-conjugate additions of propargyl and allyl groups

    Meng, Fanke; Li, Xiben; Torker, Sebastian; Shi, Ying; Shen, Xiao; Hoveyda, Amir H.


    Conjugate (or 1,4-) additions of carbanionic species to α,β-unsaturated carbonyl compounds are vital to research in organic and medicinal chemistry, and there are several chiral catalysts that facilitate the catalytic enantioselective additions of nucleophiles to enoates. Nonetheless, catalytic enantioselective 1,6-conjugate additions are uncommon, and ones that incorporate readily functionalizable moieties, such as propargyl or allyl groups, into acyclic α,β,γ,δ-doubly unsaturated acceptors are unknown. Chemical transformations that could generate a new bond at the C6 position of a dienoate are particularly desirable because the resulting products could then be subjected to further modifications. However, such reactions, especially when dienoates contain two equally substituted olefins, are scarce and are confined to reactions promoted by a phosphine-copper catalyst (with an alkyl Grignard reagent, dialkylzinc or trialkylaluminium compounds), a diene-iridium catalyst (with arylboroxines), or a bisphosphine-cobalt catalyst (with monosilyl-acetylenes). 1,6-Conjugate additions are otherwise limited to substrates where there is full substitution at the C4 position. It is unclear why certain catalysts favour bond formation at C6, and—although there are a small number of catalytic enantioselective conjugate allyl additions—related 1,6-additions and processes involving a propargyl unit are non-existent. Here we show that an easily accessible organocopper catalyst can promote 1,6-conjugate additions of propargyl and 2-boryl-substituted allyl groups to acyclic dienoates with high selectivity. A commercially available allenyl-boron compound or a monosubstituted allene may be used. Products can be obtained in up to 83 per cent yield, >98:2 diastereomeric ratio (for allyl additions) and 99:1 enantiomeric ratio. We elucidate the mechanistic details, including the origins of high site selectivity (1,6- versus 1,4-) and enantioselectivity as a function of the catalyst

  12. [Inhibition of aflatoxin production and fungal growth on stored corn by allyl isothiocyanate vapor].

    Okano, Kiyoshi; Ose, Ayaka; Takai, Mitsuhiro; Kaneko, Misao; Nishioka, Chikako; Ohzu, Yuji; Odano, Masayoshi; Sekiyama, Yasushi; Mizukami, Yuichi; Nakamura, Nobuya; Ichinoe, Masakatsu


    Studies were conducted to determine the effectiveness of allyl isothiocyanate (AIT) vapor treatment with a commercial mustard seed extract (Wasaouro(®)) in controlling aflatoxin-producing fungi on stored corn. The concentration of AIT in the closed container peaked at 54.6 ng/mL on the 14th day and remained at 21.8 ng/mL on the 42nd day. AIT inhibited visible growth of aflatoxigenic molds in unsterilized corn and in sterilized corn inoculated with various aflatoxigenic fungi. However, fungi such as Aspergillus glaucus group, A. penicillioides and A. restrictus were detected by means of culture methods.

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

    Jardosh Hardik H.


    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.

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

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


    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.

  15. N-(1-Allyl-3-chloro-4-ethoxy-1H-indazol-5-yl-4-methylbenzenesulfonamide

    Hakima Chicha


    Full Text Available In the title compound, C19H20ClN3O3S, the benzene ring is inclined to the indazole ring system by 51.23 (8°. In the crystal, molecules are linked by pairs of N—H...O hydrogen bonds, forming inversion dimers which stack in columns parallel to [011]. The atoms in the allyl group are disordered over two sets of sites with an occupancy ratio of 0.624 (8:0.376 (8.

  16. Direct catalytic asymmetric addition of allyl cyanide to ketones via soft Lewis acid/hard Brønsted base/hard Lewis base catalysis.

    Yazaki, Ryo; Kumagai, Naoya; Shibasaki, Masakatsu


    We report that a hard Lewis base substantially affects the reaction efficiency of direct catalytic asymmetric gamma-addition of allyl cyanide (1a) to ketones promoted by a soft Lewis acid/hard Brønsted base catalyst. Mechanistic studies have revealed that Cu/(R,R)-Ph-BPE and Li(OC(6)H(4)-p-OMe) serve as a soft Lewis acid and a hard Brønsted base, respectively, allowing for deprotonative activation of 1a as the rate-determining step. A ternary catalytic system comprising a soft Lewis acid/hard Brønsted base and an additional hard Lewis base, in which the basicity of the hard Brønsted base Li(OC(6)H(4)-p-OMe) was enhanced by phosphine oxide (the hard Lewis base) through a hard-hard interaction, outperformed the previously developed binary soft Lewis acid/hard Brønsted base catalytic system, leading to higher yields and enantioselectivities while using one-tenth the catalyst loading and one-fifth the amount of 1a. This second-generation catalyst allows efficient access to highly enantioenriched tertiary alcohols under nearly ideal atom-economical conditions (0.5-1 mol % catalyst loading and a substrate molar ratio of 1:2).

  17. Biphilic Organophosphorus Catalysis: Regioselective Reductive Transposition of Allylic Bromides via P(III)/P(V) Redox Cycling.

    Reichl, Kyle D; Dunn, Nicole L; Fastuca, Nicholas J; Radosevich, Alexander T


    We report that a regioselective reductive transposition of primary allylic bromides is catalyzed by a biphilic organophosphorus (phosphetane) catalyst. Spectroscopic evidence supports the formation of a pentacoordinate (σ(5)-P) hydridophosphorane as a key reactive intermediate. Kinetics experiments and computational modeling are consistent with a unimolecular decomposition of the σ(5)-P hydridophosphorane via a concerted cyclic transition structure that delivers the observed allylic transposition and completes a novel P(III)/P(V) redox catalytic cycle. These results broaden the growing repertoire of reactions catalyzed within the P(III)/P(V) redox couple and suggest additional opportunities for organophosphorus catalysis in a biphilic mode.

  18. Mechanism of the cobalt oxazoline palladacycle (COP)-catalyzed asymmetric synthesis of allylic esters.

    Cannon, Jeffrey S; Kirsch, Stefan F; Overman, Larry E; Sneddon, Helen F


    The catalytic enantioselective S(N)2' displacement of (Z)-allylic trichloroacetimidates catalyzed by the palladium(II) complex [COP-OAc](2) is a broadly useful method for the asymmetric synthesis of chiral branched allylic esters. A variety of experiments aimed at elucidating the nature of the catalytic mechanism and its rate- and enantiodetermining steps are reported. Key findings include the following: (a) the demonstration that a variety of bridged-dipalladium complexes are present and constitute resting states of the COP catalyst (however, monomeric palladium(II) complexes are likely involved in the catalytic cycle); (b) labeling experiments establishing that the reaction proceeds in an overall antarafacial fashion; (c) secondary deuterium kinetic isotope effects that suggest substantial rehybridization at both C1 and C3 in the rate-limiting step; and (d) DFT computational studies (B3-LYP/def2-TZVP) that provide evidence for bidentate substrate-bound intermediates and an anti-oxypalladation/syn-deoxypalladation pathway. These results are consistent with a novel mechanism in which chelation of the imidate nitrogen to form a cationic palladium(II) intermediate activates the alkene for attack by external carboxylate in the enantiodetermining step. Computational modeling of the transition-state structure for the acyloxy palladation step provides a model for enantioinduction.

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

    Alireza Shakoori


    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.

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

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


    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

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

    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


    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•.

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

    David Porter


    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.

  3. [Alcohol experience, alcohol knowledge, and alcohol expectancy in early adolescents].

    Tak, Young-Ran; Yun, E-hwa; An, Ji-Yeon


    This study was to explore the prevalence of alcohol experiences and to identify the expectancy on the effects of alcohol and alcohol knowledge in early adolescents. The cross-sectional survey of 1854 students from seven middle schools in one district of Seoul was conducted by convenience sampling. Alcohol experience and early onset of alcohol use were measured by the Youth Risk Behavior Survey. Alcohol expectancy was measured by an Alcohol Effects Questionnaire. Over sixty five percent of adolescents reported that they had previous drinking experiences. The participants with no alcohol drinking experience had a lower level of alcohol knowledge than those with experience(t=2.73, p=.007). In expectancy on effects of alcohol, girls had a more positive alcohol expectation than boys(t=-2.54, p=.011). Alcohol knowledge negatively correlated with alcohol expectancy(r=-.40 p=.000). In regression of alcohol expectancy, gender and alcohol knowledge were significant predictors explaining 17%. The results support that alcohol expectancy is an important link with early drinking experiences and alcohol knowledge, focusing on the importance of gender differences. Therefore, an alcohol prevention program in early adolescence is needed and should be focused on multidimensionality of the alcohol expectancy with developmental and psychosocial factors for early adolescents.

  4. A Double Activation Method for the Conversion of Vinyl Epoxides into vic-Amino Alcohols and Chiral Benzoxazine/Quinoxaline Derivatives.

    Srikanth, Gourishetty; Ramakrishna, Kallaganti V S; Sharma, Gangavaram V M


    A new method for the synthesis of 1,2-syn-vic amino alcohols (with double inversion of configuration) from vinyl epoxides, by the amination of a π-allyl palladium-borate complex generated by using Pd(0) and phenyl-o-phenylene borate (a double activation technique), is reported. Further, this new method with broad functional group compatibility was extended to a one-pot/two-step synthesis of chiral benzoxazine and quinoxaline derivatives.

  5. Anti-Inflammatory and Antioxidant Effects of Repeated Exposure to Cruciferous Allyl Nitrile in Sensitizer-Induced Ear Edema in Mice.

    Tanii, Hideji; Sugitani, Kayo; Saijoh, Kiyofumi


    Skin sensitizers induce allergic reactions through the induction of reactive oxygen species. Allyl nitrile from cruciferous vegetables has been reported to induce antioxidants and phase II detoxification enzymes in various tissues. We assessed the effects of repeated exposure to allyl nitrile on sensitizer-induced allergic reactions. Mice were dosed with allyl nitrile (0-200 µmol/kg), and then received a dermal application of 1 of 3 sensitizers on the left ear or 1 of 2 vehicles on the right ear. Quantitative assessment of edema was carried out by measuring the difference in weight between the portions taken from the right and left ears. We tested enzymes (superoxide dismutase (SOD), catalase (CAT), glutathione peroxidase (GPx), and thiobarbituric acid reactive substances (TBARS) in ears. Repeated exposure to allyl nitrile reduced edemas induced by glutaraldehyde and by 2, 4-dinitrochlorobenzene (DNCB), but not by formaldehyde. The repeated exposure decreased levels of TBARS, a marker of oxidative stress, induced by glutaraldehyde and by DNCB, but not by formaldehyde. Allyl nitrile elevated SOD levels for the 3 sensitizers, and CAT levels for formaldehyde and DNCB. Allyl nitrile also increased GPx levels for formaldehyde and DNCB, but not for glutaraldehyde. The reduced edemas were associated with changes in oxidative stress levels and antioxidant enzymes. Repeated exposure to allyl nitrile reduced allergic reactions induced by glutaraldehyde and by DNCB, but not by formaldehyde. This reduction was associated with changes in ROS levels and antioxidant enzyme activities.

  6. [(p-Cymene)RuCl2 ]2 : an efficient catalyst for highly regioselective allylic alkylations of chelated amino acid ester enolates.

    Bayer, Anton; Kazmaier, Uli


    Chelated amino acid ester enolates are excellent nucleophiles for ruthenium-catalyzed allylic alkylations. Although [Cp*Ru(MeCN)3 ]PF6 was found to be the most reactive catalyst investigated, with the resulting allyl complexes reacting at temperatures as low as -78 °C, unfortunately the process took place with only moderate regio- and diastereoselectivity. In contrast, [(p-cymene)RuCl2 ]2 allowed allylations to be performed with a high degree of regioretention. Secondary allyl carboxylates with a terminal double bond were found to be the most reactive substrates, giving rise to the branched amino acids with perfect regioretention and chirality transfer. In this case, no isomerization of the Ru-allyl complex formed in situ was observed, in contrast to the analogues palladium complexes. This isomerization-free protocol can also be used for the synthesis of (Z)-configured γ,δ-unsaturated amino acid derivatives, starting from (Z)-allylic substrates. Here, the more reactive phosphates were found to be superior to the carboxylates, providing the required amino acids in almost quantitative yield with perfect regio- and stereoretention. Therefore, the Ru-catalyzed allylation reactions are well positioned to overcome the drawbacks of Pd-catalyzed processes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Regio- and Enantioselective Copper-Catalyzed Allylic Alkylation of Ortho-Substituted Cinnamyl Bromides with Grignard Reagents

    van der Molen, Nathalie C; Tiemersma-Wegman, Theodora D; Fañanás-Mastral, Martín; Feringa, Ben L


    A highly efficient method for the copper-catalyzed asymmetric allylic alkylation of ortho-substituted cinnamyl bromides with Grignard reagents is reported. The use of a catalytic system comprising CuBr center dot SMe2 and TaniaPhos as chiral ligands gives rise to a range of branched products with

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

    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...

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

    Jia Di Huang; Xiang Ping Hu; Zhuo Zheng


    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.

  10. Lewis base-promoted rearrangement of allylic cyanohydrins: construction of functionalized nitriles bearing 1,3-diketone moieties.

    Zhang, Yan-Jing; Hou, Qi-Lan; Wang, Hai-Jing; Liao, Wei-Wei


    A novel Lewis base-promoted rearrangement of allylic cyanohydrins has been developed, in which the cyano group was rearranged, directly coupled with the generation of new functional groups. This protocol provides a unique and facile way to prepare highly functionalized nitriles bearing 1,3-diketone moieties under mild reaction conditions. Furthermore, the synthetic transformations of the functionalized products have also been demonstrated.

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

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


    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

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

    Wamser, Carl C.; Scott, Lawrence T.


    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)

  13. Enantioselective Construction of Acyclic Quaternary Carbon Stereocenters: Palladium-Catalyzed Decarboxylative Allylic Alkylation of Fully Substituted Amide Enolates.

    Starkov, Pavel; Moore, Jared T; Duquette, Douglas C; Stoltz, Brian M; Marek, Ilan


    We report a divergent and modular protocol for the preparation of acyclic molecular frameworks containing newly created quaternary carbon stereocenters. Central to this approach is a sequence composed of a (1) regioselective and -retentive preparation of allyloxycarbonyl-trapped fully substituted stereodefined amide enolates and of a (2) enantioselective palladium-catalyzed decarboxylative allylic alkylation reaction using a novel bisphosphine ligand.

  14. Diastereoselective Allylation of "N"-"Tert"-Butanesulfinyl Imines: An Asymmetric Synthesis Experiment for the Undergraduate Organic Laboratory

    Chen, Xiao-Yang; Sun, Li-Sen; Gao, Xiang; Sun, Xing-Wen


    An asymmetric synthetic experiment that encompasses both diastereoselectivity and enantioselectivity is described. In this experiment, Zn-mediated allylation of an ("R")-"N"-"tert"-butanesulfinyl imine is first performed to obtain either diastereomer using two different solvent systems, followed by oxidation of the…

  15. New chiral N, S-ligands with Thiophenyl at Benzylic Position. Palladium(Ⅱ)-catalyzed Enantioselective Allylic Alkylation

    WU,Hao(吴昊); WU,Xun-Wei(巫循伟); HOU,Xue-Long(侯雪龙); DAI,Li-Xin(戴立信); WANG,Quan-Rui(王全瑞)


    New chiral N, S-ligands with oxazoline and thiphenyl substituents at benzene ring and benzylic position have been prepared and applied in palladium-catalyzed asymmetric allylic alkylation reaction to provide the product with high yield and entantioselectivity (82%-93% ee).

  16. Copper-Catalyzed Intermolecular Trifluoromethylazidation and Trifluoromethylthiocyanation of Allenes: Efficient Access to CF3-Containing Allyl Azides and Thiocyanates.

    Zhu, Na; Wang, Fei; Chen, Pinhong; Ye, Jinxing; Liu, Guosheng


    A mild and efficient method for copper-catalyzed trifluoromethylazidation and trifluoromethylthiocyanation of allenes was explored. A series of CF3-containing allyl azides and thiocyanates were obtained with high yields and good stereoselectivities, which can be used for further transformation to some valuable compounds.

  17. Phosphine-catalyzed [4 + 1] annulation between α,β-unsaturated imines and allylic carbonates: synthesis of 2-pyrrolines.

    Tian, Junjun; Zhou, Rong; Sun, Haiyun; Song, Haibin; He, Zhengjie


    In this report, a phosphine-catalyzed [4 + 1] annulation between α,β-unsaturated imines and allylic carbonates is described. This reaction represents the first realization of catalytic [4 + 1] cyclization of 1,3-azadienes with in situ formed phosphorus ylides, which provides highly efficient and diastereoselective synthesis of 2-pyrrolines.

  18. Spectra of carbanions formed from allyl cyanide during isomerization in zeolite NaY-FAU with strong basic sites

    Hannus, István; Förster, Horst; Tasi, Gyula; Kiricsi, Imre; Molnár, Árpád


    Double bond isomerization of allyl cyanide to crotononitrile over a basic zeolite catalyst was monitored by IR and UV-VIS spectroscopy in order to get information on the surface intermediates involved. Due to the spectral changes the occurence of a carbanionic intermediate seems to be highly probable characterized by an absorption at 400 nm.

  19. Alcohol withdrawal.

    Manasco, Anton; Chang, Shannon; Larriviere, Joseph; Hamm, L Lee; Glass, Marcia


    Alcohol withdrawal is a common clinical condition that has a variety of complications and morbidities. The manifestations can range from mild agitation to withdrawal seizures and delirium tremens. The treatments for alcohol withdrawal include benzodiazepines, anticonvulsants, beta-blockers and antihypertensives. Although benzodiazepines are presently a first-line therapy, there is controversy regarding the efficacies of these medications compared with others. Treatment protocols often involve one of two contrasting approaches: symptom-triggered versus fixed-schedule dosing of benzodiazepines. We describe these protocols in our review and examine the data supporting symptom-triggered dosing as the preferred method for most patients in withdrawal.The Clinical Institute Withdrawal Assessment for Alcohol scoring system for alcohol withdrawal streamlines care, optimizes patient management, and is the best scale available for withdrawal assessment. Quality improvement implications for inpatient management of alcohol withdrawal include increasing training for signs of withdrawal and symptom recognition, adding new hospital protocols to employee curricula, and ensuring manageable patient-to-physician and patient-to-nurse ratios.

  20. Hepatic progenitor cell lines from allyl alcohol-treated adult rats are derived from gamma-irradiated mouse STO cells.

    Zhang, Mingjun; Sell, Stewart; Leffert, Hyam L


    In attempts to recharacterize several markers of putative rat liver progenitor cells, single-stage reverse transcription-polymerase chain reaction (RT-PCR) analyses failed to confirm the reported immunochemical detection of albumin, alpha(1)-fetoprotein, and cytochrome P450-1A2 in the clonal line, 3(8)#21, and the cloned derivative, 3(8)#21-EGFP (enhanced green fluorescent protein). Undetectable expression occurred whether or not both lines were cultured on or off feeder layers of gamma-irradiated mouse embryonic STO (SIM [Sandoz inbred Swiss mouse] thioguanine-resistant ouabain-resistant) cells. PCR amplification of liver progenitor cell chromosomal (rat and mouse Pigr, rat INS1, mouse INS2) and mitochondrial (rat and mouse COX1) genes revealed only mouse sequences. Further analyses of rat and mouse COX1 sequences in cells from untampered storage vials of all 11 reported liver progenitor cell lines and strains revealed only mouse sequences. In addition, uniquely similar metaphase spreads were observed in STO, 3(8)#21, and 3(8)#21-EGFP cells. The combined results suggest that the previously reported "rat" liver progenitor cell lines were most likely generated during early derivation in cell culture from gamma-radiation-resistant or ineffectively irradiated mouse STO cells used as the feeder layers. These findings reveal new types of artifacts encountered in cocultures of tissue progenitor cells and feeder layer cell lines, and they sound a cautionary note: phenotypic and genotypic properties of feeder layers should be well-characterized before and during coculture with newly derived stem cells and clonal derivatives.

  1. Chiral amino alcohol derived bis-phosphoramidite pincer palladium complexes and their applications in asymmetric allylation of aldimines

    Li, J.; Lutz, M.; Spek, A.L.; van Klink, G.P.M.; van Koten, G.; Klein Gebbink, R.J.M.


    Novel P-stereogenic bis-phosphoramidite pincer palladium complexes 1 and 2 derived from (S)-(-)-R,R-diphenyl-2-pyrrolidinemethanol and (S)-(þ)-indolinemethanol, respectively, were synthesized in reasonable yields (i.e., 55-62%) by using a flexible, modular synthetic approach and were characterized

  2. Alcohol and Hepatitis

    ... code here Enter ZIP code here Daily Living: Alcohol for Veterans and the Public Alcohol and Hepatitis: Entire Lesson Overview Alcohol is one ... related to choices you make about your lifestyle . Alcohol and fibrosis Fibrosis is the medical term for ...

  3. The Palladium-Catalyzed Aerobic Kinetic Resolution of Secondary Alcohols: Reaction Development, Scope, and Applications

    Ebner, Davidâ C.


    The first palladium-catalyzed enantioselective oxidation of secondary alcohols has been developed, utilizing the readily available diamine (-)-sparteine as a chiral ligand and molecular oxygen as the stoichiometric oxidant. Mechanistic insights regarding the role of the base and hydrogen-bond donors have resulted in several improvements to the original system. Namely, addition of cesium carbonate and tert-butyl alcohol greatly enhances reaction rates, promoting rapid resolutions. The use of chloroform as solvent allows the use of ambient air as the terminal oxidant at 23 degrees C, resulting in enhanced catalyst selectivity. These improved reaction conditions have permitted the successful kinetic resolution of benzylic, allylic, and cyclopropyl secondary alcohols to high enantiomeric excess with good-to-excellent selectivity factors. This catalyst system has also been applied to the desymmetrization of meso-diols, providing high yields of enantioenriched hydroxyketones.

  4. Rationalizing Ring-Size Selectivity in Intramolecular Pd-Catalyzed Allylations of Resonance-Stabilized Carbanions

    Norrby, Per-Ola; Mader, Mary M.; Vitale, Maxime


    Computational methods were applied to the Pd-catalyzed intramolecular allylations of resonance-stabilized carbanions obtained from amide and ketone substrates, with the aim of rationalizing the endo- vs. exo-selectivity in the cyclizations. In addition, ester substrates were prepared and subjected...... to the Pd-catalyzed cyclization conditions, and were found to form lactones via exo attack. DFT calculations using BP86/LACVP*+level of theory with a CH2Cl2 solvation correction reproduce the relative transition state energies. The preference for exo-cyclization of the nitrogen-containing starting material...... appears to result from the preference for near-planarity of the amide N. Both the oxygen- and nitrogen tethers are too short to allow efficient endo-cyclization, whereas the carbon-tether is long enough to allow favorable endo-cyclization. The carbon tether also disfavors the exo-cyclization transition...

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

    Behenna, Douglas C.


    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.

  6. An Efficient Amide-Aldehyde-Alkene Condensation: Synthesis for the N-Allyl Amides.

    Quan, Zheng-Jun; Wang, Xi-Cun


    The allylamine skeleton represents a significant class of biologically active nitrogen compounds that are found in various natural products and drugs with well-recognized pharmacological properties. In this personal account, we will briefly discuss the synthesis of allylamine skeletons. We will focus on showing a general protocol for Lewis acid-catalyzed N-allylation of electron-poor N-heterocyclic amides and sulfonamide via an amide-aldehyde-alkene condensation reaction. The substrate scope with respect to N-heterocyclic amides, aldehydes, and alkenes will be discussed. This method is also capable of preparing the Naftifine motif from N-methyl-1-naphthamide or methyl (naphthalene-1-ylmethyl)carbamate, with paraformaldehyde and styrene in a one-pot manner.

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

    郑勇; 张锁江; 吕兴梅; 王倩; 左勇; 刘恋


    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^-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.

  8. The Reaction of Allyl Isothiocyanate with Hydroxyl/Water and β-Cyclodextrin Using Ultraviolet Spectrometry

    Zi-Tao Jiang


    Full Text Available The reaction of allyl isothiocyanate (AITC with hydroxyl/water and β-cyclodextrin (β-CD in different acidic-alkaline media has been investigated by ultraviolet spectrometry. The kinetic parameters of the reaction were measured. It was found that after AITC translating into thiourea, the absorption peak shifted from 240 to 226 nm and the molar absorptivity increased about 16 times. The reaction can be seen as a pseudo first order reaction because the concentration of hydroxyl was constant. β-CD can inhibit the reaction of AITC with hydroxyl/water, i.e. the hydrolysis of AITC. The formation constant (Ka and thermodynamic parameters of the complex reaction were calculated. Ka decreased with the increase of temperature. The experimental results indicated that the inclusive process was an exothermic and enthalpy-driven process accompanied with a negative entropic contribution.

  9. The allyl radical revisited: a theoretical study of the electronic spectrum

    Aquilante, Francesco; Jensen, Kasper P.; Roos, Björn O.


    In this Letter, we report the electronic spectrum of the allyl radical, obtained with multiconfigurational perturbation theory (MS-CASPT2). The assignment of the spectrum is in accordance with experiment to within 0.2 eV. We have computed the complete first Rydberg series and the beginning of the second Rydberg series. A new valence-excited 2B 1 state has been found which has hitherto been hidden by Rydberg transitions. A rationalisation of the electronic spectrum is provided in terms of resonance forms in ground and excited states. This model shows that while a multiconfigurational wavefunction is necessary to qualitatively model the system, the large ionic character of the valence electronic states makes an accurate treatment of the dynamical correlation necessary for a quantitative description of the spectrum.

  10. Decarboxylative-coupling of allyl acetate catalyzed by group 10 organometallics, [(phen)M(CH3)]+.

    Woolley, Matthew; Ariafard, Alireza; Khairallah, George N; Kwan, Kim Hong-Yin; Donnelly, Paul S; White, Jonathan M; Canty, Allan J; Yates, Brian F; O'Hair, Richard A J


    Gas-phase carbon-carbon bond forming reactions, catalyzed by group 10 metal acetate cations [(phen)M(O2CCH3)](+) (where M = Ni, Pd or Pt) formed via electrospray ionization of metal acetate complexes [(phen)M(O2CCH3)2], were examined using an ion trap mass spectrometer and density functional theory (DFT) calculations. In step 1 of the catalytic cycle, collision induced dissociation (CID) of [(phen)M(O2CCH3)](+) yields the organometallic complex, [(phen)M(CH3)](+), via decarboxylation. [(phen)M(CH3)](+) reacts with allyl acetate via three competing reactions, with reactivity orders (% reaction efficiencies) established via kinetic modeling. In step 2a, allylic alkylation occurs to give 1-butene and reform metal acetate, [(phen)M(O2CCH3)](+), with Ni (36%) > Pd (28%) > Pt (2%). Adduct formation, [(phen)M(C6H11O2)](+), occurs with Pt (24%) > Pd (21%) > Ni(11%). The major losses upon CID on the adduct, [(phen)M(C6H11O2)](+), are 1-butene for M = Ni and Pd and methane for Pt. Loss of methane only occurs for Pt (10%) to give [(phen)Pt(C5H7O2)](+). The sequences of steps 1 and 2a close a catalytic cycle for decarboxylative carbon-carbon bond coupling. DFT calculations suggest that carbon-carbon bond formation occurs via alkene insertion as the initial step for all three metals, without involving higher oxidation states for the metal centers.

  11. A broadly applicable NHC-Cu-catalyzed approach for efficient, site-, and enantioselective coupling of readily accessible (pinacolato)alkenylboron compounds to allylic phosphates and applications to natural product synthesis.

    Gao, Fang; Carr, James L; Hoveyda, Amir H


    A set of protocols for catalytic enantioselective allylic substitution (EAS) reactions that allow for additions of alkenyl units to readily accessible allylic electrophiles is disclosed. Transformations afford 1,4-dienes that contain a tertiary carbon stereogenic site and are promoted by 1.0-5.0 mol % of a copper complex of an N-heterocyclic carbene (NHC). Aryl- as well as alkyl-substituted electrophiles bearing a di- or trisubstituted alkene may be employed. Reactions can involve a variety of robust alkenyl-(pinacolatoboron) [alkenyl-B(pin)] compounds that can be either purchased or prepared by various efficient, site-, and/or stereoselective catalytic reactions, such as cross-metathesis or proto-boryl additions to terminal alkynes. Vinyl-, E-, or Z-disubstituted alkenyl-, 1,1-disubstituted alkenyl-, acyclic, or heterocyclic trisubstituted alkenyl groups may be added in up to >98% yield, >98:2 SN2':SN2, and 99:1 enantiomeric ratio (er). NHC-Cu-catalyzed EAS with alkenyl-B(pin) reagents containing a conjugated carboxylic ester or aldehyde group proceed to provide the desired 1,4-diene products in good yield and with high enantioselectivity despite the presence of a sensitive stereogenic tertiary carbon center that could be considered prone to epimerization. In most instances, the alternative approach of utilizing an alkenylmetal reagent (e.g., an Al-based species) represents an incompatible option. The utility of the approach is illustrated through applications to enantioselective synthesis of natural products such as santolina alcohol, semburin, nyasol, heliespirone A, and heliannuol E.

  12. Dietary S-Allyl-L-cysteine Reduces Mortality with Decreased Incidence of Stroke and Behavioral Changes in Stroke-Prone Spontaneously Hypertensive Rats

    KIM, Ji-Myung; CHANG, Namsoo; KIM, Won-Ki; CHUN, Hyang Sook


    S-Allyl-L-cysteine (SAC), an active organosulfur compound derived from garlic, was found to reduce mortality with lesser incidence of stroke and also to lower the overall stroke-related behavioral score in stroke-prone...

  13. DFT mechanistic study of the selective terminal C–H activation of n-pentane with a tungsten allyl nitrosyl complex

    Lee, Richmond; Tan, Davin; Liu, Chaoli; Li, Huaifeng; Guo, Hao; Shyue, Jing-Jong; Huang, Kuo-Wei


    Mechanistic insights into the selective C–H terminal activation of n-pentane with tungsten allyl nitrosyl complex reported by Legzdins were gained by employing density functional theory with B3LYP hybrid functional. Using...

  14. LiBF4-mediated C-glycosylation of glycals with allyltrimethylsilane: a facile synthesis of allyl C-glycosylic compounds.

    Yadav, J S; Reddy, B V; Chandraiah, L; Reddy, K S


    The treatment of glycals with allyltrimethylsilane in the presence of lithium tetrafluoroborate in acetonitrile gave the corresponding allyl 2,3-unsaturated C-glycosylic compounds in excellent yields with high anomeric selectivity.

  15. Modular access to vicinally functionalized allylic (thio)morpholinonates and piperidinonates by substrate-controlled annulation of 1,3-azadienes with hexacyclic anhydrides.

    Braunstein, Hannah; Langevin, Spencer; Khim, Monique; Adamson, Jonathan; Hovenkotter, Katie; Kotlarz, Lindsey; Mansker, Brandon; Beng, Timothy K


    A modular substrate-controlled hexannulation of inherently promiscuous 1,3-azadienes with hexacyclic anhydrides, which affords versatile vicinally functionalized allylic lactams, in high yields, regio- and stereoselectivities is described.

  16. Oxidation reaction of 4-allyl-4-hydroperoxy-2-methoxycyclohexa-2,5-dienone in the presence of potassium permanganate without a co-oxidant

    Mehmet Serdar Gültekin


    Full Text Available 4-Allyl-4-hydroperoxy-2-methoxycyclohexa-2,5-dienone (5 was synthesized by photooxygenation of commercially available Eugenol in the presence of tetraphenylporphyrin (TPP as a singlet oxygen sensitizer. The brief and one-pot syntheses of some natural product skeletons were conducted using the corresponding allylic hydroperoxide at different temperatures (0 oC and room temperature with potassium permanganate (KMnO 4 in mild condition at N 2(g atm.

  17. A convenient and stereoselective synthesis of (Z)-allyl selenides via Sm/TMSCI system-promoted coupling of Baylis-Hillman adducts with diselenides

    LIU Yun-kui; XU Dan-qian; XU Zhen-yuan; ZHANG Yong-min


    A simple and convenient procedure for stereoselective synthesis of (Z)-allyl selenides has been developed by a one-pot reaction of diselenides with Baylis-Hillman adducts in the presence of samarium metal-trimethylsilyl chloride under mild conditions. Presumably, the diselenides are cleaved by Sm/TMSCl system to form selenide anions, which then undergo SN2' substitution of Baylis-Hillman adducts to produce the (Z)-allyl selenides.

  18. NaBH4/NaNO3/H2O: A Convenient System for Selective Reduction of Aldehydes VS. Ketones to their Corresponding Alcohols

    Soheila Ghaderi


    Full Text Available NaBH4 (1.25 equivalents & NaNO3 (3 equivalents reduce a variety of aldehydes in the presence of ketones to their corresponding alcohols. Also, regioselectivity and exclusive 1,2-reduction enals to their corresponding allylic alcohols in high to excellent yields was achieved successfully with this reducing system. The reduction reactions were carried out in water as green solvent in high to excellent yields of the products. A nitrate-borane complex [H3B-NO3]Na is possibly the active reductant in the reaction mixture.

  19. Asymmetric allylation of α-ketoester-derived N-benzoylhydrazones promoted by chiral sulfoxides/N-oxides Lewis bases: highly enantioselective synthesis of quaternary α-substituted α-allyl-α-amino acids.

    Reyes-Rangel, Gloria; Bandala, Yamir; García-Flores, Fred; Juaristi, Eusebio


    Chiral sulfoxides/N-oxides (R)-1 and (R,R)-2 are effective chiral promoters in the enantioselective allylation of α-keto ester N-benzoylhydrazone derivatives 3a-g to generate the corresponding N-benzoylhydrazine derivatives 4a-g, with enantiomeric excesses as high as 98%. Representative hydrazine derivatives 4a-b were subsequently treated with SmI2, and the resulting amino esters 5a-b with LiOH to obtain quaternary α-substituted α-allyl α-amino acids 6a-b, whose absolute configuration was assigned as (S), with fundament on chemical correlation and electronic circular dichroism (ECD) data. © 2013 Wiley Periodicals, Inc.


    K.C. Gupta; H.K. Abdulkadir; S. Chand


    A new chelating polymer support has been prepared by suspension copolymeriz a tion of synthesized N,N'-bis(3-allyl salicylidene)ethylenediamine monomer Schiff base (N,N'-BSEDA) with styrene (St) and divinylbenzene (DVB) using azobisisobutyronitrile (AIBN) as initiator in the presence of poly(vinyl alcohol). The content and complexation ability of monomer Schiff base (N,N'-BSEDA) for cobalt(II) ions in prepared crosslinked polymer beads have shown dependence on the amount of DVB used in reaction mixture. The amount of monomer Schiff base (N,N'-BSEDA) in crosslinked beads showed a substantial decreasing trend at high concentration of DVB in the reaction mixture (> 1.5 mol dm-3), hence the efficiency of complexation (EC%) and cobalt(II) ion loading (EL%) of polymer beads showed a decreasing trend. The structure of monomer Schiff base (N,N'-BSEDA) and its cobalt(II) complex on polymer support was elucidated by IR, UV and magnetic measurements. The catalytic activity of polymer bound cobalt(Ⅱ) Schiff base complex was evaluated by analyzing kinetic data of decomposition of hydrogen peroxide in the presence of either supported cobalt (II) complex or free cobalt(II) complex. The activation energy for the decomposition of hydrogen peroxide by polymer supported cobalt(II)complex was found to be low (33.37 kJ mol-l) in comparison with unsupported cobalt(II) complex (56.35 kJ mol-1). On the basis of experimental observations, reaction steps are proposed and a suitable rate expression derived.

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

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


    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


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


    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.

  3. Crystal structure of (Z-3-allyl-5-(3-bromobenzylidene-2-sulfanylidene-1,3-thiazolidin-4-one

    Rahhal El Ajlaoui


    Full Text Available In the title compound, C13H10BrNOS2, the rhodanine (systematic name: 2-sulfanylidene-1,3-thiazolidin-4-one and the 3-bromobenzylidene ring systems are inclined slightly, forming a dihedral angle of 5.86 (12°. The rhodanine moiety is linked to an allyl group at the N atom and to the 3-bromobenzylidene ring system. The allyl group, C=C—C, is nearly perpendicular to the mean plane through the rhodanine ring, maling a dihedral angle of 87.2 (5°. In the crystal, molecules are linked by pairs of C—H...O hydrogen bonds, forming inversion dimers with an R22(10 ring motif.

  4. Deconvoluting the memory effect in Pd-catalyzed allylic alkylation; effect of leaving group and added chloride

    Fristrup, Peter; Jensen, Thomas; Hoppe, Jakob


    An analysis of product distributions in the Tsuji-Trost reaction indicates that several instances of reported memory effects can be attributed to slow interconversion of the initially formed syn- and anti-[Pd(eta3-allyl)] complexes. Addition of chloride triggers a true memory effect, in which the...... that the position trans to the phosphine ligand is more reactive both in the initial ionization and in the subsequent nucleophilic attack....

  5. Allyl group as a protecting group for internucleotide phosphate and thiophosphate linkages in oligonucleotide synthesis: facile oxidation and deprotection conditions.

    Manoharan, M; Lu, Y; Casper, M D; Just, G


    [reaction: see text] The allyl group, which serves as a protecting group for an internucleotide bond for both phosphates and phosphorothioates, can be easily removed by good nucleophiles under weakly basic or neutral conditions. For a practical synthesis on solid support, camphorsulfonyloxaziridine was used as the oxidizing agent for synthesizing DNA, while the Beaucage reagent was used for preparing phosphorothioate oligomers. Both types of oligonucleotides were easily deprotected by concentrated ammonium hydroxide containing 2% mercaptoethanol.

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

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


    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.

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

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


    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.

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

    刘洋; 刘诗薇; 李志强; 于景坤


    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.

  9. Alcoholic liver disease

    Liver disease due to alcohol; Cirrhosis or hepatitis - alcoholic; Laennec's cirrhosis ... Alcoholic liver disease occurs after years of heavy drinking. Over time, scarring and cirrhosis can occur. Cirrhosis is the ...

  10. Breath alcohol test

    Alcohol test - breath ... There are various brands of breath alcohol tests. Each one uses a different method to test the level of alcohol in the breath. The machine may be electronic or manual. One ...

  11. Weight loss and alcohol

    ... 19548203 . National Institute on Alcohol Abuse and Alcoholism. Rethinking Drinking: Alcohol and Your Health. rethinkingdrinking.niaaa.nih. ... about A.D.A.M.'s editorial policy , editorial process and privacy policy . A.D.A.M. is ...

  12. Behind the Label "Alcoholic."

    Wright, Deborah M.


    Relates individual's personal story of her childhood influenced by her parent's alcoholism, her own alcoholism as a young adult, and her experiences with counseling. Asks others not to reject her because of the label "alcoholic." (ABL)

  13. Effects of Allyl Isothiocyanate, Acetaminophen, and Dipyrone in the Guinea-Pig Ileum.

    Donnerer, Josef; Liebmann, Ingrid


    Allyl isothiocyanate (AITC, mustard oil, 50-200 µmol/l), depending on specific dosages, inhibited the cholinergic twitch response in the longitudinal muscle-myenteric plexus (LMMP) strip of the guinea-pig ileum. AITC also induced short-lasting contractile responses, and decreases of the basal tone of the LMMP strip at low concentrations and increases at high concentrations. Hexamethonium, a blocker of nicotinic ganglionic transmission, was able to prevent the AITC-evoked inhibitory effect, an effect that was also observed with the opioid antagonist naloxone. The P2 purinoceptor antagonist pyridoxalphosphate-6-azophenyl-2'-4'-disulphonic acid and guanethidine had no significant influence on the inhibitory effect of AITC. Since AITC also reduced the electrical stimulation-induced myogenic smooth muscle contractions in the LMMP preparation, its contractile and relaxant actions can be regarded as neurogenic and myogenic in nature. The analgesics, acetaminophen (paracetamol, 100-500 µmol/l) and dipyrone (metamizole, 100-500 µmol/l), reduced both the cholinergic twitch and the myogenic contractions in the LMMP strip to the same extent; therefore, their action in the intestinal smooth muscle can be regarded as myogenic spasmolytic in nature. © 2016 S. Karger AG, Basel.

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

    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)


    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.

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

    Bjørnar Sporsheim


    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.

  16. Hydrolysis of cellulose catalyzed by quaternary ammonium perrhenates in 1-allyl-3-methylimidazolium chloride.

    Wang, Jingyun; Zhou, Mingdong; Yuan, Yuguo; Zhang, Quan; Fang, Xiangchen; Zang, Shuliang


    Quaternary ammonium perrhenates were applied as catalyst to promote the hydrolysis of cellulose in 1-allyl-3-methylimidazolium chloride ([Amim]Cl). The quaternary ammonium perrhenates displayed good catalytic performance for cellulose hydrolysis. Water was also proven to be effective to promote cellulose hydrolysis. Accordingly, 97% of total reduced sugar (TRS) and 42% of glucose yields could be obtained under the condition of using 5mol% of tetramethyl ammonium perrhenate as catalyst, 70μL of water, ca. 0.6mmol of microcrystalline cellulose (MCC) and 2.0g of [Amim]Cl as solvent under microwave irradiation for 30min at 150°C (optimal conditions). The influence of quaternary ammonium cation on the efficiency of cellulose hydrolysis was examined based on different cation structures of perrhenates. The mechanism on perrhenate catalyzed cellulose hydrolysis is also discussed, whereas hydrogen bonding between ReO4 anion and hydroxyl groups of cellulose is assumed to be the key step for depolymerization of cellulose. Copyright © 2015. Published by Elsevier Ltd.

  17. Pharmacokinetics, Tissue Distribution, and Anti-Lipogenic/Adipogenic Effects of Allyl-Isothiocyanate Metabolites.

    Yang-Ji Kim

    Full Text Available Allyl-isothiocyanate (AITC is an organosulfur phytochemical found in abundance in common cruciferous vegetables such as mustard, wasabi, and cabbage. Although AITC is metabolized primarily through the mercapturic acid pathway, its exact pharmacokinetics remains undefined and the biological function of AITC metabolites is still largely unknown. In this study, we evaluated the inhibitory effects of AITC metabolites on lipid accumulation in vitro and elucidated the pharmacokinetics and tissue distribution of AITC metabolites in rats. We found that AITC metabolites generally conjugate with glutathione (GSH or N-acetylcysteine (NAC and are distributed in most organs and tissues. Pharmacokinetic analysis showed a rapid uptake and complete metabolism of AITC following oral administration to rats. Although AITC has been reported to exhibit anti-tumor activity in bladder cancer, the potential bioactivity of its metabolites has not been explored. We found that GSH-AITC and NAC-AITC effectively inhibit adipogenic differentiation of 3T3-L1 preadipocytes and suppress expression of PPAR-γ, C/EBPα, and FAS, which are up-regulated during adipogenesis. GSH-AITC and NAC-AITC also suppressed oleic acid-induced lipid accumulation and lipogenesis in hepatocytes. Our findings suggest that AITC is almost completely metabolized in the liver and rapidly excreted in urine through the mercapturic acid pathway following administration in rats. AITC metabolites may exert anti-obesity effects through suppression of adipogenesis or lipogenesis.

  18. On the antioxidant, neuroprotective and anti-inflammatory properties of S-allyl cysteine: An update.

    Colín-González, Ana Laura; Ali, Syed F; Túnez, Isaac; Santamaría, Abel


    Therapeutic approaches based on isolated compounds obtained from natural products to handle central and peripheral disorders involving oxidative stress and inflammation are more common nowadays. The validation of nutraceutics vs. pharmaceutics as tools to induce preventive and protective profiles in human health alterations is still far of complete acceptance, but the basis to start more solid experimental and clinical protocols with natural products has already begun. S-allyl cysteine (SAC) is a promising garlic-derived organosulfur compound exhibiting a considerable number of positive actions in cell models and living systems. An update, in the form of review, is needed from time to time to get access to the state-of-the-art on this topic. In this review we visited recent and refreshing evidence of new already proven and potential targets to explain the benefits of using SAC against toxic and pathological conditions. The broad spectrum of protective actions covered by this molecule comprises antioxidant, redox modulatory and anti-inflammatory activities, accompanied by anti-apoptotic, pro-energetic and signaling capacities. Herein, we detail the evidence on these aspects to provide the reader a more complete overview on the promising aspects of SAC in research.

  19. Study on the interaction of bioactive compound S-allyl cysteine from garlic with serum albumin

    Yue-e Sun


    Full Text Available Multispectroscopic techniques were used to investigate the interaction of S-allyl cysteine (SAC from garlic with human serum albumin (HSA. UV–Vis absorption measurements prove the formation of the HSA–SAC complex. An analysis of fluorescence spectra revealed that in the presence of SAC, the quenching mechanism of HSA is considered static. The quenching rate constant Kq, KSV, and the binding constant KA were estimated. According to the Van’t Hoff equation, the thermodynamic parameters enthalpy change (ΔH and entropy change (ΔS were calculated to be −1.00×105 J/mol and −255 J/mol/K, respectively. These indicate that hydrogen bonds and van der Waals forces are the major forces between SAC and HSA. The changes in the secondary structure of HSA, which was induced by SAC, were determined by circular dichroism spectroscopy. Energy transfer was confirmed and the distance between donor and acceptor was calculated to be 2.83 nm.

  20. Non-Directed Allylic C-H Acetoxylation in the Presence of Lewis Basic Heterocycles.

    Malik, Hasnain A; Taylor, Buck L H; Kerrigan, John R; Grob, Jonathan E; Houk, K N; Du Bois, J; Hamann, Lawrence G; Patterson, Andrew W


    We outline a strategy to enable non-directed Pd(II)-catalyzed C-H functionalization in the presence of Lewis basic heterocycles. In a high-throughput screen of two Pd-catalyzed C-H acetoxylation reactions, addition of a variety of N-containing heterocycles is found to cause low product conversion. A pyridine-containing test substrate is selected as representative of heterocyclic scaffolds that are hypothesized to cause catalyst arrest. We pursue two approaches in parallel that allow product conversion in this representative system: Lewis acids are found to be effective in situ blocking groups for the Lewis basic site, and a pre-formed pyridine N-oxide is shown to enable high yield of allylic C-H acetoxylation. Computational studies with density functional theory (M06) of binding affinities of selected heterocycles to Pd(OAc)2 provide an inverse correlation of the computed heterocycle-Pd(OAc)2 binding affinities with the experimental conversions to products. Additionally, (1)H NMR binding studies provide experimental support for theoretical calculations.

  1. Synergistic effect of allyl isothiocyanate (AITC) on cisplatin efficacy in vitro and in vivo.

    Ling, Xiang; Westover, David; Cao, Felicia; Cao, Shousong; He, Xiang; Kim, Hak-Ryul; Zhang, Yuesheng; Chan, Daniel Cf; Li, Fengzhi


    Although in vitro studies have shown that isothiocyanates (ITCs) can synergistically sensitize cancer cells to cisplatin treatment, the underlying mechanisms have not been well defined, and there are no in vivo demonstrations of this synergy. Here, we report the in vitro and in vivo data for the combination of allyl isothiocyanate (AITC), one of the most common naturally occurring ITCs, with cisplatin. Our study revealed that cisplatin and AITC combination synergistically inhibits cancer cell growth and colony formation, and enhances apoptosis in association with the downregulation of antiapoptotic proteins Bcl-2 and survivin. Importantly, the in vivo combination treatment suppresses human tumor growth in animal models without observable increases in toxicity (body weight loss) in comparison with single agent treatment. Furthermore, our data revealed that addition of AITC to cisplatin treatment changes the profile of G2/M arrest (e.g. increase in M phase cell number) and significantly extends the duration of G2/M arrest in comparison with cisplatin treatment alone. To explore the underlying mechanism, we found that AITC treatment rapidly depletes b-tubulin. Combination of AITC and cisplatin inhibits the expression of G2/M checkpoint-relevant proteins including CDC2, cyclin B1 and CDC25. Together, our findings reveal a novel mechanism for AITC enhancing cisplatin efficacy and provides the first in vivo evidence to support ITCs as potential candidates for developing new regimens to overcome platinum resistance.

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

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


    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.

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

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


    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.


    O. D. Ostroumova


    Full Text Available The article considers the questions of the relationship between the amount of the consumed alcohol, the type of alcoholic beverage, pattern of alcohol consumption and the blood pressure level. The article presents data on the positive effect of alcohol intake restrictions and recommendations for permissible limits of alcohol consumption. New possibilities of drug therapy aimed at limiting alcohol consumption are being reported.

  5. Genetics and alcoholism

    Edenberg, Howard J; Foroud, Tatiana


    Alcohol is widely consumed, but excessive use creates serious physical, psychological and social problems and contributes to many diseases. Alcoholism (alcohol dependence, alcohol use disorders) is a maladaptive pattern of excessive drinking leading to serious problems. Abundant evidence indicates that alcoholism is a complex genetic disease, with variations in a large number of genes affecting risk. Some of these genes have been identified, including two genes of alcohol me...

  6. Alcoholism and alcohol drinking habits predicted from alcohol dehydrogenase genes

    Tolstrup, Janne Schurmann; Nordestgaard, Børge Grønne; Rasmussen, Søren


    Alcohol drinking habits and alcoholism are partly genetically determined. Alcohol is degraded primarily by alcohol dehydrogenase (ADH) wherein genetic variation that affects the rate of alcohol degradation is found in ADH1B and ADH1C. It is biologically plausible that these variations may...... be associated with alcohol drinking habits and alcoholism. By genotyping 9080 white men and women from the general population, we found that men and women with ADH1B slow vs fast alcohol degradation drank more alcohol and had a higher risk of everyday drinking, heavy drinking, excessive drinking...... and of alcoholism. For example, the weekly alcohol intake was 9.8 drinks (95% confidence interval (CI): 9.1-11) among men with the ADH1B.1/1 genotype compared to 7.5 drinks (95% CI: 6.4-8.7) among men with the ADH1B.1/2 genotype, and the odds ratio (OR) for heavy drinking was 3.1 (95% CI: 1.7-5.7) among men...

  7. Highly practical copper(I)/TEMPO catalyst system for chemoselective aerobic oxidation of primary alcohols.

    Hoover, Jessica M; Stahl, Shannon S


    Aerobic oxidation reactions have been the focus of considerable attention, but their use in mainstream organic chemistry has been constrained by limitations in their synthetic scope and by practical factors, such as the use of pure O(2) as the oxidant or complex catalyst synthesis. Here, we report a new (bpy)Cu(I)/TEMPO catalyst system that enables efficient and selective aerobic oxidation of a broad range of primary alcohols, including allylic, benzylic, and aliphatic derivatives, to the corresponding aldehydes using readily available reagents, at room temperature with ambient air as the oxidant. The catalyst system is compatible with a wide range of functional groups and the high selectivity for 1° alcohols enables selective oxidation of diols that lack protecting groups.

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

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


    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.

  9. Health risks of alcohol use

    Alcoholism - risks; Alcohol abuse - risks; Alcohol dependence - risks; Risky drinking ... Beer, wine, and liquor all contain alcohol. If you are drinking any of these, you are using alcohol. Your drinking patterns may vary, depending on who you are with ...

  10. Alcoholism and alcohol drinking habits predicted from alcohol dehydrogenase genes

    Tolstrup, J.S.; Nordestgaard, Børge; Rasmussen, S.


    Alcohol is degraded primarily by alcohol dehydrogenase (ADH) wherein genetic variation that affects the rate of alcohol degradation is found in ADH1B and ADH1C. It is biologically plausible that these variations may be associated with alcohol drinking habits and alcoholism. By genotyping 9080 white...... men and women from the general population, we found that men and women with ADH1B slow vs fast alcohol degradation drank more alcohol and had a higher risk of everyday drinking, heavy drinking, excessive drinking and of alcoholism. For example, the weekly alcohol intake was 9.8 drinks (95% confidence......, individuals with ADH1C slow vs fast alcohol degradation had a higher risk of heavy and excessive drinking. For example, the OR for heavy drinking was 1.4 (95% CI: 1.1-1.8) among men with the ADH1C.1/2 genotype and 1.4 (95% CI: 1.0-1.9) among men with the ADH1B.2/2 genotype, compared with men with the ADH1C.1...

  11. [Representations of alcoholism in a former alcoholics' association: Alcoholics Anonymous].

    Campos, Edemilson Antunes de


    This article is designed to review the representations of alcoholism provided by members of an association of former alcoholics, namely Alcoholics Anonymous (AA), based on partial results from a qualitative survey conducted in the Sapopemba group of AA in a neighborhood on the outskirts of the city of Sao Paulo, Brazil. The article thus analyzes alcoholism from an emic perspective, i.e., how it is conceived and managed by those who acknowledge themselves as being "sick as alcoholics", how they explain the sickness, how they experience it, and how they endeavor to overcome it. The purpose is to present AA and its treatment strategy and to highlight the link made by the association by conceiving of alcoholism as a physical, moral, and spiritual illness.

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

    Verena Weidmann


    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.

  13. New copolymer of acrylamide with allyl methacrylate and its capacity for the removal of azo dyes

    Yeliz Yildirim


    Full Text Available The copolymerization reactions of Acrylamide (AA with the different mole ratios of allyl methacrylate (AMA such as 25/75, 50/50 and 75/25 were studied by radical polymerization under argon atmosphere using 2,2’-Azobis (isobutyronitri1e (AIBN as initiator. The copolymers were characterized with Fourier transform infrared spectroscopy (FTIR and thermogravimetric analysis (TG. FTIR spectra showed that the C=O, C-N and N-H groups in copolymers remained during the copolymerization. It is concluded from the thermograms that Poly(AA-co-AMA copolymers which contained different ratios of monomer and comonomer exhibit similar thermal behavior. Adsorption capacity, kinetic and isotherm studies of Direct Brown 2 onto the copolymers have been evaluated. Different factors such as the monomer ratio, pH, initial dye concentration, copolymer dosage and contact time affecting the removal process were studied. It was found that the adsorption process agreed with the Freundlich and Dubinin-Raduskevich model and the adsorption of Direct Brown 2 depended on the acrylamide content and pH of the solution. The standard Gibb’s free energy was determined as - 14.7 kJ/mol, which means that adsorption occurred spontaneously and the process is feasible. Increasing the acrylamide content led to increased adsorption of Direct Brown 2 on the copolymer. Moreover, adsorption kinetic studies showed that the adsorption followed a pseudo-second-order kinetic model, indicating that the chemical adsorption was the rate-limiting step. These results show that Poly(AA-co-AMA can be used as adsorbent for water pollutants such as Direct Brown 2 and has potential applications in related industrial and environmental areas.

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

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


    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.

  15. Mechanisms of transient receptor potential vanilloid 1 activation and sensitization by allyl isothiocyanate.

    Gees, Maarten; Alpizar, Yeranddy A; Boonen, Brett; Sanchez, Alicia; Everaerts, Wouter; Segal, Andrei; Xue, Fenqin; Janssens, Annelies; Owsianik, Grzegorz; Nilius, Bernd; Voets, Thomas; Talavera, Karel


    Allyl isothiocyanate (AITC; aka, mustard oil) is a powerful irritant produced by Brassica plants as a defensive trait against herbivores and confers pungency to mustard and wasabi. AITC is widely used experimentally as an inducer of acute pain and neurogenic inflammation, which are largely mediated by the activation of nociceptive cation channels transient receptor potential ankyrin 1 and transient receptor potential vanilloid 1 (TRPV1). Although it is generally accepted that electrophilic agents activate these channels through covalent modification of cytosolic cysteine residues, the mechanism underlying TRPV1 activation by AITC remains unknown. Here we show that, surprisingly, AITC-induced activation of TRPV1 does not require interaction with cysteine residues, but is largely dependent on S513, a residue that is involved in capsaicin binding. Furthermore, AITC acts in a membrane-delimited manner and induces a shift of the voltage dependence of activation toward negative voltages, which is reminiscent of capsaicin effects. These data indicate that AITC acts through reversible interactions with the capsaicin binding site. In addition, we show that TRPV1 is a locus for cross-sensitization between AITC and acidosis in nociceptive neurons. Furthermore, we show that residue F660, which is known to determine the stimulation by low pH in human TRPV1, is also essential for the cross-sensitization of the effects of AITC and low pH. Taken together, these findings demonstrate that not all reactive electrophiles stimulate TRPV1 via cysteine modification and help understanding the molecular bases underlying the surprisingly large role of this channel as mediator of the algesic properties of AITC.

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

    Sadhana Shrivastava


    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

  17. Rheological and mechanical behavior of polyacrylamide hydrogels chemically crosslinked with allyl agarose for two-dimensional gel electrophoresis.

    Suriano, R; Griffini, G; Chiari, M; Levi, M; Turri, S


    Two-dimensional (2-D) gel electrophoresis currently represents one of the most standard techniques for protein separation. In addition to the most commonly employed polyacrylamide crosslinked hydrogels, acrylamide-agarose copolymers have been proposed as promising systems for separation matrices in 2-D electrophoresis, because of the good resolution of both high and low molecular mass proteins made possible by careful control and optimization of the hydrogel pore structure. As a matter of fact, a thorough understanding of the nature of the hydrogel pore structure as well as of the parameters by which it is influenced is crucial for the design of hydrogel systems with optimal sieving properties. In this work, a series of acrylamide-based hydrogels covalently crosslinked with different concentrations of allyl agarose (0.2-1%) is prepared and characterized by creep-recovery measurements, dynamic rheology and tensile tests, in the attempt to gain a clearer understanding of structure-property relationships in crosslinked polyacrylamide-based hydrogels. The rheological and mechanical properties of crosslinked acrylamide-agarose hydrogels are found to be greatly affected by crosslinker concentration. Dynamic rheological tests show that hydrogels with a percentage of allyl agarose between 0.2% and 0.6% have a low density of elastically effective crosslinks, explaining the good separation of high molecular mass proteins in 2-D gel electrophoresis. Over the same range of crosslinker concentration, creep-recovery measurements reveal the presence of non-permanent crosslinks in the hydrogel network that justifies the good resolution of low molecular mass proteins as well. In tensile tests, the hydrogel crosslinked with 0.4% of allyl agarose exhibits the best results in terms of mechanical strength and toughness. Our results show how the control of the viscoelastic and the mechanical properties of these materials allow the design of mechanically stable hydrogels with improved

  18. Alcohol and Breastfeeding

    Haastrup, Maija Bruun; Pottegård, Anton; Damkier, Per


    While the harmful effects of alcohol during pregnancy are well-established, the consequences of alcohol intake during lactation have been far less examined. We reviewed available data on the prevalence of alcohol intake during lactation, the influence of alcohol on breastfeeding......, the pharmacokinetics of alcohol in lactating women and nursing infants and the effects of alcohol intake on nursing infants. A systematic search was performed in PubMed from origin to May 2013, and 41 publications were included in the review. Approximately half of all lactating women in Western countries consume...... alcohol while breastfeeding. Alcohol intake inhibits the milk ejection reflex, causing a temporary decrease in milk yield. The alcohol concentrations in breast milk closely resemble those in maternal blood. The amount of alcohol presented to nursing infants through breast milk is approximately 5...


    陈春武; 谢令德; 陈雅群; 何君; 贺艳萍


    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.

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

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


    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.

  1. Rhodium-Catalyzed Regioselective Domino Azlactone-Alkyne Coupling/Aza-Cope Rearrangement: Facile Access to 2-Allyl-3-oxazolin-5-ones and Trisubstituted Pyridines.

    Kuang, Jinqiang; Parveen, Shaista; Breit, Bernhard


    Rhodium-catalyzed regioselective addition of azlactones to internal alkynes combined with aza-Cope rearrangement provides efficient atom economic access to 2-allyl-3-oxazolin-5-one derivatives. Extension to a triple domino process, in which the above process is combined with in situ azlactone formation starting from amino acids renders this process even more attractive. Subsequent thermolysis of the 2-allyl-3-oxazolines enabled the de novo synthesis of trisubstituted pyridines. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. [bmim][Br] as a solvent and activator for the Ga-mediated Barbier allylation: direct formation of an N-heterocyclic carbene from Ga metal.

    Goswami, Dibakar; Chattopadhyay, Angshuman; Sharma, Anubha; Chattopadhyay, Subrata


    The room-temperature ionic liquid (RTIL) [bmim][Br] has been found to be an excellent green and inexpensive medium for the Ga-mediated allylation of aromatic and aliphatic aldehydes and ketones. The RTIL activated the metal via formation of a Ga-N-heterocyclic carbene complex that assisted in the completion of the reaction at ambient temperature with only 0.5 equiv of Ga and 1.2 equiv of allyl bromide with respect to the carbonyl substrates. The present protocol required a much shorter time than those reported in the literature using other metals and solvents and proceeded with good yields and excellent selectivity.

  3. Mg(OMe)2 promoted allylic isomerization of γ-hydroxy-α,β-alkenoic esters to synthesize γ-ketone esters.

    Lai, Luhao; Li, A-Ni; Zhou, Jiawei; Guo, Yarong; Lin, Li; Chen, Wei; Wang, Rui


    This work concerns the Mg(OMe)2 promoted allylic isomerization of γ-hydroxy-α,β-alkenoic esters with TMEDA as an additive. The isomerization proceeded under mild conditions and afforded γ-keto esters in high yield (up to 96%) within 2 h. Both (Z)- and (E)-γ-hydroxy-α,β-alkenoic esters were tolerated under the reaction conditions. This transformation involves the in situ formation of a dienolate intermediate from the easily accessible γ-hydroxy-α,β-alkenoic ester. The in situ generated dienolate can react with benzaldehyde and undergo a practical, useful tandem allylic isomerization-Aldol reaction to afford more functionalized compounds.

  4. Pressure-Resistant Plane Disc Viewports from Allyl Diglycol Carbonate Plastic for Hyperbaric Chambers.


    DISINFECTANT DEPTH OF CRAZING, in. STCP*, psi 6blu Vii-o-Ter 0.129 250 6b2u Lysol 0.159 220 6b3u methyl alcohol 0.184 120 6b4u Staphene 0.126 300 6b5u Amphyl...FOR 60 MIN SPECIMEN NO. DISINFECTANT DEPTH CRAZING, in. STCP*, psi 6alc Viro-Tec 0.117 270 6a2c Lysol failed after 18.5 min 6a3c methyl alcohol

  5. Alcoholism and alcohol drinking habits predicted from alcohol dehydrogenase genes.

    Tolstrup, Janne Schurmann; Nordestgaard, Børge Grønne; Rasmussen, Søren; Tybjaerg-Hansen, Anne; Grønbaek, Morten


    Alcohol drinking habits and alcoholism are partly genetically determined. Alcohol is degraded primarily by alcohol dehydrogenase (ADH) wherein genetic variation that affects the rate of alcohol degradation is found in ADH1B and ADH1C. It is biologically plausible that these variations may be associated with alcohol drinking habits and alcoholism. By genotyping 9080 white men and women from the general population, we found that men and women with ADH1B slow vs fast alcohol degradation drank more alcohol and had a higher risk of everyday drinking, heavy drinking, excessive drinking and of alcoholism. For example, the weekly alcohol intake was 9.8 drinks (95% confidence interval (CI): 9.1-11) among men with the ADH1B.1/1 genotype compared to 7.5 drinks (95% CI: 6.4-8.7) among men with the ADH1B.1/2 genotype, and the odds ratio (OR) for heavy drinking was 3.1 (95% CI: 1.7-5.7) among men with the ADH1B.1/1 genotype compared to men with the ADH1B.1/2 genotype. Furthermore, individuals with ADH1C slow vs fast alcohol degradation had a higher risk of heavy and excessive drinking. For example, the OR for heavy drinking was 1.4 (95% CI: 1.1-1.8) among men with the ADH1C.1/2 genotype and 1.4 (95% CI: 1.0-1.9) among men with the ADH1B.2/2 genotype, compared with men with the ADH1C.1/1 genotype. Results for ADH1B and ADH1C genotypes among men and women were similar. Finally, because slow ADH1B alcohol degradation is found in more than 90% of the white population compared to less than 10% of East Asians, the population attributable risk of heavy drinking and alcoholism by ADH1B.1/1 genotype was 67 and 62% among the white population compared with 9 and 24% among the East Asian population.

  6. Deciding to quit drinking alcohol

    ... quitting drinking; Quitting drinking; Quitting alcohol; Alcoholism - deciding to quit ... drinking problem when your body depends on alcohol to function and your drinking is causing problems with ...

  7. Alcohol Dependence and Alcoholic Liver Disease

    Karl Mann


    Full Text Available Alcohol dependence is a disabling condition that has a high prevalence, but in Europe only a small fraction of the people diagnosed with alcohol abuse and dependence are treated, representing the widest treatment gap, as compared with other mental disorders. Early diagnosis and monitoring of alcoholic liver disease (ALD is still insufficiently solved. Although ALD is the most common cause for liver disease in the Western world, it largely remains underestimated and underdiagnosed for many reasons. The recent introduction of non-invasive elastographic techniques such as transient elastography (TE has significantly improved the early diagnosis of alcoholic liver cirrhosis (ALC. As demonstrated in the literature, inflammation-associated liver stiffness (LS rapidly decreases during alcohol detoxification, and is also directly correlated to change in LS in both abstinent and relapsing patients. Newly published data show that LS could be used to monitor and validate hepatoprotective effects during nalmefene usage. Nalmefene is an opioid system modulator that diminishes the reinforcing effects of alcohol, helping the patient to reduce drinking. Three randomised, multicentre, double-blind, placebo-controlled, parallelgroup Phase III studies were designed to assess the efficacy and safety of nalmefene in reducing alcohol consumption. Patients with a high or very high drinking risk level (DRL at baseline and randomisation show a clinically significant effect from nalmefene treatment, which is generally well tolerated. Moreover, reduced alcohol consumption supported by nalmefene in combination with psychosocial support may indeed help to reduce the alcohol-related burden and the large treatment gap.

  8. The - - and Submm-Wave Spectrum of Allyl Isocyanide and Radioastronomical Observations in Orion KL and the Primos Line Survey

    Haykal, I.; Motiyenko, R. A.; Margules, L.; Huet, T. R.; Ecija, P.; Cocinero, E. J.; Basterretxea, F.; Fernandez, J. A.; Castano, F.; Tercero, B.; Cernicharo, J.; Lesarri, A.; Guillemin, J. C.


    Last year we presented the first rotational analysis of the ground state of the two conformers of allyl isocyanide from 4 GHz to 905 GHz. The analysis of the rotational spectrum of the cis conformer of allyl isocyanide was extended. We resolved Coriolis interactions of a and b types between the excited vibrational states ν_1=1 and ν_2=1, calculated to be at 156 cm^{-1} (A^{'}) and 167 cm^{-1} (A^{''}) respectively (MP2/aug-cc-pvtz), from 150 GHz to 600 GHz. Strong perturbations were observed in the 150-310 GHz range for low values of the quantum number K_a starting from K_a = 0, 1. The anharmonicities appeared as well at higher frequencies for larger quantum numbers. The two modes were fitted together with the SPFIT/SPCAT suite of programs and a set of Coriolis parameters was accurately determined. The fit contains more than 3000 lines up to J = 99 and K_a = 12 for both modes. We did not detect these species neither in the IRAM 30-m line survey of Orion KL nor in the PRIMOS survey towards SgrB2. Nevertheless, we provided upper limits to their column density in Orion KL. This work was supported by the CNES and the Action sur Projets de l'INSU, PCMI. I. Haykal et al. manuscript in preparation H. Pickett J. Mol. Spec.{148}, 371-377, 1991.

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

    Sun, Y-E; Wang, W-D


    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.

  10. Allylic H-Abstraction Mechanism:  The Potential Energy Surface of the Reaction of Propene with OH Radical.

    Szori, Milan; Fittschen, Christa; Csizmadia, Imre G; Viskolcz, Bela


    The allylic H-atom abstraction reaction plays a more dominant role, especially at lower temperature, than addition reactions in the case of the CH2 [Formula: see text] CH-CH3 + •OH system. Different computational methods including ab initio as well as density functional methods have been used to examine allylic H-abstraction. Both the energetically less favorable direct H-abstraction and the more favorable indirect H-abstractions have been investigated. Using first principles computations, for the indirect abstraction, a stable π- or reactantlike as well as a late productlike complex were found on the potential energy surface. Based on higher level single point calculations (QCISD(T)/6-311+G(3df,2p)), a new activation enthalpy value, Δ(⧧)H° = 0.3 ± 2 kJ/mol, is suggested for the title reaction. The computed reaction enthalpy ΔrH° = -124.7 ± 2 kJ/mol is in good agreement with the experimental value. The stability of the initial π-complex was found to be ΔH°π-complex = -7.1 kJ/mol. The product complex between the transition state and the product was found with the stability of -127.2 kJ/mol.

  11. Consumo de alcohol alcoholismo

    Rodríguez Páez, Pablo E.; Fundación Valle de Lili


    ¿Qué es el alcohol?/¿Cómo actual el alcohol en el organismo?/¿Qué efectos causa?/Efectos por el consumo crónico/¿El consumo de alcohol durante el embarazo afecta el embrión?/¿Qué otras consecuencias tiene el consumo de alcohol?/¿Cuándo se considera que una persona tiene problemas con su consumo de alcohol?/¿Cuándo se debe sospechar que alguien tiene problemas con el consumo de alcohol?/Características del saber beber adecuadamente?/¿Cuales son las alternativas de tratamiento para este problem...

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

    Sávio, André Luiz Ventura, E-mail: [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)


    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

  13. Alcohol homograph priming in alcohol-dependent inpatients

    Woud, M.L.; Salemink, E.; Gladwin, T.E.; Wiers, R.W.H.J.; Becker, E.S.; Lindenmeyer, J.; Rinck, M.


    Aim: Alcohol dependency is characterized by alcohol-related interpretation biases (IBs): Individuals with high levels of alcohol consumption generate more alcohol-related than alcohol-unrelated interpretations in response to ambiguous alcohol-related cues. However, a response bias could be an altern

  14. Close correlation between heat shock response and cytotoxicity in Neurospora crassa treated with aliphatic alcohols and phenols

    Meyer, U.; Schweim, P.; Fracella, F.; Rensing, L. [Univ. of Bremen (Germany)


    In Neurospora crassa the aliphatic alcohols methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, ethylene glycol, glycerol, and allyl alcohol and the phenolic compounds phenol, hydroquinone, resorcinol, pyrogallol, phloroglucinol, sodium salicylate, and acetylsalicylic acid were analyzed with respect to their capacities to induce heat shock proteins (HSP) and to inhibit protein synthesis. Both the alcohols and phenols showed the greatest levels of HSP induction at concentrations which inhibited the overall protein synthesis by about 50%. The abilities of the different alcohols to induce the heat shock response are proportional to their lipophilicities: the lipophilic alcohol isobutanol is maximally inductive at about 0.6 M, whereas the least lipophilic alcohol, methanol, causes maximal induction at 5.7 M. The phenols, in general, show a higher capability to induce the heat shock response. The concentrations for maximal induction range between 25 mM (sodium salicylate) and 100 mM (resorcinol). Glycerol (4.1 M) shifted the concentration necessary for maximal HSP induction by hydroquinone from 50 to 200 mM. The results reveal that the induction of HSP occurs under conditions which considerably constrain cell metabolism. The heat shock response, therefore, does not represent a sensitive marker for toxicity tests but provides a good estimate for the extent of cell damage.

  15. Alcohol Use and Older Adults

    ... version of this page please turn Javascript on. Alcohol Use and Older Adults Alcohol and Aging Adults of any age can have ... Escape (Esc) button on your keyboard.) What Is Alcohol? Alcohol, also known as ethanol, is a chemical ...

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

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


    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 ...

  17. An Expeditious Synthesis of [1,2]Isoxazolidin-5-ones and [1,2]Oxazin-6-ones from Functional Allyl Bromide Derivatives

    Imen Beltaïef


    Full Text Available Reaction of allyl bromide (Z-1 and (Z-2 with N-substituted hydroxylamine hydrochlorides in presence of tert-butoxide in tert-butanol at reflux provides a short and effective route to [1,2]isoxazolidin-5-ones 3 and [1,2]oxazin-6-ones 4.

  18. Ruthenium(III)-catalysed phenylselenylation of allyl acetates by diphenyl diselenide and indium(I) bromide in neat: isolation and identification of intermediate.

    Saha, Amit; Ranu, Brindaban C


    A fast and efficient phenylselenylation of allyl acetates by diphenyl diselenide and indium(I) bromide has been achieved in neat under the catalysis of Ru(acac)(3). The intermediate complex of diphenyl diselenide and indium has been isolated and identified as a polymeric pentacoordinated In(III) selenolate complex, [In(SePh)(3)](n).

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

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


    the cyclization reactions to take place in up to 94:6 enantiomeric ratio. A model Pd-allyl complex has been prepared and studied through NMR spectroscopic analysis, which provided insight into the processes responsible for the observed enantiomeric ratios. DFT studies were used to characterize the diastereomeric...

  20. Highly enantio- and diastereoselective one-pot reactions in aqueous media : Combined asymmetric Rh-catalyzed conjugate addition/metal-mediated allylation

    Kallstrom, Sara; Jagt, Richard B. C.; Sillanpaa, Reijo; Feringa, Ben L.; Minnaard, Adriaan J.; Leino, Reko; Källström, Sara; Sillanpää, Reijo


    1,3-Disubstituted, enantiopure cyclohexanols have been prepared in very high diastereoselectivities and good yields by a concise one-pot method combining the enantioselective rhodium-catalyzed conjugate addition of arylboronic acids with indium-mediated allylation into a highly efficient one-pot rea

  1. Alcohol and Cancer Risk

    ... is through the activity of an enzyme called alcohol dehydrogenase, or ADH. Many individuals of Chinese, Korean, and ... Abstract] Yokoyama A, Omori T. Genetic polymorphisms of alcohol and aldehyde dehydrogenases and risk for esophageal and head and neck ...

  2. Alcohol Facts and Statistics

    ... Standard Drink? Drinking Levels Defined Alcohol Facts and Statistics Print version Alcohol Use in the United States: ... 1245, 2004. PMID: 15010446 11 National Center for Statistics and Analysis. 2014 Crash Data Key Findings (Traffic ...

  3. Alcohol in moderation

    Mueller, Simone; Lockshin, Larry; Louviere, Jordan J.


    Purpose: The study examines the market potential for low and very low alcohol wine products under two different tax regimes. The penetration and market share of low alcohol wine are estimated under both tax conditions. Consumers’ alcoholic beverage purchase portfolios are analysed and those...... products identified, which are jointly purchased with low alcohol wines. The effect of a tax increase on substitution patterns between alcoholic beverages is examined. Methodology: In a discrete choice experiment, based on their last purchase, consumers select one or several different alcoholic beverages...... volume is estimated under the current tax regime. Between six to eight percent of consumers are expected to adopt low alcohol wine alternatives as part of their alcoholic beverage portfolio. Consumers of cask wine and light beer are more likely and consumers of medium-full strength beer and spirits...

  4. Benzyl Alcohol Topical

    Benzyl alcohol lotion is used to treat head lice (small insects that attach themselves to the skin) in adults ... children less than 6 months of age. Benzyl alcohol is in a class of medications called pediculicides. ...

  5. Alcohol Use Screening

    ... Centers Diseases + Condition Centers Mental Health Medical Library Alcohol Use Screening (AUDIT-C) - Instructions The following questions ... this tool, there is also text-only version . Alcohol Use Screening (AUDIT-C) - Manual Instructions The following ...

  6. Women and Alcohol

    ... turn JavaScript on. Feature: Rethinking Drinking Women and Alcohol Past Issues / Spring 2014 Table of Contents Women react differently than men to alcohol and face higher risks from it. Pound for ...

  7. Children of alcoholics

    Robert Oravecz


    Full Text Available The author briefly interprets the research – results, referring to the phenomenon of children of alcoholics, especially the psychological and psychopathological characteristics of children of alcoholics in adolescence and young adulthood. The author presents a screening study of adolescents. The sample contains 200 high school students at age 18. The aim of the survey was to discover the relationship between alcohol consumption of parents, PTSD - related psychopathological symptoms and reported life quality of their children. The study confirmed the hypothesis about a substantial correlation between high alcohol consumption of parents, higher psychopathological symptom - expression and lower reported life quality score of their children. Higher PTSD-related symptomatology in children of alcoholics is probably resulted by home violence, which is very often present in family of alcoholics. The article also evaluated the results regarding suicide ideation of children of alcoholics, which is definitely more frequent and more intense than in their peers living in non alcohol – dependent families.

  8. Comparative Studies on Conventional and Ultrasound-Assisted Synthesis of Novel Homoallylic Alcohol Derivatives Linked to Sulfonyl Dibenzene Moiety in Aqueous Media

    Mohamed F. Mady


    Full Text Available Novel homoallylic alcohols incorporating sulfone moieties were synthesized by the treatment of different carbonyl compounds with allylic bromides in aqueous media via sonochemical Barbier-type reaction conditions. Sulfonation of α-bromoketones with sodium benzenesulfinate in presence of CuI/2,6-lutidine rapidly gave β-keto-sulfones in good yields. In general, ultrasound irradiation offered the advantages of high yields, short reaction times, and simplicity compared to the conventional methods. The structures of all the compounds were confirmed by analytical and spectral data.

  9. Alcohol and Atherosclerosis

    Gao Yinglan; Song Jingyu; Jin Junshuo; Zhong Xiuhong; Ren Xiangshan; Liu Shuangping


    Objectives To study the relationship between alcohol and atherosclerosis (AS).Methods The paper reviewed the mechanism of the alcohol leading to AS from four aspects such as the introduction of alcohol and AS, imbalance of oxidationantioxidation system, oxygen free radical (OFR) and endothelium cell (EC) apoptosis, apoptosis and AS.Results Excessive alcohol could lead to imbalance of oxidation-antioxidation system, and increase OFR, in the meanwhile, OFR could lead to EC apoptosis,which could lead to AS.

  10. Fetal Alcohol Exposure

    ... her child’s genetic make-up, and changes in gene activity caused by prenatal alcohol exposure. NIH . . . Turning Discovery Into Health ® National Institute on Alcohol Abuse and Alcoholism www. niaaa. nih. gov • 301.443.3860 Interventions ...

  11. Hispanic Alcoholic Treatment Considerations.

    Costello, Raymond M.


    A path analytic model for Hispanic alcoholics relating socioclinical prognostic variables to outcome following treatment in a therapeutic community differs markedly from that fitted to Anglo alcoholics. The differential relationship of education to alcoholism severity and outcome was noted specifically as reflecting different racial-ethnic paths…

  12. Alcohol and liver

    Natalia Osna


    @@ Liver is a primary site of ethanol metabolism, which makes this organ susceptible to alcohol-induced damage.Alcoholic liver disease (ALD) has many manifestations and complicated pathogenesis. In this Topic Highlight, we included the key reviews that characterize new findings about the mechanisms of ALD development and might be of strong interest for clinicians and researchers involved in liver alcohol studies.

  13. Alcoholism and Lesbians

    Gedro, Julie


    This chapter explores the issues involved in the relationship between lesbianism and alcoholism. It examines the constellation of health and related problems created by alcoholism, and it critically interrogates the societal factors that contribute to the disproportionately high rates of alcoholism among lesbians by exploring the antecedents and…

  14. Television: Alcohol's Vast Adland.


    Concern about how much television alcohol advertising reaches underage youth and how the advertising influences their attitudes and decisions about alcohol use has been widespread for many years. Lacking in the policy debate has been solid, reliable information about the extent of youth exposure to television alcohol advertising. To address this…

  15. Alcohol and plasma triglycerides.

    Klop, Boudewijn; do Rego, Ana Torres; Cabezas, Manuel Castro


    This study reviews recent developments concerning the effects of alcohol on plasma triglycerides. The focus will be on population, intervention and metabolic studies with respect to alcohol and plasma triglycerides. Alcohol consumption and fat ingestion are closely associated and stimulated by each other via hypothalamic signals and by an elevated cephalic response. A J-shaped relationship between alcohol intake and plasma triglycerides has been described. A normal body weight, polyphenols in red wine and specific polymorphisms of the apolipoprotein A-V and apolipoprotein C-III genes may protect against alcohol-associated hypertriglyceridemia. In contrast, obesity exaggerates alcohol-associated hypertriglyceridemia and therefore the risk of pancreatitis. High alcohol intake remains harmful since it is associated with elevated plasma triglycerides, but also with cardiovascular disease, alcoholic fatty liver disease and the development of pancreatitis. Alcohol-induced hypertriglyceridemia is due to increased very-low-density lipoprotein secretion, impaired lipolysis and increased free fatty acid fluxes from adipose tissue to the liver. However, light to moderate alcohol consumption may be associated with decreased plasma triglycerides, probably determined by the type of alcoholic beverage consumed, genetic polymorphisms and lifestyle factors. Nevertheless, patients should be advised to reduce or stop alcohol consumption in case of hypertriglyceridemia.

  16. Alcohol and Minority Youth.

    Wright, Roosevelt, Jr.; Watts, Thomas D.


    Maintains that minority youth who use (or abuse) alcohol in American society deal with using alcohol, being minority, and being young, three dimensions viewed by society with mixed, sometimes hostile and/or fearful reactions. Suggests that examining alcoholism among minority youth involves coming to grips with poverty, education, income, and life…

  17. Simple and Efficient Ruthenium-Catalyzed Oxidation of Primary Alcohols with Molecular Oxygen.

    Ray, Ritwika; Chandra, Shubhadeep; Maiti, Debabrata; Lahiri, Goutam Kumar


    Oxidative transformations utilizing molecular oxygen (O2 ) as the stoichiometric oxidant are of paramount importance in organic synthesis from ecological and economical perspectives. Alcohol oxidation reactions that employ O2 are scarce in homogeneous catalysis and the efficacy of such systems has been constrained by limited substrate scope (most involve secondary alcohol oxidation) or practical factors, such as the need for an excess of base or an additive. Catalytic systems employing O2 as the "primary" oxidant, in the absence of any additive, are rare. A solution to this longstanding issue is offered by the development of an efficient ruthenium-catalyzed oxidation protocol, which enables smooth oxidation of a wide variety of primary, as well as secondary benzylic, allylic, heterocyclic, and aliphatic, alcohols with molecular oxygen as the primary oxidant and without any base or hydrogen- or electron-transfer agents. Most importantly, a high degree of selectivity during alcohol oxidation has been predicted for complex settings. Preliminary mechanistic studies including (18) O labeling established the in situ formation of an oxo-ruthenium intermediate as the active catalytic species in the cycle and involvement of a two-electron hydride transfer in the rate-limiting step.

  18. Genetics and alcoholism.

    Edenberg, Howard J; Foroud, Tatiana


    Alcohol is widely consumed; however, excessive use creates serious physical, psychological and social problems and contributes to the pathogenesis of many diseases. Alcohol use disorders (that is, alcohol dependence and alcohol abuse) are maladaptive patterns of excessive drinking that lead to serious problems. Abundant evidence indicates that alcohol dependence (alcoholism) is a complex genetic disease, with variations in a large number of genes affecting a person's risk of alcoholism. Some of these genes have been identified, including two genes involved in the metabolism of alcohol (ADH1B and ALDH2) that have the strongest known affects on the risk of alcoholism. Studies continue to reveal other genes in which variants affect the risk of alcoholism or related traits, including GABRA2, CHRM2, KCNJ6 and AUTS2. As more variants are analysed and studies are combined for meta-analysis to achieve increased sample sizes, an improved picture of the many genes and pathways that affect the risk of alcoholism will be possible.

  19. [Physical diseases in alcoholism].

    Takase, Kojiro


    Rapid excessive alcohol drinking frequently causes disturbance of consciousness due to head trauma, brain edema, hypoglycemia, hyponatremia, hepatic coma and so on, provoked by acute alcohol intoxication. Rapid differential diagnosis and management are extremely important to save a life. On the other hands, the chronic users of alcohol so called alcoholism has many kinds of physical diseases such as liver diseases (i.e., fatty liver, alcoholic hepatitis, alcoholic liver cirrhosis and miscellaneous liver disease), diabetes mellitus, injury to happen in drunkenness, pancreas disease (i.e., acute and chronic pancreatitis and deterioration of chronic pancreatitis), gastrontestinal diseases (i.e., gastroduodenal ulcer), and so on. Enough attention should be paid to above mentioned diseases, otherwise they would turn worse more with continuation and increase in quantity of the alcohol. It should be born in its mind that the excessive drinking becomes the weapon threatening life.

  20. Alcohol and atherosclerosis

    Tolstrup, Janne; Grønbaek, Morten


    (CHD). The cardioprotective effect of alcohol seems to be larger among middle-aged and elderly adults than among young adults, who do not have a net beneficial effect of a light to moderate alcohol intake in terms of reduced all-cause mortality. The levels of alcohol at which the risk of CHD is lowest......Light to moderate alcohol intake is known to have cardioprotective properties; however, the magnitude of protection depends on other factors and may be confined to some subsets of the population. This review focuses on factors that modify the relationship between alcohol and coronary heart disease...... and the levels of alcohol at which the risk of CHD exceeds the risk among abstainers are lower for women than for men. The pattern of drinking seems important for the apparent cardioprotective effect of alcohol, and the risk of CHD is generally lower for steady versus binge drinking. Finally, there is some...

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

    T. Mohandas


    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.

  2. Near-silence of isothiocyanate carbon in (13)C NMR spectra: a case study of allyl isothiocyanate.

    Glaser, Rainer; Hillebrand, Roman; Wycoff, Wei; Camasta, Cory; Gates, Kent S


    (1)H and (13)C NMR spectra of allyl isothiocyanate (AITC) were measured, and the exchange dynamics were studied to explain the near-silence of the ITC carbon in (13)C NMR spectra. The dihedral angles α = ∠(C1-C2-C3-N4) and β = ∠(C2-C3-N4-C5) describe the conformational dynamics (conformation change), and the bond angles γ = ∠(C3-N4-C5) and ε = ∠(N4-C5-S6) dominate the molecular dynamics (conformer flexibility). The conformation space of AITC contains three minima, Cs-M1 and enantiomers M2 and M2'; the exchange between conformers is very fast, and conformational effects on (13)C chemical shifts are small (νM1 - νM2 silence of the ITC carbon in (13)C NMR spectra of organic isothiocyanates.

  3. Synthesis, spectroscopic characterization and solution behavior of new tin tetrachloride adducts with γ-keto allyl phosphonates

    Elleuch, Haitham; Sanhoury, M. A. K.; Rezgui, F.


    Four new octahedral complexes of the type [SnCl4L2] (L = γ-keto allyl phosphonate) (1-4) were prepared and characterized by multinuclear (1H, 13C, 31P and 119Sn) NMR, IR spectroscopy and elemental analysis. The NMR data show, as expected, that these complexes exist in solution as mixtures of cis and trans isomers. More importantly, the solution structure was confirmed by 119Sn NMR spectra which show two triplets corresponding to the two isomers. In addition, the solution behavior of these complexes in the presence of excess ligand was studied by variable temperature NMR using the coalescence temperature method. The metal-ligand exchange activation energies were therefore determined and found to be in the range 57-60 kJ/mol. The effect of remote substituents on the metal-ligand interaction was studied and compared with closely related tin-phosphoryl complexes.

  4. Isolation and recovery of cellulose from waste nylon/cotton blended fabrics by 1-allyl-3-methylimidazolium chloride.

    Lv, Fangbing; Wang, Chaoxia; Zhu, Ping; Zhang, Chuanjie


    Development of a simple process for separating cellulose and nylon 6 from their blended fabrics is indispensable for recycling of waste mixed fabrics. An efficient procedure of dissolution of the fabrics in an ionic liquid 1-allyl-3-methylimidazolium chloride ([AMIM]Cl) and subsequent filtration separation has been demonstrated. Effects of treatment temperature, time and waste fabrics ratio on the recovery rates were investigated. SEM images showed that the cotton cellulose dissolved in [AMIM]Cl while the nylon 6 fibers remained. The FTIR spectrum of regenerated cellulose (RC) was similar with that of virgin cotton fibers, which verified that no other chemical reaction occurred besides breakage of hydrogen bonds during the processes of dissolution and separation. TGA curves indicated that the regenerated cellulose possessed a reduced thermal stability and was effectively removed from waste nylon/cotton blended fabrics (WNCFs). WNCFs were sufficiently reclaimed with high recovery rate of both regenerated cellulose films and nylon 6 fibers.

  5. Crystal structure of N-(1-allyl-3-chloro-4-ethoxy-1H-indazol-5-yl-4-methoxybenzenesulfonamide

    Hakima Chicha


    Full Text Available In the title compound, C19H20ClN3O4S, the benzene ring is inclined to the indazole ring system (r.m.s. deviation = 0.014 Å by 65.07 (8°. The allyl and ethoxy groups are almost normal to the indazole ring, as indicated by the respective torsion angles [N—N—C—C = 111.6 (2 and C—C—O—C = −88.1 (2°]. In the crystal, molecules are connected by N—H...N hydrogen bonds, forming helical chains propagating along [010]. The chains are linked by C—H...O hydrogen bonds, forming a three-dimensional network.

  6. Crystal structure of (Z-3-allyl-5-(4-chlorobenzylidene-2-sulfanylidene-1,3-thiazolidin-4-one

    Rahhal El Ajlaoui


    Full Text Available In the title compound, C13H10ClNOS2, the dihedral angle between the rhodanine (r.m.s. deviation = 0.008 Å and 4-chlorobenzylidene rings is 1.79 (11°. The allyl group attached to the N atom, which lies almost perpendicular to the rhodanine ring, is disordered over two orientations in a 0.519 (13:0.481 (13 ratio. A short intramolecular C—H...S interaction closes an S(6 ring. In the crystal, molecules are linked by π–π stacking interactions [centroid–centroid separation = 3.600 (15 Å], generating inversion dimers.

  7. Alcohol disrupts sleep homeostasis.

    Thakkar, Mahesh M; Sharma, Rishi; Sahota, Pradeep


    Alcohol is a potent somnogen and one of the most commonly used "over the counter" sleep aids. In healthy non-alcoholics, acute alcohol decreases sleep latency, consolidates and increases the quality (delta power) and quantity of NREM sleep during the first half of the night. However, sleep is disrupted during the second half. Alcoholics, both during drinking periods and during abstinences, suffer from a multitude of sleep disruptions manifested by profound insomnia, excessive daytime sleepiness, and altered sleep architecture. Furthermore, subjective and objective indicators of sleep disturbances are predictors of relapse. Finally, within the USA, it is estimated that societal costs of alcohol-related sleep disorders exceeds $18 billion. Thus, although alcohol-associated sleep problems have significant economic and clinical consequences, very little is known about how and where alcohol acts to affect sleep. In this review, we have described our attempts to unravel the mechanism of alcohol-induced sleep disruptions. We have conducted a series of experiments using two different species, rats and mice, as animal models. We performed microdialysis, immunohistochemical, pharmacological, sleep deprivation and lesion studies which suggest that the sleep-promoting effects of alcohol may be mediated via alcohol's action on the mediators of sleep homeostasis: adenosine (AD) and the wake-promoting cholinergic neurons of the basal forebrain (BF). Alcohol, via its action on AD uptake, increases extracellular AD resulting in the inhibition of BF wake-promoting neurons. Since binge alcohol consumption is a highly prevalent pattern of alcohol consumption and disrupts sleep, we examined the effects of binge drinking on sleep-wakefulness. Our results suggest that disrupted sleep homeostasis may be the primary cause of sleep disruption observed following binge drinking. Finally, we have also shown that sleep disruptions observed during acute withdrawal, are caused due to impaired

  8. Modulation of the multidrug efflux pump EmrD-3 from Vibrio cholerae by Allium sativum extract and the bioactive agent allyl sulfide plus synergistic enhancement of antimicrobial susceptibility by A. sativum extract.

    Bruns, Merissa M; Kakarla, Prathusha; Floyd, Jared T; Mukherjee, Mun Mun; Ponce, Robert C; Garcia, John A; Ranaweera, Indrika; Sanford, Leslie M; Hernandez, Alberto J; Willmon, T Mark; Tolson, Grace L; Varela, Manuel F


    The causative agent of cholera, Vibrio cholerae, is a public health concern. Multidrug-resistant V. cholerae variants may reduce chemotherapeutic efficacies of severe cholera. We previously reported that the multidrug efflux pump EmrD-3 from V. cholerae confers resistance to multiple structurally distinct antimicrobials. Medicinal plant compounds are potential candidates for EmrD-3 efflux pump modulation. The antibacterial activities of garlic Allium sativum, although poorly understood, predicts that a main bioactive component, allyl sulfide, modulates EmrD-3 efflux. Thus, we tested whether A. sativum extract acts in synergy with antimicrobials and that a main bioactive component allyl sulfide inhibits EmrD-3 efflux. We found that A. sativum extract and allyl sulfide inhibited ethidium bromide efflux in cells harboring EmrD-3 and that A. sativum lowered the MICs of multiple antibacterials. We conclude that A. sativum and allyl sulfide inhibit EmrD-3 and that A. sativum extract synergistically enhances antibacterial agents.

  9. 超硬材料磨具用烯丙基化酚醛改性双马来酰亚胺树脂的研究%Bismaleimide Modified by Allyl Novolak for Superabrasives

    郑红飞; 李志宏; 朱玉梅


    A novel thermosetting resin system for superabrasives based on novolak and bismaleimide (BMI) was developed.The novolak resin was allylated and then copolymerized with BMI.The structure of allyl novolak and reaction mechanism were analyzed by FTIR.Thermal and mechanical properties were characterized by using comprehensive thermal analyzer (DSC-TG) and strength tester,respectively.The results showed that high molecular weight of novolak was advantageous for heat-resistance,but was unfavorable for the bending strength.High allyl content improved the heat-resistance but lowered the bending strength.When the molecular weight of novolak was 450 and allyl content was 50%,the best resin system with good heat-resistance and bending strength was obtained.It was suitable for the manufacturing of superabrasive tools.

  10. A one-pot stereoselective synthesis of 1,4-dienyl selenides by hydrostannylation-Stille tandem reaction of acetylenic selenides with Bu3SnH and allylic bromides

    La Mei Yu; Wen Yan Hao; Ming Zhong Cai


    1,4-Dienyl selenides can be stereoselectively synthesized in one pot under mild conditions in good yields by the palladium-catalyzed hydrostannylation of acetylenic selenides, followed by Stille coupling with allylic bromides.

  11. Alcohol and pregnancy

    Anna Maria Paoletti


    Full Text Available Alcohol exerts teratogenic effects in all the gestation times, with peculiar features in relationship to the trimester of pregnancy in which alcohol is assumed. Alcohol itself and its metabolites modify DNA synthesis, cellular division, cellular migration and the fetal development. The characteristic facies of feto-alcoholic syndrome (FAS-affected baby depends on the alcohol impact on skull facial development during the first trimester of pregnancy. In association there are cerebral damages with a strong defect of brain development up to the life incompatibility. Serious consequences on fetal health also depends on dangerous effects of alcohol exposure in the organogenesis of the heart, the bone, the kidney, sensorial organs, et al. It has been demonstrated that maternal binge drinking is a high factor risk of mental retardation and of delinquent behaviour. Unfortunately, a lower alcohol intake also exerts deleterious effects on fetal health. In several countries of the world there is a high alcohol use, and this habit is increased in the women. Therefore, correct information has to be given to avoid alcohol use by women in the preconceptional time and during the pregnancy. Preliminary results of a study performed by the authors show that over 80% of pregnant and puerperal women are not unaware that more than 2 glasses of alcohol/week ingested during pregnancy can create neurological abnormalities in the fetus. However, after the information provided on alcoholic fetopathy, all women are conscious of the damage caused by the use of alcohol to the fetus during pregnancy. This study confirms the need to provide detailed information on the negative effects of alcohol on fetal health. Proceedings of the 9th International Workshop on Neonatology · Cagliari (Italy · October 23rd-26th, 2013 · Learned lessons, changing practice and cutting-edge research

  12. Role of cluster size and substrate in the gas phase CC bond coupling reactions of allyl halides mediated by Agn+ and Agn-1H+ cluster cations

    Wang, Farrah Qiuyun; Khairallah, George N.; O'Hair, Richard A. J.


    Previous studies have demonstrated that the silver hydride cluster cation Ag4H+ promotes CC bond coupling of allylbromide [G.N. Khairallah, R.A.J. O'Hair, Angewandte Chemie International Edition 44 (2005) 728]. Here the influence of both the nature and the size of the silver cluster cation and the substrate on CC bond coupling are examined. Thus each of the cations Ag2H+, Ag4H+, Ag3+, and Ag5+ were allowed to react with three different halides: allyl chloride, allyl bromide and allyl iodide. No CC bond coupling is observed in the reactions of the cluster cations with allyl chloride. There are four main reaction sequences that result in CC bond coupling for allyl bromide and allyl iodide mediated by Agn+ and Agn-1H+ clusters: (i) A sequence involving the reactions of silver cluster cations with two molecules of C3H5X: Agn+ --> Agn(C3H5X)+ --> AgnX2+. This only occurs in the cases of: n = 3 and X = I; n = 5 and X = Br. (ii) A sequence involving the reactions of silver cluster cations with two molecules of C3H5X via an organometallic intermediate: Agn+ --> Agn-1(C3H5)+ --> Agn-1X+. This only occurs in the cases of: n = 5 and X = Br and I. (iii) A sequence involving the reactions of silver hydride cluster cations with three molecules of C3H5X: Agn-1H+ --> Agn-1X+ --> Agn-1X(C3H5X)+ --> Ag(C3H5)2+ and Agn-1X3+. This only occurs in the cases of: n = 5 and X = Br and I. (iv) A sequence involving the reactions of silver hydride cluster cations with three molecules of C3H5X via an organometallic intermediate: Agn-1H+ --> Agn-1X+ --> Agn-3(C3H5)+ --> Ag(C3H5)2+ and Agn-3X+. This only occurs in the cases of: n = 5 and X = I.

  13. Alcohol Expectancies in Young Adult Sons of Alcoholics and Controls.

    Brown, Sandra A.; And Others

    Adolescent offspring of alcoholics have been found to have higher alcohol reinforcement expectancies than do teenagers from nonalcoholic families. In particular, those with a positive family history of alcoholism expect more cognitive and motor enhancement with alcohol consumption. This study examined the alcohol expectancies of 58 matched pairs…

  14. [Alcohol and nutrition].

    Maillot, F; Farad, S; Lamisse, F


    Alcoholism and alcohol-associated organ injury is one of the major health problems worldwide. Alcohol may lead to an alteration in intermediary metabolism and the relation between alcohol intake and body weight is a paradox. The effect of alcohol intake on resting metabolic rate, assessed by indirect calorimetry, and lipid oxidation, is still controversial. Small quantities of ethanol seem to have no effect on body weight. Ingestion of moderate amounts may lead to an increase in body weight, via a lipid-oxidizing suppressive effect. Chronic intake of excessive amounts in alcoholics leads to a decrease in body weight, probably via increased lipid oxidation and energy expenditure. Chronic ethanol abuse alters lipid-soluble (vitamins A, D and E) and water-soluble (B-complex vitamins, vitamin C) vitamins status, and some trace elements status such as magnesium, selenium or zinc.

  15. [Upgrade on alcohol abuse].

    Bordini, L; Riboldi, L


    Problematic use of alcohol configures an element of interest in the context of preventive interventions aimed to ensuring the performance of any work in safety conditions. To contrast the acute alcohol abuse in the workplace the existing legislation provides alcoholimeters controls and prohibition of recruitment and administration of alcohol. Recent legislation (D.Lgs. 81/08) establishes health surveillance for alcohol dependence and appears still incomplete and difficult to apply. Clinical diagnostic tools available to the physician for alcohol dependence identification are well-defined and recently improved thanks to new laboratory markers with high sensitivity and specificity (CDT) and self-administered questionnaires. In this contest we are awaiting for legislative action to specify conditions and procedures for inspections in the workplace in order to face the problem of alcohol dependence without excessive bureaucracy and with more attention to preventive aspects.

  16. Alcohol, aggression, and violence

    Darja Škrila


    Full Text Available Background: The association between alcohol and aggression has long been recognized, but the systematic research to understand the causal basis for this relationship and the processes that underlie it has only been undertaken in the past 25 years. In the article the most important mechanisms, by which alcohol affects behavior, are explained. Aggression in persons with alcohol dependence and the connection between antisocial (dissocial personality disorder, alcohol and aggression are described. In addition different forms of aggression or violence, that have been committed under the influence of alcohol, such as inter-partner violence, sexual assault, child abuse, crime and traffic accidents are described.Conclusions: The research findings can be used in the prevention and treatment of alcohol-related aggression.

  17. Alcohol and atherosclerosis

    Murilo Foppa


    Full Text Available Observational studies have attributed a protective effect to alcohol consumption on the development of atherosclerosis and cardiovascular morbidity and mortality. Alcohol intake in the amount of one to two drinks per day results in an estimated 20-40% reduction in cardiovascular events. An additional protective effect, according to major cohort studies, has been attributed to wine, probably due to antioxidant effects and platelet antiaggregation agents. On the other hand, the influence of different patterns of alcohol consumption and environmental factors may explain a great part of the additional effect of wine. Protection may be mediated by modulation of other risk factors, because alcohol increases HDL-C, produces a biphasic response on blood pressure, and modulates the endothelial function, while it neither increases body weight nor impairs glucose-insulin homeostasis. Alcohol may also have a direct effect on atherogenesis. Despite these favorable effects, the current evidence is not enough to justify prescribing alcohol to prevent cardiovascular disease.

  18. Alcohol use and menopause.

    Wilsnack, Richard W; Wilsnack, Sharon C


    Clinicians should periodically assess their menopausal patients' alcohol use. Specific health hazards from excessive alcohol consumption, as well as potential benefits of low-level consumption (for cardiovascular disease, bone health, and type 2 diabetes), should be discussed with their patients who drink. The information in this Practice Pearl can help clinicians provide evidence-based guidance about alcohol consumption and its relationship to common health concerns.

  19. Alcoholism and Diabetes Mellitus

    Soo-Jeong Kim; Dai-Jin Kim


    Chronic use of alcohol is considered to be a potential risk factor for the incidence of type 2 diabetes mellitus (T2DM), which causes insulin resistance and pancreatic β-cell dysfunction that is a prerequisite for the development of diabetes. However, alcohol consumption in diabetes has been controversial and more detailed information on the diabetogenic impact of alcohol seems warranted. Diabetes, especially T2DM, causes dysregulation of various metabolic processes, which includes a defect i...

  20. Alcohol-Induced Blackout

    Dai Jin Kim


    Full Text Available For a long time, alcohol was thought to exert a general depressant effect on the central nervous system (CNS. However, currently the consensus is that specific regions of the brain are selectively vulnerable to the acute effects of alcohol. An alcohol-induced blackout is the classic example; the subject is temporarily unable to form new long-term memories while relatively maintaining other skills such as talking or even driving. A recent study showed that alcohol can cause retrograde memory impairment, that is, blackouts due to retrieval impairments as well as those due to deficits in encoding. Alcoholic blackouts may be complete (en bloc or partial (fragmentary depending on severity of memory impairment. In fragmentary blackouts, cueing often aids recall. Memory impairment during acute intoxication involves dysfunction of episodic memory, a type of memory encoded with spatial and social context. Recent studies have shown that there are multiple memory systems supported by discrete brain regions, and the acute effects of alcohol on learning and memory may result from alteration of the hippocampus and related structures on a cellular level. A rapid increase in blood alcohol concentration (BAC is most consistently associated with the likelihood of a blackout. However, not all subjects experience blackouts, implying that genetic factors play a role in determining CNS vulnerability to the effects of alcohol. This factor may predispose an individual to alcoholism, as altered memory function during intoxication may affect an individual‟s alcohol expectancy; one may perceive positive aspects of intoxication while unintentionally ignoring the negative aspects. Extensive research on memory and learning as well as findings related to the acute effects of alcohol on the brain may elucidate the mechanisms and impact associated with the alcohol- induced blackout.

  1. Affordability of alcohol and alcohol-related mortality in Belarus.

    Razvodovsky, Yury E


    Alcohol abuse has numerous adverse health and social consequences. The consumer response to changes in alcohol affordability is an important issue on alcohol policy debates. Studies from many countries have shown an inverse relationship between alcohol prices and alcohol consumption in the population. There are, however, suggestions that increasing the price of alcohol by rising taxes may have limited effect on alcohol-related problems, associated with long-term heavy drinking. The aim of the present study was to evaluate the relationship between alcohol affordability and alcohol-related mortality rates in post-Soviet Belarus. For this purpose trends in alcohol-related mortality rates (mortality from liver cirrhosis, pancreatitis, alcoholism and alcohol psychoses) and affordability of vodka between 1990 and 2010 were compared. The time series analysis revealed that 1% increase in vodka affordability is associated with an increase in liver cirrhosis mortality of 0,77%, an increase in pancreatitis mortality of 0.53%, an increase in mortality from alcoholism and alcohol psychoses of 0,70%. The major conclusion emerging from this study is that affordability of alcohol is one of the most important predictor of alcohol-related problems in a population. These findings provide additional evidence that decreasing in affordability of alcohol is an effective strategy for reducing alcohol consumption and alcohol-related harm.

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

    Giuseppe Marchionni


    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.

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

    Rim, Kyung-Taek; Kim, Soo-Jin


    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.

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

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


    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.

  5. Highly diastereo- and enantioselective allylboration of aldehydes using α-substituted allyl/crotyl pinacol boronic esters via in situ generated borinic esters.

    Chen, Jack L-Y; Scott, Helen K; Hesse, Matthew J; Willis, Christine L; Aggarwal, Varinder K


    Readily available, α-substituted allyl/crotyl pinacol boronic esters often give low E/Z selectivity (with Z favored) in reactions with aldehydes. We found that addition of nBuLi to the pinacol boronic ester followed by trapping of the alkoxide with TFAA leads to an intermediate allyl borinic ester which undergoes allylboration with very high E selectivity. The substrate scope includes primary to tertiary alkyl α-substituents, crotyl substrates, and the previously unreported β-methallyl pinacol boronic esters. The latter give very high Z selectivity under standard conditions which is completely reversed to high E selectivity under the new conditions. Monitoring the reaction by (11)B NMR confirmed that the reaction proceeds through a borinic ester intermediate.

  6. Remarkable rate acceleration of SmI3-mediated iodination of acetates of Baylis-Hillman adducts in ionic liquid: facile synthesis of (Z)-allyl iodides


    Stereoselective transformation of Baylis-Hillman acetates 1 into corresponding (Z)-allyl iodides 2 has been achieved by treatment of 1 with samarium triiodide in THF. Remarkable rate acceleration of samarium triiodide-mediated iodination of 1 was found when ionic liquid 1-n-butyl-3-methyl-imidazolium tetrafluroborate ([bmim]BF4) was used as reaction media in stead of THF. This novel approach proceeds readily at 50 ℃ within a few minutes to afford (Z)-allyl iodides 2 in excellent yields. A mechanism involving stereoselective iodination of the acetates of Baylis-Hillman adducts by samarium triiodide is described, in which a six-membered ring transition state played a key role in the stereoselective formation of 2.

  7. Immobilization of Chiral Ferrocenyl Ligands on Silica Gel and their Testing in Pd-catalyzed Allylic Substitution and Rh-catalyzed Hydrogenation

    Duncan J. Macquarrie


    Full Text Available Five different silica gels containing two chiral ferrocenyl ligands were prepared by various synthetic routes and tested in an enantioselective Pd(0-catalyzed allylic substitution and Rh-catalyzed hydrogenation. All the prepared anchored ligands were characterized by porosimetry data, DRIFTS spectra, thermal data and AAS. The aim of the work was to compare the influence of the carrier, surface properties and immobilization strategy on the performance of the catalyst.

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

    Wafa Gati


    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.

  9. Divergent synthetic routes for ring expansion or cyclization from 1,4-allylic diol derivatives via gold(I) catalysis or zinc(II) mediation.

    Zhu, Li-Li; Li, Xiao-Xiao; Zhou, Wen; Li, Xin; Chen, Zili


    A new efficient method was developed to transform cyclic alkanols into one-carbon higher homologated ketones using various esters as the leaving groups through gold-catalyzed allylic cation-promoted pinacol-type rearrangement. This reaction, coupled with oxy-Cope rearrangement, provided a new strategy to synthesize five-carbon homologated ring ketones. In addition, using ZnBr(2), 2,5-dihydrofuran products were obtained in moderate to good yields via an intramolecular cyclization process.

  10. Palladium complexes with a tridentate PNO ligand. Synthesis of eta1-allyl complexes and cross-coupling reactions promoted by boron compounds.

    Crociani, Bruno; Antonaroli, Simonetta; Burattini, Marcello; Paoli, Paola; Rossi, Patrizia


    The iminophosphine 2-(2-Ph(2)P)C(6)H(4)N=CHC(6)H(4)OH (P-N-OH) reacts with [Pd(mu-Cl)(eta(3)-C(3)H(5))](2) yielding [PdCl(P-N-O)] and propene. In the presence of NEt(3), the reaction of P-N-OH with [Pd(mu-Cl)(eta(3)-1-R(1),3-R(2)C(3)H(3))](2) (R(1) = R(2) = H, Ph; R(1) = H, R(2) = Ph) affords the eta(1)-allyl derivatives [Pd(eta(1)-1-R(1),3-R(2)C(3)H(3))](P-N-O)] (R(1) = R(2) = H: 1; R(1) = H, R(2) = Ph: 2; R(1) = R(2) = Ph: 3). In solution, the complexes 1 and 3 undergo a slow dynamic process which interconverts the bonding site of the allyl ligand. The X-ray structural analysis of 1 indicates a square-planar coordination geometry around the palladium centre with a P,N,O,-tridentate ligand and a sigma bonded allyl group. The complexes [PdR(P-N-O)] (R = C(6)H(4)Me-4, C[triple bond]CPh) react slowly with p-bromoanisole in the presence of p-tolylboronic acid to give [PdBr(P-N-O)] and the coupling product RC(6)H(4)OMe-4. The latter reactions also proceed at a low rate under catalytic conditions. The coupling of allyl bromide with p-tolylboronic acid is catalyzed by [PdCl(P-N-O)]/K(2)CO(3) to give 4-allyltoluene.

  11. Atmospheric oxidation of vinyl and allyl acetate: product distribution and mechanisms of the OH-initiated degradation in the presence and absence of NO(x).

    Blanco, María B; Bejan, Iustinian; Barnes, Ian; Wiesen, Peter; Teruel, Mariano A


    The products formed from the reactions of OH radicals with vinyl acetate and allyl acetate have been studied in a 1080 L quartz-glass chamber in the presence and absence of NO(x) using in situ FTIR spectroscopy to monitor the reactant decay and product formation. The yields of the primary products formed in the reaction of OH with vinyl acetate were: formic acetic anhydride (84 ± 11)%; acetic acid (18 ± 3)% and formaldehyde (99 ± 15)% in the presence of NO(x) and formic acetic anhydride (28 ± 5)%; acetic acid (87 ± 12)% and formaldehyde (52 ± 8)% in the absence of NO(x). For the reaction of OH with allyl acetate the yields of the identified products were: acetoxyacetaldehyde (96 ± 15)% and formaldehyde (90 ± 12)% in the presence of NO(x) and acetoxyacetaldehyde (26 ± 4)% and formaldehyde (12 ± 3)% in the absence of NO(x). The present results indicate that in the absence of NO(x) the main fate of the 1,2-hydroxyalkoxy radicals formed after addition of OH to the double bond in the compounds is, in the case of vinyl acetate, an α-ester rearrangement to produce acetic acid and CH(2)(OH)CO(•) radicals and in the case of allyl acetate reaction of the radical with O(2) to form acetic acid 3-hydroxy-2-oxo-propyl ester (CH(3)C(O)OCH(2)C(O)CH(2)OH). In contrast, in the presence of NO(x) the main reaction pathway for the 1,2-hydroxyalkoxy radicals is decomposition. The results are compared with the available literature data and implications for the atmospheric chemistry of vinyl and allyl acetate are assessed.

  12. Alcohol: A Women's Health Issue

    ... to drink than their peers. Staying Away From Alcohol. Young women under age 21 should not drink alcohol. ... talk frankly with their daughters about not drinking alcohol. Women in Young and Middle Adulthood Young women in their twenties ...


    Haykal, I.; Margulès, L.; Huet, T. R.; Motyienko, R. A. [Laboratoire de Physique des Lasers, Atomes, et Molécules, UMR CNRS 8523, Université de Lille 1, F-59655 Villeneuve d' Ascq Cédex (France); Écija, P.; Cocinero, E. J.; Basterretxea, F.; Fernández, J. A.; Castaño, F. [Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco, Barrio Sarriena s/n, E-48940 Leioa (Spain); Lesarri, A. [Departamento de Química Física y Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, E-47011 Valladolid (Spain); Guillemin, J. C. [Institut des Sciences Chimiques de Rennes, Ecole Nationale Supérieure de Chimie de Rennes, CNRS, UMR 6226, Allèe de Beaulieu, CS 50837, F-35708 Rennes Cedex 7 (France); Tercero, B.; Cernicharo, J., E-mail: [Centro de Astrobiología (CSIC-INTA), Laboratory of Molecular Astrophysics, Department of Astrophysics, Ctra. De Ajalvir, km 4, E-28850 Torrejón de Ardoz, Madrid (Spain)


    Organic isocyanides have an interesting astrochemistry and some of these molecules have been detected in the interstellar medium (ISM). However, rotational spectral data for this class of compounds are still scarce. We provide laboratory spectra of the four-carbon allyl isocyanide covering the full microwave region, thus allowing a potential astrophysical identification in the ISM. We assigned the rotational spectrum of the two cis (synperiplanar) and gauche (anticlinal) conformations of allyl isocyanide in the centimeter-wave region (4-18 GHz), resolved its {sup 14}N nuclear quadrupole coupling (NQC) hyperfine structure, and extended the measurements into the millimeter and submillimeter-wave (150-900 GHz) ranges for the title compound. Rotational constants for all the monosubstituted {sup 13}C and {sup 15}N isotopologues are additionally provided. Laboratory observations are supplemented with initial radioastronomical observations. Following analysis of an extensive dataset (>11000 rotational transitions), accurate ground-state molecular parameters are reported for the cis and gauche conformations of the molecule, including rotational constants, NQC parameters, and centrifugal distortion terms up to octic contributions. Molecular parameters have also been obtained for the two first excited states of the cis conformation, with a dataset of more than 3300 lines. The isotopic data allowed determining substitution and effective structures for the title compound. We did not detect allyl isocyanide either in the IRAM 30 m line survey of Orion KL or in the PRIMOS survey toward SgrB2. Nevertheless, we provided an upper limit to its column density in Orion KL.

  14. Thin film of Poly(acrylic acid-co-allyl acrylate as a Sacrificial Protective Layer for Hydrophilic Self Cleaning Glass

    Jānis Lejnieks


    Full Text Available Poly(acrylic acid-co-allyl acrylate statistical copolymers were synthesized in a controlled manner in two steps: first tert.butyl acrylate and allyl acrylate were polymerized via atom transfer radical polymerization (ATRP and afterwords the tert.butyl protective groups were removed via hydrolysis. Samples of self cleaning glass (SCG were coated with thin films of poly(acrylic acid-co-allyl acrylate and cross-linked afterwards by UV irradiation (in the presence of a photoinitiator and an accelerator. Solution cast thin films were transparent and homogeneous before and after UV cross-linking. The irradiated samples were found to be hydrophilic (Θ < 20° and water insoluble. The coating prevented the spontaneous hydrophobization of the SCG by residual silicon exhaled from the sealing material. The TiO2 photocatalyst that covers the glass surface was found to strip the protective coating. The rate of the photooxidation process was measured by IR spectroscopy. The real field performance of the protective coating was also tested.

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

    S. Kharchouf


    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.

  16. Alcohol and atherosclerosis



    Full Text Available Atherosclerosis is manifested as coronary artery disease (CAD, ischemic stroke and peripheral vascular disease. Moderate alcohol consumption has been associated with reduction of CAD complications. Apparently, red wine offers more benefits than any other kind of drinks, probably due to flavonoids. Alcohol alters lipoproteins and the coagulation system. The flavonoids induce vascular relaxation by mechanisms that are both dependent and independent of nitric oxide, inhibits many of the cellular reactions associated with atherosclerosis and inflammation, such as endothelial expression of vascular adhesion molecules and release of cytokines from polymorphonuclear leukocytes. Hypertension is also influenced by the alcohol intake. Thus, heavy alcohol intake is almost always associated with systemic hypertension, and hence shall be avoided. In individuals that ingest excess alcohol, there is higher risk of coronary occlusion, arrhythmias, hepatic cirrhosis, upper gastrointestinal cancers, fetal alcohol syndrome, murders, sex crimes, traffic and industrial accidents, robberies, and psychosis. Alcohol is no treatment for atherosclerosis; but it doesn't need to be prohibited for everyone. Thus moderate amounts of alcohol (1-2 drinks/day, especially red wine, may be allowed for those at risk for atherosclerosis complications.

  17. Leisure and Alcohol Expectancies.

    Carruthers, Cynthia P.


    Presents the results of a study that investigated the ways individuals expected drinking to affect their leisure experiences, and the relationship of those expectancies to alcohol consumption patterns. Data from a sample of 144 adults indicated they expected alcohol to positively affect their leisure experiences. (SM)

  18. Pellagra In An Alcoholic

    Thappa Devinder Mohan


    Full Text Available Pellagra is a nutritional disorder that occurs due to niacin deficiency. In the present day context, in western world, pellagra is confined to individuals who have improper food intake, such as psychiatry patients, alcoholics and recluses. Here with we report a case of pellagra occurring in a 60 year old male who was a chronic alcoholic.

  19. Alcohol and atherosclerosis

    Tolstrup, Janne; Grønbaek, Morten


    Light to moderate alcohol intake is known to have cardioprotective properties; however, the magnitude of protection depends on other factors and may be confined to some subsets of the population. This review focuses on factors that modify the relationship between alcohol and coronary heart diseas...

  20. Alcoholism and diabetes mellitus.

    Kim, Soo-Jeong; Kim, Dai-Jin


    Chronic use of alcohol is considered to be a potential risk factor for the incidence of type 2 diabetes mellitus (T2DM), which causes insulin resistance and pancreatic β-cell dysfunction that is a prerequisite for the development of diabetes. However, alcohol consumption in diabetes has been controversial and more detailed information on the diabetogenic impact of alcohol seems warranted. Diabetes, especially T2DM, causes dysregulation of various metabolic processes, which includes a defect in the insulin-mediated glucose function of adipocytes, and an impaired insulin action in the liver. In addition, neurobiological profiles of alcoholism are linked to the effects of a disruption of glucose homeostasis and of insulin resistance, which are affected by altered appetite that regulates the peptides and neurotrophic factors. Since conditions, which precede the onset of diabetes that are associated with alcoholism is one of the crucial public problems, researches in efforts to prevent and treat diabetes with alcohol dependence, receives special clinical interest. Therefore, the purpose of this mini-review is to provide the recent progress and current theories in the interplay between alcoholism and diabetes. Further, the purpose of this study also includes summarizing the pathophysiological mechanisms in the neurobiology of alcoholism.

  1. Alcoholism and Diabetes Mellitus

    Soo-Jeong Kim


    Full Text Available Chronic use of alcohol is considered to be a potential risk factor for the incidence of type 2 diabetes mellitus (T2DM, which causes insulin resistance and pancreatic β-cell dysfunction that is a prerequisite for the development of diabetes. However, alcohol consumption in diabetes has been controversial and more detailed information on the diabetogenic impact of alcohol seems warranted. Diabetes, especially T2DM, causes dysregulation of various metabolic processes, which includes a defect in the insulin-mediated glucose function of adipocytes, and an impaired insulin action in the liver. In addition, neurobiological profiles of alcoholism are linked to the effects of a disruption of glucose homeostasis and of insulin resistance, which are affected by altered appetite that regulates the peptides and neurotrophic factors. Since conditions, which precede the onset of diabetes that are associated with alcoholism is one of the crucial public problems, researches in efforts to prevent and treat diabetes with alcohol dependence, receives special clinical interest. Therefore, the purpose of this mini-review is to provide the recent progress and current theories in the interplay between alcoholism and diabetes. Further, the purpose of this study also includes summarizing the pathophysiological mechanisms in the neurobiology of alcoholism.

  2. Molecular basis of alcoholism.

    Most, Dana; Ferguson, Laura; Harris, R Adron


    Acute alcohol intoxication causes cellular changes in the brain that last for hours, while chronic alcohol use induces widespread neuroadaptations in the nervous system that can last a lifetime. Chronic alcohol use and the progression into dependence involve the remodeling of synapses caused by changes in gene expression produced by alcohol. The progression of alcohol use, abuse, and dependence can be divided into stages, which include intoxication, withdrawal, and craving. Each stage is associated with specific changes in gene expression, cellular function, brain circuits, and ultimately behavior. What are the molecular mechanisms underlying the transition from recreational use (acute) to dependence (chronic)? What cellular adaptations result in drug memory retention, leading to the persistence of addictive behaviors, even after prolonged drug abstinence? Research into the neurobiology of alcoholism aims to answer these questions. This chapter will describe the molecular adaptations caused by alcohol use and dependence, and will outline key neurochemical participants in alcoholism at the molecular level, which are also potential targets for therapy.

  3. Children of Alcoholics

    ... 11) • Abuse of drugs or alcohol; or • Aggression towards other children • Risk taking behaviors • Depression or suicidal thoughts or behavior Some children of alcoholics may cope by taking the role of responsible "parents" within the family and among friends. They may ...

  4. Alcohol, Medicines and Aging

    ... declines with age, older people reach higher blood alcohol concentrations after each drink than younger people. Meanwhile, as we age we become more sensitive to some of the impairments alcohol produces. On tests that require ... younger adults after a few drinks. Similarly, balance, concentration, ...

  5. Alcohol Use and Cancer

    ... a chemical that has been shown to cause cancer in lab animals. Alcohol and its byproducts can also damage the liver, leading to inflammation and scarring. As liver cells try to repair the ... to cancer. Effects on other harmful chemicals Alcohol may help ...

  6. Adolescents' Perceptions of Alcohol

    Roy, Amit; Ikonen, Risto; Keinonen, Tuula; Kumar, Kuldeep


    Purpose: Rising trends in alcohol consumption and early drinking initiation pose serious health risks especially for adolescents. Learner's prior knowledge about alcohol gained from the social surroundings and the media are important sources that can impact the learning outcomes in health education. The purpose of this paper is to map adolescents'…

  7. Fetal Alcohol Spectrum Disorder

    Caley, Linda M.; Kramer, Charlotte; Robinson, Luther K.


    Fetal alcohol spectrum disorder (FASD) is a serious and widespread problem in this country. Positioned within the community with links to children, families, and healthcare systems, school nurses are a critical element in the prevention and treatment of those affected by fetal alcohol spectrum disorder. Although most school nurses are familiar…

  8. Alcohol and sex.

    Vijayasenan, M E


    Diminished sexual functioning among individuals dependent upon alcohol has been assessed. Ninety-seven male patients entered the study, all inpatients as the unit for treatment of alcoholism and drug addiction (Villa 6) in Porirua Hospital, Porirua. The sexual ability of these patients before the development of alcoholism was also rated for the same items and this rating was used as a control. Of the 97 patients, 69 (71 percent) suffered from sexual dysfunction for a period more than 12 months prior to admission to hospital. The disturbances noted were diminished sexual desire (58 percent of patients), erectile impotence (16 percent), premature ejaculation (4 percent), ejaculatory in competence (22 percent). A high proportion of the alcoholics showed signs of sexual deviation-19 percent having performed sexual crimes and a further 28 percent having repeated thought of sexual crimes. The possible causes of alcohol induced sexual dysfunction are discussed.

  9. Alcoholic hallucinosis: case report

    Bárbara Werner Griciunas


    Full Text Available Case report of patient who has been an alcoholic for 40 years and, after reducing alcohol intake, developed auditory and visual hallucinations, which caused behavior change. Neurological issues, electrolyte disturbances and other organ dysfunctions were excluded as cause of said change. After intake of haloperidol and risperidone, the patient had regression of symptoms and denied having presented hallucinatory symptoms. The Manual Diagnóstico e Estatístico de Transtornos Mentais – 5ª edição (DSM-V includes alcoholic hallucinosis in the Substance-Induced Psychotic Disorder (alcohol, beginning during abstinence; however, the document is not yet very well accepted among the medical community. The difficulty of the team to confirm the diagnosis of alcoholic hallucinosis lies in the differential diagnosis, as Delirium tremens and severe withdrawal syndrome with psychotic symptoms. Thus, psychopathological differentiation is important, as well as continuity of research and collaboration of other clinical teams in the evaluation.

  10. Alcohol consumption in adolescents

    Ilona Plevová


    Full Text Available Aim: To determine the level of alcohol consumption in a selected group of adolescents. Design: A descriptive cross-sectional study. Methods: The data were obtained using a part of the standardized ESPAD questionnaire for assessing consumption of alcoholic beverages. The sample comprised 422 students from seven secondary schools of different types in the city of Ostrava. For statistical analysis, the chi-squared test and Fisher's exact test (for n ≤ 5 were used. The data were processed using Stata v. 10. Results: More than half of respondents first tried alcohol before the age of 15. The most frequent alcohol-related problems were unprotected sex, decreased school performance and problems with parents or friends. Incomplete families were found to be an important factor in adolescents preferring and more frequently drinking beer. Conclusion: The study confirmed results reported by the Europe-wide survey ESPAD, namely that adolescents start to drink alcohol as early as before they turn fifteen.

  11. Homocysteine and alcoholism.

    Bleich, S; Degner, D; Javaheripour, K; Kurth, C; Kornhuber, J


    Chronic alcohol consumption can induce alterations in the function and morphology of most if not all brain systems and structures. However, the exact mechanism of brain damage in alcoholics remains unknown. Partial recovery of brain function with abstinence suggests that a proportion of the deficits must be functional in origin (i.e. plastic changes of nerve cells) while neuronal loss from selected brain regions indicates permanent and irreversible damage. There is growing evidence that chronic alcoholism is associated with a derangement in the sulfur amino acid metabolism. Recently, it has been shown that excitatory amino acid (EAA) neurotransmitters and homocysteine levels are elevated in patients who underwent withdrawal from alcohol. Furthermore, it has been found that homocysteine induces neuronal cell damage by stimulating NMDA receptors as well as by producing free radicals. Homocysteine neurotoxicity via overstimulation of N-methyl-D-aspartate receptors may contribute to the pathogenesis of both brain shrinkage and withdrawal seizures linked to alcoholism.

  12. Development and validation of a scale of attitudes towards alcohol, alcoholism and alcoholics.

    Vargas, Divane de; Luis, Margarita Antonia Villar


    The objective of this study was the construction and validation of a scale that would measure the attitudes towards alcohol, alcoholism and the alcoholic, called the Scale of Attitudes Towards Alcohol, Alcoholism and the Alcoholic. The face and content validations, as well as the factor analysis of the data obtained in a preliminary test with 144 nursing students resulted in a scale consisting of 96 items, divided into 5 factors: Attitudes towards the alcoholic person: care and interpersonal relations; Etiology; Disease; Repercussions deriving from alcohol use/abuse; Alcoholic beverages. The general scale presented a consistency level of 0.90. The resulting instrument is concluded to be a reliable tool to evaluate attitudes towards alcohol, alcoholism and alcohol addicts.

  13. 75 FR 57473 - National Institute on Alcohol Abuse and Alcoholism; Notice of Closed Meeting


    ... HUMAN SERVICES National Institutes of Health National Institute on Alcohol Abuse and Alcoholism; Notice... personal privacy. Name of Committee: National Institute on Alcohol Abuse and Alcoholism Special Emphasis... Officer, National Institute on Alcohol Abuse and Alcoholism, Office of Extramural Activities,...

  14. 78 FR 42530 - National Institute on Alcohol Abuse and Alcoholism; Notice of Closed Meeting


    ... HUMAN SERVICES National Institutes of Health National Institute on Alcohol Abuse and Alcoholism; Notice... personal privacy. Name of Committee: National Institute on Alcohol Abuse and Alcoholism Initial Review..., Ph.D., Scientific Review Officer, National Institute on Alcohol Abuse & Alcoholism,...

  15. 76 FR 78014 - National Institute on Alcohol Abuse and Alcoholism; Notice of Closed Meeting


    ... HUMAN SERVICES National Institutes of Health National Institute on Alcohol Abuse and Alcoholism; Notice... personal privacy. Name of Committee: National Institute on Alcohol Abuse and Alcoholism Initial Review...., Scientific Review Administrator, National Institutes on Alcohol Abuse & Alcoholism, National Institutes...

  16. 75 FR 10808 - National Institute on Alcohol Abuse and Alcoholism; Notice of Closed Meeting


    ... HUMAN SERVICES National Institutes of Health National Institute on Alcohol Abuse and Alcoholism; Notice... personal privacy. Name of Committee: National Institute on Alcohol Abuse and Alcoholism Special Emphasis... Officer, National Institute on Alcohol Abuse & Alcoholism, National Institutes of Health, 5635...

  17. 78 FR 42529 - National Institute on Alcohol Abuse and Alcoholism; Notice of Closed Meeting


    ... HUMAN SERVICES National Institutes of Health National Institute on Alcohol Abuse and Alcoholism; Notice... personal privacy. Name of Committee: National Institute on Alcohol Abuse and Alcoholism Initial Review....D., Scientific Review Administrator, National Institutes on Alcohol Abuse & Alcoholism,...

  18. 75 FR 24961 - National Institute on Alcohol Abuse and Alcoholism; Notice of Closed Meetings


    ... HUMAN SERVICES National Institutes of Health National Institute on Alcohol Abuse and Alcoholism; Notice... personal privacy. Name of Committee: National Institute on Alcohol Abuse and Alcoholism Special Emphasis... Extramural Activities, National Institutes of Health, National Institute on Alcohol Abuse & Alcoholism,...

  19. 76 FR 26308 - National Institute on Alcohol Abuse and Alcoholism; Notice of Closed Meeting


    ... HUMAN SERVICES National Institutes of Health National Institute on Alcohol Abuse and Alcoholism; Notice... personal privacy. Name of Committee: National Institute on Alcohol Abuse and Alcoholism Initial Review..., Scientific Review Administrator, National Institutes On Alcohol Abuse & Alcoholism National, Institutes...

  20. 75 FR 63494 - National Institute on Alcohol Abuse and Alcoholism; Notice of Closed Meeting


    ... HUMAN SERVICES National Institutes of Health National Institute on Alcohol Abuse and Alcoholism; Notice... personal privacy. Name of Committee: National Institute on Alcohol Abuse and Alcoholism Special Emphasis..., Extramural Project Review Branch, EPRB, National Institute on Alcohol Abuse and Alcoholism,...

  1. 77 FR 22794 - National Institute on Alcohol Abuse and Alcoholism; Notice of Closed Meeting


    ... HUMAN SERVICES National Institutes of Health National Institute on Alcohol Abuse and Alcoholism; Notice... personal privacy. Name of Committee: National Institute on Alcohol Abuse and Alcoholism Initial Review..., Ph.D., Scientific Review Administrator, National Institutes on Alcohol Abuse & Alcoholism...

  2. Radical graft polymerization of an allyl monomer onto hydrophilic polymers and their antibacterial nanofibrous membranes.

    Wang, Dong; Xu, Weilin; Sun, Gang; Chiou, Bor-Sen


    Hydrophilic poly (vinyl alcohol-co-ethylene) (PVA-co-PE) copolymers with 27 mol %, 32 mol % and 44 mol % ethylene were functionalized by melt radical graft copolymerization with 2,4-diamino-6-diallylamino-1,3,5-triazine (NDAM) using reactive extrusion. This functionalization imparts antibacterial properties. The covalent attachments of the NDAM as side chains onto the PVA-co-PE polymer backbones were confirmed. The effects of initiator concentrations and ethylene contents in PVA-co-PE polymers on grafting of NDAM were studied. The chain scissions of PVA-co-PE polymers during reactive extrusion were investigated by monitoring changes in the melt torque and FTIR spectra. The NDAM grafted PVA-co-PE polymers were successfully fabricated into hydrophilic nanofibers and nanofibrous membranes with sufficient surface exposure of the grafted NDAM. The hydrophilicity of the PVA-co-PE polymers and the large specific surface area offered by the nanofiber membranes significantly facilitated the chlorine activation process, enhanced the active chlorine contents of the grafted PVA-co-PE nanofiber membranes, and therefore led to their superior antibacterial properties.

  3. Alcohol Alert: Alcohol's Damaging Effects on the Brain

    ... 44). Markers such as the P3 can help identify people who may be at greatest risk for developing problems with alcohol. END OF SIDEBAR ... Meta–analysis of P300 amplitude from males at risk for alcoholism. Psychological Bulletin 115:55–73, ... appeared in the journal Alcohol Research & Health, “Alcoholic Brain Damage” (Vol. 27, ...

  4. Benzimidazole-triazole ligands with pendent triazole functionality: unexpected formation and effects on copper-catalyzed aerobic alcohol oxidation.

    Kongkaew, Manisa; Sitthisuwannakul, Kannika; Nakarajouyphon, Vasut; Pornsuwan, Soraya; Kongsaeree, Palangpon; Sangtrirutnugul, Preeyanuch


    A series of benzimidazole-triazole ligands (NN') having a pendent triazole arm with different triazole substituents including CH2Ph (3a), cyclo-C6H11 (3b), and CH2SiMe3 (3c) were obtained in moderate yields from Cu-catalyzed oxidative C-N cyclization of the respective amine-triazole compounds N,N'-bis((1-R-1,2,3-triazol-4-yl)methyl)benzene-1,2-diamine (2a-2c). Treatment of CuCl2 with one equiv. of the benzimidazole-triazole ligands afforded the corresponding Cu(II) complexes with the empirical formula of Cu(NN')Cl2 (4a-4c). Crystal structures of 4b and 4c reveal mononuclear and dinuclear Cu(II) complexes, respectively. Despite the differences in triazole substituents and their solid state structures, ESR spectra indicate the same molecular structures in CH3CN solution whereas CV data suggest similar redox potentials for 4a-4c. Catalytic activities for aerobic oxidation of benzyl alcohol to benzaldehyde follow this trend: 4c > 4a > 4b. In addition, the catalytic system 4c/TEMPO/Cu(0)/NMI (TEMPO = 2,2,6,6-tetramethyl-1-piperidinyloxyl, NMI = N-methylimidazole) exhibited high activities for oxidation of activated alcohols (i.e., benzyl alcohol derivatives and allylic alcohol) in CH3CN at room temperature.

  5. Alcoholism: genes and mechanisms.

    Oroszi, Gabor; Goldman, David


    Alcoholism is a chronic relapsing/remitting disease that is frequently unrecognized and untreated, in part because of the partial efficacy of treatment. Only approximately one-third of patients remain abstinent and one-third have fully relapsed 1 year after withdrawal from alcohol, with treated patients doing substantially better than untreated [1]. The partial effectiveness of strategies for prevention and treatment, and variation in clinical course and side effects, represent a challenge and an opportunity to better understand the neurobiology of addiction. The strong heritability of alcoholism suggests the existence of inherited functional variants of genes that alter the metabolism of alcohol and variants of other genes that alter the neurobiologies of reward, executive cognitive function, anxiety/dysphoria, and neuronal plasticity. Each of these neurobiologies has been identified as a critical domain in the addictions. Functional alleles that alter alcoholism-related intermediate phenotypes include common alcohol dehydrogenase 1B and aldehyde dehydrogenase 2 variants that cause the aversive flushing reaction; catechol-O-methyltransferase (COMT) Val158Met leading to differences in three aspects of neurobiology: executive cognitive function, stress/anxiety response, and opioid function; opioid receptor micro1 (OPRM1) Asn40Asp, which may serve as a gatekeeper molecule in the action of naltrexone, a drug used in alcoholism treatment; and HTTLPR, which alters serotonin transporter function and appears to affect stress response and anxiety/dysphoria, which are factors relevant to initial vulnerability, the process of addiction, and relapse.

  6. Fuel Class Higher Alcohols

    Sarathy, Mani


    This chapter focuses on the production and combustion of alcohol fuels with four or more carbon atoms, which we classify as higher alcohols. It assesses the feasibility of utilizing various C4-C8 alcohols as fuels for internal combustion engines. Utilizing higher-molecular-weight alcohols as fuels requires careful analysis of their fuel properties. ASTM standards provide fuel property requirements for spark-ignition (SI) and compression-ignition (CI) engines such as the stability, lubricity, viscosity, and cold filter plugging point (CFPP) properties of blends of higher alcohols. Important combustion properties that are studied include laminar and turbulent flame speeds, flame blowout/extinction limits, ignition delay under various mixing conditions, and gas-phase and particulate emissions. The chapter focuses on the combustion of higher alcohols in reciprocating SI and CI engines and discusses higher alcohol performance in SI and CI engines. Finally, the chapter identifies the sources, production pathways, and technologies currently being pursued for production of some fuels, including n-butanol, iso-butanol, and n-octanol.

  7. Epoxidation of allyl-glycidyl ether with hydrogen peroxide over Ti-SBA-15 catalyst and in methanol medium

    Walasek Marika


    Full Text Available This work presents the studies on the epoxidation of allyl-glycidyl ether (AGE over the Ti-SBA-15 catalyst. In these studies an aqueous hydrogen peroxide was used as an oxidizing agent and as a solvent methanol was applied. The studies on the influence the following parameters: temperature (20–80°C, molar ratio of AGE/H2O2 (1:1.5–5:1, methanol concentration (10–90 wt%, catalyst content (1–9 wt% and reaction time (15–240 min. were carried out and the most favourable values of these parameters were chosen (temperature 80°C, molar ratio of AGE/H2O2 = 5:1, methanol concentration 30 wt%, catalyst content 3 wt% and the reaction time 240 min.. At these conditions the functions describing the process reached the following values: the selectivity of diglycidyl ether (DGE 9.2 mol%, the conversion of AGE 13.9 mol% and the efficiency of H2O2 conversion 89.9 mol%.

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

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


    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.

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

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


    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. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. Allyl triphenyl phosphonium bromide based DES-functionalized carbon nanotubes for the removal of mercury from water.

    AlOmar, Mohamed Khalid; Alsaadi, Mohammed Abdulhakim; Hayyan, Maan; Akib, Shatirah; Ibrahim, Muhammad; Hashim, Mohd Ali


    Recently, deep eutectic solvents (DESs) have shown their new and interesting ability for chemistry through their involvement in variety of applications. This study introduces carbon nanotubes (CNTs) functionalized with DES as a novel adsorbent for Hg(2+) from water. Allyl triphenyl phosphonium bromide (ATPB) was combined with glycerol as the hydrogen bond donor (HBD) to form DES, which can act as a novel CNTs functionalization agent. The novel adsorbent was characterized using Raman, FTIR, XRD, FESEM, EDX, BET surface area, TGA, TEM and Zeta potential. Response surface methodology was used to optimize the removal conditions for Hg(2+). The optimum removal conditions were found to be pH 5.5, contact time 28 min, and an adsorbent dosage of 5 mg. Freundlich isotherm model described the adsorption isotherm of the novel adsorbent, and the maximum adsorption capacity obtained from the experimental data was 186.97 mg g(-1). Pseudo-second order kinetics describes the adsorption rate order.

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

    Rosenani A Haque; M A Salam


    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.

  12. Modification in surface properties of poly-allyl-diglycol-carbonate (CR-39 implanted by Au+ ions at different fluences

    Sagheer Riffat


    Full Text Available Ion implantation has a potential to modify the surface properties and to produce thin conductive layers in insulating polymers. For this purpose, poly-allyl-diglycol-carbonate (CR-39 was implanted by 400 keV Au+ ions with ion fluences ranging from 5 × 1013 ions/cm2 to 5 × 1015 ions/cm2. The chemical, morphological and optical properties of implanted CR-39 were analyzed using Raman, Fourier transform infrared (FT-IR spectroscopy, atomic force microscopy (AFM and UV-Vis spectroscopy. The electrical conductivity of implanted samples was determined through four-point probe technique. Raman spectroscopy revealed the formation of carbonaceous structures in the implanted layer of CR-39. From FT-IR spectroscopy analysis, changes in functional groups of CR-39 after ion implantation were observed. AFM studies revealed that morphology and surface roughness of implanted samples depend on the fluence of Au ions. The optical band gap of implanted samples decreased from 3.15 eV (for pristine to 1.05 eV (for sample implanted at 5 × 1015 ions/cm2. The electrical conductivity was observed to increase with the ion fluence. It is suggested that due to an increase in ion fluence, the carbonaceous structures formed in the implanted region are responsible for the increase in electrical conductivity.

  13. Palladium-catalyzed asymmetric allylic substitution of 2-arylcyclohexenol derivatives: asymmetric total syntheses of (+)-crinamine, (-)-haemanthidine, and (+)-pretazettine.

    Nishimata, Toyoki; Sato, Yoshihiro; Mori, Miwako


    Much interest has been shown in Amaryllidaceae alkaloids as synthetic targets due to their wide range of biological activities. Over 100 alkaloids have been isolated from members of the Amaryllidaceae family; most of them can be classified into eight skeletally homogeneous groups. We have succeeded in the first asymmetric total syntheses of the crinane-type alkaloids (+)-crinamine (1), (-)-haemanthidine (2), and (+)-pretazettine (3). The starting cyclohexenylamine 14 was obtained from allyl phosphonate 11c by palladium-catalyzed asymmetric amination in 82% yield and with 74% ee. The product was recrystallized from MeOH. Interestingly, (-)-14 with 99% ee was obtained from the mother liquor (74% recovery). Intramolecular carbonyl-ene reaction of (-)-10 proceeds in a highly stereoselective manner to give hexahydroindole derivative 9 as the sole product. In the Lewis-acid-catalyzed carbonyl-ene reaction, an interesting rearrangement product, 20, was isolated in high yield. From 9, (+)-crinamine was synthesized. Thus, the asymmetric total synthesis of (+)-crinamine was achieved in 10 steps from 11c, and the overall yield is 19%. The total synthesis of (-)-haemanthidine was also achieved from 9 by a short sequence of steps.

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

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


    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. Copyright © 2015 Elsevier Ltd. All rights reserved.

  15. [Genetic variations in alcohol dehydrogenase, drinking habits and alcoholism

    Tolstrup, J.S.; Rasmussen, S.; Tybjaerg-Hansen, A.


    Alcohol is degraded primarily by alcohol dehydrogenase (ADH), and genetic variation that affects the rate of alcohol degradation is found in ADH1B and ADH1C. By genotyping 9,080 white men and women from the general population, we found that men and women with ADH1B slow versus fast alcohol...... degradation drank approximately 30% more alcohol per week and had a higher risk of everyday and heavy drinking, and of alcoholism. Individuals with ADH1C slow versus fast alcohol degradation had a higher risk of heavy drinking Udgivelsesdato: 2008/8/25...


    A. O. Yusupova


    Full Text Available Alcohol abuse and particularly extension of alcohol consumption in alcohol diseas increases the risk of cardiac arrhythmias development and aggravates existing arrhythmias. Patients do not always receive the necessary specific treatment due to lack of detection of the ethanol genesis of these arrhythmias. Management of patients with alcohol abuse and alcohol dependence, including its cardiac complications among other cardiac arrhythmias should use both antiarrhythmic and anti-alcohol drugs and antidepressants. Such issues as diagnosis and management of patients with alcohol-induced cardiac arrhythmias are presented.

  17. Alcohol use disorder

    ... be a combination of a person's: Genes Environment Psychology, such as being impulsive or having low self- ... Examine you Ask about your medical and family history Ask about your alcohol use, and if you ...

  18. When alcohol acts

    Demant, Jakob


      Sociological studies into alcohol use seem to find it difficult to deal with the substance itself. Alcohol tends to be reduced to a symbol of a social process and in this way the sociological research loses sight of effects beyond the social. This paper suggests a new theoretical approach...... to the study of alcohol and teenagers' (romantic) relationships, inspired by actor-network theory (ANT). The central feature of ANT is to search for relationships, or rather networks, between all things relevant to the phenomenon. All material and semantic structures, things, persons, discourses, etc....... that influence a given situation are described as actants and are entered into the analysis. The aim of this paper is to propose a way of including materiality in sociological analyses of alcohol and to explore ways of using focus group interview material in ANT-inspired analysis. By analyzing a girl...

  19. an Unrecorded Alcohol Beverage


    alcohol consumption, including malnutrition, selfneglect, poor hygiene, pale skin, weight .... Table 2 Analytical performance parameters of the GC-FID for the stan- dards (n = 3). .... Kluwer Academic Plenum Publishers,. New York, 1999, pp.

  20. Pentoxifylline for alcoholic hepatitis

    Whitfield, Kate; Rambaldi, Andrea; Wetterslev, Jørn


    -cause mortality and mortality due to hepatorenal syndrome, and conversely, an increase in serious and non-serious adverse events. However, the evidence is not firm; no conclusions can be drawn regarding whether pentoxifylline has a positive, negative, or neutral effect on participants with alcoholic hepatitis....... analysis did not support this result. Data from one trial suggests that pentoxifylline may increase the occurrence of serious and non-serious adverse events compared to control. AUTHORS' CONCLUSIONS: The current available data may indicate a possible positive intervention effect of pentoxifylline on all......BACKGROUND: Alcoholic hepatitis is a life-threatening disease, with an average mortality of approximately 40%. There is no widely accepted, effective treatment for alcoholic hepatitis. Pentoxifylline is used to treat alcoholic hepatitis, but there has been no systematic review to assess its effects...

  1. Antidepressants and Alcohol

    ... Medication-FAQ/Can-I-drink-alcohol-while-taking-antidepressants. Accessed May 2, 2017. Back SE, et al. Treatment of co-occurring substance use disorder and anxiety-related disorders in adults. ...

  2. Alcohol en snelverkeer.

    Esser, P.H.


    Dr Esser voert diverse redenen aan om zo snel mogelijk te starten met ademanalyse op tijden en plaatsen dat bestuurders, die alcohol gebruikt hebben, verwacht kunnen worden. Hij wijst op de preventieve waarde hiervan. Zie ook A 1469.

  3. Alcohol advertising and youth.

    Martin, Susan E; Snyder, Leslie B; Hamilton, Mark; Fleming-Milici, Fran; Slater, Michael D; Stacy, Alan; Chen, Meng-Jinn; Grube, Joel W


    This article presents the proceedings of a symposium at the 2001 Research Society on Alcoholism meeting in Montreal, Canada. The symposium was organized and chaired by Joel W. Grube. The presentations and presenters were (1) Introduction and background, by Susan E. Martin; (2) The effect of alcohol ads on youth 15-26 years old, by Leslie Snyder, Mark Hamilton, Fran Fleming-Milici, and Michael D. Slater; (3) A comparison of exposure to alcohol advertising and drinking behavior in elementary versus middle school children, by Phyllis L. Ellickson and Rebecca L. Collins; (4) USC health and advertising project: assessment study on alcohol advertisement memory and exposure, by Alan Stacy; and (5) TV beer and soft drink advertising: what young people like and what effects? by Meng-Jinn Chen and Joel W. Grube.

  4. Alcohol and liver, 2010

    Natalia; A; Osna


    Liver is known as an organ that is primarily affected by alcohol. Alcoholic liver disease (ALD) is the cause of an increased morbidity and mortality worldwide. Progression of ALD is driven by "second hits". These second hits include the complex of nutritional, pharmacological, genetic and viral factors, which aggravate liver pathology. However, in addition to liver failure, ethanol causes damage to other organs and systems. These extrahepatic manifestations are regulated via the similar hepatitis mechanisms...

  5. Alcohol: Pleasures and Problems.

    Finn, Peter; Lawson, Jane

    This student booklet is to be used in conjunction with the Teacher Manual and films of the DIAL A-L-C-O-H-O-L series. It presents facts and illustrations on the use of alcohol, and is intended to aid young people in deciding whether or not to drink. This booklet is divided into the following parts: (1) Introduction; (2) The Enjoyment of Drinking;…

  6. Consumo de alcohol

    Luís Gustavo del Sol Padrón; Orestes Álvarez Fernández; Juan De Dios Rivero Berovides


    En este artículo se emite una definición clasificatoria de los individuos que consumen alcohol, según supuestos establecidos por Manconi. Se estratifican las personas atendiendo a los diferentes riesgos para este consumo. Se describen las afectaciones a la salud que produce el consumo de alcohol, y además se plantean las medidas estratégicas para propiciar una conducta efectiva antialcohólica. Por último, se presenta un flujograma para la inter...

  7. Alcohol-attributable and alcohol-preventable mortality in Denmark

    Eliasen, Marie; Becker, Ulrik; Grønbæk, Morten


    The aim of the study was to quantify alcohol-attributable and -preventable mortality, totally and stratified on alcohol consumption in Denmark 2010, and to estimate alcohol-related mortality assuming different scenarios of changes in alcohol distribution in the population. We estimated alcohol......-attributable and -preventable fractions based on relative risks of conditions causally associated with alcohol from meta-analyses and information on alcohol consumption in Denmark obtained from 14,458 participants in the Danish National Health Survey 2010 and corrected for adult per capita consumption. Cause-specific mortality...... data were obtained from the Danish Register of Causes of Death. In total, 1,373 deaths among women (5.0 % of all deaths) and 2,522 deaths among men (9.5 % of all deaths) were attributable to alcohol, while an estimated number of 765 (2.8 %) and 583 (2.2 %) deaths were prevented by alcohol...

  8. Alcohol drinking pattern and risk of alcoholic liver cirrhosis

    Askgaard, Gro; Grønbæk, Morten; Kjær, Mette Skalshøi


    BACKGROUND & AIMS: Alcohol is the main contributing factor of alcoholic cirrhosis, but less is known about the significance of drinking pattern. METHODS: We investigated the risk of alcoholic cirrhosis among 55,917 participants (aged 50-64 years) in the Danish Cancer, Diet, and Health study (1993......-2011). Baseline information on alcohol intake, drinking pattern, and confounders was obtained from a questionnaire. Follow-up information came from national registers. We calculated hazard ratios (HRs) for alcoholic cirrhosis in relation to drinking frequency, lifetime alcohol amount, and beverage type. RESULTS......: We observed 257 and 85 incident cases of alcoholic cirrhosis among men and women, respectively, none among lifetime abstainers. In men, HR for alcoholic cirrhosis among daily drinkers was 3.65 (95% CI: 2.39; 5.55) compared to drinking 2-4 days/week. Alcohol amount in recent age periods (40-49 and 50...

  9. Perspectives on the neuroscience of alcohol from the National Institute on Alcohol Abuse and Alcoholism.

    Reilly, Matthew T; Noronha, Antonio; Warren, Kenneth


    Mounting evidence over the last 40 years clearly indicates that alcoholism (alcohol dependence) is a disorder of the brain. The National Institute on Alcohol Abuse and Alcoholism (NIAAA) has taken significant steps to advance research into the neuroscience of alcohol. The Division of Neuroscience and Behavior (DNB) was formed within NIAAA in 2002 to oversee, fund, and direct all research areas that examine the effects of alcohol on the brain, the genetic underpinnings of alcohol dependence, the neuroadaptations resulting from excessive alcohol consumption, advanced behavioral models of the various stages of the addiction cycle, and preclinical medications development. This research portfolio has produced important discoveries in the etiology, treatment, and prevention of alcohol abuse and dependence. Several of these salient discoveries are highlighted and future areas of neuroscience research on alcohol are presented.

  10. Comparing Alcohol Marketing and Alcohol Warning Message Policies Across Canada.

    Wettlaufer, Ashley; Cukier, Samantha N; Giesbrecht, Norman


    In order to reduce harms from alcohol, evidence-based policies are to be introduced and sustained. To facilitate the dissemination of policies that reduce alcohol-related harms by documenting, comparing, and sharing information on effective alcohol polices related to restrictions on alcohol marketing and alcohol warning messaging in 10 Canadian provinces. Team members developed measurable indicators to assess policies on (a) restrictions on alcohol marketing, and (b) alcohol warning messaging. Indicators were peer-reviewed by three alcohol policy experts, refined, and data were collected, submitted for validation by provincial experts, and scored independently by two team members. The national average score was 52% for restrictions on marketing policies and 18% for alcohol warning message policies. Most provinces had marketing regulations that went beyond the federal guidelines with penalties for violating marketing regulations. The provincial liquor boards' web pages focused on product promotion, and there were few restrictions on sponsorship activities. No province has implemented alcohol warning labels, and Ontario was the sole province to have legislated warning signs at all points-of-sale. Most provinces provided a variety of warning signs to be displayed voluntarily at points-of-sale; however, the quality of messages varied. Conclusions/Importance: There is extensive alcohol marketing with comparatively few messages focused on the potential harms associated with alcohol. It is recommended that governments collaborate with multiple stakeholders to maximize the preventive impact of restrictions on alcohol marketing and advertising, and a broader implementation of alcohol warning messages.

  11. Allyl isothiocyanate, a constituent of cruciferous vegetables, inhibits growth of PC-3 human prostate cancer xenografts in vivo.

    Srivastava, Sanjay K; Xiao, Dong; Lew, Karen L; Hershberger, Pamela; Kokkinakis, Demetrius M; Johnson, Candace S; Trump, Donald L; Singh, Shivendra V


    We have shown previously that allyl isothiocyanate (AITC), a constituent of cruciferous vegetables, significantly inhibits survival of PC-3 and LNCaP human prostate cancer cells in culture, whereas proliferation of a normal prostate epithelial cell line is minimally affected by AITC even at concentrations that are highly cytotoxic to the prostate cancer cells. The present studies were designed to test the hypothesis that AITC administration may retard growth of human prostate cancer xenografts in vivo. Bolus i.p. injection of 10 micromol AITC, three times per week (Monday, Wednesday and Friday) beginning the day of tumor cell implantation, significantly inhibited the growth of PC-3 xenograft (P < 0.05 by two-way ANOVA). For example, 26 days after tumor cell implantation, the average tumor volume in control mice (1025 +/- 205 mm3) was approximately 1.7-fold higher compared with AITC-treated mice. Histological analysis of tumors excised at the termination of the experiment revealed a statistically significant increase in number of apoptotic bodies with a concomitant decrease in cells undergoing mitosis in the tumors of AITC-treated mice compared with that of control mice. Western blot analysis indicated an approximately 70% reduction in the levels of anti-apoptotic protein Bcl-2 in the tumor lysate of AITC-treated mice compared with that of control mice. Moreover, the tumors from AITC-treated mice, but not control mice, exhibited cleavage of BID, which is known to promote apoptosis. Statistically significant reduction in the expression of several proteins that regulate G2/M progression, including cyclin B1, cell division cycle (Cdc)25B and Cdc25C (44, 45 and 90% reduction, respectively, compared with control), was also observed in the tumors of AITC-treated mice relative to control tumors. In conclusion, the results of the present study indicate that AITC administration inhibits growth of PC-3 xenografts in vivo by inducing apoptosis and reducing mitotic activity.

  12. From a cycloheptatrienylzirconium allyl complex to a cycloheptatrienylzirconium imidazolin-2-iminato "pogo stick" complex with imido-type reactivity.

    Glöckner, Andreas; Bannenberg, Thomas; Daniliuc, Constantin G; Jones, Peter G; Tamm, Matthias


    The reaction of the cycloheptatrienylzirconium half-sandwich complex [(η(7)-C(7)H(7))ZrCl(tmeda)] (1) (tmeda = N,N,N',N'-tetramethylethylenediamine) with Li(Im(Dipp)N), generated from bis(2,6-diisopropylphenyl)imidazolin-2-imine (Im(Dipp)NH) with methyllithium, yields the imidazolin-2-iminato complex [(η(7)-C(7)H(7))Zr(Im(Dipp)N)(tmeda)] (2). The corresponding tmeda-free complex [(η(7)-C(7)H(7))Zr(Im(Dipp)N)] (5) can be synthesized via the 1,3-bis(trimethylsilyl)allyl complex [(η(7)-C(7)H(7))Zr{η(3)-C(3)H(3)(TMS)(2)}(THF)] (3; TMS = SiMe(3)), which undergoes an acid-base reaction with Im(Dipp)NH to form 5 and 1,3-bis(trimethylsilyl)propene. 5 exhibits an unusual one-legged piano stool ("pogo stick") geometry with a particularly short Zr-N bond of 1.997(2) Å. Addition of 2,6-dimethylphenyl or tert-butyl isocyanide affords the complexes [(η(7)-C(7)H(7))Zr(Im(Dipp)N)(CNR)] (R = o-Xy, 6; R = t-Bu, 7), while the reaction with 2,6-dimethylphenyl isocyanate results in a [2 + 2] cycloaddition to form the ureato(1-) complex [(η(7)-C(7)H(7))Zr{Im(Dipp)N(C═O)N-o-Xy}] (8). 5 can also act as an initiator for the ring-opening polymerization of ε-caprolactone. These reactivity patterns together with density functional theory calculations reveal a marked similarity of the bonding in imidazolin-2-iminato and conventional imido transition-metal complexes.

  13. Verbal reasoning deficits in alcoholics.

    Yohman, J R; Parsons, O A


    The Conceptual Level Analogies Test (CLAT), a well-constructed test of analogical reasoning, was given to groups of middle-aged male alcoholics and control subjects in two separate studies. As predicted, the alcoholics had lower CLAT scores than nonalcoholics in both studies. These results support the generalized-diffuse model of the neuropsychological effects of alcoholism. Contrary to prediction, alcoholics differed from control subjects as much on the easy analogies as they did on the hard analogies, which suggested that alcoholics differ both qualitatively and quantitatively from nonalcoholics in cognitive impairment. Finally, in two of three studies in our laboratory, familial alcoholics had significantly lower CLAT scores than nonfamilial alcoholics. These findings emphasize the importance of considering familial history of alcoholism when studying the neuropsychological functioning of alcoholics.

  14. Oropharynx microbiota among alcoholics and non-alcoholics

    Valdir Golin

    Full Text Available CONTEXT: The oropharynx microbiota plays an important role in the origin of infections, especially among alcoholics whose airway defenses are impaired. OBJECTIVE: To compare the normal oropharingeal flora in heavy alcohol drinker and non-alcoholics. PATIENTS: 117 persons, 58 heavy alcohol drinkers and 59 non-alcoholics. SETTING: Santa Casa de São Paulo Emergency Service. DESIGN: A blind prospective study. MAIN OUTCOMES MEASURES: Prevalence of aerobic and anaerobic bacteria, and fungi. RESULTS: The study of the oropharynx microbiota among heavy alcohol drinkers demonstrated the presence of anaerobic microorganisms in 84.5% of them, including: Bacteroides sp, Prevotella melaninogenica, Fusobacterium sp, Veilonella sp, Peptostreptococcus sp, Propionibacterium sp, Bifidobacterium sp and Clostridium sp, versus 30.5% (p<0.005 of non-alcoholics. Candida sp was present in 34.5% of heavy alcohol drinkers and 5.1% of non-alcoholics (p<0.005. Enterobacteria predominated among heavy alcohol drinkers (25% compared with non-alcoholics (5.5% only in the age group 14 to 34 years (p<0.05. CONCLUSION: Based upon these results, it was possible to conclude that the knowledge of the oropharynx microbiota among heavy drinkers and non-alcoholics has an important predictive value concerning probable etiologic agents of lower airway infections. Infections caused by anaerobic microorganisms and fungi should be taken into consideration during the choice of empirical therapy for heavy alcohol drinkers.

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

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


    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 frequently...... invoked in the title reaction, but in the presence of halides, the neutral, unsymmetrically substituted eta(3)-CoMplex will be formed rapidly from anionic Pd(0) complexes in solution. Since the latter will prefer both leaving group ionization and reaction with nucleophiles in the position trans...

  16. Nucleophilic phosphine-catalyzed intramolecular Michael reactions of N-allylic substituted α-amino nitriles: construction of functionalized pyrrolidine rings via 5-endo-trig cyclizations.

    En, Da; Zou, Gong-Feng; Guo, Yuan; Liao, Wei-Wei


    Pyrrolidine rings are common moieties for pharmaceutical candidates and natural compounds, and the construction of these skeletons has received much attention. α-Amino nitriles are versatile intermediates in synthetic chemistry and have been widely used in the generation of multiple polyfunctional structures. Herein, a novel nucleophilic phosphine-catalyzed intramolecular Michael reaction of N-allylic substituted α-amino nitriles has been developed for the efficient construction of functionalized 2,4-disubstituted pyrrolidines (N-heterocyclic α-amino nitriles) via 5-endo-trig cyclization. Furthermore, the one-pot sequence of the synthesis of pyrrolidine and the subsequent transformations of the functionalized products have also been demonstrated.

  17. (4R-4-(2-Allyl-2H-1,2,3-triazol-4-yl-1,2-O-isopropylidene-l-threose

    David J. Watkin


    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.

  18. A configurational switch based on iridium-catalyzed allylic cyclization: application in asymmetric total syntheses of prosopis, dendrobate, and spruce alkaloids.

    Gnamm, Christian; Brödner, Kerstin; Krauter, Caroline M; Helmchen, Günter


    A method for the stereoselective synthesis of 2,6-disubstituted piperidines has been developed that is based on the use of an intramolecular iridium-catalyzed allylic substitution as a configurational switch. The procedure allows the preparation of 2-vinylpiperidines with enantiomeric excesses (ee) of greater than 99%. As applications, total syntheses of piperidine alkaloids have been elaborated, most often by using Ru-catalyzed cross-metatheses as a key step for introduction of a side chain. Asymmetric total syntheses of the prosopis alkaloids (+)-prosopinine, (+)-prosophylline, (+)-prosopine, and of the dendrobate alkaloid (+)-241D and its C6 epimer are described.

  19. Substituent Effects on Regioselectivity of the Diels-Alder Reactions: Reactions of 10-Allyl-1,8-dichloroanthracene with 2-Chloroacrylonitrile, 1-Cyanovinyl Acetate and Phenyl Vinyl Sulfone

    Mujeeb A. Sultan


    Full Text Available Diels-Alder reaction of 10-allyl-1,8-dichloroanthracene (3 with 2-chloroacrylonitrile (4 and 1-cyanovinyl acetate (5 gives exclusively the ortho isomer while its reaction with phenyl vinyl sulfone (10 yields a mixture of two isomeric adducts with priority to ortho isomer. The reactions proceeded under microwave condition in xylene. Configurations of these isomers have been assigned with the help of NMR spectra. The results indicated that the steric effect is dominating toward the isomer regioselectivity in the Diels-Alder reaction of the present compounds.

  20. Crystal structure of methyl 1-allyl-4-methyl-1H-benzo[c][1,2]thiazine-3-carboxylate 2,2-dioxide

    Liliana Azotla-Cruz


    Full Text Available In the title compound, C14H15NO4S, the dihydrothiazine ring adopts a distorted sofa conformation with the S atom displaced from the mean plane through the N and C ring atoms by 0.767 (1 Å. The allyl substituent (C—C=C is inclined to this mean plane by 78.5 (7° and the acetate group [C(=O—O—C] by 66.5 (3°. In the crystal, molecules are linked by C—H...π interactions forming chains propagating along the a-axis direction.

  1. Alcohol combustion chemistry

    Sarathy, Mani


    Alternative transportation fuels, preferably from renewable sources, include alcohols with up to five or even more carbon atoms. They are considered promising because they can be derived from biological matter via established and new processes. In addition, many of their physical-chemical properties are compatible with the requirements of modern engines, which make them attractive either as replacements for fossil fuels or as fuel additives. Indeed, alcohol fuels have been used since the early years of automobile production, particularly in Brazil, where ethanol has a long history of use as an automobile fuel. Recently, increasing attention has been paid to the use of non-petroleum-based fuels made from biological sources, including alcohols (predominantly ethanol), as important liquid biofuels. Today, the ethanol fuel that is offered in the market is mainly made from sugar cane or corn. Its production as a first-generation biofuel, especially in North America, has been associated with publicly discussed drawbacks, such as reduction in the food supply, need for fertilization, extensive water usage, and other ecological concerns. More environmentally friendly processes are being considered to produce alcohols from inedible plants or plant parts on wasteland. While biofuel production and its use (especially ethanol and biodiesel) in internal combustion engines have been the focus of several recent reviews, a dedicated overview and summary of research on alcohol combustion chemistry is still lacking. Besides ethanol, many linear and branched members of the alcohol family, from methanol to hexanols, have been studied, with a particular emphasis on butanols. These fuels and their combustion properties, including their ignition, flame propagation, and extinction characteristics, their pyrolysis and oxidation reactions, and their potential to produce pollutant emissions have been intensively investigated in dedicated experiments on the laboratory and the engine scale

  2. Anticonvulsants for alcohol withdrawal.

    Minozzi, Silvia; Amato, Laura; Vecchi, Simona; Davoli, Marina


    Alcohol abuse and dependence represents a most serious health problem worldwide with major social, interpersonal and legal interpolations. Besides benzodiazepines, anticonvulsants are often used for the treatment of alcohol withdrawal symptoms. Anticonvulsants drugs are indicated for the treatment of alcohol withdrawal syndrome, alone or in combination with benzodiazepine treatments. In spite of the wide use, the exact role of the anticonvulsants for the treatment of alcohol withdrawal has not yet bee adequately assessed. To evaluate the effectiveness and safety of anticonvulsants in the treatment of alcohol withdrawal. We searched Cochrane Drugs and Alcohol Group' Register of Trials (December 2009), PubMed, EMBASE, CINAHL (1966 to December 2009), EconLIT (1969 to December 2009). Parallel searches on web sites of health technology assessment and related agencies, and their databases. Randomized controlled trials (RCTs) examining the effectiveness, safety and overall risk-benefit of anticonvulsants in comparison with a placebo or other pharmacological treatment. All patients were included regardless of age, gender, nationality, and outpatient or inpatient therapy. Two authors independently screened and extracted data from studies. Fifty-six studies, with a total of 4076 participants, met the inclusion criteria. Comparing anticonvulsants with placebo, no statistically significant differences for the six outcomes considered.Comparing anticonvulsant versus other drug, 19 outcomes considered, results favour anticonvulsants only in the comparison carbamazepine versus benzodiazepine (oxazepam and lorazepam) for alcohol withdrawal symptoms (CIWA-Ar score): 3 studies, 262 participants, MD -1.04 (-1.89 to -0.20), none of the other comparisons reached statistical significance.Comparing different anticonvulsants no statistically significant differences in the two outcomes considered.Comparing anticonvulsants plus other drugs versus other drugs (3 outcomes considered), results

  3. Stress, epigenetics, and alcoholism.

    Moonat, Sachin; Pandey, Subhash C


    Acute and chronic stressors have been associated with alterations in mood and increased anxiety that may eventually result in the development of stress-related psychiatric disorders. Stress and associated disorders, including anxiety, are key factors in the development of alcoholism because alcohol consumption can temporarily reduce the drinker's dysphoria. One molecule that may help mediate the relationship between stress and alcohol consumption is brain-derived neurotrophic factor (BDNF), a protein that regulates the structure and function of the sites where two nerve cells interact and exchange nerve signals (i.e., synapses) and which is involved in numerous physiological processes. Aberrant regulation of BDNF signaling and alterations in synapse activity (i.e., synaptic plasticity) have been associated with the pathophysiology of stress-related disorders and alcoholism. Mechanisms that contribute to the regulation of genetic information without modification of the DNA sequence (i.e., epigenetic mechanisms) may play a role in the complex control of BDNF signaling and synaptic plasticity-for example, by modifying the structure of the DNA-protein complexes (i.e., chromatin) that make up the chromosomes and thereby modulating the expression of certain genes. Studies regarding the epigenetic control of BDNF signaling and synaptic plasticity provide a promising direction to understand the mechanisms mediating the interaction between stress and alcoholism.

  4. Genetics of alcoholism.

    Edenberg, Howard J; Foroud, Tatiana


    Multiple lines of evidence strongly indicate that genetic factors contribute to the risk for alcohol use disorders (AUD). There is substantial heterogeneity in AUD, which complicates studies seeking to identify specific genetic factors. To identify these genetic effects, several different alcohol-related phenotypes have been analyzed, including diagnosis and quantitative measures related to AUDs. Study designs have used candidate gene analyses, genetic linkage studies, genomewide association studies (GWAS), and analyses of rare variants. Two genes that encode enzymes of alcohol metabolism have the strongest effect on AUD: aldehyde dehydrogenase 2 and alcohol dehydrogenase 1B each has strongly protective variants that reduce risk, with odds ratios approximately 0.2-0.4. A number of other genes important in AUD have been identified and replicated, including GABRA2 and alcohol dehydrogenases 1B and 4. GWAS have identified additional candidates. Rare variants are likely also to play a role; studies of these are just beginning. A multifaceted approach to gene identification, targeting both rare and common variations and assembling much larger datasets for meta-analyses, is critical for identifying the key genes and pathways important in AUD.

  5. Diabetes mellitus and alcohol.

    van de Wiel, Albert


    Alcohol influences glucose metabolism in several ways in diabetic patients as well as in non-diabetic patients. Since alcohol inhibits both gluconeogenesis and glycogenolysis, its acute intake without food may provoke hypoglycaemia, especially in cases of depleted glycogen stores and in combination with sulphonylurea. Consumed with a meal including carbohydrates, it is the preferred fuel, which may initially lead to somewhat higher blood glucose levels and hence an insulin response in type 2 diabetic patients. Depending on the nature of the carbohydrates in the meal, this may be followed by reactive hypoglycaemia. Moderate consumption of alcohol is associated with a reduced risk of atherosclerotic disorders. Diabetic patients benefit from this favourable effect as much as non-diabetic patients. Apart from effects on lipid metabolism, haemostatic balance and blood pressure, alcohol improves insulin sensitivity. This improvement of insulin sensitivity may also be responsible for the lower incidence of type 2 diabetes mellitus reported to be associated with light-to-moderate drinking. In case of moderate and sensible use, risks of disturbances in glycaemic control, weight and blood pressure are limited. Excessive intake of alcohol, however, may not only cause loss of metabolic control, but also annihilate the favourable effects on the cardiovascular system.

  6. Invertebrate models of alcoholism.

    Scholz, Henrike; Mustard, Julie A


    For invertebrates to become useful models for understanding the genetic and physiological mechanisms of alcoholism related behaviors and the predisposition towards alcoholism, several general requirements must be fulfilled. The animal should encounter ethanol in its natural habitat, so that the central nervous system of the organism will have evolved mechanisms for responding to ethanol exposure. How the brain adapts to ethanol exposure depends on its access to ethanol, which can be regulated metabolically and/or by physical barriers. Therefore, a model organism should have metabolic enzymes for ethanol degradation similar to those found in humans. The neurons and supporting glial cells of the model organism that regulate behaviors affected by ethanol should share the molecular and physiological pathways found in humans, so that results can be compared. Finally, the use of invertebrate models should offer advantages over traditional model systems and should offer new insights into alcoholism-related behaviors. In this review we will summarize behavioral similarities and identified genes and mechanisms underlying ethanol-induced behaviors in invertebrates. This review mainly focuses on the use of the nematode Caenorhabditis elegans, the honey bee Apis mellifera and the fruit fly Drosophila melanogaster as model systems. We will discuss insights gained from those studies in conjunction with their vertebrate model counterparts and the implications for future research into alcoholism and alcohol-induced behaviors.

  7. On the regiochemistry of nucleophilic attack on 2-halo pi-allyl complexes. 4. The effect of silver acetate and nucleophile concentrations in competitive nucleophilic attack with malonate and phenoxide nucleophiles.

    Organ, Michael G; Arvanitis, Elena A; Hynes, Stephen J


    2,3-Dibromo-1-propene or its allyl carbonate analogue are ionized under Pd catalysis to generate the 2-bromo Pd-pi-allyl complex (triphenylphosphine ligand), which alkylates with malonate nucleophile at the terminal position. The presence of acetate ion in the reaction mixture results in some malonate attack being redirected to the central carbon. The acetate ion can come from the ionization of 1-acetoxy-2-bromo-2-propene or by the addition of silver acetate to the reaction mixture. The addition of phenoxide ion to the reaction also causes the same regiochemical phenomena, although harder anions such as methoxide exert no such effect.

  8. 78 FR 65347 - National Institute on Alcohol Abuse and Alcoholism; Notice of Closed Meeting


    ... HUMAN SERVICES National Institutes of Health National Institute on Alcohol Abuse and Alcoholism; Notice... personal privacy. Name of Committee: National Institute on Alcohol Abuse and Alcoholism Special Emphasis... Abuse and Alcoholism, 5635 Fishers Lane (Teleconference), Rockville, MD 20855. Contact Person:...

  9. 78 FR 21615 - National Institute on Alcohol Abuse and Alcoholism; Notice of Closed Meeting


    ... HUMAN SERVICES National Institutes of Health National Institute on Alcohol Abuse and Alcoholism; Notice... personal privacy. Name of Committee: National Institute on Alcohol Abuse and Alcoholism Initial ] Review... Foster, Ph.D., Scientific Review Administrator, National Institutes on Alcohol Abuse &...

  10. Alcoholic liver disease and pancreatitis: global health problems being addressed by the US National Institute on Alcohol Abuse and Alcoholism.

    Warren, Kenneth R; Murray, Margaret M


    The review article summarizes the mission of the National Institute on Alcohol Abuse and Alcoholism (NIAAA) with focus on the NIAAA's current and future research version for alcoholic liver disease and alcoholic pancreatitis.

  11. When alcohol acts

    Demant, Jakob


      Sociological studies into alcohol use seem to find it difficult to deal with the substance itself. Alcohol tends to be reduced to a symbol of a social process and in this way the sociological research loses sight of effects beyond the social. This paper suggests a new theoretical approach...... to the study of alcohol and teenagers' (romantic) relationships, inspired by actor-network theory (ANT). The central feature of ANT is to search for relationships, or rather networks, between all things relevant to the phenomenon. All material and semantic structures, things, persons, discourses, etc......'s development from being a non-drinker at the age of 14, to a heavy drinker at 16, the paper investigates how the actants brought out by young people themselves constitute different forms of agency. The analysis is based on a qualitative study consisting of 37 focus groups conducted with teenagers in Denmark...

  12. The Risks Associated With Alcohol Use and Alcoholism

    Rehm, Jürgen


    Alcohol consumption, particularly heavier drinking, is an important risk factor for many health problems and, thus, is a major contributor to the global burden of disease. In fact, alcohol is a necessary underlying cause for more than 30 conditions and a contributing factor to many more. The most common disease categories that are entirely or partly caused by alcohol consumption include infectious diseases, cancer, diabetes, neuropsychiatric diseases (including alcohol use disorders), cardiov...

  13. Receptivity to alcohol marketing predicts initiation of alcohol use.

    Henriksen, Lisa; Feighery, Ellen C; Schleicher, Nina C; Fortmann, Stephen P


    This longitudinal study examined the influence of alcohol advertising and promotions on the initiation of alcohol use. A measure of receptivity to alcohol marketing was developed from research about tobacco marketing. Recall and recognition of alcohol brand names were also examined. Data were obtained from in-class surveys of sixth, seventh, and eighth graders at baseline and 12-month follow-up. Participants who were classified as never drinkers at baseline (n = 1,080) comprised the analysis sample. Logistic regression models examined the association of advertising receptivity at baseline with any alcohol use and current drinking at follow-up, adjusting for multiple risk factors, including peer alcohol use, school performance, risk taking, and demographics. At baseline, 29% of never drinkers either owned or wanted to use an alcohol branded promotional item (high receptivity), 12% students named the brand of their favorite alcohol ad (moderate receptivity), and 59% were not receptive to alcohol marketing. Approximately 29% of adolescents reported any alcohol use at follow-up; 13% reported drinking at least 1 or 2 days in the past month. Never drinkers who reported high receptivity to alcohol marketing at baseline were 77% more likely to initiate drinking by follow-up than those were not receptive. Smaller increases in the odds of alcohol use at follow-up were associated with better recall and recognition of alcohol brand names at baseline. Alcohol advertising and promotions are associated with the uptake of drinking. Prevention programs may reduce adolescents' receptivity to alcohol marketing by limiting their exposure to alcohol ads and promotions and by increasing their skepticism about the sponsors' marketing tactics.

  14. Neuropathology of alcoholism.

    Harper, C G; Kril, J J


    There are wide ranging effects of alcohol on the nervous system. Some interfere with physiological and neurochemical functions but ultimately structural damage occurs. During life one of the most impressive changes is brain shrinkage which can be visualized using neuroradiological imaging techniques. This article reviews the pathological explanations for brain shrinkage and addresses the question of the pathogenesis of the reversible component of this damage in relation to prolonged abstinence from alcohol. This shrinkage seems to relate to a loss of white matter. However, the cortex is also abnormal in that there is a loss of neurones from the frontal region. In this and other regions of the cortex examined there is shrinkage of the neuronal soma. This is reflected in a retraction of the neuronal dendritic arbor which plays a crucial role in cell-to-cell communication. In addition, the cerebellum appears to be vulnerable in alcoholic patients although it may well be that associated nutritional deficiencies play an important role. The Wernicke-Korsakoff syndrome is another important deficiency disorder which is seen most frequently in alcoholic patients. Two important population groups which are considered in this review are females and moderate ('social') drinkers. Females are thought to be more susceptible to the damaging effects of alcohol than males and this is examined in the light of the scant data available. Similarly, there are few neuropathological data on people who drink 30-80 grams of alcohol per day. In order to assess so-called 'safe levels of drinking' this is an important group to study.

  15. A comparison of blood alcohol concentration using non-alcohol- and alcohol-containing skin antiseptics.

    Goldfinger, T M; Schaber, D


    We simultaneously obtained blood samples in emergency patients for ethanol content from both antecubital fossae using an alcohol prep pad on one arm and a non-alcohol-containing germicidal solution on the other. Fifty patients with ethanol concentrations greater than zero were statistically analyzed. Twenty patients surveyed had no measurable alcohol level by either technique. There was no significant difference in the blood alcohol concentration obtained by either method of skin preparation in both groups (P less than .01). Blood alcohol concentration incidentally obtained in the emergency department by routine isopropyl alcohol skin preparation is an accurate laboratory parameter.

  16. Chicano Alcohol Abuse and Alcoholism in the Barrio.

    Jasso, Ricardo

    Conducted in January 1977, the community survey examined alcohol abuse and alcoholism among Chicanos in the barrios. Data were obtained from 160 respondents (119 females and 41 males) from 3 geographic areas in San Antonio: the Special Impact Area of Casa Del Sol (an alcoholism program) and the cities of San Antonio and Alamo Heights. Information…

  17. Alcohol consumption, alcohol dehydrogenase 3 polymorphism, and colorectal adenomas

    Tiemersma, E.W.; Wark, P.A.; Ocké, M.C.; Bunschoten, A.; Otten, M.H.; Kok, F.J.; Kampman, E.


    Alcohol is a probable risk factor with regard to colorectal neoplasm and is metabolized to the carcinogen acetaldehyde by the genetically polymorphic alcohol dehydrogenase 3 (ADH3) enzyme. We evaluated whether the association between alcohol and colorectal adenomas is modified by ADH3 polymorphism.


    Lilijana Šprah


    Our study demonstrated that some alcohol-related cognitive, emotional and motivationaldeficits can also persist to certain extent after several weeks of sobriety. Especially alcoholabstainers with suicidal history revealed a specific neuropsychological profile in this regard. Employed neurocognitive assessment proved as useful approach for clinical evaluation of alcohol abstainers functioning, since cognitive deficits have been also hypothesizedto affect the efficacy of alcoholism treatment

  19. Values and Recovery from Alcoholism through Alcoholics Anonymous.

    Brown, Howard P. Jr.; Peterson, John H. Jr.


    Analyzed Rokeach Value Surveys completed by 57 alcoholics and addicts who had obtained at least 3 years' abstinence using a 12-step program of recovery. Data suggested a shift in values is involved in recovery from alcoholism through participation in Alcoholics Anonymous and that values clarification and value therapy may be useful in chemical…

  20. Alcohols as gasoline additives

    Jawetz, P.


    This paper showed that, when using alcohol octane-boosting additives to gasoline, one attains several goals at the same time: (a) there is an increased saving in petroleum crude, since the alcohol is not merely a substitute for gasoline but rather a substitute for the octane-boosting additives used in the manufacture of unleaded gasoline; and (b) the production of fermentation ethanol for a fuel purpose can help revitalize the agricultural sector in different economics systems, thus becoming a road to economic development.