Sample records for acid catalyzed friedel-crafts

  1. The synthesis of mono- and diacetyl-9H-fluorenes. Reactivity and selectivity in the Lewis acid catalyzed Friedel-Crafts acetylation of 9H-fluorene

    Titinchi, Salam J. J.; Kamounah, Fadhil S.; Abbo, Hanna S.


    Friedel-Crafts acetylation of 9H-fluorene is an effective route for the preparation of mono- and diacetyl-9H-fluorenes. Using acetylchloride as the reagent and aluminum chloride as the Lewis acid catalyst the effect of the solvent polarity, the temperature, the reaction time and the mode...

  2. SPINOL-derived phosphoric acids: synthesis and application in enantioselective Friedel-Crafts reaction of indoles with imines.

    Xu, Fangxi; Huang, Dan; Han, Chao; Shen, Wei; Lin, Xufeng; Wang, Yanguang


    A new class of chiral phosphoric acids with spirobiindane as scaffold were conveniently synthesized from (S)-1,1'-spirobiindane-7,7'-diol ((S)-SPINOL) and employed to catalyze the asymmetric Friedel-Crafts reaction of indoles with imines to afford 3-indolyl methanamines. High yields (68-97%) and excellent enantioselectivities (up to 99% ee) were obtained.

  3. Asymmetric and efficient synthesis of homophenylalanine derivatives via Friedel-Crafts reaction with trifluoromethanesulfonic acid

    Murashige, Ryo; Hayashi, Yuka; Hashimoto, Makoto; 橋本, 誠


    An efficient Friedel-Crafts reaction of TFA-Asp(Cl)-OMe and stoichiometric amounts of benzene was established by using neat trifluoromethanesulfonic acid (TfOH) as solvent and catalyst under a mild condition. This methodology has been applied to many aromatic compounds and enabled synthesis of several homophenylalanine derivatives.

  4. Effective synthesis of optically active trifluoromethyldiazirinyl homophenylalanine and aroylalanine derivatives with the Friedel-Crafts reaction in triflic acid.

    Murashige, Ryo; Murai, Yuta; Hatanaka, Yasumaru; Hashimoto, Makoto


    The Friedel-Crafts reaction with 3-(3-methoxyphenyl)-3-(trifluoromethyl)-3H-diazirine and optically active N-TFA-Asp(Cl)-OMe in triflic acid afforded homophenylalanine derivatives without any loss of the optical purity.

  5. A practical synthesis of 3,4-diethoxybenzthioamide based on Friedel-Crafts reaction with potassium thiocyanate in methanesulfonic acid.

    Aki, Shinji; Fujioka, Takafumi; Ishigami, Masashi; Minamikawa, Jun-ichi


    The synthesis of 3,4-diethoxybenzthioamide, the key intermediate for OPC-6535, is achieved by employing Friedel-Crafts reaction of 1,2-diethoxybenzene with potassium thiocyanate in methanesulfonic acid at ambient temperature.

  6. One-pot Synthesis of Lewis Acidic Ionic Liquids for Friedel-Crafts Alkylation


    Novel Lewis acidic ionic liquids containing thionyl cations and chloroaluminate anions were obtained by one-pot synthesis for the first time. Their acidities were determined by acetonitrile probe on IR spectrography. The ionic liquids were used as catalyst for Friedel-Crafts alkylation of benzene and 1-dodecene. The turnovers of 1-dodecene were higher than 99%. Monoalkylbenzene selectivity was 98%, while the 2-substituent product selectivity was 45%.

  7. A novel mesoporous sulfated zirconium solid acid catalyst for Friedel-Crafts benzylation reaction

    Miao, Zhichao; Zhou, Jin; Zhao, Jinping; Liu, Dandan; Bi, Xu; Chou, Lingjun; Zhuo, Shuping


    In this paper, a novel mesoporous sulfated zirconium (M-ZrO2/SO42-) has been gotten by one-pot evaporation-induced self-assembly (one-pot EISA) strategy. The SXRD, N2-physisorption and TEM characterization techniques indicated that M-ZrO2/SO42- possessed distinct mesostructure with big specific surface area (133.5 m2 g-1), large pore volume (0.18 cm3 g-1) and narrow pore size distribution (4.90 nm). Moreover, the existing states and the influence in mesostructure of introduced S species were detailedly investigated by the XRD, N2-physisorption, TEM, TG-DSC, FT-IR and XPS techniques and the results showed that the S species, which existed as the type of SO42-, improved the textural properties of prepared materials. In addition, the NH3-TPD and IR spectra of adsorbed pyridine indicated the existence of strong Brønsted and Lewis acid sites in M-ZrO2/SO42- even evacuated at 400 °C. Furthermore, the M-ZrO2/SO42- was used as a promise solid acid catalyst and displayed excellent catalytic performance and reusability in Friedel-Crafts benzylation reaction.

  8. Metal halide hydrates as lewis acid catalysts for the conjugated friedel-crafts reactions of indoles and activated olefins

    Schwalm, Cristiane S.; Ceschi, Marco Antonio; Russowsky, Dennis, E-mail: dennis@iq.ufrgs.b [Universidade Federal do Rio Grande do Sul (IQ/UFRGS), Porto Alegre, RS (Brazil). Inst. de Quimica


    Metal halide hydrates such as SnCl{sub 2{center_dot}}2H{sub 2}O, MnCl{sub 2{center_dot}}4H{sub 2}O, SrCl{sub 2{center_dot}}6H{sub 2}O, CrCl{sub 2{center_dot}}6H{sub 2}O, CoCl{sub 2{center_dot}}6H{sub 2}O e CeCl{sub 3{center_dot}}7H{sub 2}O were investigated as mild Lewis acids catalysts for the conjugate Friedel-Crafts reaction between indoles and activated olefins. The reactions were carried out with aliphatic unsaturated ketones over a period of days at room temperature, while chalcones reacted only under reflux conditions. The reactions with nitrostyrene s were either performed in solvent or under solventless conditions. In all cases reasonable to good yields were obtained. (author)

  9. Methanetrisulfonic Acid: A Highly Efficient Strongly Acidic Catalyst for Wagner-Meerwein Rearrangement, Friedel-Crafts Alkylation and Acylation Reactions. Examples from Vitamin E Synthesis

    Francesco Pace


    Full Text Available Methanetrisulfonic acid had been prepared for the first time over 140 years ago, but it was used only scarcely in chemical transformations. In the course of our activities dealing with key-steps of industrial syntheses of vitamins, e.g. economically important vitamin E (acetate, we found that methanetrisulfonic acid is an extremely effective catalyst in a variety of reactions. Examples of its applications are Wagner-Meerwein rearrangements, Friedel-Crafts alkylations and ring closures, as well as acylation reactions. Use of this catalyst in truly catalytic amounts (0.04-1.0 mol% resulted in highly selective transformations and yields over 95%. (Remark by the authors: We are describing only one example each for the various types of reactions. Therefore, it would be more appropriate to write (here and in the Introduction and in the Conclusion sections: “Wagner-Meerwein rearrangement, Friedel-Crafts alkylation and ring closure, as well as acylation reactions”

  10. A Quinine-Squaramide Catalyzed Enantioselective Aza-Friedel-Crafts Reaction of Cyclic Trifluoromethyl Ketimines with Naphthols and Electron-Rich Phenols.

    Zhou, Ding; Huang, Zheng; Yu, Xueting; Wang, Youxin; Li, Jian; Wang, Wei; Xie, Hexin


    A highly enantioselective aza-Friedel-Crafts (aza-F-C) reaction of cyclic trifluoromethyl ketimines and naphthols/phenols was developed with fluorenyl-substituted quinine-squaramide as the catalyst. This protocol enables direct access to biologically important chiral trifluoromethyl dihydroquinazolinones with up to 99% yields and up to 99% ee's.

  11. Friedel-Crafts amidoalkylation via thermolysis and oxidative photocatalysis.

    Dai, Chunhui; Meschini, Francesco; Narayanam, Jagan M R; Stephenson, Corey R J


    Friedel-Crafts amidoalkylation was achieved by oxidation of dialkylamides using persulfate (S(2)O(8)(2-)) in the presence of the visible light catalyst, Ru(bpy)(3)Cl(2), at room temperature, via a reactive N-acyliminium intermediate. Alternatively, mild heating of the dialkylamides and persulfate afforded a metal and Lewis acid-free Friedel-Crafts amidoalkylation. Alcohols and electron-rich arenes served as effective nucleophiles, forming new C-O or C-C bonds. In general, photocatalysis provided higher yields and better selectivities.

  12. Acilação de Friedel-Crafts do 2-metoxinaftaleno usando o ácido dodecafosfotúngstico suportado em sílica (HPW/SiO2 como catalisador e acetonitrila como solvente Friedel-Crafts acylation of the 2-methoxynaphthalene using the silica-supported dodecatungstophosphoric acid (HPW/SiO2 as catalyst and acetonitrile as solvent

    Gil Luciano Guedes dos Santos


    Full Text Available The synthesis of fine chemicals intermediates using Friedel-Crafts acylation is one of the most important methods in chemical technology. In this work, the acylation of 2-methoxynaphthalene with acetic anhydride using a silica-supported dodecatungstophosphoric acid catalyst (HPW/SiO2 and acetonitrila as solvent was studied, showing that this reaction is a feasible alternative to produce intermediaries to replace the current methods of production. The reactions using acetonitrile solvent showed yields greater than or equal to the reactions using traditional solvents such as nitrobenzene and dichloroethane. Finally, the modified Eley-Rideal mechanism was proposed to elucidate the experimental data obtained.

  13. 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.

  14. Greener Friedel-Crafts Acylation using Microwave-enhanced reactivity of Bismuth Triflate in the Friedel-Crafts Benzoylation of Aromatic Compounds with Benzoic Anhydride

    Tran, Phuong Hoang; Nguyen, hai Truong; Hansen, Poul Erik


    An efficient and facile bismuth trifluoromethanesulfonate-catalyzed benzoylation of aromatic compounds using benzoic anhydride under solvent-free microwave irradiation has been developed. The microwave-assisted Friedel-Crafts benzoylation results in good yields within short reaction times. Bismut...

  15. Asymmetric Friedel-Crafts Reaction of Indoles with Imines by an Organic Catalyst

    Wang, Yong-Qiang; Song, Jun; Hong, Ran; Li, Hongming; Deng, Li


    In this communication, we report an asymmetric Friedel-Crafts reaction of indoles with imines catalyzed by a bifunctional cinchona alkaloid catalyst. This is the first efficient organocatalytic asymmetric Friedel-Crafts reaction of indoles with imines. This reaction is operationally simple and, unprecedently, affords high enantioselectivity for a wide range of indoles and both aryl and alkyl imines. This establishes a direct, convergent and versatile approach to optically active 3-indolyl-methanamines, a structural motif embedded in numerous indole alkaloids and synthetic indole derivatives. PMID:16787078

  16. A review of new developments in the Friedel-Crafts alkylation - From green chemistry to asymmetric catalysis.

    Rueping, Magnus; Nachtsheim, Boris J


    The development of efficient Friedel-Crafts alkylations of arenes and heteroarenes using only catalytic amounts of a Lewis acid has gained much attention over the last decade. The new catalytic approaches described in this review are favoured over classical Friedel-Crafts conditions as benzyl-, propargyl- and allyl alcohols, or styrenes, can be used instead of toxic benzyl halides. Additionally, only low catalyst loadings are needed to provide a wide range of products. Following a short introduction about the origin and classical definition of the Friedel-Crafts reaction, the review will describe the different environmentally benign substrates which can be applied today as an approach towards greener processes. Additionally, the first diastereoselective and enantioselective Friedel-Crafts-type alkylations will be highlighted.

  17. One-Pot Synthesis of Pyrrolo[1,2-a]indoles by Chiral N-Triflyl Phosphoramide Catalyzed Friedel-Crafts Alkylation of 4,7-Dihydroindole with ②, y-Unsaturated a-Keto Esters

    曾蜜; 张玮; 游书力


    Chiral N-triflyl phosphoramide was found an efficient catalyst for the enantioselective Friedel-Crafts alkylation reaction of 4,7-dihydroindole with β, γ-unsaturated a-keto esters. In the presence of 5 tool% of the optimized catalyst, various pyrrolo[1,2-a]indoles were obtained in excellent enantioselectivity, moderate yields and up to 3 : 1 di- astereoselectivity based on the one-pot synthesis including the Friedel-Crafts alkylation reaction and the subsequent p-benzoquinone oxidation.

  18. A Research-Based Undergraduate Organic Laboratory Project: Investigation of a One-Pot, Multicomponent, Environmentally Friendly Prins-Friedel-Crafts-Type Reaction

    Dintzner, Matthew R.; Maresh, Justin J.; Kinzie, Charles R.; Arena, Anthony F.; Speltz, Thomas


    Students in the undergraduate organic laboratory synthesize tetrahydro-2-(4-nitrophenyl)-4-phenyl-2"H"-pyran via the Montmorillonite K10 clay-catalyzed reaction of p-nitrobenzaldehye with methanol, 3-buten-1-ol, and benzene. The synthesis comprises an environmentally friendly tandem Prins-Friedel-Crafts-type multicomponent reaction (MCR) and sets…

  19. Reactions on a solid surface. A simple, economical and efficient Friedel-Crafts acylation reaction over zinc oxide (ZnO) as a new catalyst.

    Sarvari, Mona Hosseini; Sharghi, Hashem


    Zinc oxide (ZnO) brings about a rapid Friedel-Crafts acylation of a range of activated and unactivated aromatic compounds such as anisole and chlorobenzene with acid chlorides in solvent-free conditions at room temperature. The ZnO powder can be reused up to three times after simple washing with dichloromethane. Copyright 2004 American Chemical Society

  20. IBX-mediated oxidation of unactivated cyclic amines: application in highly diastereoselective oxidative Ugi-type and aza-Friedel-Crafts reactions.

    de Graaff, C; Bensch, L; van Lint, Matthijs J; Ruijter, E; Orru, R V A


    The first o-iodoxybenzoic acid (IBX) mediated oxidation of unactivated amines to imines is described. A range of meso-pyrrolidines were shown to be suitable substrates. The chemical space was further explored with one-pot oxidative Ugi-type and aza-Friedel-Crafts reactions, which proved to be highly diastereoselective.

  1. Lewis acid catalyzed cascade reaction of 3-(2-benzenesulfonamide)propargylic alcohols to spiro[indene-benzosultam]s.

    Sun, Lang; Zhu, Yuanxun; Wang, Jing; Lu, Ping; Wang, Yanguang


    A highly efficient and convenient construction of the spiro[indene-benzosultam] skeleton from propargylic alcohols has been developed. The reaction proceeded in a Lewis acid catalyzed cascade process, including the trapping of allene carbocation with sulfonamide, electrophilic cyclization, and intramolecular Friedel-Crafts alkylation. In the presence of NIS or NBS, iodo/bromo-substituted spiro[indene-benzosultam]s could be prepared in excellent yields.

  2. A Zeolite Imidazolate Framework ZIF-8 Catalyst for Friedel-Crafts Acylation

    LienT.L.NGUYEN; Ky K.A.LE; Nam T.S.PHAN


    A zeolite imidazolate framework,ZIF-8,was synthesized and characterized by dynamic laser light scattering,X-ray powder diffraction,scanning electron microscopy,transmission electron microscopy,thermogravimetric analysis,Fourier transform infrared,atomic absorption spectrophotometry,and nitrogen adsorption measurements.The ZIF-8 was highly crystalline and porous with a surface area of over 1600 m2/g.Friedel-Crafts acylation of anisole and benzoyl chloride proceeded well in the presence of ZIF-8 (2-6 mol%) without the need for an inert atmosphere.The reaction afforded a selectivity of 93%-95% to the p-isomer.The solid catalyst can be separated from the reaction mixture by simple centrifugation and reused without significant degradation in catalytic activity.There was no leaching of active acid species into the reaction solution.

  3. A reactivity-selectivity study of the Friedel-Crafts acetylation of 3,3'-dimethylbiphenyl and the oxidation of the acetyl derivatives

    Titinchi, Salam J.J.; Kamounah, Fadhil S.; Abbo, Hanna S.;


    converted to the carboxylic acids by hypochlorite oxidation. The relative stabilities of the isomeric products and the corresponding s-complexes were studied by DFT calculations and the data indicated that mono-and diacetylation followed different mechanisms. Conclusions: Friedel-Crafts acetylation of 3...... the less selective diacetylations of the deactivated 4-Ac-3,3'-dmbp are suggested to include the acetyl cation as the electrophile. The DFT data also showed that complexation of intermediates and products with AlCl3 does not seem to be important in determining the mechanism.......Background: Friedel-Crafts acetylation is an important route to aromatic ketones, in research laboratories and in industry. The acetyl derivatives of 3,3'-dimethylbiphenyl (3,3'-dmbp) have applications in the field of liquid crystals and polymers and may be oxidized to the dicarboxylic acids...

  4. Poly(vinyl chloride-grafted multi-walled carbon nanotubes via Friedel-Crafts alkylation


    Full Text Available A novel approach was developed for the surface modification of the multi-walled carbon nanotubes (MWCNTs with high percentage of grafting (PG% by the grafting of polymer via the Friedel-Crafts alkylation. The graft reaction conditions, such as the amount of catalyst added, the reaction temperature, and the reaction time were optimized for the Friedel-Crafts alkylation of the MWCNTs with poly(vinyl chloride (PVC with anhydrous aluminum chloride (AlCl3 as catalyst in chloroform (CHCl3. The Fourier Transform Infrared (FT-IR, Raman, and thermogravimetric (TGA analysis showed that PVC had been successfully grafted onto MWCNTs both at the ends and on the sidewalls by the proposed Friedel-Crafts alkylation. The PVC grafted MWCNTs (PVC-MWCNTs could be dispersed well in organic solvent and the dispersion was more stable.

  5. The synthesis of mono- and diacetyl-9H-fluorenes. Reactivity and selectivity in the Lewis acid catalyzed Friedel-Crafts acetylation of 9H-fluorene

    Titinchi, Salam J.J.; Kamounah, Fadhil S.; Abbo, Hanna S.;


    and the Gibbs free energies at 298K for 9H-fluorene, the five isomeric monoacetyl-9H-fluorenes and the four σ-complexes leading to 1-, 2-, 3- and 4-acetyl-9H-fluorene, respectively, were computed at the DFT B3LYP 6-31G** level of theory. The data serve as a basis for the discussion of the reactivity...

  6. Lewis Acid Catalyzed Selective Reactions of Donor-Acceptor Cyclopropanes with 2-Naphthols.

    Kaicharla, Trinadh; Roy, Tony; Thangaraj, Manikandan; Gonnade, Rajesh G; Biju, Akkattu T


    Lewis acid-catalyzed reactions of 2-substituted cyclopropane 1,1-dicarboxylates with 2-naphthols is reported. The reaction exhibits tunable selectivity depending on the nature of Lewis acid employed and proceed as a dearomatization/rearomatization sequence. With Bi(OTf)3 as the Lewis acid, a highly selective dehydrative [3+2] cyclopentannulation takes place leading to the formation of naphthalene-fused cyclopentanes. Interestingly, engaging Sc(OTf)3 as the Lewis acid, a Friedel-Crafts-type addition of 2-naphthols to cyclopropanes takes place, thus affording functionalized 2-naphthols. Both reactions furnished the target products in high regioselectivity and moderate to high yields. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Hierarchical zeolite beta: an efficient and eco-friendly nanocatalyst for the Friedel-Crafts acylation of toluene.

    Selvin, Rosilda; Roselin, L Selva; Khayyat, Suzan A; Umar, Ahmad


    P-Methyacetophenone, the acylated product of toluene finds a wide range of applications in the flavors and fragrance industry. It is typically produced on an industrial scale by Friedel-Crafts acylation of toluene with acetic anhydride using homogeneous, corrosive and polluting acid catalysts such as aluminium chloride. The pollution problems related to this process such as the disposal of catalyst and treatment of acidic effluent needs to be replaced by a green process. The current work reports on the activity of hierarchical zeolite Beta in the liquid phase acylation of toluene with acetic anhydride. The liquid phase reactions were carried out in the temperature range of 60-140 degrees C in an autoclave. The effect of various reaction parameters such as time-on-stream (TOS), mole ratio of reactants, catalyst loading, and reaction temperature on the rates of reaction has been investigated. Under the optimum reaction conditions the performance of hierarchical zeolite Beta was compared with nanocrystalline zeolite Beta. It was found that hierarchical zeolite Beta catalyst exhibit higher activity, which is due to the hierarchical porosity and to the nano size of the Beta zeolite catalyst particles allows faster diffusion of the products out of the catalyst.

  8. Friedel-Crafts Crosslinked Highly Sulfonated Polyether Ether Ketone (SPEEK) Membranes for a Vanadium/Air Redox Flow Battery.

    Merle, Géraldine; Ioana, Filipoi Carmen; Demco, Dan Eugen; Saakes, Michel; Hosseiny, Seyed Schwan


    Highly conductive and low vanadium permeable crosslinked sulfonated poly(ether ether ketone) (cSPEEK) membranes were prepared by electrophilic aromatic substitution for a Vanadium/Air Redox Flow Battery (Vanadium/Air-RFB) application. Membranes were synthesized from ethanol solution and crosslinked under different temperatures with 1,4-benzenedimethanol and ZnCl2 via the Friedel-Crafts crosslinking route. The crosslinking mechanism under different temperatures indicated two crosslinking pathways: (a) crosslinking on the sulfonic acid groups; and (b) crosslinking on the backbone. It was observed that membranes crosslinked at a temperature of 150 °C lead to low proton conductive membranes, whereas an increase in crosslinking temperature and time would lead to high proton conductive membranes. High temperature crosslinking also resulted in an increase in anisotropy and water diffusion. Furthermore, the membranes were investigated for a Vanadium/Air Redox Flow Battery application. Membranes crosslinked at 200 °C for 30 min with a molar ratio between 2:1 (mol repeat unit:mol benzenedimethanol) showed a proton conductivity of 27.9 mS/cm and a 100 times lower VO2+ crossover compared to Nafion.

  9. Friedel-Crafts Polyketones: Synthesis, Characterization and Antimicrobial Properties of Unsaturated Polyketones and Copolyketones Based on Difurfurylidene Cycloheptanone

    Nayef S. Al-Muaikel


    Full Text Available A new type of unsaturated polyketones and copolyketones having cycloheptanone moiety in a p-conjugated main chain were synthesized via Friedel-Crafts reaction through the polymerization of the monomer: 2,7-bis furfurylidene cycloheptanone I with different diacid chlorides. The model compound was synthesized by reacting I with benzoyl chloride and characterized by 1H-NMR, IR, and elemental analyses. The polyketones and copolyketones were soluble easily in protic solvents like H2SO4 and trifluoroacetic acid. The thermal properties of these polyketones and copolyketones were evaluated and correlated to their structural units by TGA and DSC measurements. The crystallinity of some polymers was tested by X-ray analyses; also the morphological properties of selected examples of poly and copolyketones were detected by SEM. All the polyketones were tested for their biological activity against bacteria, fungi, and yeast. It was observed that the majority of the polyketones and its copolymers synthesized can be used as antibacterial and antifungal agents.

  10. Friedel-Crafts Alkylation of o-xylene over V2O5/ZrO2 Catalysts

    Kesavan Pillai, Sreejarani


    Full Text Available The present study has undertaken the Friedel-Crafts benzylation of aromatics over the V2O5/ZrO2 catalysts systems. Catalysts with different V2O5 content (0-15wt %) was prepared by wet impregnation method and characterized by XRD, BET surface area...

  11. DNA-Accelerated Copper Catalysis of Friedel-Crafts Conjugate Addition/Enantioselective Protonation Reactions in Water

    García-Fernández, Almudena; Megens, Rik P.; Villarino, Lara; Roelfes, Gerard


    DNA-induced rate acceleration has been identified as one of the key elements for the success of the DNA-based catalysis concept. Here we report on a novel DNA-based catalytic Friedel-Crafts conjugate addition/enantioselective protonation reaction in water, which represents the first example of a


    李侃社; 黄虎; 李锦; 牛红梅; 闫兰英


    With tetrahydrofuran or cyclohexanone as dissolvent, Friedel-Crafts reaction grafting of polyvinyl chloride and polystyrene was realized through microwave irradiation. Graft of PVC-g-PS was successfully prepared. Influence of heating method, reaction temperature, type and mass fraction of catalyst on grafting reaction and grafting ratio was investigated. Graft structure of PVC-g-PS was characterized through FTIR,the mechanism and features were discussed. Results showed that Friedel-Crafts reaction grafting of polyvinyl chloride and polystyrene can carry out through heating by oil bath or microwave irradiation. Under heating with oil bath the graft of PVC-g-PS occurs at the meta position of the benzene ring, and the graft ratio is only 0. 27% ; while in the case of microwave irradiation,the graft of PVC-g-PS occurs at ortho-para positions of the benzene ring,and the graft ratio reaches up to 23%. Anhydrous AlCl3 ,FeCl3 or SnCl4 can all catalyze Friedel-Crafts reaction grafting of polyvinyl chloride and polystyrene, but the best catalytic activity is observed for anhydrous AlCl3. When the mass fraction of anhydrous AlCl3 is 3% ,the highest graft ratio reaches up to 29% , but when mass fraction of anhydrous AlCl3 is over 3% ,the graft ratio declines, PVC begins degradation and produces olefinic bonds. Research results demonstrate that microwave irradiation is an effective way of realizing Friedel-Crafts reaction grafting of polyvinyl chloride and polystyrene.%在四氢呋喃、环己酮等溶液中实现了聚氯乙烯(PVC)与聚苯乙烯(PS)的Friedel-Crafts接枝反应,考察了加热方式、反应温度、催化剂种类、催化剂用量对接枝反应的影响,通过FTIR表征了PVC-g-PS接枝物的结构,探讨了反应的机理和特点.研究发现,油浴加热和微波辐照都能使PVC和PS发生接枝反应,但微波辐照效果更好,油浴加热,接枝率仅0.27%,而微波辐照接枝率高达23%;油浴加热时产物少且多为间位,微波辐照

  13. A facile Friedel-Crafts acylation for the synthesis of polyethylenimine-grafted multi-walled carbon nanotubes as efficient gene delivery vectors.

    Nia, Azadeh Hashem; Amini, Abbas; Taghavi, Sahar; Eshghi, Hossein; Abnous, Khalil; Ramezani, Mohammad


    Low chemical reactivity of carbon nanotubes is one of the major obstacles in their functionalization via chemical reactions. As a non-destructive method, Friedel-Crafts acylation was suggested among the explored reactions for which only a few methods have been reported under harsh reaction conditions, e.g., high temperature all leading to low yields. In this study, we propose a novel method for the acylation of multi-walled carbon nanotubes (MWCNTs) at a low temperature (i.e., 42°C), using SiO2-Al2O3 as a catalyst and 6-bromohexanoic acid as the acylating agent to produce high yield functionalized MWCNTs. After acylation, MWCNTs are conjugated with polyethylenimines (PEIs) with three molecular weights (1.8, 10 and 25kDa). Three different MWCNT-PEI conjugates are synthesized and evaluated for their condensation ability, viability, size and zeta potential properties. The transfection efficiency of the functionalized MWCNTs is evaluated using luciferase assay and flow cytometry in a Neuroblastoma cell line. MWCNT-PEI (10 kDa) conjugate shows the highest transfection efficacy compared to others. For this carrier transfection efficacy exceeds the amount of PEI 25 kDa at similar carrier to plasmid weight ratio (C/P) and is around 3 times higher compared to PEI 25 kDa at C/P=0.8 as positive control regarding its high transfection efficiency and low cytotoxicity.

  14. Fe3+-Exchanged Titanate Nanotubes: A New Kind of Highly Active Heterogeneous Catalyst for Friedel-Crafts Type Benzylation

    Yunchen Du


    Full Text Available Heterogeneous catalysis for Friedel-Crafts type benzylation has received much attention in recent years due to its characteristic of environmental benefits. In this paper, titanate nanotubes (TNTs were employed as heterogeneous catalyst support, and a new kind of Fe3+-exchanged titanate nanotubes (Fe-TNTs catalyst with highly dispersed ferric sites was constructed by an ion exchange technique. The obtained catalyst was systematically characterized by XRD, TEM, N2 adsorption, XPS, and UV-vis spectra. As expected, Fe-TNTs showed excellent catalytic activities in the benzylation of benzene and benzene derivatives. The recycling tests for Fe-TNTs were also carried out, where the reason for the gradually decreased activity was carefully investigated. Superior to some reported catalysts, the catalytic ability of used Fe-TNTs could be easily recovered by ion exchange again, indicating that Fe-TNTs herein were a highly active and durable heterogeneous catalyst for Friedel-Crafts type benzylation. These results might be helpful for the design and preparation of novel heterogeneous catalysts by combining the structural advantages of titanate nanotubes and active metal ions.

  15. Use of a Tandem Prins/Friedel-Crafts Reaction in the Construction of the Indeno-Tetrahydropyridine Core of the Haouamine Alkaloids: Formal Synthesis of (−)-Haouamine A

    Fenster, Erik; Fehl, Charlie; Aubé, Jeffrey


    A tandem Prins/Friedel-Crafts reaction useful for the construction of the indeno-tetrahydropyridine core of the haouamine alkaloids and a formal synthesis of (−)-haouamine A are described. PMID:21517105

  16. Super absorbent polymer as nanoreactors for preparation of hematite nanoparticles and application of the prepared nanocatalyst for the Friedel-Crafts acylation

    Saeidian, Hamdollah; Moghaddam, Firouz Matloubi; Pourjavadi, Ali; Barzegar, Shahram; Soleyman, Rouhollah [Sharif University of Technology, Tehran (Iran, Islamic Republic of). Dept. of Chemistry]. E-mail:; Sohrabi, Abouzar [Sharif University of Technology, Tehran (Iran, Islamic Republic of). Inst. for Nanoscience and Nanotechnology


    The synthesis of pure {alpha}-Fe{sub 2}O{sub 3} nanoparticles (30 nm) using a superabsorbent nanopolymer (SANP) by the thermal decomposition is reported. Synthesized {alpha}-Fe{sub 2}O{sub 3} nanoparticles were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electronic microscopy (TEM) and thermogravimetric analysis (TG) techniques. The applicability of this nanostructure material was assessed by its catalytic effect on the Friedel-Crafts acylation. (author)

  17. Micro-Cu4I4-MOF: reversible iodine adsorption and catalytic properties for tandem reaction of Friedel-Crafts alkylation of indoles with acetals.

    Zhu, Neng-Xiu; Zhao, Chao-Wei; Wang, Jian-Cheng; Li, Yan-An; Dong, Yu-Bin


    We report a convenient approach, the first of its kind, to construct a microscale non-metal@MOF composite catalytic host-guest system for an organic tandem reaction. The reported porous Cu4I4-MOF is able to reversibly adsorb molecular iodine at room temperature. The obtained I2@Cu4I4-MOF host-guest system can be a highly heterogeneous catalyst to promote the Friedel-Crafts alkylation of indoles with acetals in a one-pot two-step fashion under solvent-free conditions at room temperature.

  18. An efficient and green synthesis of 1-indanone and 1-tetralone via intramolecular Friedel-Crafts acylation reaction

    Tran, Phuong Hoang; Huynh, Vy Hieu; Hansen, Poul Erik;


    Metal-triflate-catalyzed intramolecular Friedel–Crafts acylation of 3-arylpropanoic and 4-arylbutanoic acids in triflate-anion ionic liquids under monomodal microwave irradiation is reported. The environmentally benign synthetic procedure allows the formation of cyclic ketones in good yields with...

  19. Utilization of acidic α-amino acids as acyl donors: an effective stereo-controllable synthesis of aryl-keto α-amino acids and their derivatives.

    Wang, Lei; Murai, Yuta; Yoshida, Takuma; Okamoto, Masashi; Tachrim, Zetryana Puteri; Hashidoko, Yasuyuki; Hashimoto, Makoto


    Aryl-keto-containing α-amino acids are of great importance in organic chemistry and biochemistry. They are valuable intermediates for the construction of hydroxyl α-amino acids, nonproteinogenic α-amino acids, as well as other biofunctional components. Friedel-Crafts acylation is an effective method to prepare aryl-keto derivatives. In this review, we summarize the preparation of aryl-keto containing α-amino acids by Friedel-Crafts acylation using acidic α-amino acids as acyl-donors and Lewis acids or Brönsted acids as catalysts.

  20. A Large Scale Formal Synthesis of CoQ{sub 10}: Highly Stereoselective Friedel-Crafts Allylation Reaction of Tetramethoxytoluene with (E)-4-Chloro-2-methyl-1-phenylsulfonyl-2-butene in the Presence of Montmorillonite K-10

    Lee, Sang Who; Lee, Hee Bong; Kim, Bong Chan; Sadaiah, Kadivendi; Lee, Kyuwoong; Shin, Hyunik [LG Life Sciences, Ltd., Daejeon (Korea, Republic of)


    We disclosed that MK-10 is a highly effective catalyst for the Friedel-Crafts reaction of 6 and 7 in terms of yield and of stereoselectivity. Although there are numerous applications of clays in Friedel-Crafts reaction, there is very limited example which demonstrated its effect on the stereoselectivity. In that context, our result is significant and further expansion in this direction is highly envisioned. Ubiquinone, as its name represents, exists ubiquitously in human body, particularly in the heart. It mediates the electron transfer process in mitochondria and also exerts strong antioxidant effect in its reduced form. In clinical trial, it showed beneficial effect on heart-related diseases such as myocardial infarction, angina, and other related symptoms to cause decreased mortality compared to the placebo group.

  1. Friedel-Crafts alkylations of electron-rich aromatics with 3-hydroxy-2-oxindoles: scope and limitations.

    Kinthada, Lakshmana K; Ghosh, Santanu; Babu, K Naresh; Sharique, Mohd; Biswas, Soumava; Bisai, Alakesh


    A Lewis acid-catalyzed nucleophilic addition of electron rich aromatics with 3-hydroxy-2-oxindoles 5 was developed. The reaction is believed to proceed through the 2H-indol-2-one ring system 9, which eventually reacts with various electron-rich aromatics to afford a variety of 2-oxindoles with an all-carbon quaternary center at the pseudobenzylic position (4, 8, 13, and 16) in high yields. The methodology provides an expeditious route to the tetracyclic core (3) of diazonamide (1), and azonazine (2) as well as the tricyclic core of asperazine (6a), idiospermuline (6b), and calycosidine (6c) viz. C(3a)-arylpyrroloindolines 7 having an all-carbon quaternary center on further synthetic elaboration.


    Geovanna Tafurt


    Full Text Available En este trabajo se reporta el estudio experimental de la alquilación intramolecular de Friedel-Crafts de orto alilanilinas Nbencilo sustituidas, que explica desde los puntos de vista cinético y termodinámico la formación de dihidrodibenzo [b,e]azepinas y tetrahidrodibenzo[b,f] azocinas. El seguimiento de los cambios en concentración resultantes del tratamiento en condiciones heterogéneas se llevó a cabo por Cromatografía de Gases-Detector de Ionización en Llama (CG-DILL, mientras que la espectroscopía Ultravioleta-Visible (UV Vis y el análisis quimiométrico con el Método Multivariante de Resolución de Curvas-Mínimos Cuadrados Alternados (MMRC-MCA se usaron para examinar los efectos de las condiciones de reacción en fase homogénea e in situ. Con los resultados obtenidos se puede concluir que la supervisión de parámetros, tales como constantes de velocidad y energías de activación, hizo posible evidenciar los efectos de sustituyente, temperatura, velocidad de agitación y concentración, sobre la velocidad y regio selectividad e la reacción.

  3. 以氯代酰氯为试剂的聚砜膜材料的付-克酰基化反应%Friedel-Crafts Acylation Reaction of Polysulfone Membrane Material with Chloroacyl Chlorides

    杜瑞奎; 高保娇; 李延斌; 曾庆湘


    采用氯乙酰氯和氯丁酰氯两种ω-氯代酰氯化试剂,在Lewis酸催化剂存在下,于室温下分别对聚砜(PSF)材料实施了Friedel-Crafts酰基化反应,制备了氯代酰基化(CA)聚砜材料CAPSF。用FT-IR、1H-NMR与佛尔哈德分析法表征了该产物的化学结构与组成。结果表明:在室温(25°C)下,以CH2Cl2为溶剂,以SnCl4为Lewis酸催化剂,聚砜的氯代酰基化反应可以顺利地进行,反应3 h,即可制得氯含量为0.5 mmol/g的产物;采用氯丁酰氯对PSF进行氯代酰基化反应的效果明显好于氯乙酰氯。%Friedel-Crafts acylation reactions of polysulfone(PSF) membrane material were conducted in the presence of Lewis acid catalysts at room temperature using two kinds of ω-chloroacyl chloride,chloroacetyl chloride and chlorobutyryl chloride,and chloroacylated polysulfone(CAPSF) were prepared.The chemical structure and composition of the product were characterized by FT-IR,1H-NMR and Volhard methods.The reaction processes on the chloroacylation reactions of PSF were primarily investigated.The experimental results show that the chloroacylation reaction of PSF can be carried out successfully,and a product CAPSF with a chlorine content of 0.5 mmol/g can be obtained in 3 h at room temperature(25°C) with CH2Cl2 as solvent and SnCl4 as Lewis acid catalyst.The experimental results also indicate that chlorobutyryl chloride is better than chloroacetyl chloride in the chloroacylation reactions.

  4. 三丁基锡/SBA-15功能配合物的合成、表征及对Friedel-Crafts反应的选择性催化%Synthesis, Characterization and Catalytic Performance Toward the Friedel-Crafts Acylation of Tributyltin Functionalized SBA-15

    荆涛; 覃志乐; 宋伟明; 赵云鹏; 邓启刚


    将三丁基氯化锡与SBA-15介孔分子筛在N2气气氛中进行回流反应,得到有机锡无机配合物(C4H9)3Sn-O-SBA-15[Bu3SnS].利用X射线衍射(XRD)、透射电子显微镜(TEM)、氮气吸附脱附、固体核磁(NMR)和吡啶吸附脱附红外光谱分析(Py-IR)等方法对产物的组成、结构和性质进行了表征.结果表明,产物Bu3 SnS具有高度有序的六方介孔结构,与SBA-15相比,Bu3 SnS比表面积、孔容和孔径变小,酸性增强.Bu3 SnS对苯甲醚Friedel-Crafts酰基化反应具有优异的催化性能,当反应温度为130℃,n(苯甲醚)∶n(苯甲酰氯)=1.0∶2.0,w(cat) =6%(相对于苯甲醚用量),反应时间为5h,苯甲醚的转化率达到76.0%,对甲氧基二苯酮(p-MBP)选择性达到97.8%.%The organotin inorganic complexes (C4H9) 3Sn-O-SBA-15 [Bu3SnS] were successfully synthesized by grafting tributyhin on SBA-15 mesoporous molecular sieves in a nitrogen atmosphere.The composition,structure and properties of the samples were characterized by X-ray diffraction (XRD),transmittance electron microscopy(TEM),Hammett indicator method,N2 adsorption-desorption,solid nuclear magnetic resonance (NMR),in-situ pyridine infrared spectroscopy(Py-IR) and so on.The results show that the hexagonal P6mm mesostructure of parent siliceous SBA-15 is maintained in Bu3SnS.The surface areas,proe size and volume of Bu3 SnS are all deceased with the increase of acidity,compared to those of SBA-15.Friedel-Crafts acylation of anisole and benzoyl chloride can be efficiently catalyzed in the presence of Bu3 SnS.The reaction conversion of anisole and the selectivity ofp-benzoylanisole are 76.0% and 97.8%,respectively,when the molar ratio of anisole to benzoyl chloride is 0.5∶ 1.0,the amount of catalyst is 6%,the reaction temperature is 130 ℃ and the reaction time is 5 h.

  5. Use of AlCl3 in Friedel Crafts arylation type reactions and beyond: an overview on the development of unique methodologies leading to N-heteroarenes.

    Sunke, Rajnikanth; Nallapati, Suresh Babu; Kumar, Jetta Sandeep; Shiva Kumar, K; Pal, Manojit


    As a privileged class of heterocyclic compounds N-heteroarenes have found enormous applications in many areas including medicinal/pharmaceutical chemistry and drug discovery. Consequently, a wide variety of methods have been reported for their synthesis. While not free from their own limitations the AlCl3 mediated methods appeared to have some particular advantages in preparing a number of useful N-heteroarenes. Besides the famous Friedel-Crafts (FC) alkylation/acylation reactions one such example is AlCl3-induced heteroarylation of arenes and heteroarenes (FC arylation type reactions) that can be used to prepare a certain class of N-heteroarenes in an operationally simple, efficient and cost effective manner. Interestingly, pyridine is not a good substrate in FC alkylation/acylation reactions whereas 2-chloropyridines are indeed effective in heteroarylation reaction. However, no systematic and detailed study regarding the application potential of this method was performed until 2002. Some other examples that emerged in the recent past include AlCl3 induced heteroarylation-cyclization, hydroarylation-heteroarylation, sulfonyl group migration etc. All these innovative methodologies allowed the direct access to several unique and novel N-heteroarenes some of which showed interesting pharmacological properties including anti-inflammatory, anti-cancer and antibacterial activities when tested in vitro. While unlike FC reactions many of these AlCl3 mediated methodologies are still in their initial stage of developments, a continuing effort to uncover their further potential in organic synthesis/medicinal chemistry is necessary. The current article provides an overview of these unique methodologies that highlight the use of AlCl3 beyond FC reactions leading to new N-heteroarenes.

  6. Efficient One-Pot Synthesis of Indol-3-yl-Glycines via Uncatalyzed Friedel-Crafts Reaction in Water

    Mehdi Ghandi


    Full Text Available The three component reaction of primary aliphatic amines, glyoxalic acid and indole or N-methylindole in water at ambient temperature affords indol-3-yl or N-methylindol-3-yl-glycine in almost quantitative yields.

  7. Indium triflate in 1-isobutyl-3-methylimidazolium dihydrogenphosphate: an efficient and green catalytic system for Friedel-Crafts acylation

    Tran, Phuong Hoang; Hoang, Huy Manh; Chau, Duy-Khiem Nguyen;


    Indium triflate in the ionic liquid, 1-isobutyl-3-methylimidazolium dihydrogen phosphate ([i-BMIM]H2PO4), was found to show enhanced catalytic activity in the Friedel–Crafts acylation of various aromatic compounds with acid anhydrides. The catalytic system was easily recovered and reused without ...

  8. Lewis Acid Catalyzed Benzylic Bromination

    Shibatomi, Kazutaka; Zhang, Yanhua; Yamamoto, Hisashi


    Lewis acid catalyzed bromination on aromatic side chain was achieved efficiently by using 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) as a bromination reagent under mild conditions. Zirconium(IV) chloride showed the highest catalytic activity for the benzylic bromination. It was revealed that the present Lewis acid catalysis proceeds via the radical generation pathway. In contrast to Lewis acid catalysis, Brønsted acid promoted aromatic ring bromination without any benzylic bromination. Monobro...

  9. Highly Efficient Synthesis of Unsymmetrical 3,3'-Bis(1H-indol-3-yl)methanes in Water%Highly Efficient Synthesis of Unsymmetrical 3,3'-Bis(1H-indol-3-yl)methanes in Water

    林华; 臧扬; 孙兴文; 林国强


    A simple and practical approach for the preparation of unsymmetric bis(indolyl)methanes (BIMs) was realized by Lewis acid InBr3-catalyzed Friedel-Crafts reaction of indoles with 3-indolyl-substituted phthalides in water.

  10. Study on In-situ Compatibilization of SAN/POE Blends Using Friedel-Crafts Alkylation Reaction%Friedel-Crafts烷基化反应原位增容SAN/POE研究

    徐建平; 张敏华


    Using Friedel-Crafts alkylation reaction in situ compatibilizing SAN/POE blends in the melting state, the effect of the A1C13 on the performance of the system were evaluated. The results showed that for SAN/POE (70/30) blends, adding 0.4% A1Cl3 the tensile strength was improved by 31% and the elongation at break was raised by 123%. The analysis of FT-IR indicated that A1Cl3 could initiate Friedel-Crafts alkylation reaction between SAN and POE; The dynamic rheological analysis, the thermal analysis and the phase morphology analysis showed that the apparent viscosity, the thermal stability and the dispersal uniformity of the compatibilized SAN/POE blends were improved due to the formation of SAN-g-POE graft copolymer.%在熔融状态下,利用Friedel-Crafts烷基化反应原位增容苯乙烯-丙烯腈共聚物(SAN)/乙烯-辛烯共聚物(POE)共混物,考察了AlCl3对该共混物性能的影响.结果表明,对于SAN/POE(70/30,质量比)共混物,加入0.4% AlCl3时,共混物的拉伸强度提高了31%,断裂伸长率提高了123%;红外光谱分析表明,AlCl3可以引发SAN与POE发生Friedel-Crafts烷基化反应生成SAN-g-POE接枝物;旋转流变分析、热分析以及微观结构分析表明,由于增容体系中有SAN-g-POE接枝物生成,共混体系的表观黏度增加,热稳定性提高,分散均匀性提高.

  11. Chiral BINOL-derived phosphoric acids: privileged Brønsted acid organocatalysts for C-C bond formation reactions.

    Zamfir, Alexandru; Schenker, Sebastian; Freund, Matthias; Tsogoeva, Svetlana B


    BINOL-derived phosphoric acids have emerged during the last five years as powerful chiral Brønsted acid catalysts in many enantioselective processes. The most successful transformations carried out with chiral BINOL phosphates include C-C bond formation reactions. The recent advances have been reviewed in this article with a focus being placed on hydrocyanations, aldol-type, Mannich, Friedel-Crafts, aza-ene-type, Diels-Alder, as well as cascade and multi-component reactions.

  12. Highly Chemo- and Regioselective Reaction of Hydroxybenzenes in Acidic Ionic Liquid

    Guo, Hui; Zhuang, Yu Wei; Cao, Jian; Zhang, Guo Bao [High New Technology Research Center of Henan Academy of Sciences, Zhengzhou (China)


    Highly chemo- and regioselective reaction of hydroxybenzenes with α,β-unsaturated compounds in acidic ionic liquid l-butyl-3-methylimidazolium hydrogen sulphate ([BMIM]HSO{sub 4}) was reported for the first time. A series of oxa-Michael adducts and Friedel-Crafts alkylated products were synthesized with good yields. The acidic ionic liquid could be easily recycled for at least 5 times with only minor loss in activity.

  13. Phenylalanine Ammonia-Lyase-Catalyzed Deamination of an Acyclic Amino Acid: Enzyme Mechanistic Studies Aided by a Novel Microreactor Filled with Magnetic Nanoparticles.

    Weiser, Diána; Bencze, László Csaba; Bánóczi, Gergely; Ender, Ferenc; Kiss, Róbert; Kókai, Eszter; Szilágyi, András; Vértessy, Beáta G; Farkas, Ödön; Paizs, Csaba; Poppe, László


    Phenylalanine ammonia-lyase (PAL), found in many organisms, catalyzes the deamination of l-phenylalanine (Phe) to (E)-cinnamate by the aid of its MIO prosthetic group. By using PAL immobilized on magnetic nanoparticles and fixed in a microfluidic reactor with an in-line UV detector, we demonstrated that PAL can catalyze ammonia elimination from the acyclic propargylglycine (PG) to yield (E)-pent-2-ene-4-ynoate. This highlights new opportunities to extend MIO enzymes towards acyclic substrates. As PG is acyclic, its deamination cannot involve a Friedel-Crafts-type attack at an aromatic ring. The reversibility of the PAL reaction, demonstrated by the ammonia addition to (E)-pent-2-ene-4-ynoate yielding enantiopure l-PG, contradicts the proposed highly exothermic single-step mechanism. Computations with the QM/MM models of the N-MIO intermediates from L-PG and L-Phe in PAL show similar arrangements within the active site, thus supporting a mechanism via the N-MIO intermediate.

  14. Unravelling the properties of supported copper oxide: can the particle size induce acidic behaviour?

    Zaccheria, Federica; Scotti, Nicola; Marelli, Marcello; Psaro, Rinaldo; Ravasio, Nicoletta


    There is a renewed interest in designing solid acid catalysts particularly due to the significance of Lewis acid catalyzed processes such as Friedel-Crafts acylation and alkylation and cellulose hydrolysis for the development of sustainable chemistry. This paper reports a new focus point on the properties of supported CuO on silica, a material that up to now has been considered only as the precursor of an effective hydrogenation catalyst. Thus, it deals with a re-interpretation of some of our results with supported copper oxide aimed to unveil the root of acidic activity exhibited by this material, e.g. in alcoholysis reactions. Several techniques were used to highlight the very high dispersion of the oxide phase on the support allowing us to ascribe the acidic behavior to coordinative unsaturation of the very small CuO particles. In turn this unsaturation makes the CuO particles prone to coordinate surrounding molecules present in the reaction mixture and to exchange them according to their nucleophilicity.

  15. Antisolvent Precipitation for the Synthesis of Monodisperse Mesoporous Niobium Oxide Spheres as Highly Effective Solid Acid Catalysts

    Li, Cheng Chao


    We have developed a low-cost reaction protocol to synthesize mesoporous Nb 2O 5-based solid acid catalysts with external shape control. In the synthesis, monodisperse glycolated niobium oxide spheres (GNOS) were prepared by means of a simple antisolvent precipitation approach and subsequently converted to mesoporous niobium oxide spheres (MNOS) with a large surface area of 312m 2g -1 by means of the hydrothermal treatment. The antisolvent acetone used to obtain GNOS was recovered through distillation at high purity. The obtained mesoporous MNOS were functionalized further with sulfate anions at different temperatures or incorporated with tungstophosphoric acid to obtain recyclable solid acid catalysts. These MNOS-based catalysts showed excellent performance in a wide range of acid-catalyzed reactions, such as Friedel-Crafts alkylation, esterification, and hydrolysis of acetates. As they are monodisperse spheres with diameters in the submicrometer range, the catalysts can be easily separated and reused. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Lipase catalyzed synthesis of epoxy-fatty acids

    CHEN, Qian; LI, Zu-Yi


    Lipase catalyzed synthesis of epoxy-fatty acidas from unsaturated carboxylic acids was investigated.Under mild conditions unsaturated arboxylic acids were convcveed to peroxide,then the unsaturated peroxycarboxylic acids epoxidised the C=C bond of themselves

  17. New Alkylation Route of Benzene with Ethylene Catalyzed by [bmim]Cl/FeCl3 Ionic Liquid%[bmim]Cl/FeCl3离子液体催化苯与乙烯烷基化反应的新型机理

    孙学文; 赵锁奇; 王仁安


    Up to now the mechanism of Friedel-Crafts reactions catalyzed by ionic liquid have not been fully understood, while carbocation mechanism was assumed. It was found that the source of H+ and the route of reaction initiated the alkylation of benzene with ethylene catalyzed by [bmim]Cl/FeCl3 ionic liquid. The fact that dewatered ionic liquids have catalytic activity for the alkylation of benzene with ethylene suggests that there exists a new catalytic route. The distinctly Bronsted acid properties of 2-H in [bmim]Cl were found through FT-IR and HNMR analysis of [bmim]Cl after titration with water free KOH in alcohol solution. In addition, the chemical shifts of proton on the [bmim]Cl ring, especially 2-H, are sensitive to the change of FeCl3 content and shifted downfield when FeCl3 was added into [bmim]Cl to form ionic liquid. Thus 2-H was easy to be disengaged from imidazolium ring with formation of H+ to initiate the reaction. The isotope-substituted method was employed to prove this mechanism, through the GC-MS analysis of alkylation products of deuterated benzene with ethylene. The route of alkylation catalyzed by FeCl3 ionic liquid was found to follow the carbocation mechanism, the resource of H+ was presented and proved using HNMR analysis of ionic liquid to inspect the intensity change of 2-H. It was found that the intensity of 2-H reduced 23% after reaction showing that the H+ arising from alkylation reaction was supplied by 2-H on the imidazole ring.

  18. Palladium-Catalyzed alpha-Arylation of Tetramic Acids

    Storgaard, Morten; Dorwald, F. Z.; Peschke, B.;


    A mild, racemization-free, palladium-Catalyzed alpha-arylation of tetramic acids (2,4-pyrrolidinediones) has been developed. Various amino acid-derived tetramic acids were cleanly arylated by treatment with 2 mol % of Pd(OAc)(2), 4 mol % of a sterically demanding biaryl phosphine, 2.3 equiv of K2CO...

  19. Kinetic study on the acid-catalyzed hydrolysis of cellulose to levulinic acid

    Girisuta, B.; Janssen, L. P. B. M.; Heeres, H. J.


    A variety of interesting bulk chemicals is accessible by the acid-catalyzed hydrolysis of cellulose. An interesting example is levulinic acid, a versatile precursor for fuel additives, polymers, and resins. A detailed kinetic study on the acid-catalyzed hydrolysis of cellulose to levulinic acid is

  20. Lipase-Catalyzed Modification of Canola Oil with Caprylic Acid

    Wang, Yingyao; Luan, Xia; Xu, Xuebing

    Lipase-catalyzed acidolysis of canola oil with caprylic acid was performed to produce structured lipids. Six commercial lipases from different sources were screened for their ability to incorporate the caprylic acid into the canola oil. The positional distribution of FA on the glycerol backbone o...

  1. Rhodium catalyzed arylation of diazo compounds with aryl boronic acids.

    Ghorai, Jayanta; Anbarasan, Pazhamalai


    A general and efficient synthesis of diarylacetate, a diarylmethine derivative, was accomplished through rhodium catalyzed direct arylation of diazo compounds with arylboronic acids. The reaction tolerates various boronic acid derivatives and functional groups. Notably, chemoselective arylation of diazo compounds over other electrophiles were demonstrated. The efficacy of the developed methodology is shown by the expeditious synthesis of the core structure of diclofensine.

  2. Esterification of phenolic acids catalyzed by lipases immobilized in organogels.

    Zoumpanioti, M; Merianou, E; Karandreas, T; Stamatis, H; Xenakis, A


    Lipases from Rhizomucor miehei and Candida antarctica B were immobilized in hydroxypropylmethyl cellulose organogels based on surfactant-free microemulsions consisting of n-hexane, 1-propanol and water. Both lipases kept their catalytic activity, catalyzing the esterification reactions of various phenolic acids including cinnamic acid derivatives. High reaction rates and yields (up to 94%) were obtained when lipase from C. antarctica was used. Kinetic studies have been performed and apparent kinetic constants were determined showing that ester synthesis catalyzed by immobilized lipases occurs via the Michaelis-Menten mechanism.

  3. Rh-Catalyzed arylation of fluorinated ketones with arylboronic acids.

    Dobson, Luca S; Pattison, Graham


    The Rh-catalyzed arylation of fluorinated ketones with boronic acids is reported. This efficient process allows access to fluorinated alcohols in high yields under mild conditions. Competition experiments suggest that difluoromethyl ketones are more reactive than trifluoromethyl ketones in this process, despite their decreased electronic activation, an effect we postulate to be steric in origin.

  4. Palladium-catalyzed enantioselective conjugate addition of arylboronic acids

    Gini, F; Hessen, B; Minnaard, AJ


    The first asymmetric palladium-catalyzed conjugate addition of arylboronic acids to alpha,beta-unsaturated aldehydes, ketones, and esters is described. For cyclic substrates, excellent chemo-, regio-, and enantioselectivities are achieved when a Pd(O2CCF3)(2)/DuPHOS catalyst is applied.

  5. An acid-catalyzed macrolactonization protocol.

    Trost, Barry M; Chisholm, John D


    [reaction: see text] An efficient macrolactonization protocol devoid of any base was developed derived from the use of vinyl esters in transesterification. Subjecting a hydroxy acid and ethoxyacetylene to 2 mol % [RuCl(2)(p-cymene)](2) in toluene followed by addition of camphorsulfonic acid or inverse addition provided macrolactones in good yields.

  6. Biodiesel by acid-catalyzed transesterification with butanol

    Bynes, Adrian


    Jatropha oil and Rapeseed oil was transesterified with n-butanol by the use of H2SO4. Before conducting the experiments a review of the effect of alcohol type was preformed. Alcohols from methanol to butanol, branched and straight, were reviewed for the effect on the acid catalyzed transesterification reaction. From the review it was found that propanol and butanol were the best for the acidic transesterification reaction. Variables such as time, temperature, alcohol amount and catalyst c...

  7. Facile synthesis of (S)-beta-hydroxy-beta-trichloromethylated aromatic ketones by the regioselective ring cleavage of chiral beta-trichloromethyl-beta-propiolactone under the Friedel-Crafts conditions

    Fujisawa, T; Ito, T; Fujimoto, K; Shimizu, M; Wynberg, H; Staring, EGJ


    The reaction of enantiomerically pure beta-trichloromethyl-beta-propiolactone (1) as a chiral building block with an aromatic compound in the presence of Lewis acid provided an acylated product with a chiral trichloromethyl carbinol moiety. The acylated product was used as an effective chiral syntho

  8. F-C烷基化反应原位增容工艺对PS/LLDPE合金结构与性能的影响%Effect of In-Situ Compatibilization Technique by Friedel-Crafts Alkylation Reaction on the Structure and Properties of PS/LLDPE Blends

    徐建平; 刘涛涛; 陈建定


    在熔融状态下,利用无水AlCl3引发大分子之间的Friedel-Crafts烷基化反应来增容聚苯乙烯(PS)/线性低密度聚乙烯(LLDPE)(80/20)合金。研究了"一步法"和"两步法"增容工艺对PS/LLDPE合金结构和性能的影响。结果表明,以"一步法"增容PS/LLDPE(50/50)合金40份为母料,与60份聚苯乙烯混合("两步法")制备PS/LLDPE(80/20)合金,可有效地降低聚苯乙烯降解对合金性能的影响,提高合金的热稳定性和力学性能;从扫描电镜(SEM)照片可以看出,"两步法"制备的合金的分散相更加均匀细小,韧性断裂特征明显。%In the molten state,PS/LLDPE(80/20)blends were compatibilized by Friedel-Crafts alkylation reaction with anhydrous AlCl3.The effect of structure and properties of PS/LLDPE(80/20)blends by "one-step" and "two-step" compatibilization technique were studied.The results showed that using the "one-step" compatibilized PS/LLDPE(50/50)blends 40 parts as the master batch product,mixed with 60 parts polystyrene("two-step") to prepared PS/LLDPE(80/20)blends,which could effectively reduce the influence of the degradation of polystyrene,and improving the thermal stability and mechanical properties of the blends.As can be seen from SEM photographs,the dispersed phase of "two-step" preparation blends is more homogeneous and smaller,and ductile fracture characteristics significantly.

  9. Kinetics of acid-catalyzed cleavage of cumene hydroperoxide.

    Levin, M E; Gonzales, N O; Zimmerman, L W; Yang, J


    The cleavage of cumene hydroperoxide, in the presence of sulfuric acid, to form phenol and acetone has been examined by adiabatic calorimetry. As expected, acid can catalyze cumene hydroperoxide reaction at temperatures below that of thermally-induced decomposition. At elevated acid concentrations, reactivity is also observed at or below room temperature. The exhibited reactivity behavior is complex and is significantly affected by the presence of other species (including the products). Several reaction models have been explored to explain the behavior and these are discussed.

  10. Synthesis of Rosin Acid Starch Catalyzed by Lipase

    Rihui Lin


    Full Text Available Rosin, an abundant raw material from pine trees, was used as a starting material directly for the synthesis of rosin acid starch. The esterification reaction was catalyzed by lipase (Novozym 435 under mild conditions. Based on single factor experimentation, the optimal esterification conditions were obtained as follows: rosin acid/anhydrous glucose unit in the molar ratio 2 : 1, reaction time 4 h at 45°C, and 15% of lipase dosage. The degree of substitution (DS reaches 0.098. Product from esterification of cassava starch with rosin acid was confirmed by FTIR spectroscopy and iodine coloration analysis. Scanning electron microscopy and X-ray diffraction analysis showed that the morphology and crystallinity of the cassava starch were largely destroyed. Thermogravimetric analysis indicated that thermal stability of rosin acid starch decreased compared with native starch.

  11. Acid-Catalyzed Hydration of anti-Sesquinorbornene.

    Slebocka-Tilk, H.; Brown, R. S.


    The acid-catalyzed hydration of anti-sesquinorbornene (1) has been studied at 25 degrees C in 20% DME/H(2)O from 0.001 M kinetic isotope effect for hydration of 1 is 2.7, and a plot of the observed second-order rate constant for the hydration in a mixed solvent system of H(2)O/D(2)O against the atom fraction of deuterium (n) is bowed upward. The reaction also shows marked buffer catalysis by formic, chloroacetic, and dichloroacetic acids, the Brønsted alpha being 1 for these three carboxylic acids: H(3)O(+) does not fit on this Brønsted line. A mechanism for the reaction is presented which is consistent with the generally accepted one for acid-catalyzed hydration of an alkene in which the rate-limiting step involves proton transfer from H(3)O(+) to the double bond. Whether attack of a second water on the developing carbocation occurs simultaneously with protonation cannot be ascertained from the data for 1, but if so, the extent of its C-OH(2) bond formation must be small enough that there is little change in the bonding of these O-H bonds.

  12. An Efficient Procedure for Esterification of Aryloxyacetic Acid and Arylthioacetic Acid Catalyzed by Silica Sulfuric Acid

    LI,Hong-Ya; LI,Ji-Tai; LI,Hui-Zhang


    @@ Aryloxyacetate and arylthioacetate are wildly used in herbicides, plant regulator and insecticides. Recently, Wille et al. have reported that methyl aryloxyacetate is an efficient agent to prevent and treat allergic contact dermatitis.[1] The most popular synthesis is by heating sodium phenoxide (mercaptide) with ethyl chloroacetate in DMF,[2] or by the esterification of acid with alcohol using concentrated H2SO4 as catalyst.[3] In this paper, synthesis of aryloxyacetate and aryl thioacetate from aryloxyacetic acid and arylthioacetic acid respectively in ether catalyzed by silica sulfuric acid in 83%~94% yields is described. The catalyst is reused for 3 times without significant loss of activity (Entry 4). Compared with common procedures, the present procedure possesses the advantages of the operational simplicity, short reaction time,less-corrosion, high yield and reusable catalyst.

  13. Deoxycholic acid transformations catalyzed by selected filamentous fungi.

    Kollerov, V V; Lobastova, T G; Monti, D; Deshcherevskaya, N O; Ferrandi, E E; Fronza, G; Riva, S; Donova, M V


    More than 100 filamentous fungi strains, mostly ascomycetes and zygomycetes from different phyla, were screened for the ability to convert deoxycholic acid (DCA) to valuable bile acid derivatives. Along with 11 molds which fully degraded DCA, several strains were revealed capable of producing cholic acid, ursocholic acid, 12-keto-lithocholic acid (12-keto-LCA), 3-keto-DCA, 15β-hydroxy-DCA and 15β-hydroxy-12-oxo-LCA as major products from DCA. The last metabolite was found to be a new compound. The ability to catalyze the introduction of a hydroxyl group at the 7(α/β)-positions of the DCA molecule was shown for 32 strains with the highest 7β-hydroxylase activity level for Fusarium merismoides VKM F-2310. Curvularia lunata VKM F-644 exhibited 12α-hydroxysteroid dehydrogenase activity and formed 12-keto-LCA from DCA. Acremonium rutilum VKM F-2853 and Neurospora crassa VKM F-875 produced 15β-hydroxy-DCA and 15β-hydroxy-12-oxo-LCA, respectively, as major products from DCA, as confirmed by MS and NMR analyses. For most of the positive strains, the described DCA-transforming activity was unreported to date. The presented results expand the knowledge on bile acid metabolism by filamentous fungi, and might be suitable for preparative-scale exploitation aimed at the production of marketed bile acids. Copyright © 2016 Elsevier Inc. All rights reserved.

  14. Acid-catalyzed production of biodiesel from waste frying oil

    Zheng, S.; Dube, M.A.; McLean, D.D. [Department of Chemical Engineering, University of Ottawa, Ottawa, ON (Canada); Kates, M. [Department of Biochemistry, Microbiology and Immunology, University of Ottawa, Ottawa, ON (Canada)


    The reaction kinetics of acid-catalyzed transesterification of waste frying oil in excess methanol to form fatty acid methyl esters (FAME), for possible use as biodiesel, was studied. Rate of mixing, feed composition (molar ratio oil:methanol:acid) and temperature were independent variables. There was no significant difference in the yield of FAME when the rate of mixing was in the turbulent range 100 to 600rpm. The oil:methanol:acid molar ratios and the temperature were the most significant factors affecting the yield of FAME. At 70{sup o}C with oil:methanol:acid molar ratios of 1:245:3.8, and at 80{sup o}C with oil:methanol:acid molar ratios in the range 1:74:1.9-1:245:3.8, the transesterification was essentially a pseudo-first-order reaction as a result of the large excess of methanol which drove the reaction to completion (99+/-1% at 4h). In the presence of the large excess of methanol, free fatty acids present in the waste oil were very rapidly converted to methyl esters in the first few minutes under the above conditions. Little or no monoglycerides were detected during the course of the reaction, and diglycerides present in the initial waste oil were rapidly converted to FAME. (author)

  15. Acid base catalyzed transesterification kinetics of waste cooking oil

    Jain, Siddharth; Sharma, M.P.; Rajvanshi, Shalini [Alternate Hydro Energy Centre, Indian Institute of Technology, Roorkee (India)


    The present study reports the results of kinetics study of acid base catalyzed two step transesterification process of waste cooking oil, carried out at pre-determined optimum temperature of 65 C and 50 C for esterification and transesterification process respectively under the optimum condition of methanol to oil ratio of 3:7 (v/v), catalyst concentration 1%(w/w) for H{sub 2}SO{sub 4} and NaOH and 400 rpm of stirring. The optimum temperature was determined based on the yield of ME at different temperature. Simply, the optimum concentration of H{sub 2}SO{sub 4} and NaOH was determined with respect to ME Yield. The results indicated that both esterification and transesterification reaction are of first order rate reaction with reaction rate constant of 0.0031 min{sup -1} and 0.0078 min{sup -1} respectively showing that the former is a slower process than the later. The maximum yield of 21.50% of ME during esterification and 90.6% from transesterification of pretreated WCO has been obtained. This is the first study of its kind which deals with simplified kinetics of two step acid-base catalyzed transesterification process carried under the above optimum conditions and took about 6 h for complete conversion of TG to ME with least amount of activation energy. Also various parameters related to experiments are optimized with respect to ME yield. (author)

  16. Heteropoly acid encapsulated into zeolite imidazolate framework (ZIF-67) cage as an efficient heterogeneous catalyst for Friedel–Crafts acylation

    Ammar, Muhammad; Jiang, Sai; Ji, Shengfu, E-mail:


    A new strategy has been developed for the encapsulation of the phosphotungstic heteropoly acid (H{sub 3}PW{sub 12}O{sub 40} denoted as PTA) into zeolite imidazolate framework (ZIF-67) cage and the PTA@ZIF-67(ec) catalysts with different PTA content were prepared. The structure of the catalysts was characterized by XRD, BET, SEM, FT-IR, ICP-AES and TG. The catalytic activity and recovery properties of the catalysts for the Friedel-Crafts acylation of anisole with benzoyl chloride were evaluated. The results showed that 14.6–31.7 wt% PTA were encapsulated in the ZIF-67 cage. The PTA@ZIF-67(ec) catalysts had good catalytic activity for Friedel-Crafts acylation. The conversion of anisole can reach ~100% and the selectivity of the production can reach ~94% over 26.5 wt% PTA@ZIF-67(ec) catalyst under the reaction condition of 120 °C and 6 h. After reaction, the catalyst can be easily separated from the reaction mixture by the centrifugation. The recovered catalyst can be reused five times and the selectivity can be kept over 90%. - Graphical abstract: The PTA@ZIF-67 catalysts with different PTA content were prepared by encapsulating the PTA into ZIF-67 cage and the as-synthesized catalysts exhibited good catalytic activity for the Friedel–Craft acylation of anisole with benzoyl chloride.

  17. Chiral Brønsted Acids for Asymmetric Organocatalysis

    Kampen, Daniela; Reisinger, Corinna M.; List, Benjamin

    Chiral Brønsted acid catalysis is an emerging area of organocatalysis. Since the pioneering studies of the groups of Akiyama and Terada in 2004 on the use of chiral BINOL phosphates as powerful Brønsted acid catalysts in asymmetric Mannich-type reactions, numerous catalytic asymmetric transformations involving imine activation have been realized by means of this catalyst class, including among others Friedel-Crafts, Pictet-Spengler, Strecker, cycloaddition reactions, transfer hydrogenations, and reductive aminations. More recently, chiral BINOL phosphates found application in multicomponent and cascade reactions as for example in an asymmetric version of the Biginelli reaction. With the introduction of chiral BINOL-derived N-triflyl phosphoramides in 2006, asymmetric Brønsted acid catalysis is no longer restricted to reactive substrates. Also certain carbonyl compounds can be activated through these stronger Brønsted acid catalysts. In dealing with sensitive substrate classes, chiral dicarboxylic acids proved of particular value.

  18. Acid-Catalyzed Preparation of Biodiesel from Waste Vegetable Oil: An Experiment for the Undergraduate Organic Chemistry Laboratory

    Bladt, Don; Murray, Steve; Gitch, Brittany; Trout, Haylee; Liberko, Charles


    This undergraduate organic laboratory exercise involves the sulfuric acid-catalyzed conversion of waste vegetable oil into biodiesel. The acid-catalyzed method, although inherently slower than the base-catalyzed methods, does not suffer from the loss of product or the creation of emulsion producing soap that plagues the base-catalyzed methods when…

  19. Kinetics of acid base catalyzed transesterification of Jatropha curcas oil.

    Jain, Siddharth; Sharma, M P


    Out of various non-edible oil resources, Jatropha curcas oil (JCO) is considered as future feedstock for biodiesel production in India. Limited work is reported on the kinetics of transesterification of high free fatty acids containing oil. The present study reports the results of kinetic study of two-step acid base catalyzed transesterification process carried out at an optimum temperature of 65 °C and 50 °C for esterification and transesterification respectively under the optimum methanol to oil ratio of 3:7 (v/v), catalyst concentration 1% (w/w) for H₂SO₄ and NaOH. The yield of methyl ester (ME) has been used to study the effect of different parameters. The results indicate that both esterification and transesterification reaction are of first order with reaction rate constant of 0.0031 min⁻¹ and 0.008 min⁻¹ respectively. The maximum yield of 21.2% of ME during esterification and 90.1% from transesterification of pretreated JCO has been obtained.

  20. Kinetic study of free fatty acid esterification reaction catalyzed by recoverable and reusable hydrochloric acid.

    Su, Chia-Hung


    The catalytic performance and recoverability of several homogeneous acid catalysts (hydrochloric, sulfuric, and nitric acids) for the esterification of enzyme-hydrolyzed free fatty acid (FFA) and methanol were studied. Although all tested catalysts drove the reaction to a high yield, hydrochloric acid was the only catalyst that could be considerably recovered and reused. The kinetics of the esterification reaction catalyzed by hydrochloric acid was investigated under varying catalyst loading (0.1-1M), reaction temperature (303-343K), and methanol/FFA molar ratio (1:1-20:1). In addition, a pseudo-homogeneous kinetic model incorporating the above factors was developed. A good agreement (r(2)=0.98) between the experimental and calculated data was obtained, thus proving the reliability of the model. Furthermore, the reusability of hydrochloric acid in FFA esterification can be predicted by the developed model. The recoverable hydrochloric acid achieved high yields of FFA esterification within five times of reuse.

  1. Biodiesel Production from Spent Fish Frying Oil Through Acid-Base Catalyzed Transesterification

    Abdalrahman B. Fadhil; Mohammed M. Dheyab; Kareem M. Ahmed; Marwa H. Yahya


    Biodiesel fuels were prepared from a special type of frying oil namely spent fish frying oil through two step transesterification viz. acid-base catalyzed transesterification. Hydrochloric acid and potassium hydroxide with methanol were used for this purpose. The oil was pre-treated with (1.0 wt% HCl) and methanol to reduce free fatty acids content of the oil. Then, conditions of the base catalyzed step such as base concentration, reaction temperature, methanol to oil molar ratio and reaction...

  2. Integrated Production of Xylonic Acid and Bioethanol from Acid-Catalyzed Steam-Exploded Corn Stover.

    Zhu, Junjun; Rong, Yayun; Yang, Jinlong; Zhou, Xin; Xu, Yong; Zhang, Lingling; Chen, Jiahui; Yong, Qiang; Yu, Shiyuan


    High-efficiency xylose utilization is one of the restrictive factors of bioethanol industrialization. However, xylonic acid (XA) as a new bio-based platform chemical can be produced by oxidation of xylose with microbial. So, an applicable technology of XA bioconversion was integrated into the process of bioethanol production. After corn stover was pretreated with acid-catalyzed steam-explosion, solid and liquid fractions were obtained. The liquid fraction, also named as acid-catalyzed steam-exploded corn stover (ASC) prehydrolyzate (mainly containing xylose), was catalyzed with Gluconobacter oxydans NL71 to prepare XA. After 72 h of bioconversion of concentrated ASC prehydrolyzate (containing 55.0 g/L of xylose), the XA concentration reached a peak value of 54.97 g/L, the sugar utilization ratio and XA yield were 94.08 and 95.45 %, respectively. The solid fraction was hydrolyzed to produce glucose with cellulase and then fermented with Saccharomyces cerevisiae NL22 to produce ethanol. After 18 h of fermentation of concentrated enzymatic hydrolyzate (containing 86.22 g/L of glucose), the ethanol concentration reached its highest value of 41.48 g/L, the sugar utilization ratio and ethanol yield were 98.72 and 95.25 %, respectively. The mass balance showed that 1 t ethanol and 1.3 t XA were produced from 7.8 t oven dry corn stover.

  3. Optimizing the Acid Catalyzed Synthesis of Hyperbranched Poly(Glycerol-diacids) Oligomers

    Oligomeric pre-polymers were synthesized by the acid-catalyzed condensation of glycerol with succinic acid, glutaric acid and azelaic acid in dimethylsulfoxide (DMSO) or dimethylformamide (DMF). The prepolymers were obtained, on average in 84% yield, and were characterized by proton NMR, MALDI-TOF ...

  4. Synthesis and Characterization of 9-Hydroxyphenalenone Using 2D NMR Techniques

    Caes, Benjamin; Jensen, Dell, Jr.


    9-Hydroxyphenalenone is a planar multicyclic [beta]-keto-enol, which is synthesized via a Friedel-Crafts acylation followed by acid-catalyzed intramolecular Michael addition with the loss of a phenyl group in a one-pot reaction during a four-hour lab period. Tautomerization of the [beta]-keto-enol results in C[subscript 2v] symmetry on the NMR…

  5. Solid Acid-Catalyzed Cellulose Hydrolysis Monitored by In Situ ATR-IR Spectroscopy

    Zakzeski, J.|info:eu-repo/dai/nl/326160256; Grisel, R.J.H.; Smit, A.T.; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397


    The solid acid-catalyzed hydrolysis of cellulose was studied under elevated temperatures and autogenous pressures using in situ ATR-IR spectroscopy. Standards of cellulose and pure reaction products, which include glucose, fructose, hydroxymethylfurfural (HMF), levulinic acid (LA), formic acid, and

  6. Selective and recyclable depolymerization of cellulose to levulinic acid catalyzed by acidic ionic liquid.

    Ren, Huifang; Girisuta, Buana; Zhou, Yonggui; Liu, Li


    Cellulose depolymerization to levulinic acid (LA) was catalyzed by acidic ionic liquids (ILs) selectively and recyclably under hydrothermal conditions. The effects of reaction temperature, time, water amount and cellulose intake were investigated. Dilution effect becomes more pronounced at lower cellulose intake, dramatically improving the yield of LA to 86.1%. A kinetic model has been developed based on experimental data, whereby a good fit was obtained and kinetic parameters were derived. The relationships between IL structure, polymeric structure and depolymerization efficiency were established, shedding light on the in-depth catalytic mechanism of IL, inclusive of acidity and hydrogen bonding ability. The LA product can be readily separated through extraction by methyl isobutyl ketone (MIBK) and IL can be reused over five cycles without loss of activity. This environmentally friendly methodology can be applied to selective production of LA from versatile biomass feedstocks, including cellulose and derivatives, glucose, fructose and HMF.

  7. Iodine-catalyzed disproportionation of aryl-substituted ethers under solvent-free reaction conditions.

    Jereb, Marjan; Vražič, Dejan


    Iodine was demonstrated to be an efficient catalyst for disproportionation of aryl-substituted ethers under solvent-free reaction conditions. Variously substituted 1,1,1',1'-tetraaryldimethyl ethers were transformed into the corresponding diarylketone and diarylmethane derivatives. I2-catalyzed transformation of 4-methoxyphenyl substituted ethers yielded mono- and dialkylated Friedel-Crafts products as well. Treatment of trityl alkyl and trityl benzyl ethers with a catalytic amount of iodine produced triphenylmethane and the corresponding aldehydes and ketones. The electron-donating substituents facilitated the reaction, while the electron-withdrawing groups retarded it; the difference in reactivity is not very high. Such an observation may be in favour of hydride transfer, predominantly from the less electron rich side of the ether with more stable carbocation formation. With the isotopic studies it was established that a substantial portion of the C-H bond scission took place in the rate-determining step, while the carbonyl oxygen atom originated from the starting ether, and not from the air. The transformation took place under air and under argon, and HI was not a functioning catalyst.

  8. Silver-Catalyzed Decarboxylative Addition/Cyclization of Activated Alkenes with Aliphatic Carboxylic Acids.

    Xia, Xiao-Feng; Zhu, Su-Li; Chen, Chao; Wang, Haijun; Liang, Yong-Min


    A silver-catalyzed decarboxylative addition/aryl migration/desulfonylation of N-phenyl-N-(phenylsulfonyl)methacrylamide with primary, secondary, and tertiary carboxylic acids was described. The protocol provides an efficient approach for the synthesis of α-all-carbon quaternary stereocenters amides and isoquinolinediones. It was proposed that the radical generated from the silver-catalyzed decarboxylation was involved in the sequence reaction.

  9. Brønsted Acid-Catalyzed Direct Substitution of 2-Ethoxytetrahydrofuran with Trifluoroborate Salts

    Kayla M. Fisher


    Full Text Available Metal-free transformations of organotrifluoroborates are advantageous since they avoid the use of frequently expensive and sensitive transition metals. Lewis acid-catalyzed reactions involving potassium trifluoroborate salts have emerged as an alternative to metal-catalyzed protocols. However, the drawbacks to these methods are that they rely on the generation of unstable boron dihalide species, thereby resulting in low functional group tolerance. Recently, we discovered that in the presence of a Brønsted acid, trifluoroborate salts react rapidly with in situ generated oxocarbenium ions. Here, we report Brønsted acid-catalyzed direct substitution of 2-ethoxytetrahydrofuran using potassium trifluoroborate salts. The reaction occurs when tetrafluoroboric acid is used as a catalyst to afford functionalized furans in moderate to excellent yields. A variety of alkenyl- and alkynyltrifluoroborate salts readily participate in this transformation.

  10. Formation of Linear Polyenes in Thermal Dehydration of Polyvinyl Alcohol, Catalyzed by Phosphotungstic Acid

    Tretinnikov, O. N.; Sushko, N. I.


    In order to obtain linear polyenes in polyvinyl alcohol films via acid-catalyzed thermal dehydration of the polyvinyl alcohol, we used phosphotungstic acid as the catalyst: a safe and heat-stable solid chemical compound. We established that phosphotungstic acid, introduced as solid nanoparticles into polyvinyl alcohol films, is a more effective dehydration catalyst than hydrochloric acid, since in contrast to HCl it does not evaporate from the film during heat treatment.

  11. GSTP1-1 stereospecifically catalyzes glutathione conjugation of ethacrynic acid

    Iersel, M.L.P.S. van; Lipzig, M.M.H. van; Rietjens, I.M.C.M.; Vervoort, J.; Bladeren, P.J. van


    Using 1H NMR two diastereoisomers of the ethacrynic acid glutathione conjugate (EASG) as well as ethacrynic acid (EA) could be distinguished and quantified individually. Chemically prepared EASG consists of equal amounts of both diastereoisomers. GSTP1-1 stereospecifically catalyzes formation of one

  12. GSTP1-1 stereospecifically catalyzes glutathione conjugation of ethacrynic acid

    Iersel, M.L.P.S. van; Lipzig, M.M.H. van; Rietjens, I.M.C.M.; Vervoort, J.; Bladeren, P.J. van


    Using 1H NMR two diastereoisomers of the ethacrynic acid glutathione conjugate (EASG) as well as ethacrynic acid (EA) could be distinguished and quantified individually. Chemically prepared EASG consists of equal amounts of both diastereoisomers. GSTP1-1 stereospecifically catalyzes formation of one

  13. Investigation of acetic acid-catalyzed hydrothermal pretreatment on corn stover

    Xu, Jian; Thomsen, Mette Hedegaard; Thomsen, Anne Belinda


    Acetic acid (AA)-catalyzed liquid hot water (LHW) pretreatments on raw corn stover (RCS) were carried out at 195 °C at 15 min with the acetic acid concentrations between 0 and 400 g/kg RCS. After pretreatment, the liquor fractions and water-insoluble solids (WIS) were collected separately...

  14. The Lewis-acid-catalyzed synthesis of hyperbranched poly(glycerol-diacid)s in toluene

    The first examples of monomeric glycerol-derived hyperbranched polyesters produced in a non-polar solvent system are reported here. The polymers were made by the Lewis acid (dibutyltin(IV)oxide)-catalyzed polycondensation of glycerol with either succinic acid (n (aliphatic chain length)=2), glutari...

  15. An enantioselective chiral Brønsted acid catalyzed imino-azaenamine reaction.

    Rueping, Magnus; Sugiono, Erli; Theissmann, Thomas; Kuenkel, Alexander; Köckritz, Angela; Pews-Davtyan, Anahit; Nemati, Navid; Beller, Matthias


    The enantioselective Brønsted acid catalyzed addition of methyleneaminopyrrolidine to N-Boc imines has been achieved in the presence of chiral phosphoric acids derived from 3,3'-di(phenanthryl)-H8-BINOL. The corresponding aminohydrazones have been isolated in good yields with enantiomeric excesses up to 90%. [reaction: see text

  16. Kinetics of Ethyl Acetate Synthesis Catalyzed by Acidic Resins

    Antunes, Bruno M.; Cardoso, Simao P.; Silva, Carlos M.; Portugal, Ines


    A low-cost experiment to carry out the second-order reversible reaction of acetic acid esterification with ethanol to produce ethyl acetate is presented to illustrate concepts of kinetics and reactor modeling. The reaction is performed in a batch reactor, and the acetic acid concentration is measured by acid-base titration versus time. The…

  17. Dy(OTf)3 Catalyzed Reaction of Indole with Aldehydes and Ketones in Ionic Liquids

    MI Xue-Ling; LUO San-Zhong; HE Jia-Qi; CHENG Jin-Pei


    @@ The use of environmentally benign reaction media is very important in view of today' s environmentally con scious attitude. In connect with this, room temperature ionic liquids that are air and moisture stable have received a good deal of attention in recent years as novel solvent systems for organic synthesis. A number of reactions such as Friedel-Crafts reactions, Diels-Alder cycloadditions, hydrogenations, and Heck reactions have employed ionic liquids as solvents. Among them, the Friedel-Crafts reaction[1] is of great synthetic significance in view of laboratory synthesis and industrial production. Recent studies showed that Friedel-Crafts reaction of indole with carbonyl compounds proceeded readily in aqueous media. [2] However, the aqueous reactions suffer from some common problems,such as tedious work-up, reuse of catalyst and so on.

  18. Modification of oligo-Ricinoleic Acid and Its Derivatives with 10-Undecenoic Acid via Lipase-Catalyzed Esterification

    M. Claudia Montiel


    Full Text Available Lipases were employed under solvent-free conditions to conjugate oligo-ricinoleic acid derivatives with 10-undecenoic acid, to incorporate a reactive terminal double bond into the resultant product. First, undecenoic acid was covalently attached to oligo-ricinoleic acid using immobilized Candida antarctica lipase (CAL at a 30% yield. Thirty percent conversion also occurred for CAL-catalyzed esterification between undecenoic acid and biocatalytically-prepared polyglycerol polyricinoleate (PGPR, with attachment of undecenoic acid occurring primarily at free hydroxyls of the polyglycerol moiety. The synthesis of oligo-ricinoleyl-, undecenoyl- structured triacylglycerols comprised two steps. The first step, the 1,3-selective lipase-catalyzed interesterification of castor oil with undecenoic acid, occurred successfully. The second step, the CAL-catalyzed reaction between ricinoleyl-, undecenoyl structured TAG and ricinoleic acid, yielded approximately 10% of the desired structured triacylglycerols (TAG; however, a significant portion of the ricinoleic acid underwent self-polymerization as a side-reaction. The employment of gel permeation chromatography, normal phase HPLC, NMR, and acid value measurements was effective for characterizing the reaction pathways and products that formed.

  19. Dietary phenolic acids and ascorbic acid: Influence on acid-catalyzed nitrosative chemistry in the presence and absence of lipids.

    Combet, Emilie; El Mesmari, Aziza; Preston, Tom; Crozier, Alan; McColl, Kenneth E L


    Acid-catalyzed nitrosation and production of potentially carcinogenic nitrosative species is focused at the gastroesophageal junction, where salivary nitrite, derived from dietary nitrate, encounters the gastric juice. Ascorbic acid provides protection by converting nitrosative species to nitric oxide (NO). However, NO may diffuse into adjacent lipid, where it reacts with O(2) to re-form nitrosative species and N-nitrosocompounds (NOC). In this way, ascorbic acid promotes acid nitrosation. Using a novel benchtop model representing the gastroesophageal junction, this study aimed to clarify the action of a range of water-soluble antioxidants on the nitrosative mechanisms in the presence or absence of lipids. Caffeic, ferulic, gallic, or chlorogenic and ascorbic acids were added individually to simulated gastric juice containing secondary amines, with or without lipid. NO and O(2) levels were monitored by electrochemical detection. NOC were measured in both aqueous and lipid phases by gas chromatography-tandem mass spectrometry. In the absence of lipids, all antioxidants tested inhibited nitrosation, ranging from 35.9 + or - 7.4% with gallic acid to 93 + or - 0.6% with ferulic acid. In the presence of lipids, the impact of each antioxidant on nitrosation was inversely correlated with the levels of NO they generated (R(2) = 0.95, pascorbic acid promoted nitrosation, whereas ferulic and caffeic acids markedly inhibited nitrosation.

  20. Development of melamine modified urea formaldehyde resins based o nstrong acidic pH catalyzed urea formaldehyde polymer

    Chung-Yun Hse


    To upgrade the performance of urea-formaldehyde (UF) resin bonded particleboards, melamine modified urea-formaldehyde (MUF) resins based on strong acidic pH catalyzed UF polymers were investigated. The study was conducted in a series of two experiments: 1) formulation of MUF resins based on a UF polymer catalyzed with strong acidic pH and 2) determination of the...

  1. Silver-catalyzed arylation of (hetero)arenes by oxidative decarboxylation of aromatic carboxylic acids.

    Kan, Jian; Huang, Shijun; Lin, Jin; Zhang, Min; Su, Weiping


    A long-standing challenge in Minisci reactions is achieving the arylation of heteroarenes by oxidative decarboxylation of aromatic carboxylic acids. To address this challenge, the silver-catalyzed intermolecular Minisci reaction of aromatic carboxylic acids was developed. With an inexpensive silver salt as a catalyst, this new reaction enables a variety of aromatic carboxylic acids to undergo decarboxylative coupling with electron-deficient arenes or heteroarenes regardless of the position of the substituents on the aromatic carboxylic acid, thus eliminating the need for ortho-substituted aromatic carboxylic acids, which were a limitation of previously reported methods.

  2. Monitoring the Hydrolysis of Olive Oil Catalyzed by Lipase via Acid Value Detection


    Hydrolysis of olive oil catalyzed by Candida lipolytica lipase was investigated. The relative concentration of the components in the product was determined by using high performance liquid chromatography(HPLC). Furthermore, a novel rapid method to detect the hydrolytic process of olive oil was developed based on the relationship between the acid value and the relative concentration of the different components.

  3. Palladium-catalyzed regioselective decarboxylative alkylation of arenes and heteroarenes with aliphatic carboxylic acids.

    Premi, Chanchal; Dixit, Ankit; Jain, Nidhi


    An unprecedented Pd(OAc)2-catalyzed decarboxylative alkylation of unactivated arenes, with aliphatic carboxylic acids as inexpensive alkyl sources, is reported. The alkylation, controlled by the directing group, is regioselective, shows high functional group tolerance, and provides mild access to alkylated indolines, 2-phenylpyridines, and azobenzenes under solvent-free conditions in moderate to high yields.

  4. Palladium-catalyzed homo-coupling of boronic acids with supported reagents in supercritical carbon dioxide

    Lei Zhou; Qiu Xiang Xu; Huan Feng Jiang


    Palladium-catalyzed homo-coupling of arylboronic acids could proceed smoothly with a commercially available resin functionlised by phosphino or amino group as the ligand in supercritical carbon dioxide thereby offering a simple and efficient protocol for the synthesis of symmetrical bi-aryl molecules and their higher homologues.

  5. A Meldrum's Acid Catalyzed Synthesis of Bis (indolyl) methanes in Water under Ultrasonic Condition

    WANG,Shun-Yi; JI,Shun-Jun; SU,Xiao-Ming


    A highly effective Meldrum's acid catalyzed synthesis of bis(indol-3-yl)methanes has been developed. This reaction provides the corresponding bis(indol-3-yl)methanes in high yields after short reaction time in the presence of 2 mol% catalyst in water under ultrasonic condition.

  6. Facile synthesis of small crystal ZSM-5 zeolite by acid-catalyzed hydrolysis of tetraethylorthosilicate


    Small crystal zeolites ZSM-5 with sizes of 150-300 nm were synthesized using the colloidal silicate precursors as the silica source created by the acid-catalyzed hydrolysis of tetraethylorthosilicate with tetrapropylammonium bromide as the structure-directing agent within a short crystallization time of 20-35 h. The precursors and final products were detected by XRD, SEM, ICP and DLS.

  7. Highly enantioselective rhodium-catalyzed conjugate addition of arylboronic acids to enones at room temperature

    Martina, SLX; Minnaard, AJ; Hessen, B; Feringa, BL; Martina, Sébastien L.X.; Feringa, Bernard


    The rhodium-phosphoramidite-catalyzed asymmetric conjugate addition of arylboronic acids to enones proceeds at room temperature using [Rh(OH)(cod)](2) or [RhCl(cod)](2)/KOH as stable and readily available catalyst precursors. (c) 2005 Published by Elsevier Ltd.

  8. Rhodium-Catalyzed Asymmetric Conjugate Additions of Boronic Acids Using Monodentate Phosphoramidite Ligands

    -G Boiteau, J.; Imbos, R.; J. Minnaard, A.; Feringa, B.L.


    Monodentate phosphoramidites have been used for the first time as chiral ligands in the Rh-catalyzed enantioselective conjugate addition of arylboronic acids to enones, unsaturated esters, lactones, and nitro alkenes. High reaction rates and ee’s up to 89% have been obtained.

  9. Enantioselective BINOL-phosphoric acid catalyzed Pictet-Spengler reactions of N-benzyltryptamine

    Sewgobind, N.V.; Wanner, M.J.; Ingemann, S.; de Gelder, R.; van Maarseveen, J.H.; Hiemstra, H.


    Optically active tetrahydro-beta-carbolines were synthesized via an (R)-BINOL-phosphoric acid-catalyzed asynunetric Pictet-Spengler reaction of N-benzyltryptamine with a series of aromatic and aliphatic aldehydes. The tetrahydro-beta-carbolines were obtained in yields ranging from 77% to 97% and wit

  10. Rhodium(III)-catalyzed cross-coupling of alkenylboronic acids and N-pivaloyloxylamides.

    Feng, Chao; Loh, Teck-Peng


    Rh(III)-catalyzed umpolung amidation of alkenylboronic acids for the synthesis of enamides is reported. This reaction proceeds readily at room temperature and displays an extremely wide spectrum of functional group tolerance. With cooperation of hydroboration, it enables the formal anti-Markovnikov hydroamidation of terminal alkynes, stereospecifically affording the trans-enamides in excellent yields.

  11. Furfural production from fruit shells by acid-catalyzed hydrolysis

    Demirbas, A. [Selcuk Univ., Konya (Turkey). Dept. of Chemical Engineering


    Pentosans are hydrolyzed to pentoses by dilute mineral acid hydrolysis. The main source of pentosans is hemicelluloses. Furfural can be produced by the acid hydrolysis of pentosan from fruit shells such as hazelnut, sunflower, walnut, and almond of agricultural wastes. Further dehydration reactions of the pentoses yield furfural. The hydrolysis of each shell sample was carried out in dilute sulfuric acid (0.05 to 0.200 mol/l), at high temperature (450-525 K), and short reaction times (from 30 to 600 s). (author)

  12. Silver-catalyzed decarboxylative chlorination of aliphatic carboxylic acids.

    Wang, Zhentao; Zhu, Lin; Yin, Feng; Su, Zhongquan; Li, Zhaodong; Li, Chaozhong


    Decarboxylative halogenation of carboxylic acids, the Hunsdiecker reaction, is one of the fundamental functional group transformations in organic chemistry. As the initial method requires the preparations of strictly anhydrous silver carboxylates, several modifications have been developed to simplify the procedures. However, these methods suffer from the use of highly toxic reagents, harsh reaction conditions, or limited scope of application. In addition, none is catalytic for aliphatic carboxylic acids. In this Article, we report the first catalytic Hunsdiecker reaction of aliphatic carboxylic acids. Thus, with the catalysis of Ag(Phen)(2)OTf, the reactions of carboxylic acids with t-butyl hypochlorite afforded the corresponding chlorodecarboxylation products in high yields under mild conditions. This method is not only efficient and general, but also chemoselective. Moreover, it exhibits remarkable functional group compatibility, making it of more practical value in organic synthesis. The mechanism of single electron transfer followed by chlorine atom transfer is proposed for the catalytic chlorodecarboxylation.

  13. Copper-catalyzed formic acid synthesis from CO2 with hydrosilanes and H2O.

    Motokura, Ken; Kashiwame, Daiki; Miyaji, Akimitsu; Baba, Toshihide


    A copper-catalyzed formic acid synthesis from CO2 with hydrosilanes has been accomplished. The Cu(OAc)2·H2O-1,2-bis(diphenylphosphino)benzene system is highly effective for the formic acid synthesis under 1 atm of CO2. The TON value approached 8100 in 6 h. The reaction pathway was revealed by in situ NMR analysis and isotopic experiments.

  14. Cu2+-Catalyzed Oscillatory Oxidation of Ascorbic Acid by O2 Flow


    A novel heterogeneous oscillator, the Cu2+-catalyzed oscillatory oxidation of ascorbic acid (Vitamin C) in aqueous solution by O2 flow was reported. Both the potential oscillations on Pt-electrode corresponding to [Cu2+] and the absorbance oscillations at l=260 nm corresponding to [ascorbic acid] were observed. Oscillations in the completely homogeneous system were also observed. Effects of several factors on the oscillations were investigated.

  15. A Copper-Assisted Palladium(II)-catalyzed Direct Arylation of Cyclic Enaminones with Arylboronic Acids

    Kim, Yong Wook; Niphakis, Micah J.; Georg, Gunda I.


    Described herein is a palladium(II)-catalyzed direct arylation of cyclic enaminones with arylboronic acids. The versatility of this method is that both electron-rich and electron-poor boronic acids can be coupled in high yields. A mixture of two Cu(II) additives was crucial for efficient cross-coupling. The role of each Cu(II) reagent appears to be distinct and complementary serving to assist catalyst reoxidation and transmetallation through a putative arylcopper intermediate.

  16. Copper-catalyzed intermolecular oxyamination of olefins using carboxylic acids and O-benzoylhydroxylamines

    Brett N. Hemric


    Full Text Available This paper reports a novel approach for the direct and facile synthesis of 1,2-oxyamino moieties via an intermolecular copper-catalyzed oxyamination of olefins. This strategy utilizes O-benzoylhydroxylamines as an electrophilic amine source and carboxylic acids as a nucleophilic oxygen source to achieve a modular difunctionalization of olefins. The reaction proceeded in a regioselective manner with moderate to good yields, exhibiting a broad scope of carboxylic acid, amine, and olefin substrates.

  17. On the Brønsted acid-catalyzed homogeneous hydrolysis of furans.

    Nikbin, Nima; Caratzoulas, Stavros; Vlachos, Dionisios G


    Furan affairs: Electronic structure calculations of the homogeneous Brønsted acid-catalyzed hydrolysis of 2,5-dimethylfuran show that proton transfer to the β-position is rate-limiting and provides support that the hydrolysis follows general acid catalysis. By means of projected Fukui indices, we show this to be the case for unsubstituted, 2-, and 2,5-substituted furans with electron-donating groups.

  18. Ionic liquid supported acid/base-catalyzed production of biodiesel.

    Lapis, Alexandre A M; de Oliveira, Luciane F; Neto, Brenno A D; Dupont, Jairton


    The transesterification (alcoholysis) reaction was successfully applied to synthesize biodiesel from vegetable oils using imidazolium-based ionic liquids under multiphase acidic and basic conditions. Under basic conditions, the combination of the ionic liquid 1-n-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (BMINTf2), alcohols, and K2CO3 (40 mol %) results in the production of biodiesel from soybean oil in high yields (>98%) and purity. H2SO4 immobilized in BMINTf2 efficiently promotes the transesterification reaction of soybean oil and various primary and secondary alcohols. In this multiphase process the acid is almost completely retained in the ionic liquid phase, while the biodiesel forms a separate phase. The recovered ionic liquid containing the acid could be reused at least six times without any significant loss in the biodiesel yield or selectivity. In both catalytic processes (acid and base), the reactions proceed as typical multiphasic systems in which the formed biodiesel accumulates as the upper phase and the glycerol by-product is selectively captured by the alcohol-ionic liquid-acid/base phase. Classical ionic liquids such as 1-n-butyl-3-methylimidazolium tetrafluoroborate and hexafluorophosphate are not stable under these acidic or basic conditions and decompose.

  19. Particle growth by acid-catalyzed heterogeneous reactions of organic carbonyls on preexisting aerosols.

    Jang, Myoseon; Carroll, Brian; Chandramouli, Bharadwaj; Kamens, Richard M


    Aerosol growth by the heterogeneous reactions of different aliphatic and alpha,beta-unsaturated carbonyls in the presence/absence of acidified seed aerosols was studied in a 2 m long flow reactor (2.5 cm i.d.) and a 0.5-m3 Teflon film bag under darkness. For the flow reactor experiments, 2,4-hexadienal, 5-methyl-3-hexen-2-one, 2-cyclohexenone, 3-methyl-2-cyclopentenone, 3-methyl-2-cyclohexenone, and octanal were studied. The carbonyls were selected based on their reactivity for acid-catalyzed reactions, their proton affinity, and their similarity to the ring-opening products from the atmospheric oxidation of aromatics. To facilitate acid-catalyzed heterogeneous hemiacetal/acetal formation, glycerol was injected along with inorganic seed aerosols into the flow reactor system. Carbonyl heterogeneous reactions were accelerated in the presence of acid catalysts (H2SO4), leading to higher aerosol yields than in their absence. Aldehydes were more reactive than ketones for acid-catalyzed reactions. The conjugated functionality also resulted in higher organic aerosol yieldsthan saturated aliphatic carbonyls because conjugation with the olefinic bond increases the basicity of the carbonyl leading to increased stability of the protonated carbonyl. Aerosol population was measured from a series of sampling ports along the length of the flow reactor using a scanning mobility particle sizer. Fourier transform infrared spectrometry of either an impacted liquid aerosol layer or direct reaction of carbonyls as a thin liquid layer on a zinc selenide FTIR disk was employed to demonstrate the direct transformation of chemical functional groups via the acid-catalyzed reactions. These results strongly indicate that atmospheric multifunctional organic carbonyls, which are created by atmospheric photooxidation reactions, can contribute significantly to secondary organic aerosol formation through acid-catalyzed heterogeneous reactions. Exploratory studies in 25- and 190-m3 outdoor chambers

  20. Detoxification of acidic catalyzed hydrolysate of Kappaphycus alvarezii (cottonii).

    Meinita, Maria Dyah Nur; Hong, Yong-Ki; Jeong, Gwi-Taek


    Red seaweed, Kappaphycus alvarezii, holds great promise for use in biofuel production due to its high carbohydrate content. In this study, we investigated the effect of fermentation inhibitors to the K. alvarezii hydrolysate on cell growth and ethanol fermentation. In addition, detoxification of fermentation inhibitors was performed to decrease the fermentation inhibitory effect. 5-Hydroxymethylfurfural and levulinic acid, which are liberated from acidic hydrolysis, was also observed in the hydrolysate of K. alvarezii. These compounds inhibited ethanol fermentation. In order to remove these inhibitors, activated charcoal and calcium hydroxide were introduced. The efficiency of activated charcoals was examined and over-liming was used to remove the inhibitors. Activated charcoal was found to be more effective than calcium hydroxide to remove the inhibitors. Detoxification by activated charcoal strongly improved the fermentability of dilute acid hydrolysate in the production of bioethanol from K. alvarezii with Saccharomyces cerevisiae. The optimal detoxifying conditions were found to be below an activated charcoal concentration of 5%.

  1. Silver-Catalyzed Decarboxylative Azidation of Aliphatic Carboxylic Acids.

    Zhu, Yuchao; Li, Xinyao; Wang, Xiaoyang; Huang, Xiaoqiang; Shen, Tao; Zhang, Yiqun; Sun, Xiang; Zou, Miancheng; Song, Song; Jiao, Ning


    The catalytic decarboxylative nitrogenation of aliphatic carboxylic acids for the synthesis of alkyl azides is reported. A series of tertiary, secondary, and primary organoazides were prepared from easily available aliphatic carboxylic acids by using K2S2O8 as the oxidant and PhSO2N3 as the nitrogen source. The EPR experiment sufficiently proved that an alkyl radical process was generated in the process, and DFT calculations further supported the SET process followed by a stepwise SH2 reaction to afford azide product.

  2. Acid-catalyzed rearrangements of flavans to novelbenzofuran derivatives

    Richard W. Hemingway; Weiling Peng; Anthony H. Conner; Petrus J. Steynberg; Jan P. Steynberg


    The objective of this work was to define reactions that occur when proanthocyanidins and their derivatives are reacted in the presence of acid catalysts. Pure compounds (either as the free phenols, the methyl ether, or the methyl ether-acetate derivatives) were isolated by a variety of chromatographic methods. Proof of their structure was based mainly on 2D-NMR, as...

  3. Nickel-catalyzed monofluoromethylation of aryl boronic acids.

    Su, Yi-Ming; Feng, Guang-Shou; Wang, Zhen-Yu; Lan, Quan; Wang, Xi-Sheng


    Aryl boronic acids can be monofluoromethylated under nickel catalysis. The utility of this method is demonstrated by the monofluoromethylation of a borylated and acyl-protected derivative of the statin drug ezetimibe. Mechanistic investigations indicate that a fluoromethyl radical is involved in the Ni(I)/Ni(III) catalytic cycle. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Development of Fluorous Lewis Acid-Catalyzed Reactions

    Joji Nishikido


    Full Text Available Organic synthetic methodology in the 21st century aims to conform to the principles of green sustainable chemistry (GSC and we may expect that in the future, the realization of GSC will be an important objective for chemical industries. An important aim of synthetic organic chemistry is to implement waste-free and environmentally-benign industrial processes using Lewis acids as versatile as aluminum choride. A key technological objective of our work in this area has been to achieve a “catalyst recycling system that utilizes the high activity and structural features of fluorous Lewis acid catalysts”. Thus, we have developed a series of novel fluorous Lewis acid catalysts, namely the ytterbium(III, scandium(III, tin(IV or hafnium(IV bis(perfluoroalkanesulfonylamides or tris(perfluoro- alkanesulfonylmethides. Our catalysts are recyclable and effective for acylations of alcohols and aromatics, Baeyer-Villiger reactions, direct esterifications and transesterifications in a fluorous biphasic system (FBS, in supercritical carbon dioxide and on fluorous silica gel supports.

  5. Efficient production of free fatty acids from ionic liquid-based acid- or enzyme-catalyzed bamboo hydrolysate.

    Mi, Le; Qin, Dandan; Cheng, Jie; Wang, Dan; Li, Sha; Wei, Xuetuan


    Two engineered Escherichia coli strains, DQ101 (MG1655 fadD (-))/pDQTES and DQ101 (MG1655 fadD (-))/pDQTESZ were constructed to investigate the free fatty acid production using ionic liquid-based acid- or enzyme-catalyzed bamboo hydrolysate as carbon source in this study. The plasmid, pDQTES, carrying an acyl-ACP thioesterase 'TesA of E. coli in pTrc99A was constructed firstly, and then (3R)-hydroxyacyl-ACP dehydratase was ligated after the TesA to give the plasmid pDQTESZ. These two strains exhibited efficient fatty acid production when glucose was used as the sole carbon source, with a final concentration of 2.45 and 3.32 g/L, respectively. The free fatty acid production of the two strains on xylose is not as efficient as that on glucose, which was 2.32 and 2.96 g/L, respectively. For mixed sugars, DQ101 (MG1655 fadD (-))-based strains utilized glucose and pentose sequentially under the carbon catabolite repression (CCR) regulation. The highest total FFAs concentration from the mixed sugar culture reached 2.81 g/L by DQ101 (MG1655 fadD (-))/pDQTESZ. Furthermore, when ionic liquid-based enzyme-catalyzed bamboo hydrolysate was used as the carbon source, the strain DQ101 (MG1655 fadD (-))/pDQTESZ could produce 1.23 g/L FFAs with a yield of 0.13 g/g, and while it just produced 0.65 g/L free fatty acid with the ionic liquid-based acid-catalyzed bamboo hydrolysate as the feedstock. The results suggested that enzymatic catalyzed bamboo hydrolysate with ionic liquid pretreatment could serve as an efficient feedstock for free fatty acid production.

  6. Homologation of α-aryl amino acids through quinone-catalyzed decarboxylation/Mukaiyama-Mannich addition.

    Haugeberg, Benjamin J; Phan, Johnny H; Liu, Xinyun; O'Connor, Thomas J; Clift, Michael D


    A new method for amino acid homologation by way of formal C-C bond functionalization is reported. This method utilizes a 2-step/1-pot protocol to convert α-amino acids to their corresponding N-protected β-amino esters through quinone-catalyzed oxidative decarboxylation/in situ Mukaiyama-Mannich addition. The scope and limitations of this chemistry are presented. This methodology provides an alternative to the classical Arndt-Eistert homologation for accessing β-amino acid derivatives. The resulting N-protected amine products can be easily deprotected to afford the corresponding free amines.

  7. Lewis acid catalyzed transformations of Z-ligustilide

    Rios, Maria Yolanda [Universidad Autonoma del Estado de Morelos, Cuernavaca, Morelos (Mexico); Delgado, Guillermo [Universidad Nacional Autonoma de Mexico, Mexico, D.F. (Mexico)


    Some Lewis acid mediated reactions of Z-ligustilide (1), a bioactive constituent of the medicinal species Ligusticum porteri, were investigated. These reactions provided varying mixtures of Z-butylidenephthalide (7), E-butylidenephthalide (8), n-butyphthalide (13), and novel linear dimeric phthalides (9-12) as the main products. The formation of the dimers occurred in low yields and with regio and situ-selectivity. Initial competitive O- and C- complexation of the Lewis acid with Z-ligustilide promoted the formation of the dimers occurred in low yields and with regio and situ- selectivity. Initial competitive O- and C- complexation of the Lewis acid with Z-ligustilide promoted the formation of carbocations at C(8), C(6) and C(7), which were stabilized by the addition of the C(6')-C(7') olefin of a second unit of the starting material, to provide cations at C(6') and C(7'). Subsequent isomerizations and elimination of the catalyst afforded the dimeric products 9-12. The yields and structure of the products are quite dependent on variations of the reaction conditions and the catalyst employed. [Spanish] Se investigaron algunas reacciones de Z-ligustilidas (1), un constituyente bioactivo de la planta medicinal Ligusticum porteri, catalizadas por acidos de Lewis. Estas reacciones produjeron mezclas variables de Z-butilidenftalida (7), E-butilidenftalida (8), n-butilftalida (13), y ftalidos dimetricos lineales novedosos (9-12) como productos principales. La formacion de los dimeros procedio en rendimientos bajos y con regio- y situ-selectividad. La O- y C- complejacion competitiva inicial del acido de Lewis con Z-lingustilida promueve la formacion de cationes en C(8), C(6) y C(7), los cuales son estabilizados por la adicion de la olefina C(6')-C(7') de una segunda unidad de la materia prima para generar los cationes en C(6')-C(7'). Isomerizaciones subsecuentes y la eliminacion del catalizador conducen a los productos dimericos 9


    K. Durai Murugan; S. Radhika; I. Baskaran; R. Anbarasan


    Glycolic acid was polymerized under vacuum in the presence and absence of nano sized clay. The added clay catalyzed the condensation polymerization which can be confirmed by recording FT1R spectroscopy and intrinsic viscosity (Ⅳ) values. The relative intensity of C =O/CH is increased while increasing the amount of clay. DSC showed the appearance of multiple endotherms of poly(glycolic acid). TGA showed the percentage weight residue remain above 750℃ for polymer-nano composite system was 21% and hence proved the flame retardancy (char forming) nature. TEM confirmed the nano size of the clay used to catalyze the condensation reaction. The intrinsic viscosity value was increased with the increase of percentage weight of Hectorite type clay.

  9. Stereoselectivities in α- and β-Amino Acids Catalyzed Mannich Reactions Involving Cyclohexanone

    WANG Ying; FU Ai-ping; LI Hong-liang; TIAN Feng-hui; YUAN Shu-ping; SI Hong-zong; DUAN Yun-bo; WANG Zong-hua


    The effects of two different amino acid catalysts on the stereoselectivities in the direct Mannich reactions of cyclohexanone,p-anisidine and p-nitrobenzaldehyde were studied with the aid of density functional theory.Transition states of the stereo-determining C-C bond-forming step with the addition of enamine intermediate to the imine for the L-proline(α-amino acid) and (R)-3-pyrrolidinecarboxylic acid(β-amino acid)-catalyzed processes were reported.B3LYP/6-31G** calculations provide a good explanation for the opposite syn vs.anti diastereoselectivities of these two different kinds of catalysts(syn-selectivity for the α-amino acid catalysts,anti-selectivity for the β-amino acid catalysts).Calculated and observed diastereomeric ratio and enantiomeric excess values are in reasonable agreement.

  10. Ni(ii)-catalyzed asymmetric addition of arylboronic acids to cyclic imines.

    Quan, Mao; Tang, Liang; Shen, Jiaqi; Yang, Guoqiang; Zhang, Wanbin


    A Ni(ii)-catalyzed asymmetric addition of arylboronic acids to cyclic aldimines and ketimines is reported. Our tropos phosphine-oxazoline biphenyl ligand is crucial for the high catalytic activity, which coordinates to Ni(ii) to form a complex with a single axial configuration. The desired chiral amine products could be prepared with excellent yields (up to 99%) and enantioselectivities (up to 99.8%) under mild reaction conditions.

  11. Enantioselective Brønsted acid catalyzed transfer hydrogenation: organocatalytic reduction of imines.

    Rueping, Magnus; Sugiono, Erli; Azap, Cengiz; Theissmann, Thomas; Bolte, Michael


    The first enantioselective Brønsted acid catalyzed reduction of imines has been developed. This new organocatalytic transfer hydrogenation of ketimines with Hantzsch dihydropyridine as the hydrogen source offers a mild method to various chiral amines with high enantioselectivity. The stereochemistry of the chiral amines can be rationalized by a stereochemical model derived from an X-ray crystal structure of a chiral BINOL phosphate catalyst. [reaction: see text

  12. Enantioselective aldol reaction between isatins and cyclohexanone catalyzed by amino acid sulphonamides.

    Wang, Jun; Liu, Qi; Hao, Qing; Sun, Yanhua; Luo, Yiming; Yang, Hua


    Sulphonamides derived from primary α-amino acid were successfully applied to catalyze the aldol reaction between isatin and cyclohexanone under neat conditions. More interestingly, molecular sieves, as privileged additives, were found to play a vital role in achieving high enantioselectivity. Consequently, high yields (up to 99%) along with good enantioselectivities (up to 92% ee) and diastereoselectivities (up to 95:5 dr) were obtained. In addition, this reaction was also conveniently scaled up, demonstrating the applicability of this protocol.

  13. Acetic acid-catalyzed formation of N-phenylphthalimide from phthalanilic acid: a computational study of the mechanism.

    Takahashi, Ohgi; Kirikoshi, Ryota; Manabe, Noriyoshi


    In glacial acetic acid, phthalanilic acid and its monosubstituents are known to be converted to the corresponding phthalimides in relatively good yields. In this study, we computationally investigated the experimentally proposed two-step (addition-elimination or cyclization-dehydration) mechanism at the second-order Møller-Plesset perturbation (MP2) level of theory for the unsubstituted phthalanilic acid, with an explicit acetic acid molecule included in the calculations. In the first step, a gem-diol tetrahedral intermediate is formed by the nucleophilic attack of the amide nitrogen. The second step is dehydration of the intermediate to give N-phenylphthalimide. In agreement with experimental findings, the second step has been shown to be rate-determining. Most importantly, both of the steps are catalyzed by an acetic acid molecule, which acts both as proton donor and acceptor. The present findings, along with those from our previous studies, suggest that acetic acid and other carboxylic acids (in their undissociated forms) can catalyze intramolecular nucleophilic attacks by amide nitrogens and breakdown of the resulting tetrahedral intermediates, acting simultaneously as proton donor and acceptor. In other words, double proton transfers involving a carboxylic acid molecule can be part of an extensive bond reorganization process from cyclic hydrogen-bonded complexes.

  14. Acetic Acid Can Catalyze Succinimide Formation from Aspartic Acid Residues by a Concerted Bond Reorganization Mechanism: A Computational Study

    Takahashi, Ohgi; Kirikoshi, Ryota; Manabe, Noriyoshi


    Succinimide formation from aspartic acid (Asp) residues is a concern in the formulation of protein drugs. Based on density functional theory calculations using Ace-Asp-Nme (Ace = acetyl, Nme = NHMe) as a model compound, we propose the possibility that acetic acid (AA), which is often used in protein drug formulation for mildly acidic buffer solutions, catalyzes the succinimide formation from Asp residues by acting as a proton-transfer mediator. The proposed mechanism comprises two steps: cyclization (intramolecular addition) to form a gem-diol tetrahedral intermediate and dehydration of the intermediate. Both steps are catalyzed by an AA molecule, and the first step was predicted to be rate-determining. The cyclization results from a bond formation between the amide nitrogen on the C-terminal side and the side-chain carboxyl carbon, which is part of an extensive bond reorganization (formation and breaking of single bonds and the interchange of single and double bonds) occurring concertedly in a cyclic structure formed by the amide NH bond, the AA molecule and the side-chain C=O group and involving a double proton transfer. The second step also involves an AA-mediated bond reorganization. Carboxylic acids other than AA are also expected to catalyze the succinimide formation by a similar mechanism. PMID:25588215

  15. Acetic Acid Can Catalyze Succinimide Formation from Aspartic Acid Residues by a Concerted Bond Reorganization Mechanism: A Computational Study

    Ohgi Takahashi


    Full Text Available Succinimide formation from aspartic acid (Asp residues is a concern in the formulation of protein drugs. Based on density functional theory calculations using Ace-Asp-Nme (Ace = acetyl, Nme = NHMe as a model compound, we propose the possibility that acetic acid (AA, which is often used in protein drug formulation for mildly acidic buffer solutions, catalyzes the succinimide formation from Asp residues by acting as a proton-transfer mediator. The proposed mechanism comprises two steps: cyclization (intramolecular addition to form a gem-diol tetrahedral intermediate and dehydration of the intermediate. Both steps are catalyzed by an AA molecule, and the first step was predicted to be rate-determining. The cyclization results from a bond formation between the amide nitrogen on the C-terminal side and the side-chain carboxyl carbon, which is part of an extensive bond reorganization (formation and breaking of single bonds and the interchange of single and double bonds occurring concertedly in a cyclic structure formed by the amide NH bond, the AA molecule and the side-chain C=O group and involving a double proton transfer. The second step also involves an AA-mediated bond reorganization. Carboxylic acids other than AA are also expected to catalyze the succinimide formation by a similar mechanism.

  16. Quantum chemical study of Diels-Alder reactions catalyzed by Lewis acid activated oxazaborolidines.

    Sakata, Ken; Fujimoto, Hiroshi


    The catalytic activity of Lewis acid activated oxazaborolidines in the Diels-Alder reaction between cyclopentadiene and methacrolein is investigated by using the DFT method. Oxazaborolidine is not able to coordinate to methacrolein in the absence of AlBr3 because the bonding stabilization is too small to cover the destabilization arising from the deformation of the two species. Accordingly, oxazaborolidine hardly catalyzes the cycloaddition by itself. The calculations show that the attachment of AlBr3 to the nitrogen atom of oxazaborolidine enhances the Lewis acidity of its boron center and enables it to coordinate to methacrolein. When the AlBr3-assisted oxazaborolidine is once coordinated, the catalytic activity originates mainly from the oxazaborolidine framework, and to a smaller extent from the attached AlBr3 part. The Lewis acid AlBr3 plays an additional role to facilitate the reaction by reducing the overlap repulsion between the diene and the dienophile. The attachment of AlBr3 to the oxygen atom, another Lewis basic site in oxazaborolidine, also gives a stable AlBr3-oxazaborolidine complex, but the reaction catalyzed by this complex is not preferred to that catalyzed by the complex in which AlBr3 is attached to the nitrogen atom. The electrophilicity of boron center in oxazaborolidine and those in the AlBr3-oxazaborolidine complexes are compared in terms of localized reactive orbitals.

  17. Grape skins (Vitis vinifera L.) catalyze the in vitro enzymatic hydroxylation of p-coumaric acid to caffeic acid

    Arnous, Anis; Meyer, Anne S.


    The ability of grape skins to catalyze in vitro conversion of p-coumaric acid to the more potent antioxidant caffeic acid was studied. Addition of different concentrations of p-coumaric to red grape skins (Cabernet Sauvignon) resulted in formation of caffeic acid. This caffeic acid formation (Y......) correlated positively and linearly to p-coumaric acid consumption (X): Y = 0.5 X + 9.5; R 2 = 0.96, P skin concentrations, indicated that the grape skins harboured an o......-hydroxylation activity, proposedly a monophenol- or a flavonoid 3′-monooxygenase activity (EC or EC The K m of this crude o-hydroxylation activity in the red grape skin was 0.5 mM with p-coumaric acid....

  18. Preliminary Study on Lipase-catalyzed Synthesis of Polyesters Containing L-Malic Acid Units

    Da Hu YAO; Guang Ji LI


    Terpolymer of 1, 8-octanediol, adipic acid, and L-malic acid was synthesized via a lipase-catalyzed direct polycondensation. The products were characterized by GPC and 1H NMR.The results indicated that the molecular weight of the prepared polymers decreased with increasing L-malic acid content in the monomer feed ratio, and that change in the L-malic acid content from 0to 20 mol % did not remarkably influenced on the molecular weight distribution Mw/Mn of the prepared samples. The 1H NMR spectra of the obtained copolymer samples showed that hydroxyl groups of L-malic acid did not take part in the polymerization reaction.

  19. Stability of prostacyclin analogues: an unusual lack of reactivity in acid-catalyzed alkene hydration.

    Magill, A; O'Yang, C; Powell, M F


    Prostacyclin analogue 5 undergoes specific acid-catalyzed hydration (kH+ = 1.9 x 10(-7)M-1 sec-1 at 25 degrees C) and a pH-independent oxidation reaction (k0 = 1.2 x 10(-10) sec-1 at 25 degrees C) above pH approximately 5. The hydration reaction for 5 is much slower than for other structurally similar exocyclic alkenes, even though the rate-determining step is proton transfer. This slowness of reaction and an analysis of the pH-rate profile show that 5 does not exhibit significant intramolecular general acid catalysis, as does prostacyclin.

  20. Silica-supported Copper(Ⅱ) Catalyzed Coupling of Arylboronic Acids with Imidazoles

    ZHANG Li-Yuan; WANG Lei


    Immobilized copper(Ⅱ) in organic-inorganic hybrid materials catalyzed Ar-N coupling of arylboronic acids with imidazoles has been developed. Arylboronic acids reacted with imidazoles smoothly in the presence of a 3-(2-aminoethylamino)propyl functionalized silica gel immobilized copper(Ⅱ) catalyst (10 mol%) in methanol without any additives and bases. The reactions generated the corresponding cross-coupling products in good yields.Furthermore, silica-supported copper can be recovered and recycled by a simple filtration procedure and used for five consecutive trials without decreases in activity.

  1. Base catalyzed transesterification of acid treated vegetable oil blend for biodiesel production

    Yusup, Suzana; Khan, Modhar Ali [Chemical Engineering Department, Universiti Teknologi PETRONAS, Seri Iskandar, Tronoh, Perak 31750 (Malaysia)


    Biodiesel can be produced from low cost non-edible oils and fats. However, most of these sources are of high free fatty acid content which requires two stage transesterification to reduce the acid value and produce biodiesel. The acid treatment step is usually followed by base transesterification since the latter can yield higher conversions of methyl esters at shorter reaction time when compared with acid catalyzed reaction. In the current study, base transesterification in the second stage of biodiesel synthesis is studied for a blend of crude palm/crude rubber seed oil that had been characterized and treated with acid esterification. Optimum conditions for the reaction were established and effect of each variable was investigated. The base catalyzed transesterification favored a temperature of 55 C with methanol/oil molar ratio of 8/1 and potassium hydroxide at 2% (ww{sup -1}) (oil basis). The conversion of methyl esters exceeded 98% after 5 h and the product quality was verified to match that for biodiesel with international standards. (author)

  2. Formation of linear polyenes in poly(vinyl alcohol) films catalyzed by phosphotungstic acid, aluminum chloride, and hydrochloric acid

    Tretinnikov, O. N.; Sushko, N. I.; Malyi, A. B.


    Formation of linear polyenes-(CH=CH)n-via acid-catalyzed thermal dehydration of polyvinyl alcohol in 9- to 40-µm-thick films of this polymer containing hydrochloric acid, aluminum chloride, and phosphotungstic acid as dehydration catalysts was studied by electronic absorption spectroscopy. The concentration of long-chain ( n ≥ 8) polyenes in films containing phosphotungstic acid is found to monotonically increase with the duration of thermal treatment of films, although the kinetics of this process is independent of film thickness. In films containing hydrochloric acid and aluminum chloride, the formation rate of polyenes with n ≥ 8 rapidly drops as film thickness decreases and the annealing time increases. As a result, at a film thickness of less than 10-12 µm, long-chain polyenes are not formed at all in these films no matter how long thermal duration is. The reason for this behavior is that hydrochloric acid catalyzing polymer dehydration in these films evaporates from the films during thermal treatment, the evaporation rate inversely depending on film thickness.

  3. Esterification of Oleic Acid for Biodiesel Production Catalyzed by SnCl2: A Kinetic Investigation

    Marcio J. da Silva


    Full Text Available The production of biodiesel from low-cost raw materials which generally contain high amounts of free fatty acids (FFAs is a valuable alternative that would make their production costs more competitive than petroleum-derived fuel. Currently, the production of biodiesel from this kind of raw materials comprises a two-stage process, which requires an initial acid-catalyzed esterification of the FFA, followed by a basecatalyzed transesterification of the triglycerides. Commonly, the acid H2SO4 is the catalyst on the first step of this process. It must be said, however, that major drawbacks such as substantial reactor corrosion and the great generation of wastes, including the salts formed due to neutralization of the mineral acid, are negative and virtually unsurmountable aspects of this protocol. In this paper, tin(II chloride dihydrate (SnCl2·2H2O, an inexpensive Lewis acid, was evaluated as catalyst on the ethanolysis of oleic acid, which is the major component of several fat and vegetable oils feedstocks. Tin chloride efficiently promoted the conversion of oleic acid into ethyl oleate in ethanol solution and in soybean oil samples, under mild reaction conditions. The SnCl2 catalyst was shown to be as active as the mineral acid H2SO4. Its use has relevant advantages in comparison to mineral acids catalysts, such as less corrosion of the reactors and as well as avoiding the unnecessary neutralization of products. Herein, the effect of the principal parameters of reaction on the yield and rate of ethyl oleate production has been investigated. Kinetic measurements revealed that the esterification of oleic acid catalyzed by SnCl2·2H2O is first-order in relation to both FFAs and catalyst concentration. Experimentally, it was verified that the energy of activation of the esterification reaction of oleic acid catalyzed by SnCl2 was very close those reported for H2SO4.

  4. [Asymmetric synthesis of aromatic L-amino acids catalyzed by transaminase].

    Xia, Wenna; Sun, Yu; Min, Cong; Han, Wei; Wu, Sheng


    Aromatic L-Amino acids are important chiral building blocks for the synthesis of many drugs, pesticides, fine chemicals and food additives. Due to the high activity and steroselectivity, enzymatic synthesis of chiral building blocks has become the main research direction in asymmetric synthesis field. Guided by the phylogenetic analysis of transaminases from different sources, two representative aromatic transaminases TyrB and Aro8 in type I subfamily, from the prokaryote Escherichia coli and eukaryote Saccharomyces cerevisia, respectively, were applied for the comparative study of asymmetric transamination reaction process and catalytic efficiency of reversely converting keto acids to the corresponding aromatic L-amino acid. Both TyrB and Aro8 could efficiently synthesize the natural aromatic amino acids phenylalanine and tyrosine as well as non-natural amino acid phenylglycine. The chiral HPLC analysis showed the produced amino acids were L-configuration and the e.e value was 100%. L-alanine was the optimal amino donor, and the transaminase TyrB and Aro8 could not use D-amino acids as amino donor. The optimal molar ratio of amino donor (L-alanine) and amino acceptor (aromatic alpha-keto acids) was 4:1. Both of the substituted group on the aromatic ring and the length of fatty acid carbon chain part in the molecular structure of aromatic substrate alpha-keto acid have the significant impact on the enzyme-catalyzed transamination efficiency. In the experiments of preparative-scale transamination synthesis of L-phenylglycine, L-phenylalanine and L-tyrosine, the specific production rate catalyzed by TryB were 0.28 g/(g x h), 0.31 g/(g x h) and 0.60 g/(g x h) and the specific production rate catalyzed by Aro8 were 0.61 g/(g x h), 0.48 g/(g x h) and 0.59 g/(g x h). The results obtained here were useful for applying the transaminases to asymmetric synthesis of L-amino acids by reversing the reaction balance in industry.

  5. First Palladium-Catalyzed Addition of Organoboronic Acids to Allenes: A Magic Regioselectivity Switch by Using a Base or an Acid

    MA Sheng-Ming; JIAO Ning


    @@ Organoboronic acids enjoy high prestige in the metal-catalyzed C-C bond formations. The most notable progress is the rhodium- and nickel-catalyzed conjugate addition with unsaturated carbon-carbon bond, aldehydes, N-sulfonyl imines reported by Miyaura, Hayashi and Shirakawa.[1

  6. Enantioselective Additions of Boronates to Chromene Acetals Catalyzed by a Chiral Brønsted acid-Lewis acid System

    Moquist, Philip N.; Kodama, Tomohiro; Schaus, Scott E.


    Chiral α,β-dihydroxy carboxylic acids catalyze the enantioselective addition of alkenyl- and aryl boronates to chromene acetals. The optimal carboxylic acid is a tartaric acid amide, easily synthesized via a 3-step procedure. The reaction is enhanced by the addition of Lanthanide triflate salts such as cerium(IV)-and ytterbium(III) triflate. The chiral Brønsted acid and metal Lewis acid may be used in as low as 5 mol % relative to acetal substrate. Optimization of the reaction conditions can lead to yields >70% and enantiomeric ratios as high as 99:1. Spectroscopic and kinetic mechanistic studies demonstrate an exchange process leading to a reactive dioxoborolane intermediate leading to enantioselective addition to the pyrylium generated from the chromene acetal. PMID:20721997

  7. Production of Biodiesel from High Acid Value Waste Cooking Oil Using an Optimized Lipase Enzyme/Acid-Catalyzed Hybrid Process

    N. Saifuddin


    Full Text Available The present study is aimed at developing an enzymatic/acid-catalyzed hybrid process for biodiesel production using waste cooking oil with high acid value (poor quality as feedstock. Tuned enzyme was prepared using a rapid drying technique of microwave dehydration (time required around 15 minutes. Further enhancement was achieved by three phase partitioning (TPP method. The results on the lipase enzyme which was subjected to pH tuning and TPP, indicated remarkable increase in the initial rate of transesterification by 3.8 times. Microwave irradiation was found to increase the initial reaction rates by further 1.6 times, hence giving a combined increase in activity of about 5.4 times. The optimized enzyme was used for hydrolysis and 88% of the oil taken initially was hydrolyzed by the lipase. The hydrolysate was further used in acid-catalyzed esterification for biodiesel production. By using a feedstock to methanol molar ratio of 1:15 and a sulphuric acid concentration of 2.5%, a biodiesel conversion of 88% was obtained at 50 °C for an hour reaction time. This hybrid process may open a way for biodiesel production using unrefined and used oil with high acid value as feedstock.

  8. Role of Lewis acid additives in a palladium catalyzed directed C-H functionalization reaction of benzohydroxamic acid to isoxazolone.

    Athira, C; Sunoj, Raghavan B


    Metallic salts as well as protic additives are widely employed in transition metal catalyzed C-H bond functionalization reactions to improve the efficiency of catalytic protocols. In one such example, ZnCl2 and pivalic acid are used as additives in a palladium catalyzed synthesis of isoxazolone from a readily available benzohydroxamic acid under one pot conditions. In this article, we present some important mechanistic insights into the role of ZnCl2 and pivalic acid, gained by using density functional theory (M06) computations. Two interesting modes of action of ZnCl2 are identified in various catalytic steps involved in the formation of isoxazolone. The conventional Lewis acid coordination wherein zinc chloride (ZnCl2·(DMA)) binds to the carbonyl group is found to be more favored in the C-H activation step. However, the participation of a hetero-bimetallic Pd-Zn species is preferred in reductive elimination leading to Caryl-N bond formation. Pivalic acid helps in relay proton transfer in C-H bond activation through a cyclometallation deprotonation (CMD) process. The explicit inclusion of ZnCl2 and solvent N,N-dimethyl acetamide (DMA) stabilizes the transition state and also helps reduce the activation barrier for the C-H bond activation step. The electronic communication between the two metal species is playing a crucial role in stabilizing the Caryl-N bond formation transition state through a Pd-Zn hetero-bimetallic interaction.

  9. Acid-catalyzed hydrogenation of olefins. A theoretical study of the HF- and H/sub 3/O/sup +/-catalyzed hydrogenation of ethylene

    Siria, J.C.; Duran, M.; Lledos, A.; Bertran, J.


    The HF- and H/sub 3/O/sup +/-catalyzed hydrogenation of ethylene and the direct addition of molecular hydrogen to ethylene have been studied theoretically by means of ab initio MO calculations using different levels of theory. The main results are that catalysis by HF lowers the potential energy barrier to a large extent, while catalysis by H/sub 3/O/sup +/ diminishes dramatically the barrier for the reaction. Entropic contributions leave these results unchanged. The mechanisms of the two acid-catalyzed hydrogenations are somewhat different. While catalysis by HF exhibits bifunctional characteristics, catalysis by H/sub 3/O/sup +/ proceeds via an initial formation of a carbocation. It is shown that catalysis by strong acids may be an alternate way for olefin hydrogenation.

  10. Salicylic acid-induced superoxide generation catalyzed by plant peroxidase in hydrogen peroxide-independent manner.

    Kimura, Makoto; Kawano, Tomonori


    It has been reported that salicylic acid (SA) induces both immediate spike and long lasting phases of oxidative burst represented by the generation of reactive oxygen species (ROS) such as superoxide anion radical (O2(•-)). In general, in the earlier phase of oxidative burst, apoplastic peroxidase are likely involved and in the late phase of the oxidative burst, NADPH oxidase is likely involved. Key signaling events connecting the 2 phases of oxidative burst are calcium channel activation and protein phosphorylation events. To date, the known earliest signaling event in response to exogenously added SA is the cell wall peroxidase-catalyzed generation of O2(•-) in a hydrogen peroxide (H2O2)-dependent manner. However, this model is incomplete since the source of the initially required H2O2 could not be explained. Based on the recently proposed role for H2O2-independent mechanism for ROS production catalyzed by plant peroxidases (Kimura et al., 2014, Frontiers in Plant Science), we hereby propose a novel model for plant peroxidase-catalyzed oxidative burst fueled by SA.

  11. The Acid Catalyzed Nitration of Methanol: Formation of Methyl Nitrate via Aerosol Chemistry

    Riffel, Brent G.; Michelsen, Rebecca R.; Iraci, Laura T.


    The liquid phase acid catalyzed reaction of methanol with nitric acid to yield methyl nitrate under atmospheric conditions has been investigated using gas phase infrared spectroscopy. This nitration reaction is expected to occur in acidic aerosol particles found in the upper troposphere/lower stratosphere as highly soluble methanol and nitric acid diffuse into these aerosols. Gaseous methyl nitrate is released upon formation, suggesting that some fraction of NO(x) may he liberated from nitric acid (methyl nitrate is later photolyzed to NO(x)) before it is removed from the atmosphere by wet deposition. Thus, this reaction may have important implications for the NO(x) budget. Reactions have been initiated in 45-62 wt% H2SO4 solutions at 10.0 C. Methyl nitrate production rates increased exponentially with acidity within the acidity regime studied. Preliminary calculations suggest that the nitronium ion (NO2(+) is the active nitrating agent under these conditions. The reaction order in methanol appears to depend on the water/methanol ratio and varies from first to zeroth order under conditions investigated. The nitration is first order in nitronium at all acidities investigated. A second order rate constant, kappa(sub 2), has been calculated to be 1 x 10(exp 8)/ M s when the reaction is first order in methanol. Calculations suggest the nitration is first order in methanol under tropospheric conditions. The infinitesimal percentage of nitric acid in the nitronium ion form in this acidity regime probably makes this reaction insignificant for the upper troposphere; however, this nitration may become significant in the mid stratosphere where colder temperatures increase nitric acid solubility and higher sulfuric acid content shifts nitric acid speciation toward the nitronium ion.

  12. The Acid Catalyzed Nitration of Methanol: Formation of Methyl Nitrate via Aerosol Chemistry

    Riffel, Brent G.; Michelsen, Rebecca R.; Iraci, Laura T.


    The liquid phase acid catalyzed reaction of methanol with nitric acid to yield methyl nitrate under atmospheric conditions has been investigated using gas phase infrared spectroscopy. This nitration reaction is expected to occur in acidic aerosol particles found in the upper troposphere/lower stratosphere as highly soluble methanol and nitric acid diffuse into these aerosols. Gaseous methyl nitrate is released upon formation, suggesting that some fraction of NO(x) may he liberated from nitric acid (methyl nitrate is later photolyzed to NO(x)) before it is removed from the atmosphere by wet deposition. Thus, this reaction may have important implications for the NO(x) budget. Reactions have been initiated in 45-62 wt% H2SO4 solutions at 10.0 C. Methyl nitrate production rates increased exponentially with acidity within the acidity regime studied. Preliminary calculations suggest that the nitronium ion (NO2(+) is the active nitrating agent under these conditions. The reaction order in methanol appears to depend on the water/methanol ratio and varies from first to zeroth order under conditions investigated. The nitration is first order in nitronium at all acidities investigated. A second order rate constant, kappa(sub 2), has been calculated to be 1 x 10(exp 8)/ M s when the reaction is first order in methanol. Calculations suggest the nitration is first order in methanol under tropospheric conditions. The infinitesimal percentage of nitric acid in the nitronium ion form in this acidity regime probably makes this reaction insignificant for the upper troposphere; however, this nitration may become significant in the mid stratosphere where colder temperatures increase nitric acid solubility and higher sulfuric acid content shifts nitric acid speciation toward the nitronium ion.

  13. Acid-catalyzed Furfuryl Alcohol Polymerization: Characterizations of Molecular Structure and Thermodynamic Properties

    Kim, Taejin; Assary, Rajeev A; Marshall, Christopher L; Gosztola, David J.; Curtiss, Larry A; Stair, Peter C


    The liquid-phase polymerization of furfuryl alcohol catalyzed by sulfuric acid catalysts and the identities of molecular intermediates were investigated by using Raman spectroscopy and density functional theory calculation. At room temperature, with an acid catalyst, a vigorous furfuryl alcohol polymerization reaction was observed, whereas even at a high water concentration, furfuryl alcohol was very stable in the absence of an acid catalyst. Theoretical studies were carried out to investigate the thermodynamics of protonation of furfuryl alcohol, initiation of polymerization, and formation of conjugated dienes and diketonic species by using the B3LYP level of theory. A strong aliphatic C=C band observed in the calculated and measured Raman spectra provided crucial evidence to understand the polymerization reaction mechanism. It is confirmed that the formation of a conjugated diene structure rather than a diketone structure is involved in the furfuryl alcohol polymerization reaction.

  14. Rhodium-Catalyzed Addition of Aryl Boronic Acids to 2,2-Disubstituted Malononitriles.

    Malapit, Christian A; Caldwell, Donald R; Luvaga, Irungu K; Reeves, Jonathan T; Volchkov, Ivan; Gonnella, Nina C; Han, Zhengxu S; Busacca, Carl A; Howell, Amy R; Senanayake, Chris H


    β-Ketonitriles bearing a quaternary carbon at the 2-position were prepared through Rh-catalyzed addition of aryl boronic acids to 2,2-disubstituted malononitriles. In contrast to the previously described transnitrilative cyanation of aryl boronic acids with dialkylmalononitriles, the present reaction avoids retro-Thorpe collapse of the intermediate addition product through the use of a milder base. The reaction was amenable to a variety of aryl boronic acids and disubstituted malononitriles, providing a diverse array of β-ketonitriles. The products could be further derivatized to valuable chiral α,α-disubstituted-β-aminonitriles through addition reactions to the corresponding N-tert-butanesulfinyl imines. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Biodiesel Production from Spent Fish Frying Oil Through Acid-Base Catalyzed Transesterification

    Abdalrahman B. Fadhil


    Full Text Available Biodiesel fuels were prepared from a special type of frying oil namely spent fish frying oil through two step transesterification viz. acid-base catalyzed transesterification. Hydrochloric acid and potassium hydroxide with methanol were used for this purpose. The oil was pre-treated with (1.0 wt% HCl and methanol to reduce free fatty acids content of the oil. Then, conditions of the base catalyzed step such as base concentration, reaction temperature, methanol to oil molar ratio and reaction time were optimized. The study raveled that, 0.50% KOH w/w of oil; a 6:1 methanol to oil molar ratio; a reaction temperature of 60°C and a duration of 1h were the optimal conditions because they resulted in high biodiesel yield. Fuel properties of the products were assessed and found better than those of the parent oil. Furthermore, they met the specified limits according to the ASTM standards. Thin layer chromatography was used as a simple technique to monitor the transesterification of the oil. Blending of the optimal biodiesel sample with petro diesel using specified volume percentages was done as well. The results indicated that biodiesel had slight effect on the values of the assessed properties.

  16. Hydrodeoxygenation of fatty acid esters catalyzed by Ni on nano-sized MFI type zeolites

    Schreiber, Moritz W.; Rodriguez-Niño, Daniella; Gutiérrez, Oliver Y.; Lercher, Johannes A.


    The impact of support morphology and composition on the intrinsic activity of Ni supported on MFI-type zeolite was explored in the hydrodeoxygenation of methyl stearate, tristearate, and algae oil (mixture of triglycerides). The nano-sized structure of the support (self-pillared nanosheets) is beneficial for the activity of the catalysts. Higher Ni dispersion and concomitant higher reaction rates were obtained on nano-structured supports than on zeolite with conventional morphology. Rates normalized to accessible Ni atoms (TOF), however, varied little with support morphology. Acidity of the support increases the rate of Ni-catalyzed C-O hydrogenolysis per surface metal site.

  17. Lewis Acid Pairs for the Activation of Biomass-derived Oxygenates in Aqueous Media

    Roman, Yuriy [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)


    post-synthetic modifications, layered zeolite precursors can be transformed into 2-dimensional (2D), zeolites with open architectures. These novel hierarchical microporous/mesoporous materials with exposed active sites can facilitate the conversion of bulky substrates while maintaining higher stability than amorphous mesoporous materials. However, post-synthetic exfoliation techniques are energy intensive, multi-step and require highly alkaline conditions that result in low silica yields and a partially amorphous product. In this aim, we demonstrate an effective one-pot synthesis method to generate exfoliated single-unit-cell thick MWW nanosheets. The new material, named MIT-1, is synthesized using a rationally-designed OSDA and results in a material with high crystallinity, surface area, and acidity that does not require post-synthetic treatments other than calcination. A parametric study of Al, Na, and water content reveals that MIT-1 crystallizes over a wide synthetic window. Characterization data show that MIT-1 has high mesoporosity with an external surface area exceeding 500 m2g-1 and a high external acid site density of 21 x 10-5 mol g-1. Catalytic tests demonstrate that MIT-1 has three-fold higher catalytic activity for the Friedel-Crafts alkylation of benzene with benzyl alcohol as compared to that of other 3D MWW topology zeolites.

  18. Cobalt(II)-catalyzed 1,4-addition of organoboronic acids to activated alkenes: an application to highly cis-stereoselective synthesis of aminoindane carboxylic acid derivatives.

    Chen, Min-Hsien; Mannathan, Subramaniyan; Lin, Pao-Shun; Cheng, Chien-Hong


    It all adds up: The 1,4-addition of organoboronic acids to activated alkenes catalyzed by [Co(dppe)Cl(2)] is described. A [3+2]-annulation reaction of ortho-iminoarylboronic acids with acrylates to give various aminoindane carboxylic acid derivatives with cis-stereoselectivity is also demonstrated (see scheme; dppe = 1,2-bis(diphenylphosphino)ethane).

  19. Role of apparent pKa of carboxylic acids in lipase-catalyzed esterifications in biphasic systems

    Dominguez de Maria, Pablo; Fernandez-Alvaro, Elena; Kate, ten Antoon; Bargeman, Gerrald


    Lipase-catalyzed esterifications in biphasic media (heptane–water, 1:1) were conducted by using Thermomyces lanuginosus lipase (TLL) as biocatalyst. Different carboxylic acids (from acetic to lauric) were thus esterified with 1-butanol at different pH values (2–10). For all carboxylic acids tested,

  20. Solid acid-catalyzed cellulose hydrolysis monitored by in situ ATR-IR spectroscopy.

    Zakzeski, Joseph; Grisel, Ruud J H; Smit, Arjan T; Weckhuysen, Bert M


    The solid acid-catalyzed hydrolysis of cellulose was studied under elevated temperatures and autogenous pressures using in situ ATR-IR spectroscopy. Standards of cellulose and pure reaction products, which include glucose, fructose, hydroxymethylfurfural (HMF), levulinic acid (LA), formic acid, and other compounds, were measured in water under ambient and elevated temperatures. A combination of spectroscopic and HPLC analysis revealed that the cellulose hydrolysis proceeds first through the disruption of the glycosidic linkages of cellulose to form smaller cellulose molecules, which are readily observed by their distinctive C-O vibrational stretches. The continued disruption of the linkages in these oligomers eventually results in the formation and accumulation of monomeric glucose. The solid-acid catalyst accelerated the isomerization of glucose to fructose, which then rapidly reacted under hydrothermal conditions to form degradation products, which included HMF, LA, formic acid, and acetic acid. The formation of these species could be suppressed by decreasing the residence time of glucose in the reactor, reaction temperature, and contact with the metal reactor. The hydrolysis of regenerated cellulose proceeded faster and under milder conditions than microcrystalline cellulose, which resulted in increased glucose yield and selectivity. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Evaluation of bicinchoninic acid as a ligand for copper(I)-catalyzed azide-alkyne bioconjugations.

    Christen, Erik H; Gübeli, Raphael J; Kaufmann, Beate; Merkel, Lars; Schoenmakers, Ronald; Budisa, Nediljko; Fussenegger, Martin; Weber, Wilfried; Wiltschi, Birgit


    The Cu(I)-catalyzed cycloaddition of terminal azides and alkynes (click chemistry) represents a highly specific reaction for the functionalization of biomolecules with chemical moieties such as dyes or polymer matrices. In this study we evaluate the use of bicinchoninic acid (BCA) as a ligand for Cu(I) under physiological reaction conditions. We demonstrate that the BCA-Cu(I)-complex represents an efficient catalyst for the conjugation of fluorophores or biotin to alkyne- or azide-functionalized proteins resulting in increased or at least equal reaction yields compared to commonly used catalysts like Cu(I) in complex with TBTA (tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine) or BPAA (bathophenanthroline disulfonic acid). The stabilization of Cu(I) with BCA represents a new strategy for achieving highly efficient bioconjugation reactions under physiological conditions in many application fields.

  2. Recovery of arabinan in acetic acid-catalyzed hydrothermal pretreatment on corn stover

    Xu, Jian; Hedegaard, Mette Christina; Thomsen, Anne Belinda


    Acetic acid-catalyzed hydrothermal pretreatment was done on corn stover under 195 °C, 15 min with the acetic acid ranging from 5 × 10−3 to 0.2 g g−1 corn stover. After pretreatment, the water-insoluble solids (WISs) and liquors were collected respectively. Arabinan recoveries from both WIS...... and liquors were investigated. The results indicate that there was no detectable arabinan left in the WIS when the acetic acid of 0.1 and 0.2 g g−1 corn stover were used in the pretreatment. The arabinan contents in the other WISs were not more than 10%. However, the arabinan found in the liquors...... was not covering the amount of arabinan released from the raw corn stover. For the arabinan recovery from liquor fractions, the highest of 43.57% was obtained by the pretreatment of acetic acid of 0.01 g g−1 of corn stover and the lowest was only 26.77% when the acetic acid of 0.2 g g−1 corn stover was used...

  3. Iron-catalyzed photochemical transformation of benzoic acid in atmospheric liquids: Product identification and reaction mechanisms

    Deng, Yiwei; Zhang, Kai; Chen, Hao; Wu, Taixing; Krzyaniak, Metthew; Wellons, Amina; Bolla, Dawn; Douglas, Kenneth; Zuo, Yuegang

    This study investigated iron-catalyzed photochemical oxidation of benzoic acid (BA), one of the major photodegradation products of petroleum hydrocarbons, under sunlight or monochromatic light irradiation in a wavelength range of 254-419 nm. The photochemical degradation of BA in the absence of iron (III) occurred at irradiation wavelengths below 300 nm. The photochemical transformation of BA in the presence Fe(III) was observed at both 254, 350, 419 nm and under solar irradiation. The half-life for the photodegradation of BA (100 μM) was 160±20 min in the presence of 20 μM Fe(III) at pH 3.20 on sunny August days at noon time. The degradation rate increased with increasing concentration of Fe(III). The reaction products were separated and identified using capillary electrophoresis (CE), gas chromatography/mass spectrometry (GC/MS) and UV-Visible spectrophotometry. The major reaction products were 2-hydroxybenzoic, 3-hydroxybenzoic and 4-hydroxybenzoic acids. Hydrogen peroxide (H 2O 2) and Fe(II) species were also formed during the photochemical reactions. The proposed reaction mechanisms include the photoexcitation of Fe(III) hydroxide complexes to form Fe(II) ions and hydroxyl radicals (OH rad ) that attack ortho, meta and para positions of BA to form corresponding monohydroxybenzoic acids and H 2O 2. The monohydroxybenzoic acids formed further react with hydroxyl and surperoxide radicals (HO 2- rad /O 2- rad ) to yield dihydroxybenzoic acids in atmospheric water droplets.

  4. Mechanism of arylboronic acid-catalyzed amidation reaction between carboxylic acids and amines.

    Wang, Chen; Yu, Hai-Zhu; Fu, Yao; Guo, Qing-Xiang


    Arylboronic acids were found to be efficient catalysts for the amidation reactions between carboxylic acids and amines. Theoretical calculations have been carried out to investigate the mechanism of this catalytic process. It is found that the formation of the acyloxyboronic acid intermediates from the carboxylic acid and the arylboronic acid is kinetically facile but thermodynamically unfavorable. Removal of water (as experimentally accomplished by using molecular sieves) is therefore essential for overall transformation. Subsequently C-N bond formation between the acyloxyboronic acid intermediates and the amine occurs readily to generate the desired amide product. The cleavage of the C-O bond of the tetracoordinate acyl boronate intermediates is the rate-determining step in this process. Our analysis indicates that the mono(acyloxy)boronic acid is the key intermediate. The high catalytic activity of ortho-iodophenylboronic acid is attributed to the steric effect as well as the orbital interaction between the iodine atom and the boron atom.

  5. Palladium-atom catalyzed formic acid decomposition and the switch of reaction mechanism with temperature.

    He, Nan; Li, Zhen Hua


    Formic acid decomposition (FAD) reaction has been an innovative way for hydrogen energy. Noble metal catalysts, especially palladium-containing nanoparticles, supported or unsupported, perform well in this reaction. Herein, we considered the simplest model, wherein one Pd atom is used as the FAD catalyst. With high-level theoretical calculations of CCSD(T)/CBS quality, we investigated all possible FAD pathways. The results show that FAD catalyzed by one Pd atom follows a different mechanism compared with that catalyzed by surfaces or larger clusters. At the initial stage of the reaction, FAD follows a dehydration route and is quickly poisoned by CO due to the formation of very stable PdCO. PdCO then becomes the actual catalyst for FAD at temperatures approximately below 1050 K. Beyond 1050 K, there is a switch of catalyst from PdCO to Pd atom. The results also show that dehydration is always favoured over dehydrogenation on either the Pd-atom or PdCO catalyst. On the Pd-atom catalyst, neither dehydrogenation nor dehydration follows the formate mechanism. In contrast, on the PdCO catalyst, dehydrogenation follows the formate mechanism, whereas dehydration does not. We also systematically investigated the performance of 24 density functional theory methods. We found that the performance of the double hybrid mPW2PLYP functional is the best, followed by the B3LYP, B3PW91, N12SX, M11, and B2PLYP functionals.

  6. Fatty acid methyl esters yield and phorbol esters degradation during transesterification of Jatropha curcas oil by alkaline, acid and enzyme catalyzed method

    Tosa Koji


    Full Text Available Jatropha curcas has recently been the focus of intense research as a raw material of biomass fuel. However, the carcinogenesis promoter action of the phorbol esters in the Jatropha raises concerns for health and environmental risk. The purpose of the present study is to determine the relationship between the fatty acid methyl esters yield and the phorbol esters degradation ratio during the transesterification of the Jatropha oil by alkaline, acid and enzyme catalyzed method, respectively. The phorbol esters in Jatropha oil were degraded during the transesterification of the Jatropha curcas oil by alkaline and acid catalyzed methanol methods. The degradation ratio was significantly correlated with the fatty acid methyl esters yields in alkaline catalyzed transesterification. The results obtained in this study suggest that the health and environmental risk of the phorbol esters in a Jatropha BDF can be significantly reduced by a complete transesterification of the crude oil by controlling the transesterification condition appropriately.

  7. Application of acid-catalyzed hydrolysis of dispersed organic solvent in developing new microencapsulation process technology.

    Lee, Honghwa; Lee, Sunhwa; Bhattacharjee, Himanshu; Sah, Hongkee


    The aim of this study was to evaluate a new microencapsulation technology employing an acid-catalyzed solvent extraction method in conjunction to an emulsion-based microencapsulation process. Its process consisted of emulsifying a dispersed phase of poly(D,L-lactide-co-glycolide) and isopropyl formate in an aqueous phase. This step was followed by adding hydrochloric acid to the resulting oil-in-water emulsion, in order to initiate the hydrolysis of isopropyl formate dissolved in the aqueous phase. Its hydrolysis caused the liberation of water-soluble species, that is, isopropanol and formic acid. This event triggered continual solvent leaching out of emulsion droplets, thereby initiating microsphere solidification. This new processing worked well for encapsulation of progesterone and ketoprofen that were chosen as a nonionizable model drug and a weakly acidic one, respectively. Furthermore, the structural integrity of poly(D,L-lactide-co-glycolide) was retained during microencapsulation. The new microencapsulation technology, being conceptually different from previous approaches, might be useful in preparing various polymeric particles.

  8. An atom-economic approach to carboxylic acids via Pd-catalyzed direct addition of formic acid to olefins with acetic anhydride as a co-catalyst.

    Wang, Yang; Ren, Wenlong; Shi, Yian


    An effective Pd-catalyzed hydrocarboxylation of olefins using formic acid with acetic anhydride as a co-catalyst is described. A variety of carboxylic acids are obtained in good yields with high regioselectivities under mild reaction conditions without the use of toxic CO gas.

  9. Phenylalanine Aminomutase-Catalyzed Addition of Ammonia to Substituted Cinnamic Acids : a Route to Enantiopure alpha- and beta-Amino Acids

    Szymanski, Wiktor; Wu, Bian; Weiner, Barbara; de Wildeman, Stefaan; Feringa, B.L.; B. Janssen, Dick


    An approach is described for the synthesis of aromatic alpha- and beta-amino acids that Uses phenylalanine aminomutase to catalyze a highly enantioselective addition of ammonia to substituted cinnamic acids. The reaction has a broad scope and yields Substituted alpha- and beta-phenylalanines with ex

  10. Regioselective, borinic acid-catalyzed monoacylation, sulfonylation and alkylation of diols and carbohydrates: expansion of substrate scope and mechanistic studies.

    Lee, Doris; Williamson, Caitlin L; Chan, Lina; Taylor, Mark S


    Synthetic and mechanistic aspects of the diarylborinic acid-catalyzed regioselective monofunctionalization of 1,2- and 1,3-diols are presented. Diarylborinic acid catalysis is shown to be an efficient and general method for monotosylation of pyranoside derivatives bearing three secondary hydroxyl groups (7 examples, 88% average yield). In addition, the scope of the selective acylation, sulfonylation, and alkylation is extended to 1,2- and 1,3-diols not derived from carbohydrates (28 examples); the efficiency, generality, and operational simplicity of this method are competitive with those of state-of-the-art protocols including the broadly applied organotin-catalyzed or -mediated reactions. Mechanistic details of the organoboron-catalyzed processes are explored using competition experiments, kinetics, and catalyst structure-activity relationships. These experiments are consistent with a mechanism in which a tetracoordinate borinate complex reacts with the electrophilic species in the turnover-limiting step of the catalytic cycle.

  11. Microwave-assisted facile and rapid Friedel-Crafts benzoylation of arenes catalysed by bismuth trifluoromethanesulfonate

    Tran, Phoung Hoang; Hansen, Poul Erik; Pham, Thuy Than;


    The catalytic activity of metal triflates was investigated in Friedel–Crafts benzoylation under microwave irradiation. Friedel–Crafts benzoylation with benzoyl chloride of a variety of arenes containing electron-rich and electron-poor rings using bismuth triflate under microwave irradiation is de...

  12. Intrinsic oxidation kinetics of sulfite catalyzed by peracetic acid under different water quality and light conditions


    Oxidation of sulfite is an important process in wet flue gas desulfurization.Using highly purified water or distilled water as a reaction medium and a transparent or an opaque intermittent reaction apparatus,the intrinsic oxidation kinetics of sulfite catalyzed by peracetic acid was investigated under four dif-ferent conditions.The reaction order of the reagents and the activation energy were obtained.The re-sults indicate that water quality and light have no obvious effects on the reaction order and activation energy,but have an influence on the reaction rate constant.The mechanism of the intrinsic reaction is proposed.The results derived with this mechanism are in good agreement with the experimental re-sults.

  13. Intrinsic oxidation kinetics of sulfite catalyzed by peracetic acid under different water quality and light conditions

    WANG LiDong; ZHAO Yi; LI QiangWei; CHEN ZhouYan; LIU SongTao; MA YongLiang; HAO JiMing


    Oxidation of sulfite is an important process in wet flue gas desulfurization. Using highly purified water or distilled water as a reaction medium and a transparent or an opaque intermittent reaction apparatus, the intrinsic oxidation kinetics of sulfite catalyzed by peracetic acid was investigated under four dif-ferent conditions. The reaction order of the reagents and the activation energy were obtained. The re-sults indicate that water quality and light have no obvious effects on the reaction order and activation energy, but have an influence on the reaction rate constant. The mechanism of the intrinsic reaction is proposed. The results derived with this mechanism are in good agreement with the experimental re-sults.

  14. Kinetics of Acid-Catalyzed Dehydration of Cyclic Hemiacetals in Organic Aerosol Particles in Equilibrium with Nitric Acid Vapor.

    Ranney, April P; Ziemann, Paul J


    Previous studies have shown that 1,4-hydroxycarbonyls, which are often major products of the atmospheric oxidation of hydrocarbons, can undergo acid-catalyzed cyclization and dehydration in aerosol particles to form highly reactive unsaturated dihydrofurans. In this study the kinetics of dehydration of cyclic hemiacetals, the rate-limiting step in this process, was investigated in a series of environmental chamber experiments in which secondary organic aerosol (SOA) containing cyclic hemiacetals was formed from the reaction of n-pentadecane with OH radicals in dry air in the presence of HNO3. A particle beam mass spectrometer was used to monitor the formation and dehydration of cyclic hemiacetals in real time, and SOA and HNO3 were quantified in filter samples by gravimetric analysis and ion chromatography. Measured dehydration rate constants increased linearly with increasing concentration of HNO3 in the gas phase and in SOA, corresponding to catalytic rate constants of 0.27 h(-1) ppmv(-1) and 7.0 h(-1) M(-1), respectively. The measured Henry's law constant for partitioning of HNO3 into SOA was 3.7 × 10(4) M atm(-1), ∼25% of the value for dissolution into water, and the acid dissociation constant was estimated to be water. The results indicate that HNO3 was only weakly dissociated in the SOA and that dehydration of cyclic hemiacetals was catalyzed by molecular HNO3 rather than by H(+). The Henry's law constant and kinetics relationships measured here can be used to improve mechanisms and models of SOA formation from the oxidation of hydrocarbons in dry air in the presence of NOx, which are conditions commonly used in laboratory studies. The fate of cyclic hemiacetals in the atmosphere, where the effects of higher relative humidity, organic/aqueous phase separation, and acid catalysis by molecular H2SO4 and/or H(+) are likely to be important, is discussed.

  15. Laccase-catalyzed modification of PES membranes with 4-hydroxybenzoic acid and gallic acid

    Nady, N.; Schroën, C.G.P.H.; Franssen, M.C.R.; Mohy Eldin, M.S.; Zuilhof, H.; Boom, R.M.


    We here report on the performance of poly(ethersulfone) membranes modified with 4-hydroxybenzoic acid and gallic acid as substrates, and using laccase as biocatalyst under several modification conditions. The average flux of the base membrane was never reduced more than 20% (mostly below 10% reducti

  16. Laccase-catalyzed modification of PES membranes with 4-hydroxybenzoic acid and gallic acid

    Nady, N.; Schroën, C.G.P.H.; Franssen, M.C.R.; Mohy Eldin, M.S.; Zuilhof, H.; Boom, R.M.


    We here report on the performance of poly(ethersulfone) membranes modified with 4-hydroxybenzoic acid and gallic acid as substrates, and using laccase as biocatalyst under several modification conditions. The average flux of the base membrane was never reduced more than 20% (mostly below 10%

  17. Lipase catalyzed synthesis of organic acid esters of lactic acid in non-aqueous media.

    Kiran, K R; Divakar, S


    Lipases from Rhizomucor miehei (Lipozyme IM20) and porcine pancreas (PPL) were employed as catalysts for the esterification reaction between the hydroxyl group of lactic acid and the carboxyl group of organic acids. Reactions were carried out at both shake-flask and bench-scale levels. Various parameters, such as solvent, temperature, substrate and enzyme concentrations, effect of buffer volume, buffer pH and water volume, were investigated for optimization of yields. While ethylmethyl ketone (EMK) was found to be the best solvent for shake-flask reactions, chloroform gave higher yields at bench-scale level. Detailed studies were carried out with respect to the synthesis of palmitoyl and stearoyl lactic acids. At shake-flask level, maximum yields of 37.5 and 40% were observed in case of palmitoyl and stearoyl lactic acids, respectively, with Lipozyme IM20; at bench-scale level, the maximum yields were 85.1 and 99% respectively, when PPL was employed. Of all the organic acids employed (C(2)--C(18)), only lauric, palmitic and stearic acids gave yields above 50%. At bench-scale level, PPL could be reused for up to three cycles with yields above 40%. Esters prepared were found to conform to Food Chemical Codex (FCC) specifications in terms of acid value, ester value, sodium and lactic acid contents.

  18. Mechanistic Investigation of Acid-Catalyzed Cleavage of Aryl-Ether Linkages: Implications for Lignin Depolymerization

    Sturgeon, M. R.; Kim, S.; Chmely, S. C.; Foust, T. D.; Beckham, G. T.


    Carbon-oxygen bonds are the primary inter-monomer linkages lignin polymers in plant cell walls, and as such, catalyst development to cleave these linkages is of paramount importance to deconstruct biomass to its constituent monomers for the production of renewable fuels and chemicals. For many decades, acid catalysis has been used to depolymerize lignin. Lignin is a primary component of plant cell walls, which is connected primarily by aryl-ether linkages, and the mechanism of its deconstruction by acid is not well understood, likely due to its heterogeneous and complex nature compared to cellulose. For effective biomass conversion strategies, utilization of lignin is of significant relevance and as such understanding the mechanisms of catalytic lignin deconstruction to constituent monomers and oligomers is of keen interest. Here, we present a comprehensive experimental and theoretical study of the acid catalysis of a range of dimeric species exhibiting the b-O-4 linkage, the most common inter-monomer linkage in lignin. We demonstrate that the presence of a phenolic species dramatically increases the rate of cleavage in acid at 150 degrees C. Quantum mechanical calculations on dimers with the para-hydroxyl group demonstrate that this acid-catalyzed pathway differs from the nonphenolic dimmers. Importantly, this result implies that depolymerization of native lignin in the plant cell wall will proceed via an unzipping mechanism wherein b-O-4 linkages will be cleaved from the ends of the branched, polymer chains inwards toward the center of the polymer. To test this hypothesis further, we synthesized a homopolymer of b-O-4 with a phenolic hydroxyl group, and demonstrate that it is cleaved in acid from the end containing the phenolic hydroxyl group. This result suggests that genetic modifications to lignin biosynthesis pathways in plants that will enable lower severity processes to fractionate lignin for upgrading and for easier access to the carbohydrate fraction of


    陶敬奇; 李景宁; 王广洪; 曾广益


    The Polysuccinimide is Synthesized by means of pyrocondensation catalyze polymerization,using L-aspartic acid as a monomer.Poly-aspartic Acid is achieved by hydrolization of Polysuccinimide.The effect of temperature,time,catalyzer and condition of hydrolization on yield and quality is studied.The research results show that the method has the advantages of simple equipment and high yield.

  20. Acid-Catalyzed Transesterification Reaction of Beef Tallow For Biodiesel Production By Factor Variation

    R.C. Ehiri


    Full Text Available Biodiesel is a diesel grade fuel made by transesterification reaction of vegetable oils and animal fats with alcohol. Three variable factors that affect the yield of biodiesel namely, reaction time, reaction temperature and catalyst concentration were studied in this work. The biodiesel was produced via a batchprocess acid-catalyzed transesterification reaction of beef tallow with methanol. Optimal conditions for the reaction were established in a three factor two-level (23 central composite design with the biodiesel pretreatment yield as the response surface. The results show that the mean yield of biodiesel was 92.04% with a standard deviation of 5.16. An optimal biodiesel yield of 96.30% occurred at 0.5% HCl catalyst concentration and at constant conditions of 1.5h reaction time, 60oC reaction temperature and 6:1 methanol: tallow volume ratio. Gas chromatographic analysis of the beef tallow identified palmitic, stearic and oleic acids in it while the fatty acid methyl esters in the biodiesel product were oleate and linoleate. Catalysis was the most significant factor in the transesterification process.

  1. Synthesis, isolation and characterization of methyl levulinate from cellulose catalyzed by extremely low concentration acid

    Hui; Li; Lincai; Peng; Lu; Lin; Keli; Chen; Heng; Zhang


    A direct synthesis of methyl levulinate from cellulose alcoholysis in methanol medium under mild condition(180 210 C)catalyzed by extremely low concentration sulfuric acid(0.01 mol/L)and the product isolation were developed in this study.Effects of different process variables towards the catalytic performance were performed as a function of reaction time.The results indicated that sulfuric acid concentration,temperature and initial cellulose concentration had significant effects on the synthesis of methyl levulinate.An optimized yield of around 50%was achieved at 210 C for 120 min with sulfuric acid concentration of 0.01 mol/L and initial cellulose concentration below 100 g/L.The resulting product mixture was isolated by a distillation technique that combines an atmospheric distillation with a vacuum distillation where n-dodecane was added to help distill the heavy fraction.The light fraction including mainly methanol could be reused as the reaction medium without any substantial change in the yield of methyl levulinate.The chemical composition and structural of lower heavy fraction were characterized by GC/MS,FTIR,1H-NMR and13C-NMR techniques.Methyl levulinate was found to be a major ingredient of lower heavy fraction with the content over 96%.This pathway is efficient,environmentally benign and economical for the production of pure levulinate esters from cellulose.

  2. Aryl Ketone Synthesis via Tandem Orthoplatinated Triarylphosphite-Catalyzed Addition Reactions of Arylboronic Acids with Aldehydes Followed by Oxidation

    Liao, Yuan-Xi; Hu, Qiao-Sheng


    Tandem orthoplatinated triarylphosphite-catalyzed addition reactions of arylboronic acids with aldehydes followed by oxidation to yield aryl ketones is described. 3-Pentanone was identified as a suitable oxidant for the tandem aryl ketone formation reaction. By using microwave energy, aryl ketones were obtained in high yields with the catalyst loading as low as 0.01%. PMID:20849092

  3. Kinetic studies on the Rhizomucor miehei lipase catalyzed esterification reaction of oleic acid with 1-butanol in a biphasic system

    Kraai, G.N.; Winkelman, J.G.M.; de Vries, Johannes; Heeres, H.J.


    The kinetics of the esterification of oleic acid with 1 -butanol catalyzed by free Rhizomucor miehei lipase in a biphasic system was studied in a batch reactor. The reaction appeared to proceed via a Ping Pong bi-bi mechanism with I -butanol inhibition. The kinetic constants of the model were

  4. Lipase-Catalyzed Esterification of Ferulic Acid with Oleyl Alcohol in Ionic Liquid/Isooctane Binary Systems

    Chen, Bilian; Liu, Huanzhen; Guo, Zheng


    Lipase-catalyzed synthesis of ferulic acid oleyl alcohol ester in an ionic liquid (IL)/isooctane system was investigated. Considerable bioconversion and volumetric productivity were achieved in inexpensive 1-hexyl-3-methylimidazolium hexafluorophosphate ([Hmim][PF6]) and 1-methyl-3-octylimidazoli...

  5. Ru/Me-BIPAM-Catalyzed Asymmetric Addition of Arylboronic Acids to Aliphatic Aldehydes and α-Ketoesters

    Momoko Watanabe


    Full Text Available A ruthenium-catalyzed asymmetric arylation of aliphatic aldehydes and α-ketoesters with arylboronic acids has been developed, giving chiral alkyl(arylmethanols and α-hydroxy esters in good yields. The use of a chiral bidentate phosphoramidite ligand (Me-BIPAM achieved excellent enantioselectivities.

  6. Lipase-catalyzed process in an anhydrous medium with enzyme reutilization to produce biodiesel with low acid value.

    Azócar, Laura; Ciudad, Gustavo; Heipieper, Hermann J; Muñoz, Robinson; Navia, Rodrigo


    One major problem in the lipase-catalyzed production of biodiesel or fatty acid methyl esters (FAME) is the high acidity of the product, mainly caused by water presence, which produces parallel hydrolysis and esterification reactions instead of transesterification to FAME. Therefore, the use of reaction medium in absence of water (anhydrous medium) was investigated in a lipase-catalyzed process to improve FAME yield and final product quality. FAME production catalyzed by Novozym 435 was carried out using waste frying oil (WFO) as raw material, methanol as acyl acceptor, and 3Å molecular sieves to extract the water. The anhydrous conditions allowed the esterification of free fatty acids (FFA) from feedstock at the initial reaction time. However, after the initial esterification process, water absence avoided the consecutives reactions of hydrolysis and esterification, producing FAME mainly by transesterification. Using this anhydrous medium, a decreasing in both the acid value and the diglycerides content in the product were observed, simultaneously improving FAME yield. Enzyme reuse in the anhydrous medium was also studied. The use of the moderate polar solvent tert-butanol as a co-solvent led to a stable catalysis using Novozym 435 even after 17 successive cycles of FAME production under anhydrous conditions. These results indicate that a lipase-catalyzed process in an anhydrous medium coupled with enzyme reuse would be suitable for biodiesel production, promoting the use of oils of different origin as raw materials.

  7. Kinetic studies on the Rhizomucor miehei lipase catalyzed esterification reaction of oleic acid with 1-butanol in a biphasic system

    Kraai, G.N.; Winkelman, J.G.M.; de Vries, Johannes; Heeres, H.J.


    The kinetics of the esterification of oleic acid with 1 -butanol catalyzed by free Rhizomucor miehei lipase in a biphasic system was studied in a batch reactor. The reaction appeared to proceed via a Ping Pong bi-bi mechanism with I -butanol inhibition. The kinetic constants of the model were determ

  8. (Salen)Ti(Ⅳ)-Catalyzed Asymmetric Ring-opening of meso Epoxides Using Dithiophosphorus Acid as the Nucleophile

    Zheng Hong ZHOU; Zhao Ming LI; Bing LIU; Kang Ying LI; Li Xin WANG; Guo Feng ZHAO; Qi Lin ZHOU; Chu Chi TANG


    The asymmetric ring-opening of epoxides with dithiophosphorus acids catalyzed by a (salen)Ti(Ⅳ) complex formed in situ from the reaction of Ti(OPr-i)4 and the chiral Schiff base derived from (1R,2R)-(+)-diaminocyclohexane was realized. The resulting products were obtained with low to good enantioselectivity (up to 73% ee).

  9. Ru/Me-BIPAM-catalyzed asymmetric addition of arylboronic acids to aliphatic aldehydes and α-ketoesters.

    Yamamoto, Yasunori; Shirai, Tomohiko; Watanabe, Momoko; Kurihara, Kazunori; Miyaura, Norio


    A ruthenium-catalyzed asymmetric arylation of aliphatic aldehydes and α-ketoesters with arylboronic acids has been developed, giving chiral alkyl(aryl)methanols and α-hydroxy esters in good yields. The use of a chiral bidentate phosphoramidite ligand (Me-BIPAM) achieved excellent enantioselectivities.

  10. Rh(III)-catalyzed selective coupling of N-methoxy-1H-indole-1-carboxamides and aryl boronic acids.

    Zheng, Jing; Zhang, Yan; Cui, Sunliang


    A Rh(III)-catalyzed selective coupling of N-methoxy-1H-indole-1-carboxamide and aryl boronic acids is reported. The coupling is mild and efficient toward diverse product formation, with selective C-C and C-C/C-N bond formation. Kinetic isotope effects studies were conducted to reveal a mechanism of C-H activation and electrophilic addition.

  11. Superior acidic catalytic activity and stability of Fe-doped HTaWO6 nanotubes

    Liu, He


    Fe-doped HTaWO6 (H1-3xFexTaWO6, x = 0.23) nanotubes as highly active solid acid catalysts were prepared via an exfoliation-scrolling-exchange process. The specific surface area and pore volume of undoped nanotubes (20.8 m2 g-1, 0.057 cm3 g-1) were remarkably enhanced through Fe3+ ion-exchange (>100 m2 g-1, 0.547 cm3 g-1). Doping Fe ions into the nanotubes endowed them with improved thermal stability due to the stronger interaction between the intercalated Fe3+ ions and the host layers. This interaction also facilitated the preservation of effective Brønsted acid sites and the generation of new acid sites. The integration of these functional roles resulted in Fe-doped nanotubes with high acidic catalytic activities in the Friedel-Crafts alkylation of anisole and the esterification of acetic acid. Facile accessibility to active sites, generation of effective Brønsted acid sites, high stability of the tubular structure and strong acid sites were found to synergistically contribute to the excellent acidic catalytic efficiency. Additionally, the activity of cycled nanocatalysts can be easily recovered through annealing treatment.

  12. Pilot-scale study on the acid-catalyzed steam explosion of rice straw using a continuous pretreatment system.

    Chen, Wen-Hua; Tsai, Chia-Chin; Lin, Chih-Feng; Tsai, Pei-Yuan; Hwang, Wen-Song


    A continuous acid-catalyzed steam explosion pretreatment process and system to produce cellulosic ethanol was developed at the pilot-scale. The effects of the following parameters on the pretreatment efficiency of rice straw feedstocks were investigated: the acid concentration, the reaction temperature, the residence time, the feedstock size, the explosion pressure and the screw speed. The optimal presteaming horizontal reactor conditions for the pretreatment process are as follows: 1.7 rpm and 100-110 °C with an acid concentration of 1.3% (w/w). An acid-catalyzed steam explosion is then performed in the vertical reactor at 185 °C for 2 min. Approximately 73% of the total saccharification yield was obtained after the rice straw was pretreated under optimal conditions and subsequent enzymatic hydrolysis at a combined severity factor of 0.4-0.7. Moreover, good long-term stability and durability of the pretreatment system under continuous operation was observed.

  13. Potential of phosphoric acid-catalyzed pretreatment and subsequent enzymatic hydrolysis for biosugar production from Gracilaria verrucosa.

    Kwon, Oh-Min; Kim, Sung-Koo; Jeong, Gwi-Taek


    This study combined phosphoric acid-catalyzed pretreatment and enzymatic hydrolysis to produce biosugars from Gracilaria verrucosa as a potential renewable resource for bioenergy applications. We optimized phosphoric acid-catalyzed pretreatment conditions to 1:10 solid-to-liquid ratio, 1.5 % phosphoric acid, 140 °C, and 60 min reaction time, producing a 32.52 ± 0.06 % total reducing sugar (TRS) yield. By subsequent enzymatic hydrolysis, a 68.61 ± 0.90 % TRS yield was achieved. These results demonstrate the potential of phosphoric acid to produce biosugars for biofuel and biochemical production applications.

  14. Chiral Lewis base-assisted Brønsted acid (LBBA)-catalyzed enantioselective cyclization of 2-geranylphenols.

    Sakakura, Akira; Sakuma, Masayuki; Ishihara, Kazuaki


    Chiral Lewis base-assisted Brønsted acids (Chiral LBBAs) have been designed as new organocatalysts for biomimetic enantioselective cyclization. A salt of a chiral phosphonous acid diester with FSO(3)H catalyzes the enantioselective cyclization of 2-geranylphenols to give the desired trans-fused cyclized products with high diastereo- and enantioselectivities (up to 98:2 dr and 93% ee). © 2011 American Chemical Society

  15. Enantioselective Direct Mannich-Type Reactions Catalyzed by Frustrated Lewis Acid/Brønsted Base Complexes.

    Shang, Ming; Cao, Min; Wang, Qifan; Wasa, Masayuki


    An enantioselective direct Mannich-type reaction catalyzed by a sterically frustrated Lewis acid/Brønsted base complex is disclosed. Cooperative functioning of the chiral Lewis acid and achiral Brønsted base components gives rise to in situ enolate generation from monocarbonyl compounds. Subsequent reaction with hydrogen-bond-activated aldimines delivers β-aminocarbonyl compounds with high enantiomeric purity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Inhibition of Homo-coupling of Arylboronic Acids in Ligand Free Pd(Ⅱ)-Catalyzed Suzuki Reaction

    TAO,Xiao-Chun; ZHANG,Yue-Ping; HE,Tian-Xiong; SHEN,Dong


    A series of solvents were examined for the ligand free Pd(Ⅱ)-catalyzed Suzuki reaction of 4-bromotoluene with phenylboronic acid. It was found that the PdCl2/i-PrOH system could efficiently inhibit the homo-coupling of phenylboronic acid and give a cross-coupling product in high yields. The substrates with a wide variety of functional groups were tolerated in the system. A possible mechanism for this system was proposed.

  17. Recovery of slaughterhouse Animal Fatty Wastewater Sludge by conversion into Fatty Acid Butyl Esters by acid-catalyzed esterification.

    Wallis, Christopher; Cerny, Muriel; Lacroux, Eric; Mouloungui, Zéphirin


    Two types of Animal Fatty Wastewater Sludges (AFWS 1 and 2) were analyzed and fully characterized to determine their suitability for conversion into biofuel. AFWS 1 was determined to be unsuitable as it contains 68.8wt.% water and only 32.3wt.% dry material, of which only around 80% is lipids to be converted. AFWS 2 has only 15.7wt.% water and 84.3wt.% dry material of which is assumed to 100% lipids as the protein and ash contents were determined to be negligible. The 4-dodecylbenzenesulfonic acid (DBSA) catalyzed esterification of AFWS with 1-butanol was performed in a novel batch reactor fitted with a drying chimney for the "in situ" removal of water and optimized using a non-conventional Doehlert surface response methodology. The optimized condition was found to be 1.66mol equivalent of 1-butanol (with respect to total fatty acid chains), 10wt.% of DBSA catalyst (with respect to AFWS) at 105°C for 3h. Fatty Acid Butyl Esters (FABEs) were isolated in good yields (95%+) as well as a blend of FABEs with 1-butanol (16%). The two potential biofuels were analyzed in comparison with current and analogous biofuels (FAME based biodiesel, and FABE products made from vegetable oils) and were found to exhibit high cetane numbers and flash point values. Copyright © 2016 Elsevier Ltd. All rights reserved.

  18. Rh(III)-catalyzed decarboxylative ortho-heteroarylation of aromatic carboxylic acids by using the carboxylic acid as a traceless directing group.

    Qin, Xurong; Sun, Denan; You, Qiulin; Cheng, Yangyang; Lan, Jingbo; You, Jingsong


    Highly selective decarboxylative ortho-heteroarylation of aromatic carboxylic acids with various heteroarenes has been developed through Rh(III)-catalyzed two-fold C-H activation, which exhibits a wide substrate scope of both aromatic carboxylic acids and heteroarenes. The use of naturally occurring carboxylic acid as the directing group avoids troublesome extra steps for installation and removal of an external directing group.

  19. Lipase-catalyzed modification of rice bran oil to incorporate capric acid.

    Jennings, B H; Akoh, C C


    Capric acid (C10:0) was incorporated into rice bran oil with an immobilized lipase from Rhizomucor miehei as the biocatalyst. Effects of incubation time, substrate mole ratio, enzyme load, and water addition on mole percent incorporation of C10:0 were studied. Transesterification was performed in an organic solvent, hexane, and under solvent-free condition. Pancreatic lipase-catalyzed sn-2 positional analysis and tocopherol analysis were performed before and after enzymatic modification. Products were analyzed by gas-liquid chromatography (GLC) for fatty acid composition. After 24 h of incubation in hexane, there was an average of 26.5 +/- 1.8 mol % incorporation of C10:0 into rice bran oil. The solvent-free reaction produced an average of 24.5 +/- 3.7 mol % capric acid. In general, as the enzyme load, substrate mole ratio, and incubation time increased, the mole percent of capric acid incorporation also increased. Time course reaction indicated C10:0 incorporation increased up to 27.0 mol % at 72 h, for the reaction in hexane, and up to 29.6 mol % at 12 h, for the solvent-free reaction. The highest C10:0 incorporations (53.1 and 43.2 mol %) for the mole ratio experiment occurred at a mole ratio of 1:8 for solvent and solvent-free reactions, respectively. The highest C10:0 incorporation (27.9 mol %) for the reaction in hexane occurred at 10% enzyme load, and the highest incorporation (34.4 mol %) for the solvent-free reaction occurred at 20% enzyme load. Incorporation of C10:0 into rice bran oil declined with the addition of increasing amounts of water after reaching 30.3 mol % at 2% water addition in hexane, and in the solvent-free reaction after reaching 35.9 mol %.

  20. Glycolic Acid-Catalyzed Deamidation of Asparagine Residues in Degrading PLGA Matrices: A Computational Study

    Noriyoshi Manabe


    Full Text Available Poly(lactic-co-glycolic acid (PLGA is a strong candidate for being a drug carrier in drug delivery systems because of its biocompatibility and biodegradability. However, in degrading PLGA matrices, the encapsulated peptide and protein drugs can undergo various degradation reactions, including deamidation at asparagine (Asn residues to give a succinimide species, which may affect their potency and/or safety. Here, we show computationally that glycolic acid (GA in its undissociated form, which can exist in high concentration in degrading PLGA matrices, can catalyze the succinimide formation from Asn residues by acting as a proton-transfer mediator. A two-step mechanism was studied by quantum-chemical calculations using Ace-Asn-Nme (Ace = acetyl, Nme = NHCH3 as a model compound. The first step is cyclization (intramolecular addition to form a tetrahedral intermediate, and the second step is elimination of ammonia from the intermediate. Both steps involve an extensive bond reorganization mediated by a GA molecule, and the first step was predicted to be rate-determining. The present findings are expected to be useful in the design of more effective and safe PLGA devices.

  1. Dual Lewis Acid/Lewis Base Catalyzed Acylcyanation of Aldehydes: A Mechanistic Study.

    Laurell Nash, Anna; Hertzberg, Robin; Wen, Ye-Qian; Dahlgren, Björn; Brinck, Tore; Moberg, Christina


    A mechanistic investigation, which included a Hammett correlation analysis, evaluation of the effect of variation of catalyst composition, and low-temperature NMR spectroscopy studies, of the Lewis acid-Lewis base catalyzed addition of acetyl cyanide to prochiral aldehydes provides support for a reaction route that involves Lewis base activation of the acyl cyanide with formation of a potent acylating agent and cyanide ion. The cyanide ion adds to the carbonyl group of the Lewis acid activated aldehyde. O-Acylation by the acylated Lewis base to form the final cyanohydrin ester occurs prior to decomplexation from titanium. For less reactive aldehydes, the addition of cyanide is the rate-determining step, whereas, for more reactive, electron-deficient aldehydes, cyanide addition is rapid and reversible and is followed by rate-limiting acylation. The resting state of the catalyst lies outside the catalytic cycle and is believed to be a monomeric titanium complex with two alcoholate ligands, which only slowly converts into the product. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Glycolic acid-catalyzed deamidation of asparagine residues in degrading PLGA matrices: a computational study.

    Manabe, Noriyoshi; Kirikoshi, Ryota; Takahashi, Ohgi


    Poly(lactic-co-glycolic acid) (PLGA) is a strong candidate for being a drug carrier in drug delivery systems because of its biocompatibility and biodegradability. However, in degrading PLGA matrices, the encapsulated peptide and protein drugs can undergo various degradation reactions, including deamidation at asparagine (Asn) residues to give a succinimide species, which may affect their potency and/or safety. Here, we show computationally that glycolic acid (GA) in its undissociated form, which can exist in high concentration in degrading PLGA matrices, can catalyze the succinimide formation from Asn residues by acting as a proton-transfer mediator. A two-step mechanism was studied by quantum-chemical calculations using Ace-Asn-Nme (Ace = acetyl, Nme = NHCH3) as a model compound. The first step is cyclization (intramolecular addition) to form a tetrahedral intermediate, and the second step is elimination of ammonia from the intermediate. Both steps involve an extensive bond reorganization mediated by a GA molecule, and the first step was predicted to be rate-determining. The present findings are expected to be useful in the design of more effective and safe PLGA devices.

  3. Ion-exchange Resin Catalyzed Esterification of Lactic Acid with Isopropanol: a Kinetic Study

    Amrit P. Toor


    Full Text Available The kinetic behavior of esterification of lactic acid with isopropanol over an acidic cation exchange resin, Amberlyst 15, was studied under isothermal condition. Isopropyl lactate synthesized in this reaction is an important pharmaceutical intermediate. The experiments were carried out in a stirred batch reactor in the temperature range of 323.15 to 353.15 K. The effect of various parameters such as temperature, molar ratio and catalyst loading was studied. Variation in parameters on rate of reaction demonstrated that the reaction was intrinsically controlled. Kinetic modeling was performed using Eley-Rideal model which acceptably fits the experimental data. The activation energy was found to be 22.007 kJ/mol and frequency factor was 0.036809 l2 g-1 mol-1 min-1 for forward reaction. The value of entropy for the forward reaction was found to be 182.317 J K-1 mol-1 . © 2011 BCREC UNDIP. All rights reserved(Received: 19th January 2011, Revised: 16th March 2011; Accepted: 16th March 2011[How to Cite: A.P. Toor, M. Sharma, S. Thakur, and R. K. Wanchoo. (2011. Ion-exchange Resin Catalyzed Esterification of Lactic Acid with Isopropanol: a Kinetic Study. Bulletin of Chemical Reaction Engineering and Catalysis, 6(1: 39-45. doi:10.9767/bcrec.6.1.791.39-45][How to Link / DOI: || or local: ] | View in  

  4. Lipase-catalyzed Synthesis of Caffeic Acid Phenethyl Ester in Ionic Liquids:Effect of Specific Ions and Reaction Parameters

    王俊; 李晶; 张磊霞; 顾双双; 吴福安


    Caffeic acid phenethyl ester (CAPE) is a rare, naturally occurring phenolic food additive. This work systematically reported fundamental data on conversion of caffeic acid (CA), yield of CAPE, and reactive selectiv-ity during the lipase-catalyzed esterification process of CA and phenylethanol (PE) in ionic liquids (ILs). Sixteen ILs were selected as the reaction media, and the relative lipase-catalyzed synthesis properties of CAPE were meas-ured in an effort to enhance the yield of CAPE with high selectivity. The results indicated that ILs containing weakly coordinating anions and cations with adequate alkyl chain length improved the synthesis of CAPE. [Emim][Tf2N] was selected as the optimal reaction media. The optimal parameters were as follows by response surface methodology (RSM):reaction temperature, 84.0 °C;mass ratio of Novozym 435 to CA, 14︰1;and molar ratio of PE to CA, 16︰1. The highest reactive selectivity of CAPE catalyzed by Novozym 435 in [Emim][Tf2N] reached 64.55%(CA conversion 98.76%and CAPE yield 63.75%, respectively). Thus, lipase-catalyzed esterifica-tion in ILs is a promising method suitable for CAPE production.

  5. Disproportionation Kinetics of Hypoiodous Acid As Catalyzed and Suppressed by Acetic Acid-Acetate Buffer.

    Urbansky, Edward T.; Cooper, Brian T.; Margerum, Dale W.


    The kinetics of the disproportionation of hypoiodous acid to give iodine and iodate ion (5HOI right harpoon over left harpoon 2I(2) + IO(3)(-) + H(+) + 2H(2)O) are investigated in aqueous acetic acid-sodium acetate buffer. The rate of iodine formation is followed photometrically at -log [H(+)] = 3.50, 4.00, 4.50, and 5.00, &mgr; = 0.50 M (NaClO(4)), and 25.0 degrees C. Both catalytic and inhibitory buffer effects are observed. The first process is proposed to be a disproportionation of iodine(I) to give HOIO and I(-); the iodide then reacts with HOI to give I(2). The reactive species (acetato-O)iodine(I), CH(3)CO(2)I, is postulated to increase the rate by assisting in the formation of I(2)O, a steady-state species that hydrolyzes to give HOIO and I(2). Inhibition is postulated to result from the formation of the stable ion bis(acetato-O)iodate(I), (CH(3)CO(2))(2)I(-), as buffer concentration is increased. This species is observed spectrophotometrically with a UV absorption shoulder (lambda = 266 nm; epsilon = 530 M(-)(1) cm(-)(1)). The second process is proposed to be a disproportionation of HOIO to give IO(3)(-) and I(2). Above 1 M total buffer, the reaction becomes reversible with less than 90% I(2) formation. Rate and equilibrium constants are resolved and reported for the proposed mechanism.

  6. Palladium-Catalyzed, Copper(I)-Mediated Coupling of Boronic Acids and Benzylthiocyanate. A Cyanide-Free Cyanation of Boronic Acids

    Zhang, Zhihui; Liebeskind, Lanny S.


    A new method for the synthesis of nitriles is described. As a complement to the classic cyanation of aryl halides using cyanide sources and a transition metal catalyst, the palladium-catalyzed cross-coupling of thiocyanates with boronic acids in the presence of copper(I) thiophene-2-carboxylate (CuTC) affords nitriles in good to excellent yields. PMID:16956219

  7. Oxygenase-Catalyzed Desymmetrization of N,N-Dialkyl-piperidine-4-carboxylic Acids**

    Rydzik, Anna M; Leung, Ivanhoe K H; Kochan, Grazyna T; McDonough, Michael A; Claridge, Timothy D W; Schofield, Christopher J


    γ-Butyrobetaine hydroxylase (BBOX) is a 2-oxoglutarate dependent oxygenase that catalyzes the final hydroxylation step in the biosynthesis of carnitine. BBOX was shown to catalyze the oxidative desymmetrization of achiral N,N-dialkyl piperidine-4-carboxylates to give products with two or three stereogenic centers. PMID:25164544

  8. Lewis acid promoted ruthenium(II)-catalyzed etherifications by selective hydrogenation of carboxylic acids/esters.

    Li, Yuehui; Topf, Christoph; Cui, Xinjiang; Junge, Kathrin; Beller, Matthias


    Ethers are of fundamental importance in organic chemistry and they are an integral part of valuable flavors, fragrances, and numerous bioactive compounds. In general, the reduction of esters constitutes the most straightforward preparation of ethers. Unfortunately, this transformation requires large amounts of metal hydrides. Presented herein is a bifunctional catalyst system, consisting of Ru/phosphine complex and aluminum triflate, which allows selective synthesis of ethers by hydrogenation of esters or carboxylic acids. Different lactones were reduced in good yields to the desired products. Even challenging aromatic and aliphatic esters were reduced to the desired products. Notably, the in situ formed catalyst can be reused several times without any significant loss of activity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Drosophila melanogaster CYP6A8, an insect P450 that catalyzes lauric acid (omega-1)-hydroxylation.

    Helvig, Christian; Tijet, Nathalie; Feyereisen, René; Walker, F Ann; Restifo, Linda L


    Only a handful of P450 genes have been functionally characterized from the approximately 90 recently identified in the genome of Drosophila melanogaster. Cyp6a8 encodes a 506-amino acid protein with 53.6% amino acid identity with CYP6A2. CYP6A2 has been shown to catalyze the metabolism of several insecticides including aldrin and heptachlor. CYP6A8 is expressed at many developmental stages as well as in adult life. CYP6A8 was produced in Saccharomyces cerevisiae and enzymatically characterized after catalytic activity was reconstituted with D. melanogaster P450 reductase and NADPH. Although several saturated or non-saturated fatty acids were not metabolized by CYP6A8, lauric acid (C12:0), a short-chain unsaturated fatty acid, was oxidized by CYP6A8 to produce 11-hydroxylauric acid with an apparent V(max) of 25 nmol/min/nmol P450. This is the first report showing that a member of the CYP6 family catalyzes the hydroxylation of lauric acid. Our data open new prospects for the CYP6 P450 enzymes, which could be involved in important physiological functions through fatty acid metabolism.

  10. Oligomerization of 10,16-Dihydroxyhexadecanoic Acid and Methyl 10,16-Dihydroxyhexadecanoate Catalyzed by Lipases

    Daniel Arrieta-Baez


    Full Text Available The main monomer of tomato cuticle, 10,16-dihydroxyhexadecanoic acid (10,16-DHPA and its methyl ester derivative (methyl-10,16-dihydroxyhexadecanote; methyl-10,16-DHHD, were used to study their oligomerization reactions catalyzed by five lipases: Candida antarctica lipase B (CAL-B, Rhizomucor miehei lipase (RM, Thermomyces lanuginosus lipase (TL, Pseudomonas cepacia lipase (PCL and porcine pancreatic lipase (PPL. For 10,16-DHPA, optimum yields were obtained at 60 °C using toluene and 2-methyl-2-butanol (2M2B as solvent, while for methyl-10,16-DHHD the bests yields were obtained in toluene and acetonitrile. Both reactions leaded to linear polyesters according to the NMR and FT-IR analysis, and there was no data indicating the presence of branched polymers. Using optimized conditions, poly(10,16-DHPA and poly(methyl-10,16-DHHD with Mw = 814 and Mn = 1,206 Da, and Mw = 982 and Mn = 860 Da, respectively, were formed according to their MALDI-TOF MS and ESI-MS data. The self-assembly of the polyesters obtained were analyzed by AFM.

  11. Synthesis of deuterium-labeled imipramine using acid-catalyzed exchange reaction

    Baba, S.; Furuta, T.; Sasaki, Y.; Kasuya, Y. (Tokyo Coll. of Pharmacy (Japan))


    Synthesis of three forms of selectively deuterated imipramine with high isotopic purity using acid catalyzed hydrogen-deuterium exchange reaction is described. Deuterated imipramine labeled at the positions of 2,4,6 and 8 (IP-d/sub 4/(I)) was prepared directly by heating imipramine in 10% DC1-D/sub 2/O at 80/sup 0/ for 8hr. Imipramine labeled at all of the eight aromatic positions (IP-d/sub 8/) was synthesized from iminodibenzyl-1,2,3,4,6,7,8,9-d/sub 8/ which was prepared by treating iminodibenzyl (IDB) in 37% DC1-D/sub 2/O at 160/sup 0/ for 24hr. An imipramine labeled at the positions of 1,3,7 and 9 (IP-d/sub 4/(II)) was obtained by ''back-exchange'' of IP-d/sub 8/ under the protio condition according to the exchange procedure of IP-d/sub 4/(I).

  12. Acetic Acid Catalyzed Steam Explosion for Improving the Sugar Recovery of Wheat Straw

    Mengru Liu


    Full Text Available Acetic acid-catalyzed steam explosion pretreatment was applied to wheat straw at temperatures of 190 and 210 °C for 2, 6, and 10 min of residence time. The effects of pretreatment conditions on the total gravimetric recovery, hemicellulose sugars, glucose content, and yield of the enzymatic hydrolysis of cellulose were studied. The results indicated that the total gravimetric recovery decreases while the solubility of hemicellulose and the yield of cellulose enzymatic hydrolysis increase as the pretreatment severity increases. Pretreatment at 190 °C with a 2-min residence time resulted in the highest total gravimetric recovery, 58.9%. The optimum defiberation, glucose content, and enzymatic hydrolysis yields of 70.4 and 79.6%, respectively, occurred following pretreatment at 210 °C with a 10-min residence time. The optimal pretreatment condition was determined to be 190 °C for 10 min. Under the optimum conditions, the recovery yield of all sugars reached 42.7%. This pretreatment resulted in the highest recovery yield of all sugars.

  13. Synthesis of 24-phenyl-24-oxo steroids derived from bile acids by palladium-catalyzed cross coupling with phenylboronic acid. NMR characterization and X-ray structures.

    Mayorquín-Torres, Martha C; Romero-Ávila, Margarita; Flores-Álamo, Marcos; Iglesias-Arteaga, Martin A


    Palladium-catalyzed cross coupling of phenyboronic acid with acetylated bile acids in which the carboxyl functions have been activated by formation of a mixed anhydride with pivalic anhydride afforded moderate to good yield of 24-phenyl-24-oxo-steroids. Unambiguous assignments of the NMR signals were made with the aid of combined 1D and 2D NMR techniques. X-ray diffraction studies confirmed the obtained structures.

  14. Stereoselective Alkane Oxidation with meta-Chloroperoxybenzoic Acid (MCPBA) Catalyzed by Organometallic Cobalt Complexes.

    Shul'pin, Georgiy B; Loginov, Dmitriy A; Shul'pina, Lidia S; Ikonnikov, Nikolay S; Idrisov, Vladislav O; Vinogradov, Mikhail M; Osipov, Sergey N; Nelyubina, Yulia V; Tyubaeva, Polina M


    Cobalt pi-complexes, previously described in the literature and specially synthesized and characterized in this work, were used as catalysts in homogeneous oxidation of organic compounds with peroxides. These complexes contain pi-butadienyl and pi-cyclopentadienyl ligands: [(tetramethylcyclobutadiene)(benzene)cobalt] hexafluorophosphate, [(C₄Me₄)Co(C₆H₆)]PF₆ (1); diiodo(carbonyl)(pentamethylcyclopentadienyl)cobalt, Cp*Co(CO)I₂ (2); diiodo(carbonyl)(cyclopentadienyl)cobalt, CpCo(CO)I₂ (3); (tetramethylcyclobutadiene)(dicarbonyl)(iodo)cobalt, (C₄Me₄)Co(CO)₂I (4); [(tetramethylcyclobutadiene)(acetonitrile)(2,2'-bipyridyl)cobalt] hexafluorophosphate, [(C₄Me₄)Co(bipy)(MeCN)]PF₆ (5); bis[dicarbonyl(B-cyclohexylborole)]cobalt, [(C₄H₄BCy)Co(CO)₂]₂ (6); [(pentamethylcyclopentadienyl)(iodo)(1,10-phenanthroline)cobalt] hexafluorophosphate, [Cp*Co(phen)I]PF₆ (7); diiodo(cyclopentadienyl)cobalt, [CpCoI₂]₂ (8); [(cyclopentadienyl)(iodo)(2,2'-bipyridyl)cobalt] hexafluorophosphate, [CpCo(bipy)I]PF₆ (9); and [(pentamethylcyclopentadienyl)(iodo)(2,2'-bipyridyl)cobalt] hexafluorophosphate, [Cp*Co(bipy)I]PF₆ (10). Complexes 1 and 2 catalyze very efficient and stereoselective oxygenation of tertiary C-H bonds in isomeric dimethylcyclohexanes with MCBA: cyclohexanols are produced in 39 and 53% yields and with the trans/cis ratio (of isomers with mutual trans- or cis-configuration of two methyl groups) 0.05 and 0.06, respectively. Addition of nitric acid as co-catalyst dramatically enhances both the yield of oxygenates and stereoselectivity parameter. In contrast to compounds 1 and 2, complexes 9 and 10 turned out to be very poor catalysts (the yields of oxygenates in the reaction with cis-1,2-dimethylcyclohexane were only 5%-7% and trans/cis ratio 0.8 indicated that the oxidation is not stereoselective). The chromatograms of the reaction mixture obtained before and after reduction with PPh₃ are very similar, which testifies that alkyl

  15. Kinetically controlled synthesis of monoglyceryl esters from chiral and prochiral acids methyl esters catalyzed by immobilized Rhizomucor miehei lipase.

    Acosta, Andreina; Filice, Marco; Fernandez-Lorente, Gloria; Palomo, Jose M; Guisan, Jose M


    Partial acylation of only one primary hydroxyl group of glycerol generates a chiral center at position 2. Rhizomucor miehei lipase (RML) catalyzes the kinetically controlled transesterification of different aromatic carboxylic acids methyl esters with glycerol. High synthetic yields of glyceryl esters (around 70-80%) were obtained even in the presence of significant concentrations of water (from 5% to 20%). After a long incubation of the reaction mixture in the presence of the biocatalyst only pure free acid was obtained. Other lipases (from Geobacillus thermocatenulatus and from Thermomyces lanuginose) also catalyzed similar kinetically controlled transesterifications although less efficiently. RML immobilized on Sepharose-Q showed a high activity and specificity, compared to the immobilization by other techniques, only producing monoglyceryl esters with all substrates. In particular, monoglyceryl-phenylmalonate product was synthesized in 82% overall yield and >99% diastereomeric excess at pH 7.0 and 37°C and 90% glycerol.

  16. Stereocontrol in proline-catalyzed asymmetric amination: a comparative assessment of the role of enamine carboxylic acid and enamine carboxylate.

    Sharma, Akhilesh K; Sunoj, Raghavan B


    The transition state models in two mechanistically distinct pathways, involving (i) an enamine carboxylic acid (path-A, 4) and (ii) an enamine carboxylate (path-B, 8), in the proline-catalyzed asymmetric α-amination have been examined using DFT methods. The path-A predicts the correct product stereochemistry under base-free conditions while path-B accounts for reversal of configuration in the presence of a base.

  17. Preparation of (Z)-α,β-disubstituted enamides via palladium-catalyzed addition of boronic acids to ynamides.

    Yang, Yuanfa; Wang, Lina; Zhang, Fang; Zhu, Gangguo


    A Pd-catalyzed, highly regio- and stereoselective addition of boronic acids to ynamides has been realized. This protocol generates (Z)-α,β-disubstituted enamides in high yields with excellent regio- and stereoselectivity under the mild reaction conditions, thereby providing a good complementary method for the diverse synthesis of multifunctional enamides. A wide collection of functional groups are found to be tolerated. It represents a straightforward and useful means to assemble stereodefined enamides from readily available starting materials.

  18. High efficient acetalization of carbonyl compounds with diols catalyzed by novel carbon-based solid strong acid catalyst


    The novel carbon-based acid catalyst has been applied to catalyzing the acetalization and ketalization. The results showed that the catalyst was very efficient with the average yield over 93%. The novel heterogeneous catalyst has the advantages of high activity, wide applicability even to 7-membered ring acetals, strikingly simple workup procedure, non-pollution, and reusability, which will contribute to the green process greatly.

  19. DFT Mechanistic Study of Rh(III)-Catalyzed [3 + 2]/[5 + 2] Annulation of 4-Aryl-1,2,3-triazoles and Alkynes Unveils the Dual C-H Activation Strategy.

    Zhang, Zhongchao; Yang, Shengwen; Li, Juan; Liao, Xiaojian


    Li and co-workers recently developed a dual C-H bond activation strategy, using a Rh(III) catalyst, for [3 + 2]/[5 + 2] annulation of primary 4-aryl-1,2,3-triazoles and alkynes. The Rh(III)-catalyzed dual annulation of 4-aryl-1,2,3-triazoles and alkynes is challenging because only single annulation is achieved using Rh(II) and Ni(0) catalysts. Intrigued by the novel strategy, we performed a density functional theory study to unravel this challenging dual C-H bond activation. A Friedel-Crafts type mechanism proved be more favorable than a concerted metalation-deprotonation (CMD) mechanism for the first C-H bond activation. The second C-H bond activation proceeded via a CMD mechanism. More importantly, the calculation explained why only AgSbF6, among several candidates, performed perfectly, whereas others failed, and why the dual annulation of 4-aryl-1,2,3-triazoles with alkynes was achieved with a Rh(III) catalyst but not with Rh(II) and Ni(0) catalysts. Due to the active catalyst being [Cp*Rh(OAc)](+), AgSbF6, in which SbF6(-) is a stable anion, among several candidates performed perfectly. The success of the Rh(III)-catalyzed dual C-H bond activation has two origins: (i) the active catalyst [Cp*Rh(OAc)](+) is more stable than Cp*Rh(OAc)2 when the Ag salt is AgSbF6, and this facilitates the first alkyne insertion; and (ii) a rhodium-carbene is easily formed.

  20. Recent Progress in Metal-Catalyzed Reactions of 2(5H)-Furanones%金属催化的2(5H)-呋喃酮反应研究进展

    毛超旭; 汪朝阳; 谭越河; 薛福玲


    2(5H)-呋喃酮结构单元广泛存在于天然产物中,同时许多2(5H)-呋喃酮类化合物也是重要的有机合成中间体.因此,基于常见2(5H)-呋喃酮的有机合成研究近年来引起了人们的关注,尤其是金属催化的2(5H)-呋喃酮反应的地位日趋彰显重要,从而成为众多化学工作者的研究热点.按照反应类型的不同,对近年来金属催化的2(5H)-呋喃酮反应的研究进展进行了综述,主要包括Sonogashira,Suzuki,Stille等偶联反应,以及Michael加成反应、Friedel-Crafts烷基化反应、Baylis-Hillman反应、亲核取代反应、还原反应等.%The unique carbon skeleton of 2(5H)-furanone is widely present in a variety of natural products, and many compounds containing 2(5H)-furanone skeleton are important synthetic intermediates. Recently, more and more attentions have been attracted to the organic synthesis based on 2(5H)-furanones, especially via the metal-catalyzed reactions of 2(5H)-furanones. Classified as different types, the recent progress in metal-catalyzed reactions of 2(5H)-furanones, mainly including Sonogashira reaction, Suzuki reaction, Stille reaction, Michael addition, Friedel-Crafts alkylation, Baylis-Hillman reaction, nucleophilic substitution, and reduction reaction, is reviewed in this paper.

  1. Synthesis, characterization and adsorption properties of diethylenetriamine-modified hypercrosslinked resins for efficient removal of salicylic acid from aqueous solution.

    Huang, Jianhan; Jin, Xiaoying; Mao, Jinglin; Yuan, Bin; Deng, Rujie; Deng, Shuguang


    We report an effective approach for tailoring the pore textural properties and surface polarity of a hypercrosslinked resin to enhance its adsorption capacity and selectivity for removing salicylic acid from aqueous solution. Four hypercrosslinked resins were synthesized by controlling the reaction time of the self Friedel-Crafts reaction of chloromethylated polystyrene-co-divinylbenzene, and then modified with diethylenetriamine to adjust their surface polarity. The resins were characterized with N(2) adsorption for pore textural properties, Fourier transform infrared spectroscopy (FT-IR) for surface functional groups, chemical analysis for residual chlorine content and weak basic exchange capacity. Adsorption equilibrium, kinetics and breakthrough performance were determined for the removal of salicylic acid from aqueous solution on a selected resin HJ-M01. The equilibrium adsorption capacity of salicylic acid on HJ-M01 is significantly higher than that on its precursor HJ-11 and a few commercial adsorbents including AB-8, XAD-4 and XAD-7. The dynamic adsorption capacity of salicylic acid on HJ-M01 was found to be 456.4 mg/L at a feed concentration of 1000 mg/L and 294 K. The used resin could be fully regenerated with 1% sodium hydroxide solution. The hypercrosslinked resins being developed were promising alternatives to commercial adsorbents for removing salicylic acid and other volatile organic compounds (VOCs) from aqueous solution.

  2. The Formation of Pyrroline and Tetrahydropyridine Rings in Amino Acids Catalyzed by Pyrrolysine Synthase (PylD)

    Quitterer, Felix


    The dehydrogenase PylD catalyzes the ultimate step of the pyrrolysine pathway by converting the isopeptide L-lysine-Nε-3R-methyl-D-ornithine to the 22nd proteinogenic amino acid. In this study, we demonstrate how PylD can be harnessed to oxidize various isopeptides to novel amino acids by combining chemical synthesis with enzyme kinetics and X-ray crystallography. The data enable a detailed description of the PylD reaction trajectory for the biosynthesis of pyrroline and tetrahydropyridine rings as constituents of pyrrolysine analogues. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Preparation of highly conjugated water-dispersible graphene-butyric acid for the enhancement of electron transfer within polyamic acid-benzoxazole: potential applications in electrochemical sensing.

    Chen, Hsiao-Chien; Chen, Yen-Hsuan; Chen, Shi-Liang; Chern, Yaw-Terng; Tsai, Rung-Ywan; Hua, Mu-Yi


    To break through the long time and complex procedures for the preparation of highly conjugated reduced graphene oxide (r-GO) in developing electrochemical sensor, a time-saving and simple method is investigated in this study. One novel step of the exfoliated accompanying carboxylated graphene sheet from pristine is achieved via Friedel-Crafts acylation. By electrophilic aromatic substitution, the succinic anhydride ring is opened and attaches covalently to the graphene sheet (Gs) to form exfoliated graphene with grafted 1-one-butyric acid (Gs-BA). The grafting chain converts anions in aqueous solution to maintain Gs-BA in a stable dispersion and noticeably decreases the π-π stacking of the exfoliated Gs during the drying process. The analytical results of the absorption spectroscopy demonstrate that the conjugation of Gs-BA is not significantly destroyed by this chemical modification; Gs-BA retains the Gs electrical properties favorable for developing electrochemical sensors. When polyamic acid-benzoxazole (PAA-BO), a hydrogen peroxide (H₂O₂)-sensitive probe, hybridizes with Gs-BA to form Gs-BA-PAA-BO, the electron transfer rate relating to the response time improves markedly from 1.09 s(-1) to 38.8 s(-1). Additionally, it offers a high performance for H₂O₂ sensing in terms of sensitivity and response time, making this method applicable for developing glucose and choline biosensors.

  4. Studies of Grafted and Sulfonated Spiro Poly(isatin-ethersulfone Membranes by Super Acid-Catalyzed Reaction

    Lei Jin


    Full Text Available Spiro poly(isatin-ethersulfone polymers were prepared from isatin and bis-2,6-dimethylphenoxyphenylsulfone by super acid catalyzed polyhydroxyalkylation reactions. We designed and synthesized bis-2,6-dimethylphenoxyphenylsulfone, which is structured at the meta position steric hindrance by two methyl groups, because this structure minimized crosslinking reaction during super acid catalyzed polymerization. In addition, sulfonic acid groups were structured in both side chains and main chains to form better polymer chain morphology and improve proton conductivity. The sulfonation reactions were performed in two steps which are: in 3-bromo-1-propanesulfonic acid potassium salt and in con. sulfuric acid. The membrane morphology was studied by tapping mode atomic force microscope (AFM. The phase difference between the hydrophobic polymer main chain and hydrophilic sulfonated units of the polymer was shown to be the reasonable result of the well phase separated structure. The correlations of proton conductivity, ion exchange capacity (IEC and single cell performance were clearly described with the membrane morphology.

  5. A two-step acid-catalyzed process for the production of biodiesel from rice bran oil

    Zullaikah, S.; Lai, Chao Chin; Vali, S.R.; Ju, Yi Hsu [National Taiwan Univ. of Science and Technology, Taipei (China). Dept. of Chemical Engineering


    A study was undertaken to examine the effect of temperature, moisture and storage time on the accumulation of free fatty acid in the rice bran. Rice bran stored at room temperature showed that most triacylglyceride was hydrolyzed and free fatty acid (FFA) content was raised up to 76% in six months. A two-step acid-catalyzed methanolysis process was employed for the efficient conversion of rice bran oil into fatty acid methyl ester (FAME). The first step was carried out at 60 {sup o}C. Depending on the initial FFA content of oil, 55-90% FAME content in the reaction product was obtained. More than 98% FFA and less than 35% of TG were reacted in 2 h. The organic phase of the first step reaction product was used as the substrate for a second acid-catalyzed methanolysis at 100 {sup o}C. By this two-step methanolysis reaction, more than 98% FAME in the product can be obtained in less than 8 h. Distillation of reaction product gave 99.8% FAME (biodiesel) with recovery of more than 96%. The residue contains enriched nutraceuticals such as {gamma}-oryzanol (16-18%), mixture of phytosterol, tocol and steryl ester (19-21%). (author)

  6. Production of high-oleic acid tallow fractions using lipase-catalyzed directed interesterification, using both batch and continuous processing.

    MacKenzie; Stevenson


    Immobilized lipases were used to catalyze batch-directed interesterification of tallow, resulting in oleins containing significantly higher levels of unsaturated fatty acids than obtained by fractionation without lipase. After 14 days, a reaction catalyzed by 2% Novozym 435 yielded 57% olein unsaturation, compared with 45% in a no-enzyme control. Free fatty acid levels increased to 2-3% during reactions. Incubation of the enzyme in multiple batches of melted fat caused a gradual loss of interesterification activity, apparently due to progressive dehydration. The activity could be restored by addition of water to the reaction medium. Immobilized lipase was also used to catalyze directed interesterification in a continuous flow reactor. Melted tallow was circulated through a packed bed enzyme reactor and a separate crystallization vessel. The temperatures of the two parts of the apparatus were controlled separately to allow crystallization to occur separately from interesterification. Operation of the reactor with conventionally dry, prefractionated tallow allowed the formation of an olein consisting of up to 60% unsaturated fatty acids. The greatest changes in olein fatty acid composition were achieved when the fractionation temperature was kept constant at a value that promoted selective crystallization of trisaturated triglycerides that were continuously produced by enzymic interesterification. The enzyme could be reused without apparent loss of activity, and its activity was apparently enhanced by preincubation in melted tallow for up to several days. Control of both the water activity of the enzyme and tallow feedstock and of the absorption of atmospheric water vapor were required to maintain enzyme activity, during multiple reuse and minimize free fatty acid formation. This method may form the basis for a process to produce highly mono-unsaturated tallow fractions for use in food applications (e.g. frying) where a "healthy" low saturated fat product is required.

  7. Application of palladium-catalyzed carboxyl anhydride-boronic acid cross coupling in the synthesis of novel bile acids analogs with modified side chains.

    Mayorquín-Torres, Martha C; Flores-Álamo, Marcos; Iglesias-Arteaga, Martin A


    Palladium-catalyzed cross coupling of 4-methoxycarbonyl phenyboronic acid with acetylated bile acids in which the carboxyl functions was activated by formation of a mixed anhydride with pivalic anhydride afforded the cross coupled compounds, which were converted in novel side chain modified bile acids by one pot carbonyl reduction/removal of the protecting acetyl groups by Wolff-Kishner reduction. Unambiguous assignments of the NMR signals and crystal characterization of the heretofore unknown compounds are provided. Copyright © 2015 Elsevier Inc. All rights reserved.

  8. In situ detection of denitrifying bacteria by mRNA-targeted nucleic acid probes and catalyzed reporter deposition

    Kofoed, Michael Vedel; Stief, Peter; Poulsen, Morten

    In situ detection of denitrifying bacteria by mRNA-targeted nucleic acid probes and catalyzed reporter deposition   Michael V.W. Kofoed, Peter Stief, Morten Poulsen, and Andreas Schramm Department of Biological Sciences, Microbiology, University of Aarhus, Denmark Denitrification, the sequential...... reduction of nitrate to dinitrogen gas, is essential for the removal of fixed nitrogen from natural and engineered ecosystems. However, community structure and activity dynamics of denitrifying bacteria in most systems are poorly understood, partially due to difficulties in identifying and quantifying...... and catalyzed fluorescent reporter deposition (CARD-FISH). The general feasibility of the approach was first tested with pure cultures of Pseudomonas stutzeri and various denitrifying and nitrate-reducing isolates. Detailed studies of probe specificity and hybridization conditions using Clone-FISH of nar...

  9. Palladium(II-catalyzed Heck reaction of aryl halides and arylboronic acids with olefins under mild conditions

    Tanveer Mahamadali Shaikh


    Full Text Available A series of general and selective Pd(II-catalyzed Heck reactions were investigated under mild reaction conditions. The first protocol has been developed employing an imidazole-based secondary phosphine oxide (SPO ligated palladium complex (6 as a precatalyst. The catalytic coupling of aryl halides and olefins led to the formation of the corresponding coupled products in excellent yields. A variety of substrates, both electron-rich and electron-poor olefins, were converted smoothly to the targeted products in high yields. Compared with the existing approaches employing SPO–Pd complexes in a Heck reaction, the current strategy features mild reaction conditions and broad substrate scope. Furthermore, we described the coupling of arylboronic acids with olefins, which were catalyzed by Pd(OAc2 and employed N-bromosuccinimide as an additive under ambient conditions. The resulted biaryls have been obtained in moderate to good yields.

  10. Microwave-assisted chemoselective copper-catalyzed amination of o-chloro and o-bromobenzoic acids using aromatic amines under solvent free conditions

    Yaghoub Sarrafi; Manijeh Mohadeszadeh; Kamal Alimohammadi


    Copper-catalyzed synthesis of N-aryl anthranilic acid derivatives using effective amination of 2-chloro and 2-bromobenzoic acid under microwave irradiation is reported. Some of the advantages of this method axe high chemoselectivity, short reaction times, ease of work up procedure and elimination of the need for acid protection.

  11. Lipase-catalyzed acidolysis of canola oil with caprylic acid to produce medium-, long- and medium-chain-type structured lipids

    Wang, Yingyao; Xia, Luan; Xu, Xuebing


    Lipase-catalyzed acidolysis of canola oil with caprylic acid was performed to produce structured lipids (SLs) containing medium-chain fatty acid (M) at position sn-1,3 and long-chain fatty acid (L) at the sn-2 position in a solvent-free system. Six commercial lipases from different sources were s...

  12. Pd-catalyzed ethylene methoxycarbonylation with Brønsted acid ionic liquids as promoter and phase-separable reaction media

    Garcia-Suarez, Eduardo J.; Khokarale, Santosh Govind; Nguyen van Buu, Olivier;


    Brønsted acid ionic liquids (BAILs) were prepared and applied as combined acid promoters and reaction media in Pd–phosphine catalyzed methoxycarbonylation of ethylene to produce methyl propionate. The BAILs served as alternatives to common mineral acids required for the reaction, e.g. methanesulf...

  13. Practical synthesis of enantiomerically pure beta2-amino acids via proline-catalyzed diastereoselective aminomethylation of aldehydes.

    Chi, Yonggui; English, Emily P; Pomerantz, William C; Horne, W Seth; Joyce, Leo A; Alexander, Lane R; Fleming, William S; Hopkins, Elizabeth A; Gellman, Samuel H


    Proline-catalyzed diastereoselective aminomethylation of aldehydes using a chiral iminium ion, generated from a readily prepared precursor, provides alpha-substituted-beta-amino aldehydes with 85:15 to 90:10 dr. The alpha-substituted-beta-amino aldehydes can be reduced to beta-substituted-gamma-amino alcohols, the major diastereomer of which can be isolated via crystallization or column chromatography. The amino alcohols are efficiently transformed to protected beta2-amino acids, which are valuable building blocks for beta-peptides, natural products, and other interesting molecules. Because conditions for the aminomethylation and subsequent reactions are mild, beta2-amino acid derivatives with protected functional groups in the side chain, such as beta2-homoglutamic acid, beta2-homotyrosine, and beta2-homolysine, can be prepared in this way. The synthetic route is short, and purifications are simple; therefore, this method enables the preparation of protected beta2-amino acids in useful quantities.

  14. Microwave-Assisted Synthesis of Chiral β-Amino Acids%微波辅助法合成手性β-氨基酸

    刘发明; 冯柏年


    手性β-氨基酸是一类在药物开发和生物研究中具有广泛应用的中间体,尝试了以L-天冬氨酸为手性源合成手性β-氨基酸的研究,其合成方法:首先对天冬氨酸进行氨基保护,然后利用微波,高效地合成( S)-N-保护的丝氨酸-γ-内酯,最后通过傅克反应,合成具有芳香性的手性β氨基酸。具有路线短、操作方便、绿色经济等优点,适合工业化大生产。%Chiral β-amino acids were intermediates , having a wide range of applications in biological research and drug development.Trying to use L-aspartic acid as chiral pool to synthesis β-amino acids , the synthesis method was that protecting the amino group of aspartic acid , then the microwave efficiently synthesized ( S ) -N -protected homoserine γ-lactone , and aromatic chiral βamino acids through Friedel -Crafts reaction was obtained , which had the characteristics of a line short , easy to operate , green economy , suitable for industrial production , etc.

  15. Lewis Acid Catalyzed Ring-opening Polymerization of Epoxidized Soybean Oil in Liquid Carbon Dioxide

    Ring-opening polymerization of epoxidized soybean oil (ESO) catalyzed by boron trifluoride diethyl etherate (BF3•OEt2), in liquid carbon dioxide, was conducted in an effort to develop useful biobased biodegradable polymers. The resulting polymers (RPESO) were characterized by FTIR spectroscopy, diff...

  16. Influence of organic acids on oscillations and waves in the ferroin-catalyzed Belousov-Zhabotinsky reaction

    Krüger, Frank; Nagy-Ungvárai, Zsuzsanna; Müller, Stefan C.

    Experiments of the influence of mesoxalic and tartronic acid on the oscillatory behavior and on the spiral tip motion in a ferroin-catalyzed Belousov-Zhabotinsky (BZ) solution are reported. The oscillations were observed in batch and CSTR systems, and for the investigations of the spiral tip motion an open gel reactor was used. A characteristic shoulder in the oscillations is associated with an additional Br - production phase. The chemical parameters for a transition from a hypocycloidal to a circular tip trajectory are found. The findings are compared with the temporal and spatial dynamic behavior, occurring during the ageing process of the solution.

  17. Palladium-Catalyzed 1,3-Difunctionalization Using Terminal Alkenes with Alkenyl Nonaflates and Aryl Boronic Acids.

    McCammant, Matthew S; Shigeta, Takashi; Sigman, Matthew S


    A Pd-catalyzed 1,3-difunctionalization of terminal alkenes using 1,1-disubstituted alkenyl nonaflates and arylboronic acid coupling partners is reported. This transformation affords allylic arene products that are difficult to selectively access using traditional Heck cross-coupling methodologies. The evaluation of seldom employed 1,1-disubstituted alkenyl nonaflate coupling partners led to the elucidation of subtle mechanistic features of π-allyl stabilized Pd-intermediates. Good stereo- and regioselectivity for the formation of 1,3-addition products can be accessed through a minimization of steric interactions that emanate from alkenyl nonaflate substitution.

  18. High fluorescence emission of carboxylic acid functionalized polystyrene/BaTiO{sub 3} nanocomposites and rare earth metal complexes: Preparation and characterization

    Cao, X. T.; Showkat, A. M.; Wang, Z.; Lim, K. T., E-mail: [Department of Imaging System Engineering, Pukyong National University, Busan 608-737 (Korea, Republic of)


    Noble fluorescence nanocomposite compound based on barium titanate nanoparticles (BTO), polystyrene (PSt), and terbium ion (Tb{sup 3+}) was synthesized by a combination of surface-initiated reversible addition-fragmentation chain transfer (RAFT) polymerization, Friedel-Crafts alkylation reaction and coordinate chemistry. Initially, a modification of surface of BTO was conducted by an exchange process with S-benzyl S’-trimethoxysilylpropyltrithiocarbonate to create macro-initiator for polymerization of styrene. Subsequently, aryl carboxylic acid functionalized polystyrene grafted barium titanate (BTO-g-PSt-COOH) was generated by substitution reaction between 4-(Chloromethyl) benzoic acid and PSt chains. The coordination of the nanohybrids with Tb{sup 3+} ions afforded fluorescent Tb{sup 3+} tagged aryl carboxylic acid functionalized polystyrene grafted barium titanate (BTO-g-PSt-Tb{sup 3+}) complexes. Structure, morphology, and fluorescence properties of nanohybrid complexes were investigated by respective physical and spectral studies. FT-IR and SEM analyses confirmed the formation of BTO-g-PSt-Tb{sup 3+}nanohybrids. Furthermore, TGA profiles demonstrated the grafting of aryl carboxylic acid functionalized polystyrene on BTO surface. Optical properties of BTO-g-PSt-Tb{sup 3+} complexes were investigated by fluorescence spectroscopy.

  19. β-Amino acid catalyzed asymmetric Michael additions: design of organocatalysts with catalytic acid/base dyad inspired by serine proteases.

    Yang, Hui; Wong, Ming Wah


    A new type of chiral β-amino acid catalyst has been computationally designed, mimicking the enzyme catalysis of serine proteases. Our catalyst approach is based on the bioinspired catalytic acid/base dyad, namely, a carboxyl and imidazole pair. DFT calculations predict that this designed organocatalyst catalyzes Michael additions of aldehydes to nitroalkenes with excellent enantioselectivities and remarkably high anti diastereoselectivities. The unusual stacked geometry of the enamine intermediate, hydrogen bonding network, and the adoption of an exo transition state are the keys to understand the stereoselectivity.

  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. {beta}-Secondary and solvent deuterium kinetic isotope effects and the mechanisms of base- and acid-catalyzed hydrolysis of penicillanic acid

    Deraniyagala, S.A.; Adediran, S.A.; Pratt, R.F. [Wesleyan Univ., Middletown, CT (United States)


    {beta}-Secondary and solvent deuterium kinetic isotope effects have been determined at 25 {degrees}C for the alkaline and acid-catalyzed hydrolysis of penicillanic acid. In order to determine the former isotope effect, [6,6-{sup 2}H{sub 2}]dideuteriopenicillanic acid has been synthesized. In alkaline solution, the former isotope effect was found to be 0.95 {plus_minus} 0.01. These values support the B{sub AC}2 mechanism of hydrolysis with rate-determining formation of the tetrahedral intermediate that has been proposed for other {beta}-lactams. The measured {beta}-secondary kinetic isotope for the acid-catalyzed reaction was 1.00 {plus_minus} 0.01. The data indicates that a likely pathway of acid-catalyzed hydrolysis would be that of an A{sub AC}1 mechanism with an intermediate acylium ion. If this were so, the calculated {beta}-secondary isotope effect per hydrogen coplanar with the breaking C-N bond and corrected for the inductive effect of deuterium would be 1.06 {plus_minus} 0.01. This suggests an early A{sub AC}1 transition state, which would be reasonable in this case because of destabilization of the N-protonated amide with respect to the acylium ion because of ring strain. The absence of specific participation by solvent in the transition state, as would be expected of an A{sub AC}1 but not an associative mechanism, is supported by the strongly inverse solvent deuterium kinetic isotope effect of 0.25 {plus_minus} 0.00 in 1 M HCl and 0.22 {plus_minus} 0.01 in 33.3 wt % H{sub 2}SO{sub 4}. 1 fig., 3 tabs.

  2. Synthesis of a stable selenoaldehyde by self-catalyzed thermal dehydration of a primary-alkyl-substituted selenenic acid.

    Sase, Shohei; Kakimoto, Ryo; Goto, Kei


    The unprecedented dehydration of a selenenic acid (RCH2SeOH) to a selenoaldehyde (RCH=Se) has been demonstrated. A primary-alkyl-substituted selenenic acid was synthesized for the first time by taking advantage of a bulky cavity-shaped substituent. Upon heating in solution, the selenenic acid underwent thermal dehydration to produce a stable selenoaldehyde, which was isolated as stable crystals and crystallographically characterized. Investigation of the reaction mechanism revealed that this β dehydration reaction involves two processes, both of which reflect the characteristics of a selenenic acid: 1) dehydrative condensation of two molecules of selenenic acid to generate a selenoseleninate intermediate [RCH2SeSe(O)CH2R], an isomer of a selenenic anhydride, and 2) subsequent β elimination of the selenenic acid from this intermediate to form a C=Se double bond, which establishes the self-catalyzed β dehydration of the selenenic acid. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. [Analysis of fatty acids in Gmnocypris przewalskii oil by gas chromatography/mass spectrometry with base-catalyzed transesterification].

    Bo, Haibo; Wang, Xia; Zhai, Zongde; Li, Yongmin; Chen, Liren


    The composition of fatty acids (FA) in Gymnocypris przewalskii oil was identified and quantified by gas chromatography (GC)/electron impact (EI) mass spectrometry (MS). A base-catalyzed transesterification method was used to convert fatty acids to methyl esters. The lipids were extracted using petroleum ether and the total lipids in dried meat and skin of Gymnocypris przewalskii were about 25%. Forty-seven fatty acids were identified in the current study. Main types of fatty acids found in the oils were normal saturated, mono-branched, multi-branched, cyclopropane, furanoid, normal monounsaturated and polyunsaturated fatty acids. Saturated fatty acids were approximately 25. 7% of the total, and the main components were C(14:0) (3.4%), C(16:0) (19.4%) and C(18:0) (1.1%). Unsaturated fatty acids were totally 73.6%, and the major components of monounsaturated fatty acids were C(16:1 (9)) (19.8%), C(18:1) (9)) (18. 6%) and C(18:1 (11)) (7.3%); polyunsaturated fatty acids were mainly composed of C(18:2 (9,12)) (4.8%), C(18:3 (9, 12, 15)) (3.1%), C(20:4 (5, 8, 1, 14)) (1.2%), C(20:5 (5, 8, 11, 14, 17)) (EPA, 9.4%) and C(22:6 (4, 7, 10, 13, 16, 19)) (DHA, 6.7%). Especially, furyl-, cyclopropane- and several odd and branched chain fatty acids were found in Gymnocypris przewalskii oil. It is thus an important dietary resource of functional fatty acids.

  4. Characterization of a Cross-Linked Protein-Nucleic Acid Substrate Radical in the Reaction Catalyzed by RlmN

    Silakov, Alexey; Grove, Tyler L.; Radle, Matthew I.; Bauerle, Matthew R.; Green, Michael T.; Rosenzweig, Amy C.; Boal, Amie K.; Booker, Squire J. [NWU; (Penn)


    RlmN and Cfr are methyltransferases/methylsynthases that belong to the radical S-adenosylmethionine superfamily of enzymes. RlmN catalyzes C2 methylation of adenosine 2503 (A2503) of 23S rRNA, while Cfr catalyzes C8 methylation of the exact same nucleotide, and will subsequently catalyze C2 methylation if the site is unmethylated. A key feature of the unusual mechanisms of catalysis proposed for these enzymes is the attack of a methylene radical, derived from a methylcysteine residue, onto the carbon center undergoing methylation to generate a paramagnetic protein–nucleic acid cross-linked species. This species has been thoroughly characterized during Cfr-dependent C8 methylation, but does not accumulate to detectible levels in RlmN-dependent C2 methylation. Herein, we show that inactive C118S/A variants of RlmN accumulate a substrate-derived paramagnetic species. Characterization of this species by electron paramagnetic resonance spectroscopy in concert with strategic isotopic labeling shows that the radical is delocalized throughout the adenine ring of A2503, although predominant spin density is on N1 and N3. Moreover, 13C hyperfine interactions between the radical and the methylene carbon of the formerly [methyl-13C]Cys355 residue show that the radical species exists in a covalent cross-link between the protein and the nucleic acid substrate. X-ray structures of RlmN C118A show that, in the presence of SAM, the substitution does not alter the active site structure compared to that of the wild-type enzyme. Together, these findings have new mechanistic implications for the role(s) of C118 and its counterpart in Cfr (C105) in catalysis, and suggest involvement of the residue in resolution of the cross-linked species via a radical mediated process

  5. Improved Synthesis of 5-Substituted 1H-Tetrazoles via the [3+2] Cycloaddition of Nitriles and Sodium Azide Catalyzed by Silica Sulfuric Acid

    Du, Zhenting; Si, Changmei; Li, Youqiang; Wang, Yin; Lu, Jing


    A silica supported sulfuric acid catalyzed [3+2] cycloaddition of nitriles and sodium azide to form 5-substituted 1H-tetrazoles is described. The protocol can provide a series of 5-substituted 1H-tetrazoles using silica sulfuric acid from nitriles and sodium azide in DMF in 72%–95% yield. PMID:22606004

  6. Improved Synthesis of 5-Substituted 1H-Tetrazoles via the [3+2] Cycloaddition of Nitriles and Sodium Azide Catalyzed by Silica Sulfuric Acid

    Jing Lu


    Full Text Available A silica supported sulfuric acid catalyzed [3+2] cycloaddition of nitriles and sodium azide to form 5-substituted 1H-tetrazoles is described. The protocol can provide a series of 5-substituted 1H-tetrazoles using silica sulfuric acid from nitriles and sodium azide in DMF in 72%–95% yield.

  7. N-Substituted Imines by the Copper-Catalyzed N-Imination of Boronic Acids and Organostannanes with O-Acyl Ketoximes

    Liu, Songbai; Yu, Ying; Liebeskind, Lanny S.


    Catalytic quantities of copper (I) or copper (II) sources catalyze the N-imination of boronic acids and organostannanes through reaction with oxime O-carboxylates under non-basic conditions. This method tolerates various functional groups and takes place efficiently using aryl, heteroaryl, and alkenyl boronic acids and stannanes. PMID:17444649

  8. Nafion-assisted cross-linking of sulfonated poly(arylene ether ketone) bearing carboxylic acid groups and their composite membranes for fuel cells

    Lin, Haidan; Zhao, Chengji; Na, Hui [Alan G. MacDiarmid Institute, College of Chemistry, Jilin University, Qianjin street 2699, Changchun 130012, Jilin (China)


    In this study, a new type of cross-linked composite membrane is prepared and considered for its potential applications in direct methanol fuel cell. Nafion and sulfonated poly(arylene ether ketone) bearing carboxylic acid groups (SPAEK-C) are blended and subsequently cross-linked by a Friedel-Craft reaction using the carboxylic acid groups in the SPAEK-C to achieve lower methanol permeability. The perfluoroalkyl sulfonic acid groups of Nafion act as a benign solid catalyst, which assist the cross-linking of SPAEK-C. The physical and chemical characterizations of the cross-linked composite membranes are performed by varying the contents of SPAEK-C. The c-Nafion-15% membrane exhibits appropriate water uptake (10.49-25.22%), low methanol permeability (2.57 x 10{sup -7} cm{sup 2} s{sup -1}), and high proton conductivity (0.179 S cm{sup -1} at 80 C). DSC and FTIR analyze suggest the cross-linking reaction. These results show that the self-cross-linking of SPAEK-C in the Nafion membrane can effectively reduce methanol permeability while maintaining high proton conductivity. (author)

  9. Vascular peroxidase 1 catalyzes the formation of hypohalous acids: characterization of its substrate specificity and enzymatic properties.

    Li, Hong; Cao, Zehong; Zhang, Guogang; Thannickal, Victor J; Cheng, Guangjie


    The heme-containing peroxidase family comprises eight members in humans. The physiological and pathophysiological roles of heme-containing peroxidases are not well understood. Phagocyte-derived myeloperoxidase (MPO) utilizes chloride and bromide, in the presence of hydrogen peroxide (H(2)O(2)), to generate hypochlorous acid and hypobromous acid, potent oxidizing species that are known to kill invading pathogens. Vascular peroxidase 1 (VPO1) is a new member of the heme-containing peroxidase family; VPO1 is highly expressed in the cardiovascular system, lung, liver, pancreas, and spleen. However, functional roles of VPO1 have not been defined. In this report, we demonstrate the capacity for VPO1 to catalyze the formation of hypohalous acids, and characterize its enzymatic properties. VPO1, like MPO but unlike lactoperoxidase, is able to generate hypochlorous acid, hypobromous acid, and hypothiocyanous acid in the presence of H(2)O(2). Under physiological pH and concentrations of halides (100μM KBr, 100μM KSCN, and 100mM NaCl), VPO1 utilizes approximately 45% of H(2)O(2) for the generation of hypobromous acid, 35% for hypothiocyanous acid, and 18% for hypochlorous acid. The specific activity of VPO1 is ∼10- to 70-fold lower than that of MPO, depending on the specific substrate. These studies demonstrate that the enzymatic properties and substrate specificity of VPO1 are similar to MPO; however, significantly lower catalytic rate constants of VPO1 relative to MPO suggest the possibility of other physiologic roles for this novel heme-containing peroxidase.

  10. Palladium-catalyzed difluoroalkylation of aryl boronic acids: a new method for the synthesis of aryldifluoromethylated phosphonates and carboxylic acid derivatives.

    Feng, Zhang; Min, Qiao-Qiao; Xiao, Yu-Lan; Zhang, Bo; Zhang, Xingang


    The palladium-catalyzed difluoroalkylation of aryl boronic acids with bromodifluoromethylphosphonate, bromodifluoroacetate, and further derivatives has been developed. This method provides a facile and useful access to a series of functionalized difluoromethylated arenes (ArCF2 PO(OEt)2 , ArCF2 CO2 Et, and ArCF2 CONR(1) R(2) ) that have important applications in drug discovery and development. Preliminary mechanistic studies reveal that a single electron transfer (SET) pathway may be involved in the catalytic cycle. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Determination of DNA adducts by combining acid-catalyzed hydrolysis and chromatographic analysis of the carcinogen-modified nucleobases.

    Leung, Elvis M K; Deng, Kailin; Wong, Tin-Yan; Chan, Wan


    The commonly used method of analyzing carcinogen-induced DNA adducts involves the hydrolysis of carcinogen-modified DNA samples by using a mixture of enzymes, followed by (32)P-postlabeling or liquid chromatography (LC)-based analyses of carcinogen-modified mononucleotides/nucleosides. In the present study, we report the development and application of a new approach to DNA adduct analysis by combining the H(+)/heat-catalyzed release of carcinogen-modified nucleobases and the use of LC-based methods to analyze DNA adducts. Results showed that heating the carcinogen-modified DNA samples at 70 °C for an extended period of 4 to 6 h in the presence of 0.05% HCl can efficiently induce DNA depurination, releasing the intact carcinogen-modified nucleobases for LC analyses. After optimizing the hydrolysis conditions, DNA samples with C8- and N (2) -modified 2'-deoxyguanosine, as well as N (6) -modified 2'-deoxyadenosine, were synthesized by reacting DNA with 1-nitropyrene, acetaldehyde, and aristolochic acids, respectively. These samples were then hydrolyzed, and the released nucleobase adducts were analyzed using LC-based analytical methods. Analysis results demonstrated a dose-dependent release of target DNA adducts from carcinogen-modified DNA samples, indicating that the developed H(+)/heat-catalyzed hydrolysis method was quantitative. Comparative studies with enzymatic digestion method on carcinogen-modified DNA samples revealed that the two hydrolysis methods did not yield systematically different results.

  12. Investigation of the behaviour of solid acid catalysts for acylations and cyanisations of aromatics. Final report; Untersuchungen zur Wirkungsweise von festen sauren Katalysatoren bei Acylierungen und Cyanierungen von Aromaten. Abschlussbericht

    Kemnitz, E.


    The present state of the art in the field of FRIEDEL-CRAFTS-ACYLATIONS is characterized by the application of homogenous catalysts (at least stochiometric amounts) like AlCl{sub 3} or FeCl{sub 3}. Problems arising from this application are corrosions, difficult product separations from the catalyst and the origin of acid waste water. Hence, the aim of this project was the development of suitable solid catalysts which overcome the problems ascribed above. Sulfated zirconia (SZ) was found to be an excellent solid Br.o/nsted-acid to be used especially in their aerogel or cryogel form. Thus with this catalyst system, in the benzoylation of anisol nearly 100% conversion may be achieved. In this way it could be proved, that with SZ a solid Br.o/nsted-acid might be available which gives reasonable hope to substitute in a near future, at least for some reactions, the classical homogeneous catalysts and to overcome their problems in use. (orig.)

  13. Acid and Base Catalyzed Hydrolysis of Cyanophycin for the Biobased Production of Nitrogen Containing Chemicals

    Könst, P.M.; Scott, E.L.; Franssen, M.C.R.; Sanders, J.P.M.


    While growing on side-streams of the agro-industries, engineered microorganisms can produce ethanol and simultaneously bind L-aspartic acid and L-arginine in equimolar amounts in the polyamino acid cyanophycin. In this way, widely available amino acids can be isolated and utilized as an alternative

  14. Kinetic Study of Esterification of Acetic Acid with n-butanol and isobutanol Catalyzed by Ion Exchange Resin

    Amrit Pal Toor


    Full Text Available Esters are an important pharmaceutical intermediates and very useful perfumery agents. In this study the esterification of acetic acid with n-butanol and iso-butanol over an acidic cation exchange resin, Amberlyst 15 were carried out. The effects of certain parameters such as temperature, catalyst loading, initial molar ratio between reactants on the rate of reaction were studied. The experiments were conducted in a stirred batch reactor in the temperature range of 351.15 K to 366.15K.Variation of parameters on rate of reaction demonstrated that the reaction was intrinsically controlled.The activation energy for the esterification of acetic acid with n-butanol and iso butanol is found to be 28.45 k J/mol and 23.29 kJ/mol respectively. ©2011 BCREC UNDIP. All rights reserved.(Received: 16th December 2010, Revised: 19th March 2011; Accepted: 7th April 2011[How to Cite: A.P. Toor, M. Sharma, G. Kumar, and R. K. Wanchoo. (2011. Kinetic Study of Esterification of Acetic Acid with n-butanol and isobutanol Catalyzed by Ion Exchange Resin. Bulletin of Chemical Reaction Engineering and Catalysis, 6(1: 23-30. doi:10.9767/bcrec.6.1.665.23-30][How to Link / DOI: || or local: ] | View in 

  15. Cloning and characterization of a new laccase from Bacillus licheniformis catalyzing dimerization of phenolic acids.

    Koschorreck, Katja; Richter, Sven M; Ene, Augusta B; Roduner, Emil; Schmid, Rolf D; Urlacher, Vlada B


    A new laccase gene (cotA) was cloned from Bacillus licheniformis and expressed in Escherichia coli. The recombinant protein CotA was purified and showed spectroscopic properties, typical for blue multi-copper oxidases. The enzyme has a molecular weight of approximately 65 kDa and demonstrates activity towards canonical laccase substrates 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS), syringaldazine (SGZ) and 2,6-dimethoxyphenol (2,6-DMP). Kinetic constants KM and kcat for ABTS were of 6.5+/-0.2 microM and 83 s(-1), for SGZ of 4.3+/-0.2 microM and 100 s(-1), and for 2,6-DMP of 56.7+/-1.0 microM and 28 s(-1). Highest oxidizing activity towards ABTS was obtained at 85 degrees C. However, after 1 h incubation of CotA at 70 degrees C and 80 degrees C, a residual activity of 43% and 8%, respectively, was measured. Furthermore, oxidation of several phenolic acids and one non-phenolic acid by CotA was investigated. CotA failed to oxidize coumaric acid, cinnamic acid, and vanillic acid, while syringic acid was oxidized to 2,6-dimethoxy-1,4-benzoquinone. Additionally, dimerization of sinapic acid, caffeic acid, and ferulic acid by CotA was observed, and highest activity of CotA was found towards sinapic acid.

  16. Copolymerization of Ethylene and Vinyl Amino Acidic Ester Catalyzed by Titanium and Zirconium Complexes

    Jing Wang


    Full Text Available A series of titanium and zirconium complexes with ligands based on di-isopropyl phosphorus-phenylamine and their derivatives were synthesized and characterized. These catalysts were utilized to catalyze the copolymerization of ethylene with N-acetyl-O-(dec-9-enyl-L-tyrosine ethyl ester with high catalytic activity of 6.63 × 104 g P (mol Ti−1 h−1 after activation by methylaluminoxane (MAO. The effects of ligand structure, metal atoms (Ti, Zr and polymerization conditions were investigated in detail. The obtained polymers were characterized by 13C-NMR, DSC, FT-IR, and GPC. The results showed that the obtained copolymer had a high comonomer incorporation rate of 2.56 mol % within the copolymer chain. The melting temperature of the copolymer was up to 138.9 °C, higher than that of the obtained homopolyethylene.

  17. The Acid Hydrolysis Mechanism of Acetals Catalyzed by a Supramolecular Assembly in Basic Solution

    Pluth, Michael D.; Bergman, Robert G.; Raymond, Kenneth N.


    A self-assembled supramolecular host catalyzes the hydrolysis of acetals in basic aqueous solution. The mechanism of hydrolysis is consistent with the Michaelis-Menten kinetic model. Further investigation of the rate limiting step of the reaction revealed a negative entropy of activation ({Delta}S{double_dagger} = -9 cal mol{sup -1}K{sup -1}) and an inverse solvent isotope effect (k(H{sub 2}O)/k(D{sub 2}O) = 0.62). These data suggest that the mechanism of hydrolysis that takes place inside the assembly proceeds through an A-2 mechanism, in contrast to the A-1 mechanism operating in the uncatalyzed reaction. Comparison of the rates of acetal hydrolysis in the assembly with the rate of the reaction of unencapsulated substrates reveals rate accelerations of up to 980 over the background reaction for the substrate diethoxymethane.

  18. Mono-thioesters and di-thioesters by lipase-catalyzed reactions of alpha,omega-alkanedithiols with palmitic acid or its methyl ester.

    Weber, N; Klein, E; Vosmann, K; Mukherjee, K D


    1- S-Mono-palmitoyl-hexanedithiol and 1- S-mono-palmitoyl-octanedithiol were prepared in high yield (80-90%) by solvent-free lipase-catalyzed thioesterification of palmitic acid with the corresponding alpha,omega-alkanedithiols in vacuo. Similarly, 1,6-di- S-palmitoyl-hexanedithiol and 1,8-di- S-palmitoyl-octanedithiol were prepared in moderate yield (50-60%) by solvent-free lipase-catalyzed thioesterification of palmitic acid with 1- S-Mono-palmitoyl-hexanedithiol and 1- S-mono-palmitoyl-octanedithiol, respectively. An immobilized lipase preparation from Rhizomucor miehei (Lipozyme RM IM) was more effective than a lipase B preparation from Candida antarctica (Novozym 435) or a lipase preparation from Thermomyces lanuginosus (Lipozyme TL IM). Lipase-catalyzed transthioesterifications of methyl palmitate with alpha,omega-alkanedithiols using the same enzymes were less effective than thioesterification for the preparation of the corresponding 1- S-mono-palmitoyl thioesters.

  19. One-pot five-component synthesis of spirocyclopenta[b]chromene derivatives and their acid-catalyzed rearrangement.

    Terzidis, Michael A; Zarganes-Tzitzikas, Tryfon; Tsimenidis, Constantinos; Stephanidou-Stephanatou, Julia; Tsoleridis, Constantinos A; Kostakis, George E


    The reaction of the zwitterionic intermediate, generated in situ from either tert-butylisocyanide or cyclohexylisocyanide and acetylenedicarboxylates, with 3-cyanochromones is described, whereupon spirochromenofuran derivatives 5 or 6 were obtained in good yields. The subsequent acid-catalyzed rearrangement of the isolated 2-imino-spirochromenofurans 5 to 2-amino-spirochromenofurans 7 has also been studied. Rational mechanistic schemes for the formation of compounds 5, 6, and 7 are proposed. The structure elucidation of the products was accomplished by 1D and 2D NMR experiments and confirmed by X-ray crystallographic analysis. Full assignment of all (1)H and (13)C NMR chemical shifts has been unambiguously achieved with the aid of DFT/GIAO calculations.

  20. In situ detection of denitrifying bacteria by mRNA-targeted nucleic acid probes and catalyzed reporter deposition

    Kofoed, Michael Vedel; Stief, Peter; Poulsen, Morten

    In situ detection of denitrifying bacteria by mRNA-targeted nucleic acid probes and catalyzed reporter deposition   Michael V.W. Kofoed, Peter Stief, Morten Poulsen, and Andreas Schramm Department of Biological Sciences, Microbiology, University of Aarhus, Denmark Denitrification, the sequential...... reductase) and nosZ (encoding nitrous oxide reductase), to detect nitrate-reducing and completely denitrifying bacteria, respectively. Enzyme-labelled oligonucleotide probes and digoxygenin-labelled polynucleotide probes were evaluated for in situ hybridization in combination with immunochemical detection...... reduction of nitrate to dinitrogen gas, is essential for the removal of fixed nitrogen from natural and engineered ecosystems. However, community structure and activity dynamics of denitrifying bacteria in most systems are poorly understood, partially due to difficulties in identifying and quantifying...

  1. Brønsted-acid-catalyzed asymmetric multicomponent reactions for the facile synthesis of highly enantioenriched structurally diverse nitrogenous heterocycles.

    Yu, Jie; Shi, Feng; Gong, Liu-Zhu


    Optically pure nitrogenous compounds, and especially nitrogen-containing heterocycles, have drawn intense research attention because of their frequent isolation as natural products. These compounds have wide-ranging biological and pharmaceutical activities, offering potential as new drug candidates. Among the various synthetic approaches to nitrogenous heterocycles, the use of asymmetric multicomponent reactions (MCRs) catalyzed by chiral phosphoric acids has recently emerged as a particularly robust tool. This method combines the prominent merits of MCRs with organocatalysis, thus affording enantio-enriched nitrogenous heterocyclic compounds with excellent enantioselectivity, atom economy, bond-forming efficiency, structural diversity, and complexity. In this Account, we discuss a variety of asymmetric MCRs catalyzed by chiral phosphoric acids that lead to the production of structurally diverse nitrogenous heterocycles. In MCRs, three or more reagents are combined simultaneously to produce a single product containing structural contributions from all the components. These one-pot processes are especially useful in the construction of heterocyclic cores: they can provide a high degree of both complexity and diversity for a targeted set of scaffolds while minimizing the number of synthetic operations. Unfortunately, enantioselective MCRs have thus far been relatively underdeveloped. Particularly lacking are reactions that proceed through imine intermediates, which are formed from the condensation of carbonyls and amines. The concomitant generation of water in the condensation reaction can deactivate some Lewis acid catalysts, resulting in premature termination of the reaction. Thus, chiral catalysts typically must be compatible with water for MCRs to generate nitrogenous compounds. Recently, organocatalytic MCRs have proven valuable in this respect. Brønsted acids, an important class of organocatalysts, are highly compatible with water and thereby offer great

  2. Effect of polyvinylpyrrolidone on mesoporous silica morphology and esterification of lauric acid with 1-butanol catalyzed by immobilized enzyme

    Zhang, Jinyu; Zhou, Guowei, E-mail:; Jiang, Bin; Zhao, Minnan; Zhang, Yan


    Mesoporous silica materials with a range of morphology evolution, i.e., from curved rod-shaped mesoporous silica to straight rod-shaped mesoporous silica, were successfully prepared using polyvinylpyrrolidone (PVP) and triblock copolymer as dual template. The effects of PVP molecular weight and concentration on mesoporous silica structure parameters were studied. Results showed that surface area and pore volume continuously decreased with increased PVP molecular weight. Mesoporous silica prepared with PVP K30 also possessed larger pore diameter, interplanar spacing (d{sub 100}), and cell parameter (a{sub 0}) than that prepared with PVP K15 and PVP K90. In addition, with increased PVP concentration, d{sub 100} and a{sub 0} continuously decreased. The mechanism of morphology evolution caused by the change in PVP concentration was investigated. The conversion rate of lauric acid with 1-butanol catalyzed by immobilized Porcine pancreatic lipase (PPL) was also evaluated. Results showed that PPL immobilized on amino-functionalized straight rod-shaped mesoporous silica maintained 50% of its esterification conversion rate even after five cycles of use with a maximum conversion rate was about 90.15%. - Graphical abstract: Curved rod-shaped mesoporous silica can be obtained at low and the highest PVP concentration, while straight rod-shaped mesoporous silica can be obtained at higher PVP concentration. - Highlights: • Mesoporous silica with morphology evolution from CRMS to SRMS were prepared. • Effects of PVP molecular weight and concentration on silica morphology were studied. • A possible mechanism for the formation of morphology evolution SiO{sub 2} was proposed. • Esterification of lauric acid with 1-butanol catalyzed by immobilized PPL.

  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. Synthesis of structured triacylglycerols containing caproic acid by lipase-catalyzed acidolysis: Optimization by response surface methodology

    Zhou, D.Q.; Xu, Xuebing; Mu, Huiling


    Production in a batch reactor with a solvent-free system of structured triacylglycerols containing short-chain fatty acids by Lipozyme RM IM-catalyzed acidolysis between rapeseed oil and caproic acid was optimized using response surface methodology (RSM). Reaction time (t(r)), substrate ratio (S......-r), enzyme load (E-1, based on substrate), water content (W-c, based on enzyme), and reaction temperature (T-e), the five most important parameters for the reaction, were chosen for the optimization. The range of each parameter was selected as follows: t(r) = 5-17 h; E-1 = 6-14 wt %; T-e = 45-65 degreesC; S......-r = 2-6 mol/mol; and W-c = 2-12 wt %. The biocatalyst was Lipozyme RM IM, in which Rhizomucor miehei lipase is immobilized on a resin. The incorporation of caproic acid into rapeseed oil was the main monitoring response. In addition, the contents of mono-incorporated structured triacylglycerols and di...

  5. Two-step synthesis of fatty acid ethyl ester from soybean oil catalyzed by Yarrowia lipolytica lipase

    Chen Jinnan


    Full Text Available Abstract Background Enzymatic biodiesel production by transesterification in solvent media has been investigated intensively, but glycerol, as a by-product, could block the immobilized enzyme and excess n-hexane, as a solution aid, would reduce the productivity of the enzyme. Esterification, a solvent-free and no-glycerol-release system for biodiesel production, has been developed, and two-step catalysis of soybean oil, hydrolysis followed by esterification, with Yarrowia lipolytica lipase is reported in this paper. Results First, soybean oil was hydrolyzed at 40°C by 100 U of lipase broth per 1 g of oil with approximately 30% to 60% (vol/vol water. The free fatty acid (FFA distilled from this hydrolysis mixture was used for the esterification of FFA to fatty acid ethyl ester by immobilized lipase. A mixture of 2.82 g of FFA and equimolar ethanol (addition in three steps were shaken at 30°C with 18 U of lipase per 1 gram of FFA. The degree of esterification reached 85% after 3 hours. The lipase membranes were taken out, dehydrated and subjected to fresh esterification so that over 82% of esterification was maintained, even though the esterification was repeated every 3 hours for 25 batches. Conclusion The two-step enzymatic process without glycerol released and solvent-free demonstrated higher efficiency and safety than enzymatic transesterification, which seems very promising for lipase-catalyzed, large-scale production of biodiesel, especially from high acid value waste oil.

  6. The Optimized Synthesis of Starch-g-Lactic Acid Copolymer with High Grafting Degree Catalyzed by Sulfuric Acid

    HU Zhiying


    The starch-g-lactic acid copolymer was synthesized with catalysis of sulfuric acid by one-step process, and the structure of starch-g-lactic acid copolymer was characterized by means of IR, 13C-NMR, HMBC, XRD, and SEM. The experimental results show that the maximum grafting degree of starch can reach 75%when the starch-g-lactic acid copolymer is activated at 80℃for 2 h and reacted with lactic acid at 90℃for 4 h in vacuum.

  7. Synthesis of solution-phase phosphoramidite and phosphite ligand libraries and their in situ screening in the rhodium-catalyzed asymmetric addition of arylboronic acids

    Jagt, Richard B. C.; Toullec, Patrick Y.; Schudde, Ebe P.; de Vries, Johannes G.; Feringa, Ben L.; Minnaard, Adriaan J.


    Herein, we report the automated parallel synthesis of solution-phase libraries of phosphoramidite ligands for the development of enantioselective catalysts. The ligand libraries are screened in situ in the asymmetric rhodium-catalyzed addition of arylboronic acids to aldehydes and imines. It is show

  8. Kinetics and Mechanism of Ruthenium(III) Catalyzed Oxidation of Butanone and Uncatalyzed Oxidation of Cychlohexanone by Cerium(IV) in Acid Sulphate Medium

    Sharma, Priyamvada; Hemkar, Shalini; Khandelwal, C. L.; Sharma, P. D. [Univ. of Rajasthan, Jaipur (India)


    The kinetics of ruthenium(III) chloride catalyzed oxidation of butanone and uncatalyzed oxidation of cyclohexanone by cerium(IV) in sulphuric acid medium have been studied. The kinetic rate law(I) in case of butanone conforms to the proposed mechanism. Kinetics and activation parameters have been evaluated conventionally. Kinetically preferred mode of reaction is via ketonic and not the enolic forms.




    The liquid-phase hydration of cyclohexene, a pseudo-first-order reversible reaction catalyzed by a strong acid ion-exchange resin, was investigated in solvent mixtures of water and sulfolane. Macroporous Amberlite XE 307 was used because of its superior catalytic activity. Chemical equilibrium conve

  10. Palladium-catalyzed cross-coupling reaction of diazo compounds and vinyl boronic acids: an approach to 1,3-diene compounds.

    Xia, Yamu; Xia, Ying; Liu, Zhen; Zhang, Yan; Wang, Jianbo


    A palladium-catalyzed oxidative cross-coupling of vinyl boronic acids and cyclic α-diazocarbonyl compounds has been reported. The reaction constitutes an efficient method for the synthesis of 1,3-diene compounds bearing a ring structure. Mechanistically, the reaction involves migratory insertion of palladium carbene as the key step.

  11. The nature of fatty acid modifies the equilibrium position in the esterification catalyzed by lipase

    Flores, M.V.; Sewalt, J.J.W.; Janssen, A.E.M.; Padt, van der A.


    The equilibrium position in lipase mediated esterification of various fatty acids and butanol was studied. The influence of the chain length and the presence of unsaturations in the fatty acids on the equilibrium position was measured and predicted. To predict equilibrium position the program TREP e

  12. Lipase-catalyzed kinetic resolution of branched chain fatty acids and their esters

    Heinsman, N.W.J.T.


    Flavors and fragrances make an important contribution to the taste and smell of all kinds of food products both as natural occurring components and as additional flavors or fragrances. One of these flavor components is 4-methyloctanoic acid (4-MOA). This branched chain fatty acid contributes to the

  13. Acceleration of Enantioselective Cycloadditions Catalyzed by Second-Generation Chiral Oxazaborolidinium Triflimidates by Biscoordinating Lewis Acids.

    Thirupathi, Barla; Breitler, Simon; Mahender Reddy, Karla; Corey, E J


    The activation of second-generation fluorinated oxazaborolidines by the strong acid triflimide (Tf2NH) in CH2Cl2 solution leads to highly active chiral Lewis acids that are very effective catalysts for (4 + 2) cycloaddition. We report herein that this catalytic activity can be further enhanced by the use of Tf2NH in combination with the biscoordinating Lewis acid TiCl4 or SnCl4 as a coactivator. The effective increase in acidity of an exceedingly strong protic acid is greater for biscoordinating TiCl4 and SnCl4 than for monocoordinating salts, even the strong Lewis acids AlBr3 and BBr3 in CH2Cl2 or CH2Cl2/toluene. The increase in the effective acidity of Tf2NH can be understood in terms of a stabilized cyclic anionic complex of Tf2N(-) and TiCl4, which implies a broader utility than that described here. The utility of Tf2NH-TiCl4 activation of fluorinated oxazaborolidines is documented by examples including the first enantioselective (4 + 2) cycloaddition to α,β-unsaturated acid chlorides.

  14. Lewis acid-catalyzed depolymerization of soda lignin in supercritical ethanol/water mixtures

    Güvenatam, Burcu; Heeres, Erik H.J.; Pidko, Evgeny A.; Hensen, Emiel J M


    The depolymerization of lignin model compounds and soda lignin by super Lewis acidic metal triflates has been investigated in a mixture of ethanol and water at 400 °C. The strong Lewis acids convert representative model compounds for the structure-forming linkages in lignin, namely α-O-4, 5-O-4

  15. Upgrading of bio-oil via acid-catalyzed reactions in alcohols : a mini review

    Hu, X.; Gunawan, R.; Mourant, D.; Mahmudul Hasan, M.D.; Wu, L.; Song, Y.; Lievens, C.; Li, C.Z.


    Bio-oil is a condensable liquid produced from the pyrolysis of biomass, which can be upgraded to biofuels. Bio-oil is corrosive as it contains significant amounts of carboxylic acids, creating difficulties in handling of bio-oil and applications of bio-oil. Acid-treatment of bio-oil in alcohols is

  16. Kinetics and mechanism of S-nitrosothiol acid-catalyzed hydrolysis: sulfur activation promotes facile NO+ release.

    Moran, Ernesto E; Timerghazin, Qadir K; Kwong, Elizabeth; English, Ann M


    The denitrosation of three primary S-nitrosothiols (RSNO; S-nitrosocysteine, S-nitroso-N-acetylcysteine, and S-nitrosoglutathione) and two tertiary RSNOs (S-nitrosopenicillamine and S-nitroso-N-acetylpenicillamine) was investigated in 3.75 M H(2)SO(4) to probe the mechanism of acid-catalyzed RSNO hydrolysis and its dependence on RSNO structure. This reversible reaction was forced to proceed in the denitrosation direction by trapping the nitrosating agent with HN(3). The primary RSNOs exhibited hydrolysis k(obs) values of ∼2 × 10(-4) s(-1), and the tertiary RSNO k(obs) values were an order of magnitude higher. Product analysis by HPLC revealed that the parent thiols (RSHs) were formed in 90-100% yield on 79-99% RSNO denitrosation. Possible hydrolysis mechanisms were studied computationally at the CBS-QB3 level using S-nitrosomethanethiol (MeSNO) as a model RSNO. Consideration of RSNOs as a combination of conventional R-S-N═O, zwitterionic R-S(+)═N-O(-), and RS(-)/NO(+) ion-pair resonance structures was key in understanding the mechanistic details of acid-catalyzed hydrolysis. Protonation of the S-nitroso oxygen or nitrogen activates the sulfur and nucleophilic attack by H(2)O at this atom leads to the formation of the sulfoxide-protonated N-hydroxysulfinamide, MeS(+)(OH)NHOH, with barriers of 19 and 29 kcal/mol, respectively. Proton loss and reprotonation at the nitrogen lead to secondary hydrolysis that produces the sulfinic acid MeS(═O)OH and NH(2)OH. Notably, no low-energy RSNO hydrolysis pathway for HNO release was found in the computational analysis. Protonation of the S-nitroso sulfur gives rise to NO(+) release with a low activation barrier (ΔH(double dagger)(calc) ≈ 6 kcal/mol) and the formation of MeSH in agreement with experiment. The experimental k(obs) can be expressed as K(a)k(1), where K(a) is the acid dissociation constant for protonation of the S-nitroso sulfur and k(1) the pseudo-first-order hydrolysis rate constant. Given the low

  17. Acid-catalyzed steam pretreatment of lodgepole pine and subsequent enzymatic hydrolysis and fermentation to ethanol.

    Ewanick, Shannon M; Bura, Renata; Saddler, John N


    Utilization of ethanol produced from biomass has the potential to offset the use of gasoline and reduce CO(2) emissions. This could reduce the effects of global warming, one of which is the current outbreak of epidemic proportions of the mountain pine beetle (MPB) in British Columbia (BC), Canada. The result of this is increasing volumes of dead lodgepole pine with increasingly limited commercial uses. Bioconversion of lodgepole pine to ethanol using SO(2)-catalyzed steam explosion was investigated. The optimum pretreatment condition for this feedstock was determined to be 200 degrees C, 5 min, and 4% SO(2) (w/w). Simultaneous saccharification and fermentation (SSF) of this material provided an overall ethanol yield of 77% of the theoretical yield from raw material based on starting glucan, mannan, and galactan, which corresponds to 244 g ethanol/kg raw material within 30 h. Three conditions representing low (L), medium (M), and high (H) severity were also applied to healthy lodgepole pine. Although the M severity conditions of 200 degrees C, 5 min, and 4% SO(2) were sufficiently robust to pretreat healthy wood, the substrate produced from beetle-killed (BK) wood provided consistently higher ethanol yields after SSF than the other substrates tested. BK lodgepole pine appears to be an excellent candidate for efficient and productive bioconversion to ethanol.

  18. Acid Catalyzed Condensation of Phenylethanal Enol or Thiol Enol Ether to 2-Phenylnaphthalene

    CHANG, Yu-An


    Treatment of enol ether or thiol enol ether of phenylethanals with sulfuric or polyphosphoric acid in toluene or xylene gave 2-phenylnaphthalene in good yield. More importantly, a one-pot reaction has been developed.

  19. Flavin-catalyzed aerobic oxidation of sulfides and thiols with formic acid/triethylamine.

    Murahashi, Shun-Ichi; Zhang, Dazhi; Iida, Hiroki; Miyawaki, Toshio; Uenaka, Masaaki; Murano, Kenji; Meguro, Kanji


    An efficient and practical catalytic method for the aerobic oxidative transformation of sulfides into sulfoxides, and thiols into disulfides with formic acid/TEA in the presence of a new, readily available, and stable flavin catalyst 5d is described.

  20. An efficient synthesis of 1,5-benzodiazepine derivatives catalyzed by boric acid

    Xin Zhou; Mei Yue Zhang; Shu Tao Gao; Jing Jun Ma; Chun Wang; Chao Liu


    1,5-Benzodiazepine derivatives have been synthesized by the condensation of o-phenylenediamines and ketones in the presence of boric acid as catalyst under mild conditions. This method is simple, environmentally benign and high yielding.

  1. Sulfanilic acid catalyzed solvent-free synthesis of 1,5-benzodiazepine derivatives


    Sulfanilic acid has been found to be an efficient catalyst for the synthesis of 1,5-benzodiazepines from o-phenylenediamine and ketones. This method is simple, effective and environmentally friendly and gives better yields.

  2. Copper-catalyzed decarboxylative C-P cross-coupling of alkynyl acids with H-phosphine oxides: a facile and selective synthesis of (E)-1-alkenylphosphine oxides.

    Hu, Gaobo; Gao, Yuxing; Zhao, Yufen


    A novel and efficient copper-catalyzed decarboxylative cross-coupling of alkynyl acids for the stereoselective synthesis of E-alkenylphosphine oxides has been developed. In the presence of 10 mol % of CuCl without added ligand, base, and additive, various alkynyl acids reacted with H-phosphine oxides to afford E-alkenylphosphine oxides with operational simplicity, broad substrate scope, and the stereoselectivity for E-isomers.

  3. Lewis acid-catalyzed intramolecular [3+2] cycloaddition of cyclopropane 1,1-diesters with alkynes for the synthesis of cyclopenta[c]chromene skeletons.

    Xia, Xiao-Feng; Song, Xian-Rong; Liu, Xue-Yuan; Liang, Yong-Min


    An efficient method to construct cyclopenta[c]chromene skeletons by Lewis acid-catalyzed intramolecular [3+2] cycloaddition of cyclopropane 1,1-diesters with alkynes is presented. Two new fused cycles can be formed in one step in moderate to excellent yields (up to 94 %), and the products can be converted into bioactive barbituric acid derivatives (1) under simple reaction conditions. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. N-Heterocyclic Carbene Catalyzed [3+2] Cycloaddition of Enals with Masked Cinnamates for the Asymmetric One-Pot Synthesis of Adipic Acid Derivatives.

    Chen, Xiang-Yu; Li, Sun; Sheng, He; Liu, Qiang; Jafari, Ehsan; von Essen, Carolina; Rissanen, Kari; Enders, Dieter


    A novel short entry to 3,4-disubstituted adipic acids has been developed by employing an asymmetric NHC-catalyzed [3+2] cycloaddition of enals with masked cinnammates in moderate to good yields and high stereoselectivities. The synthetic utility of the protocol was demonstrated by the basic conversion of the masked cyclopentanone intermediates to 3S,4S-disubstituted adipic acid precursors of pharmaceutically important gababutins. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Thiol-functionalized copolymeric polyesters by lipase-catalyzed esterification and transesterification of 1,12-dodecanedioic acid and its diethyl ester, respectively, with 1-thioglycerol

    Fehling, Eberhard; Bergander, Klaus; Klein, Erika; Weber, Nikolaus; Vosmann, Klaus


    Abstract Copolymeric polyoxoesters containing branched-chain methylenethiol functions, i.e., poly(1,12-dodecanedioic acid-co-1-thioglycerol) and poly(diethyl 1,12-dodecanedioate-co-1-thioglycerol), were formed by lipase-catalyzed polyesterification and polytransesterification of 1,12-dodecanedioic acid and diethyl 1,12-dodecanedioate, respectively, with 1-thioglycerol (3-mercaptopropane-1,2-diol) using immobilized lipase B from Candida antarctica (Novozym 435) in vacuo without dryi...

  6. Role of keto–enol tautomerization in a chiral phosphoric acid catalyzed asymmetric thiocarboxylysis of meso-epoxide: a DFT study

    Ajitha, Manjaly John


    The mechanism of a chiral phosphoric acid catalyzed thiocarboxylysis of meso-epoxide was investigated by density functional theory (DFT) calculations (M06-2X). The nucleophilic ring opening of epoxide by thiobenzoic acid was found to proceed via a concerted termolecular transition state with a simultaneous dual proton transfer to yield the β-hydroxy thioester product. Electrostatic interactions together with the steric environment inside the chiral catalyst play an important role in determining the enantioselectivity of the reaction.

  7. A convenient synthesis of pyrroles catalyzed by acidic resin under solvent-free condition



    A convenient and effective Paal-Knorr condensations of 2,5-hexanedione with most amines have been carried out at room temperature under solvent-free condition. Macroporous strongly acidic styrol resin (D001) as a novel, efficient, cost-effective, and reusable solid acid catalyst for the synthesis of pyrroles under the same conditions. The pyrroles were obtained in high yields in short reaction times.

  8. Lewis base activation of Lewis acids: development of a Lewis base catalyzed selenolactonization.

    Denmark, Scott E; Collins, William R


    The concept of Lewis base activation of Lewis acids has been applied to the selenolactonization reaction. Through the use of substoichiometric amounts of Lewis bases with "soft" donor atoms (S, Se, P) significant rate enhancements over the background reaction are seen. Preliminary mechanistic investigations have revealed the resting state of the catalyst as well as the significance of a weak Brønsted acid promoter.

  9. Chiral-at-Metal Rh(III) Complex-Catalyzed Decarboxylative Michael Addition of β-Keto Acids with α,β-Unsaturated 2-Acyl Imidazoles or Pyridine.

    Li, Shi-Wu; Gong, Jun; Kang, Qiang


    A newly prepared chiral-at-metal Rh(III) complex-catalyzed, highly efficient enantioselective decarboxylative Michael addition of β-keto acids with α,β-unsaturated 2-acyl imidazoles or pyridine has been developed, affording the corresponding adducts in 94-98% yield with up to 96% enantioselectivity. This protocol exhibits remarkable reactivity, as the complex with a Rh(III) loading as low as 0.05 mol % can catalyze the decarboxylative Michael addition on a gram scale without loss of enantioselectivity.

  10. Alkylation of Catechol with tert-Butyl Alcohol Catalyzed by Mesoporous Acidic Montmorillonite Heterostructure Catalysts

    周春晖; 葛忠华; 李小年; 童东绅; 李庆伟; 郭红强


    The liquid phase alkylation of catechol with tert-butyl alcohol to produce 4-tert-butyl catechol (4-TBC) was carried out over MCM-41, HZSM-5, H-exchanged montmorillonite and novel acidic porous montmorillonite heterostructures (PMHs). Upon all catalysts tested, 4-TBC is the main product and 3-tert-butyl catechol (3-TBC) and 3,5-di-tert-butyl catechol are the side products. The synthetic PMHs showed higher conversion of catechol and better selectivity to 4-TBC compared to other solid acid catalysts tested. Over the PMHs derived from H-exchanged montmorillonite through template extraction processes, the suitable reaction temperature is ca 410 K, the ratio of catechol to tert-butyl alcohol is 1:2. Increasing the amount of catalyst (lower weight hourly space velocity) can improve the conversion of catechol and influence the selectivity slightly. The reasonable reaction time is ca 8 h.The type and strength of acidity of H-montmorillonite and PMH were determined by pyridine adsorption FT-IR and ammonia temperature-programmed desorption techniques. The medium and strong acid sites are conducive to producing 4-TBC and the weak acid sites to facilitating the 3-TBC formation. The differences between the PMHs from calcination and those fi'om extraction are attributed to proton migration and acidity change in the gallery surface.

  11. 菊粉酸降解动力学研究%Kinetic Studies on Acid Catalyzed Hydrolysis of Inulin

    许威; 罗登林; 陈瑞红; 刘建学


    通过考察温度、溶液pH值及水分含量对菊粉酸降解的影响,探索菊粉酸水解规律。结果表明:菊粉水溶液在pH 5.0~7.0、温度低于100℃时具有良好的稳定性;但当pH值低于4.0时,菊粉出现明显的水解反应。菊粉溶液在不同温度和pH值下的酸降解动力学表明,其水解反应遵循一级反应动力学方程。利用菊粉凝胶特性考察水分含量与菊粉酸降解的关系,发现相同pH值(pH=3)条件下,水分含量越高,菊粉降解速率越快,凝胶中菊粉降解速率低于菊粉水溶液降解速率。%The effects of temperature,pH and water content on inulin hydrolysis were studied to understand the acid catalyzed hydrolysis process of inulin for industrial production of high-fructose syrup.The results showed that inulin solution had a good thermal stability at a pH value in the range of 5.0-7.0 and a temperature below 100 ℃,while inulin degradation started to occur when the pH was lower than 4.0.The acid catalyzed hydrolysis dynamics of inulin at different levels of temperature and pH showed that the reaction followed the first-order kinetics well.The relation between inulin gel degradation induced by acid and water content was also investigated.At the same pH,the higher water content,the faster inulin hydrolysis,and the degradation rate of inulin was lower in gel than in aqueous solution.

  12. Lipase-catalyzed esterification of ferulic Acid with oleyl alcohol in ionic liquid/isooctane binary systems.

    Chen, Bilian; Liu, Huanzhen; Guo, Zheng; Huang, Jian; Wang, Minzi; Xu, Xuebing; Zheng, Lifei


    Lipase-catalyzed synthesis of ferulic acid oleyl alcohol ester in an ionic liquid (IL)/isooctane system was investigated. Considerable bioconversion and volumetric productivity were achieved in inexpensive 1-hexyl-3-methylimidazolium hexafluorophosphate ([Hmim][PF(6)]) and 1-methyl-3-octylimidazolium hexafluorophosphate ([Omim][PF(6)]) mediated systems, and thus, the two types of ILs were selected for further optimization of variables. The results showed that, before reaching a maximum, the increase of ferulic acid concentration, temperature, or enzyme dosage led to an increase in volumetric productivity. Variations of the ratios of IL/isooctane and concentrations of oleyl alcohol also profoundly affected the volumetric productivity. To a higher extent, [Hmim][PF(6)]/isooctane and [Omim][PF(6)]/isooctane show similar reaction behaviors. Under the optimized reaction conditions (60 °C, 150 mg of Novozym 435 and 100 mg of molecular sieves), up to 48.50 mg/mL productivity of oleyl feruleate could be achieved for the [Hmim][PF(6)]/isooctane (0.5 mL/1.5 mL) system with a substrate concentration of ferulic acid of 0.08 mmol/mL and oleyl alcohol of 0.32 mmol; while an optimum volumetric productivity of 26.92 mg/mL was obtained for the [Omim][PF(6)]/ isooctane (0.5 mL/1.5 mL) system under a similar reaction condition other than the substrate concentrations of ferulic acid at 0.05 mmol/mL and oleyl alcohol at 0.20 mmol.

  13. Synthesis of ascorbyl oleate by transesterification of olive oil with ascorbic acid in polar organic media catalyzed by immobilized lipases.

    Moreno-Perez, Sonia; Filice, Marco; Guisan, Jose M; Fernandez-Lorente, Gloria


    The reaction of transesterification between oils (e.g., olive oil) and ascorbic acid in polar anhydrous media (e.g., tert-amyl alcohol) catalyzed by immobilized lipases for the preparation of natural liposoluble antioxidants (e.g., ascorbyl oleate) was studied. Three commercial lipases were tested: Candida antarctica B lipase (CALB), Thermomyces lanuginosus lipase (TLL) and Rhizomucor miehei lipase (RML). Each lipase was immobilized by three different protocols: hydrophobic adsorption, anionic exchange and multipoint covalent attachment. The highest synthetic yields were obtained with CALB adsorbed on hydrophobic supports (e.g., the commercial derivative Novozym 435). The rates and yields of the synthesis of ascorbyl oleate were higher when using the solvent dried with molecular sieves, at high temperatures (e.g. 45°C) and with a small excess of oil (2 mol of oil per mol of ascorbic acid). The coating of CALB derivatives with polyethyleneimine (PEI) improved its catalytic behavior and allowed the achievement of yields of up to 80% of ascorbyl oleate in less than 24h. CALB adsorbed on a hydrophobic support and coated with PEI was 2-fold more stable than a non-coated derivative and one hundred-fold more stable than the best TLL derivative. The best CALB derivative exhibited a half-life of 3 days at 75°C in fully anhydrous media, and this derivative maintained full activity after 28 days at 45°C in dried tert-amyl alcohol.

  14. Enhancement of Lipase-catalyzed Synthesis of Caffeic Acid Phenethyl Ester in Ionic Liquid with DMSO Co-solvent☆

    Shuangshuang Gu; Jun Wang; Xianbin Wei; Hongsheng Cui; Xiangyang Wu; Fuan Wu


    Caffeic acid phenethyl ester (CAPE) is a natural and rare ingredient with several biological activities, but its indus-trial production using lipase-catalyzed esterification of caffeic acid (CA) and 2-phenylethanol (PE) in ionic liquids (ILs) is hindered by low substrate concentrations and long reaction time. To set up a high-efficiency bioprocess for production of CAPE, a novel dimethyl sulfoxide (DMSO)–IL co-solvent system was established in this study. The 2%(by volume) DMSO–[Bmim][Tf2N] system was found to be the best medium with higher substrate solu-bility and conversion of CA. Under the optimum conditions, the substrate concentration of CA was raised 8-fold, the reaction time was reduced by half, and the conversion reached 96.23%. The kinetics follows a ping-pong bi-bi mechanism with inhibition by PE, with kinetic parameters as follows:Vmax=0.89 mmol · min−1 · g−1, Km,CA=42.9 mmol · L−1, Km,PE=165.7 mmol · L−1, and Ki,PE=146.2 mmol · L−1. The results suggest that the DMSO co-solvent effect has great potential to enhance the enzymatic synthesis efficiency of CAPE in ILs.

  15. The Aerobic Oxidation of Bromide to Dibromine Catalyzed by Homogeneous Oxidation Catalysts and Initiated by Nitrate in Acetic Acid

    Partenheimer, Walt; Fulton, John L.; Sorensen, Christina M.; Pham, Van Thai; Chen, Yongsheng


    A small amount of nitrate, ~0.002 molal, initiates the Co/Mn catalyzed aerobic oxidation of bromide compounds (HBr,NaBr,LiBr) to dibromine in acetic acid at room temperature. At temperatures 40oC or less , the reaction is autocatalytic. Co(II) and Mn(II) themselves and mixed with ionic bromide are known homogeneous oxidation catalysts. The reaction was discovered serendipitously when a Co/Br and Co/Mn/Br catalyst solution was prepared for the aerobic oxidation of methyaromatic compounds and the Co acetate contained a small amount of impurity i.e. nitrate. The reaction was characterized by IR, UV-VIS, MALDI and EXAFS spectroscopies and the coordination chemistry is described. The reaction is inhibited by water and its rate changed by pH. The change in these variables, as well as others, are identical to those observed during homogeneous, aerobic oxidation of akylaromatics. A mechanism is proposed. Accidental addition of a small amount of nitrate compound into a Co/Mn/Br/acetic acid mixture in a large, commercial feedtank is potentially dangerous.

  16. Bio-based nitriles from the heterogeneously catalyzed oxidative decarboxylation of amino acids.

    Claes, Laurens; Matthessen, Roman; Rombouts, Ine; Stassen, Ivo; De Baerdemaeker, Trees; Depla, Diederik; Delcour, Jan A; Lagrain, Bert; De Vos, Dirk E


    The oxidative decarboxylation of amino acids to nitriles was achieved in aqueous solution by in situ halide oxidation using catalytic amounts of tungstate exchanged on a [Ni,Al] layered double hydroxide (LDH), NH4 Br, and H2 O2 as the terminal oxidant. Both halide oxidation and oxidative decarboxylation were facilitated by proximity effects between the reactants and the LDH catalyst. A wide range of amino acids was converted with high yields, often >90 %. The nitrile selectivity was excellent, and the system is compatible with amide, alcohol, and in particular carboxylic acid, amine, and guanidine functional groups after appropriate neutralization. This heterogeneous catalytic system was applied successfully to convert a protein-rich byproduct from the starch industry into useful bio-based N-containing chemicals. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Lipase-catalyzed esterification of lactic acid with straight-chain alcohols

    Rønne, Torben Harald; Xu, Xuebing; Tan, Tianwei


    Enzymatic synthesis of esters of lactic acid and straight-chain alcohols with different chain lengths (C6–C18) were investigated in batch reactions with hexadecanol (C16) as the model alcohol. Cyclohexane was the best solvent for higher ester yields, and the best biocatalyst was the immobilized...... of lactic acid to alcohol, each at a concentration of 120 mM each; a 50°C reaction temperature; 190 rpm shaking speed; and the addition of 100 mg molecular sieves (4 Å) for drying. The ester yield increased with increasing lipase load, and a yield of 79.2% could be obtained after 24 h of reaction at 20 wt......% of Novozym 435. The immobilized Candida sp. lipase prepared in the laboratory also could be used to produce esters of lactic acid and straight-chain alcohols, but it had a much lower activity than Novozym 435 with a temperature optimum of 40°C....

  18. Graphene oxide for acid catalyzed-reactions: Effect of drying process

    Gong, H. P.; Hua, W. M.; Yue, Y. H.; Gao, Z.


    Graphene oxides (GOs) were prepared by Hummers method through various drying processes, and characterized by XRD, SEM, FTIR, XPS and N2 adsorption. Their acidities were measured using potentiometric titration and acid-base titration. The catalytic properties were investigated in the alkylation of anisole with benzyl alcohol and transesterification of triacetin with methanol. GOs are active catalysts for both reaction, whose activity is greatly affected by their drying processes. Vacuum drying GO exhibits the best performance in transesterification while freezing drying GO is most active for alkylation. The excellent catalytic behavior comes from abundant surface acid sites as well as proper surface functional groups, which can be obtained by selecting appropriate drying process.

  19. Phenylalanine ammonia lyase catalyzed synthesis of amino acids by an MIO-cofactor independent pathway.

    Lovelock, Sarah L; Lloyd, Richard C; Turner, Nicholas J


    Phenylalanine ammonia lyases (PALs) belong to a family of 4-methylideneimidazole-5-one (MIO) cofactor dependent enzymes which are responsible for the conversion of L-phenylalanine into trans-cinnamic acid in eukaryotic and prokaryotic organisms. Under conditions of high ammonia concentration, this deamination reaction is reversible and hence there is considerable interest in the development of PALs as biocatalysts for the enantioselective synthesis of non-natural amino acids. Herein the discovery of a previously unobserved competing MIO-independent reaction pathway, which proceeds in a non-stereoselective manner and results in the generation of both L- and D-phenylalanine derivatives, is described. The mechanism of the MIO-independent pathway is explored through isotopic-labeling studies and mutagenesis of key active-site residues. The results obtained are consistent with amino acid deamination occurring by a stepwise E1 cB elimination mechanism.

  20. Convenient synthetic method of starch/lactic acid graft copolymer catalyzed with sodium hydroxide

    Qingling Wang; Yingmo Hu; Jianhua Zhu; Yang Liu; Xue Yang; Jing Bian


    Copolymer of starch grafted with lactic acid (LA) could be directly prepared by reaction of cornstarch with lactic acid and with sodium hydroxide (NaOH) as the catalyst. The structure of starch/LA copolymer was characterized by IR, XRD, SEM and 1H-NMR. The effects of NaOH concentration, ratios of starch and LA, reaction temperature and reaction time on the grafting degree were also investigated and the results showed that the highest grafting degree of starch could reach 33.60% when the graft copolymerization was carried out in 0.40 mol l-1 NaOH aqueous solution for 9 h at 90°C with 1: 6 ratio of starch and lactic acid.

  1. Silver-Catalyzed Decarboxylative Radical Azidation of Aliphatic Carboxylic Acids in Aqueous Solution.

    Liu, Chao; Wang, Xiaoqing; Li, Zhaodong; Cui, Lei; Li, Chaozhong


    We report herein an efficient and general method for the decarboxylative azidation of aliphatic carboxylic acids. Thus, with AgNO3 as the catalyst and K2S2O8 as the oxidant, the reactions of various aliphatic carboxylic acids with tosyl azide or pyridine-3-sulfonyl azide in aqueous CH3CN solution afforded the corresponding alkyl azides under mild conditions. A broad substrate scope and wide functional group compatibility were observed. A radical mechanism is proposed for this site-specific azidation.

  2. Preparation of fructone catalyzed by water-soluble Br(φ)nsted acid ionic liquids

    Yuan Yuan Wang; Rong Wang; Liang Chun Wu; Li Yi Dai


    Fructone (2-methyl-2-ethylacetoacetate-1,3-dioxolane), a flavouring material, has been synthesized from ethyl acetoacetate and glycol using five water-soluble Br(φ)nsted acid ionic liquids as catalysts for the first time. The used Br(φ)nsted acid ionic liquids include [Hmim]Tfa, [Hmim]Tsa, [Hmim]BF4, [Bmim]HSO4, [Bmim]H2PO4, and [Hmim]BF4 showed the highest catalytic activity for the preparation of fructone. After reaction, the product could be isolated from the reaction system automatically, and the ionic liquid could be directly reused without dehydration.

  3. Upward Trend in Catalytic Efficiency of Rare-Earth Triflate Catalysts in Friedel-Crafts Aromatic Sulfonylation Reactions

    Duus, Fritz; Le, Thach Ngoc; Nguyen, Vo Thu An


    90 % were achieved for short irradiation periods. This was the case especially for Tm(OTf)3, Yb(OTf)3, and Lu(OTf)3, of which Yb(OTf)3 was the most efficient. The upward trend in catalytic efficiency therefore correlates with the lanthanide sequence in the periodic table. The results can be explained...

  4. A combination of friedel-crafts and lawesson reactions to 5-substituted-2,2´-bithiophenes

    Raposo, M. Manuela M; Kirsch, G


    Gama-Keto esters (2) derivatives of thiophene were obtained from hemi-succinic esters and transformed to the corresponding amides (4). Lawesson´s treatment of 2 and 4 gave the corresponding bithiophenes (5) with alkoxy or amino substituents. Fundação para a Ci~Encia e Tecnologia. ICCTI/French Embassy - Technical and Scientific~Cooperation Programme.

  5. Highly active and reusable catalyst from Fe-Mg-hydrotalcite anionic clay for Friedel-Crafts type benzylation reactions

    Vasant R Choudhary; Rani Jha; Pankaj A Choudhari


    Fe-Mg-hydrotalcite (Mg/Fe = 3) anionic clay with or without calcination (at 200-800°C) has been used for the benzylation of toluene and other aromatic compounds by benzyl chloride. Hydrotalcite before and after its calcination was characterized for surface area, crystalline phases and basicity. Both the hydrotalcite, particularly after its use in the benzylation reaction, and the catalyst derived from it by its calcination at 200-800°C show high catalytic activity for the benzylation of toluene and other aromatic compounds. The catalytically active species present in the catalyst in its most active form are the chlorides and oxides of iron on the catalyst surface.

  6. Primary deuterium isotope effects for the 3-methylaspartase-catalyzed deamination of (2S)-aspartic acid, (2S,3S)-3-ethylaspartic acid, and (2S,3S)-3-ethylaspartic acid

    Botting, N.P.; Cohen, M.A.; Akhtar, M.; Gani, D.


    3-Methylaspartate ammonia-lyase catalyzes the deamination of (2S)-aspartic acid 137 times more slowly than the deamination of (2S,3S)-3-methylaspartic acid but catalyzes the amination of fumaric acid 1.8 times faster than the amination of mesaconic acid. In order to understand the mechanistic basis for these observations, the deamination reaction was examined kinetically with (2S)-aspartic acid, (2S,3S)-3-methylaspartic acid, (2S,3S)-3-ethylaspartic acid, and the corresponding C-3-deuteriated isotopomers. Comparison of the double-reciprocal plots of the initial reaction velocities for each of the three pairs of substrates revealed that the magnitude of the primary isotope effect on both V/sub max/ and VK varied with the substituent at C-3 of the substrate. These results, which are inconsistent with earlier reports that there is no primary isotope effect for 3-methylaspartic acid, suggest that for both 3-methylaspartic acid and 3-ethylaspartic acid elimination occurs via a predominantly concerted mechanism whereas for aspartic acid in El/sub cb/ mechanism prevails. It is expected that the change in mechanism arises as a result of the loss of the hydrophobic interaction between the C-3-alkyl substituent of the substrate and the complementary active site pocket of the enzyme, which leads to poor orbital alignment of the nascent negative charge with the C-N bond in the carbanion derived from aspartic acid. Substrate C-3 hydrogen exchange experiments suggest that the intermediate carbanionconjugate acid is not accessible to solvent during catalysis.

  7. Brønsted acid ionic liquid catalyzed formation of pyruvaldehyde dimethylacetal from triose sugars

    Shunmugavel, Saravanamurugan; Riisager, Anders


    A series of sulfonic acid functionalized ionic liquids (SO3H-ILs) have been synthesized, characterized and investigated as catalysts for the conversion of the triose sugars, 1,3-dihydroxyacetone (DHA) and glyceraldehyde (GLA), to pyruvaldehyde dimethylacetal (PADA) in methanol. Depending...

  8. Oxalic acid catalyzed solvent-free one pot synthesis of coumarins


    Oxalic acid was found to be an efficient catalyst for Pechmann condensation, which includes the reaction between phenols and β-keto esters leading to formation of coumarin derivatives. The advantages of present methods are the use of cheap and easy available catalyst, solvent-free reaction conditions, better yields and shorter reaction time.

  9. Oxalic Acid Catalyzed Three Component One Pot Synthesis of 3,4-Dihydroquinazolin-4-ones

    SANGSHETTI Jaiprakash-N.; KOKARE Nagnnath-D.; SHINDE Devanand-B.


    An efficient one-pot method for synthesis of an array of 3,4-dihydroquinazolin-4-ones from anthranilicacid, triethyl orthoformate, and anilines using oxalic acid as a catalyst was described. The present protocol offers im-provements for the synthesis of 3,4-dihydroquinazolin-4-ones with regard to short reaction time, high yields of products, and simplicity in operation.

  10. Studies concerning the anion ex-change resins catalyzed esterification of epichlorohydrin with organic acids

    E.I. Muresan


    Full Text Available The paper studies the esterification of carboxylic acids with epichlorohydrin over two macroporous strong base anion exchange resins with different polymer matrix. For both resins, the influence of reaction parameters (temperature, catalyst loading, molar ratio on the reaction rate and the yields of the two isomeric esters were investigated.

  11. Lewis base additives improve the zeolite ferrierite-catalyzed synthesis of isostearic acid

    Isostearic acid (IA) is of interest for industrial purposes especially in the area of biolubricants, such as cosmetics and slip additives for polyolefin and related copolymer films. This study was designed to develop a zeolitic catalysis process for IA production through isomerization of fatty aci...

  12. Intramolecular redox reaction for the synthesis of N-aryl pyrroles catalyzed by Lewis acids.

    Du, Hong-Jin; Zhen, Le; Wen, Xiaoan; Xu, Qing-Long; Sun, Hongbin


    An efficient approach to synthesize N-aryl pyrroles via Lewis acid-mediated 1,5-hydride shift and isomerization of 2-(3-pyrroline-1-yl)arylaldehydes has been achieved in up to 89% yield. This methodology is applicable to the synthesis of fluorazene derivatives as electron donor (D)/acceptor (A) molecules.

  13. Lewis Acid Catalyzed 1,3-Dipolar Cycloadditon Reactions of Stabilized Azomethine Ylides

    KANIŞKAN, Hasan KOYUNCU & DOĞAN, Özdemir


    Diethylzinc was tested for the first time as the Lewis acid in 1,3-dipolar cycloaddition reactions of azomethine ylides to synthesize pyrrolidine derivatives. A new, easily applicable and highly selective method was developed for the synthesis of highly substituted pyrrolidines. By the application of this method, the synthesis of three new pyrrolidine derivatives was achieved.

  14. A highly enantioselective phase-transfer catalyzed epoxidation of enones with a mild oxidant, trichloroisocyanuric acid.

    Ye, Jinxing; Wang, Yongcan; Liu, Renhua; Zhang, Guofu; Zhang, Qing; Chen, Jiping; Liang, Xinmiao


    The enantioselective epoxidation can be carried out using trichloroisocyanuric acid (TCCA) as oxidant in the presence of chiral quaternary ammonium salt as a phase-transfer catalyst; treatment of chalcone derivatives with TCCA under mild conditions afforded the corresponding epoxy ketones in good yields with moderate to excellent enantioselectivities of up to 96%.

  15. Lipase-catalyzed synthesis of oligoesters of 2,5-furandicarboxylic acid with aliphatic diols

    Cruz-Izquierdo, Álvaro; Broek, van den Lambertus A.M.; Serra, Juan L.; Llama, María J.; Boeriu, Carmen G.


    2,5-Furandicarboxylic acid is a platform chemical for the production of biobased polymers and materials. This study reports the synthesis of furan oligoesters via polytransesterification of dimethyl furan-2,5-dicarboxylate and linear α, ω-aliphatic diols with chain length ranging from C2 to C12,

  16. Lewis-acid catalyzed depolymerization of Protobind lignin in supercritical water and ethanol

    Guvenatam, Burcu; Heeres, Erik H.J.; Pidko, Evgeny A.; Hensen, Ernie J. M.


    The use of metal acetates, metal chlorides and metal triflates as Lewis acid catalysts for the depolymerization of soda lignin under supercritical conditions was investigated. The reactions were carried out at 400 degrees C in water and ethanol. Lignin conversion in supercritical water led to format

  17. Acid-functionalized mesoporous carbon: an efficient support for ruthenium-catalyzed γ-valerolactone production.

    Villa, Alberto; Schiavoni, Marco; Chan-Thaw, Carine E; Fulvio, Pasquale F; Mayes, Richard T; Dai, Sheng; More, Karren L; Veith, Gabriel M; Prati, Laura


    The hydrogenation of levulinic acid has been studied using Ru supported on ordered mesoporous carbons (OMCs) prepared by soft-templating. P- and S-containing acid groups were introduced by postsynthetic functionalization before the addition of 1 % Ru by incipient wetness impregnation. These functionalities and the reaction conditions mediate the activity and selectivity of the levulinic acid hydrogenation. The presence of S-containing groups (Ru/OMC-S and Ru/OMC-P/S) deactivates the Ru catalysts strongly, whereas the presence of P-containing groups (Ru/OMC-P) enhances the activity compared to that of pristine Ru/OMC. Under mild conditions (70 °C and 7 bar H2 ) the catalyst shows high selectivity to γ-valerolactone (GVL; >95 %) and high stability on recycling. However, under more severe conditions (200 °C and p H 2=40 bar) Ru/OMC-P is particularly able to promote GVL ring-opening and the consecutive hydrogenation to pentanoic acid. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.


    SPARC (SPARC Performs Automated Reasoning in Chemistry) chemical reactivity models were extended to calculate acid and neutral hydrolysis rate constants of phosphate esters in water. The rate is calculated from the energy difference between the initial and transition states of a ...

  19. Tannic acid Catalyzed an Efficient Synthesis of 2,4,5-Triaryl-1H-Imidazole

    Shitole Nana Vikram


    Full Text Available Tannic acid (C76H52O46 has been found to be an efficient catalyst for one-pot synthesis of 2,4,5-triaryl substituted imidazoles by the reaction of an arylaldehyde, benzyl/benzoin and an ammonium acetate. The short reaction time and excellent yields making this protocol practical and economically attractive.

  20. The influence of acidity on zeolite H-BEA catalyzed isobutane/n-butene alkylation

    Nivarthy, Gautam S.; Seshan, K.; Lercher, Johannes A.


    The influence of the concentration of acid sites for isobutane/n-butene alkylation on zeolite BEA with varying degrees of Na+ ion exchange is reported. All catalysts studied showed complete n-butene conversion over a significant time-on-stream. Isooctanes were the dominating products over H-BEA, whi

  1. Lipase-catalyzed synthesis of oligoesters of 2,5-furandicarboxylic acid with aliphatic diols

    Cruz-Izquierdo, Álvaro; Broek, van den Lambertus A.M.; Serra, Juan L.; Llama, María J.; Boeriu, Carmen G.


    2,5-Furandicarboxylic acid is a platform chemical for the production of biobased polymers and materials. This study reports the synthesis of furan oligoesters via polytransesterification of dimethyl furan-2,5-dicarboxylate and linear α, ω-aliphatic diols with chain length ranging from C2 to C12,

  2. Copper-catalyzed Chan-Lam coupling between sulfonyl azides and boronic acids at room temperature.

    Moon, Soo-Yeon; Nam, Jungsoo; Rathwell, Kris; Kim, Won-Suk


    A mild and efficient method for the synthesis of N-arylsulfonamides in the presence of 10 mol % of CuCl is demonstrated. The reaction proceeds readily at room temperature in an open flask using a variety of sulfonyl azides and boronic acids without any base, ligand, or additive.

  3. Nonmetal catalyzed insertion reactions of diazocarbonyls to acid derivatives in fluorinated alcohols.

    Dumitrescu, Lidia; Azzouzi-Zriba, Kaouther; Bonnet-Delpon, Danièle; Crousse, Benoit


    The insertion reaction of diazocarbonyls to acids could be performed smoothly in fluorinated alcohols in the absence of metal catalyst. This new procedure allowed the chemoselective preparation of various functionalized compounds such as acyloxyesters, depsipeptides, and sulfonate, phosphonate, or boronate derivatives.

  4. Coupling of Carbon Dioxide with Epoxides Catalyzed by Amino Acid Hydrochloride Salts


    Using amino acid hydrochloride salt as a catalyst, the coupling reaction of CO2 with epoxides could proceed smoothly to give cyclic carbonates in very good yields and high selectivity. The reaction conditions such as the pressure of carbon dioxide, reaction temperature, time and catalyst loading were carefully investigated.

  5. Interesterification of Milk Fat with Oleic Acid Catalyzed by Immobilized Rhizopus oryzae Lipase

    OBA, T; Witholt, B.


    Milk fat was interesterified with oleic acid by catalysis of an immobilized lipase in a microaqueous two-phase system. A commercial lipase from Rhizopus oryzae and a controlled pore glass carrier were selected for preparation of an immobilized lipase. The prepared immobilized lipase showed a Michael




    Milk fat was interesterified with oleic acid by catalysis of an immobilized lipase in a microaqueous two-phase system. A commercial lipase from Rhizopus oryzae and a controlled pore glass carrier were selected for preparation of an immobilized lipase. The prepared immobilized lipase showed a Michael

  7. Lewis-acid catalyzed depolymerization of Protobind lignin in supercritical water and ethanol

    Guvenatam, Burcu; Heeres, Erik H.J.; Pidko, Evgeny A.; Hensen, Ernie J. M.


    The use of metal acetates, metal chlorides and metal triflates as Lewis acid catalysts for the depolymerization of soda lignin under supercritical conditions was investigated. The reactions were carried out at 400 degrees C in water and ethanol. Lignin conversion in supercritical water led to

  8. Temperature regulated Brønsted acidic ionic liquid-catalyze esterification of oleic acid for biodiesel application

    Rafiee, Ezzat; Mirnezami, Fakhrosadat


    By combining phosphotungstic acid (PW) and SO3H- functioned zwitterion, heteropoly anion-based Brønsted acidic ionic liquids (HPA-ILs) were successfully obtained. Scanning electron microscopy and energy dispersive X-ray spectroscopy were provided the morphology and composition of the prepared material. Catalytic performance and reusability of the catalysts were evaluated through an esterification reaction between oleic acid and methanol for production of biodiesel. Relationship between catalytic activities and acidity of the catalysts have been discussed by potentiometric titration. The results showed that HPA-ILs had good activity and reusability. HPA-ILs dissolved in the reaction mixture during the reaction process and could be precipitated and separated from products at lower temperature.

  9. Imidase catalyzing desymmetric imide hydrolysis forming optically active 3-substituted glutaric acid monoamides for the synthesis of gamma-aminobutyric acid (GABA) analogs.

    Nojiri, Masutoshi; Hibi, Makoto; Shizawa, Hiroaki; Horinouchi, Nobuyuki; Yasohara, Yoshihiko; Takahashi, Satomi; Ogawa, Jun


    The recent use of optically active 3-substituted gamma-aminobutyric acid (GABA) analogs in human therapeutics has identified a need for an efficient, stereoselective method of their synthesis. Here, bacterial strains were screened for enzymes capable of stereospecific hydrolysis of 3-substituted glutarimides to generate (R)-3-substituted glutaric acid monoamides. The bacteria Alcaligenes faecalis NBRC13111 and Burkholderia phytofirmans DSM17436 were discovered to hydrolyze 3-(4-chlorophenyl) glutarimide (CGI) to (R)-3-(4-chlorophenyl) glutaric acid monoamide (CGM) with 98.1% enantiomeric excess (e.e.) and 97.5% e.e., respectively. B. phytofirmans DSM17436 could also hydrolyze 3-isobutyl glutarimide (IBI) to produce (R)-3-isobutyl glutaric acid monoamide (IBM) with 94.9% e.e. BpIH, an imidase, was purified from B. phytofirmans DSM17436 and found to generate (R)-CGM from CGI with specific activity of 0.95 U/mg. The amino acid sequence of BpIH had a 75% sequence identity to that of allantoinase from A. faecalis NBRC13111 (AfIH). The purified recombinant BpIH and AfIH catalyzed (R)-selective hydrolysis of CGI and IBI. In addition, a preliminary investigation of the enzymatic properties of BpIH and AfIH revealed that both enzymes were stable in the range of pH 6-10, with an optimal pH of 9.0, stable at temperatures below 40 °C, and were not metalloproteins. These results indicate that the use of this class of hydrolase to generate optically active 3-substituted glutaric acid monoamide could simplify the production of specific chiral GABA analogs for drug therapeutics.

  10. Dehydrogenation of Formic Acid Catalyzed by a Ruthenium Complex with an N,N′-Diimine Ligand

    Guan, Chao


    We report a ruthenium complex containing an N,N′-diimine ligand for the selective decomposition of formic acid to H and CO in water in the absence of any organic additives. A turnover frequency of 12000 h and a turnover number of 350 000 at 90 °C were achieved in the HCOOH/HCOONa aqueous solution. Efficient production of high-pressure H and CO (24.0 MPa (3480 psi)) was achieved through the decomposition of formic acid with no formation of CO. Mechanistic studies by NMR and DFT calculations indicate that there may be two competitive pathways for the key hydride transfer rate-determining step in the catalytic process.

  11. KSF-supported heteropoly acids catalyzed one-pot synthesis of α-aminonitriles

    Ezzat Rafiee


    Full Text Available In the presence of KSF-supported heteropoly acid as a heterogeneous, reusable and inexpensive catalyst, three-component reactions between aldehydes or ketones, amines, and trimethylsilyl cyanide preceded to afford α-aminonitriles in excellent yields, very short reaction times, and low loading of catalyst. This catalyst was highly selective and other functional groups including carbon-carbon double bond, and heterocyclic moieties did not affect the reaction.

  12. Acid-base jointly promoted copper(I)-catalyzed azide-alkyne cycloaddition.

    Shao, Changwei; Wang, Xinyan; Zhang, Qun; Luo, Sheng; Zhao, Jichen; Hu, Yuefei


    In this novel acid-base jointly promoted CuAAC, the combination of CuI/DIPEA/HOAc was developed as a highly efficient catalytic system. The functions of DIPEA and HOAc have been assigned, and HOAc was recognized to accelerate the conversions of the C-Cu bond-containing intermediates and buffer the basicity of DIPEA. As a result, all drawbacks occurring in the popular catalytic system CuI/NR(3) were overcome easily.

  13. Hydrolysis of Selected Tropical Plant Wastes Catalyzed by a Magnetic Carbonaceous Acid with Microwave

    Su, Tong-Chao; Fang, Zhen; Zhang, Fan; Luo, Jia; Li, Xing-Kang


    In this study, magnetic carbonaceous acids were synthesized by pyrolysis of the homogeneous mixtures of glucose and magnetic Fe3O4 nanoparticles, and subsequent sulfonation. The synthesis conditions were optimized to obtain a catalyst with both high acid density (0.75 mmol g-1) and strong magnetism [magnetic saturation, Ms = 19.5 Am2 kg-1]. The screened catalyst (C-SO3H/Fe3O4) was used to hydrolyze ball-milled cellulose in a microwave reactor with total reducing sugar (TRS) yield of 25.3% under the best conditions at 190 °C for 3.5 h. It was cycled for at least seven times with high catalyst recovery rate (92.8%), acid density (0.63 mmol g-1) and magnetism (Ms = 12.9 Am2 kg-1), as well as high TRS yield (20.1%) from the hydrolysis of ball-milled cellulose. The catalyst was further successfully tested for the hydrolysis of tropical biomass with high TRS and glucose yields of 79.8% and 58.3% for bagasse, 47.2% and 35.6% for Jatropha hulls, as well as 54.4% and 35.8% for Plukenetia hulls.

  14. Phenylsulfonic Acid Functionalized Mesoporous Silica Catalyzed Transetherification of Alcohols with Dimethoxymethane

    杨建明; 吕剑


    Phenylsulfonic acid functionalized mesoporous silica was synthesized by condensation of tetraethylorthosilicate with phenyltrimethoxysilane, and then sulfonation using 30% fuming sulfuric acid. The material was characterized using FT-IR, DSC, XPS, TEM and N2 adsorption/desorption measurements. DSC revealed that sulfonic acid group of the catalyst was decomposed at 354.8℃, indicating that the catalyst exhibited high thermal stability. XPS showed that there existed three kinds of different silicon species on surface of the catalyst. The catalytic performance of the catalyst was evaluated using transetherification of alcohols with dimethoxymethane. It was found that among primary alcohols, the selectivities of the two long-chain alcohols for n-dedocanol and n-tetradecyl alcohol were higher than 97.0% at the conversions of 43.6% and 65.3%, respectively, while the selectivities of the short-chain alcohols except for n-hexanol were less than 90.0% at the conversions of over 80.0%. Due to steric bartier, the secondary alcohols such as /so-butanol and cyclohexanol afforded conversions of 79.4% and 60.5%, and the selectivities of the two alcohols were more than 90.0%. The sequence in conversion of the substituted phenols isas follows: p-nitrophenol>p-fluorophenol≥p-bromophenol>p-cresol>m-cresol.

  15. Acid Hydrolysis of Bromazepam Catalyzed by Micelles, Reverse Micelles, and Microemulsions

    Ferdousi Begum


    Full Text Available Kinetics of the acid hydrolysis of bromazepam (Bz has been investigated in micelles, reverse micelles, and microemulcions of cetyltrimethylammonium bromide (CTAB by spectrophotometric method. The rate of the acid hydrolysis of Bz was found to be enhanced both below and above the critical micelle concentration (CMC of CTAB in aqueous solution. The pseudo-first-order rate constant (k′ shows an initial decrease for both low and high H+ concentrations. With further increase in [CTAB], at low [H+], the k′ attains an almost constant value, while, at high [H+], the k′ passes through a maximum and then decreases. The kinetic data for catalysis by micelles of CTAB was interpreted with the pseudophase ion exchange (PIE model. In CTAB/cyclohexane/1-butanol/water microemulsions, as the water to surfactant ratio (wo increases, the physicochemical properties and droplet sizes of microemulsions significantly change and distinct changes in reaction environment can be marked. The rate of the hydrolysis reaction exhibits excellent correlation with the physicochemical properties and droplet sizes of the microemulsions and reverse micelles of CTAB. At [H+] = 0.001 M, in reverse micelles and microemulsions of CTAB, the k′ of the acid hydrolysis of Bz decreases sharply followed by a slight increase with increasing wo.

  16. Asymmetric Aldol Reaction Catalyzed by L-Proline and Achiral Thiourea Fluoroboric Acid Salt

    Cho, Eun; Lee, Haney; Kim, Taek Hyeon [Chonnam National University, Gwangju (Korea, Republic of)


    Considering its ready availability and low cost, L-proline would be the first choice catalyst for preparing aldol adducts with high diastereo- and enantioselectivity. However, proline presents some major drawbacks, including poor performance in direct aldol reactions with aromatic aldehydes, limited solubility, and reactivity in nonpolar organic solvents, and side reactions that make using high catalyst loadings necessary to reach satisfactory conversions. Therefore, numerous proline-modified organo catalysts such as prolinamides, proline thioamides, sulfonamides, chiral amines, and organic salts have been designed for direct aldol reactions. An alternative is to add a readily available additive to the reactions containing proline. This last approach is clearly advantageous in avoiding tedious chemical syntheses of organo catalysts and would ultimately allow the construction of libraries of catalyst protocols by simply changing the additive. Acid additives can influence the outcome of enamine mediated reactions; however, only a few screening studies of acid additions to thiourea organo catalysts are available in the literature. The reaction between cyclohexanone and 4-nitrobenzaldehyde was selected as a standard model reaction for screening of more effective acid additives to thiourea.

  17. Hierarchical porous photoanode based on acid boric catalyzed sol for dye sensitized solar cells

    Maleki, Khatereh; Abdizadeh, Hossein; Golobostanfard, Mohammad Reza; Adelfar, Razieh


    The hierarchical porous photoanode of the dye sensitized solar cell (DSSC) is synthesized through non-aqueous sol-gel method based on H3BO3 as an acid catalyst and the efficiencies of the fabricated DSSC based on these photoanodes are compared. The sol parameters of 0.17 M, water mole ratio of 4.5, acid mole ratio of 0.45, and solvent type of ethanol are introduced as optimum parameters for photoanode formation without any detectable cracks. The optimized hierarchical photoanode mainly contains anatase phase with slight shift toward higher angles, confirming the doping of boron into titania structure. Moreover, the porous structure involves two ranges of average pore sizes of 20 and 635 nm. The diffuse reflectance spectroscopy (DRS) shows the proper scattering and blueshift in band gap. The paste parameters of solid:liquid, TiO2:ethyl cellulose, and terpineol:ethanol equal to 11:89, 3.5:7.5, and 25:64, respectively, are assigned as optimized parameters for this novel paste. The photovoltaic properties of short circuit current density, open circuit voltage, fill factor, and efficiency of 5.89 mA/cm2, 703 mV, 0.7, and 2.91% are obtained for the optimized sample, respectively. The relatively higher short circuit current of the main sample compared to other samples is mainly due to higher dye adsorption in this sample corresponding to its higher surface area and presumably higher charge transfer confirmed by low RS and Rct in electrochemical impedance spectroscopy data. Boric acid as a catalyst in titania sol not only forms hierarchical porous structure, but also dopes the titania lattice, which results in appreciated performance in this device.

  18. A green protocol for the synthesis of quinoxaline derivatives catalyzed by polymer supported sulphanilic acid

    Umesh P. Tarpada


    Full Text Available Polymer supported sulphanilic acid was found to be an effective heterogeneous catalyst for one pot synthesis of various quinoxaline derivatives from the condensation reaction between 1,2-diamines and 1,2-dicarbonyl compounds in ethanol. Synthesis was attempted under reflux as well as at room temperature using ethanol as the solvent to afford excellent yields. Heterogeneity of the catalyst allowed its recycling for five times with almost retention in catalytic activity. Prepared quinoxaline derivatives were also tested for their antioxidant activity by the FRAP assay method.

  19. Silver-catalyzed decarboxylative alkynylation of aliphatic carboxylic acids in aqueous solution.

    Liu, Xuesong; Wang, Zhentao; Cheng, Xiaomin; Li, Chaozhong


    C(sp(3))-C(sp) bond formations are of immense interest in chemistry and material sciences. We report herein a convenient, radical-mediated and catalytic method for C(sp(3))-C(sp) cross-coupling. Thus, with AgNO(3) as the catalyst and K(2)S(2)O(8) as the oxidant, various aliphatic carboxylic acids underwent decarboxylative alkynylation with commercially available ethynylbenziodoxolones in aqueous solution under mild conditions. This site-specific alkynylation is not only general and efficient but also functional group compatible. In addition, it exhibits remarkable chemo- and stereoselectivity.

  20. Acid, silver, and solvent-free gold-catalyzed hydrophenoxylation of internal alkynes

    Marcia E. Richard


    Full Text Available A range of arylgold compounds have been synthesized and investigated as single-component catalysts for the hydrophenoxylation of unactivated internal alkynes. Both carbene and phosphine-ligated compounds were screened as part of this work, and the most efficient catalysts contained either JohnPhos or IPr/SIPr. Phenols bearing either electron-withdrawing or electron-donating groups were efficiently added using these catalysts. No silver salts, acids, or solvents were needed for the catalysis, and either microwave or conventional heating afforded moderate to excellent yields of the vinyl ethers.

  1. Acid, silver, and solvent-free gold-catalyzed hydrophenoxylation of internal alkynes

    Richard, Marcia E; Fraccica, Daniel V; Garcia, Kevin J; Miller, Erica J; Ciccarelli, Rosa M; Holahan, Erin C; Resh, Victoria L; Shah, Aakash; Findeis, Peter M


    Summary A range of arylgold compounds have been synthesized and investigated as single-component catalysts for the hydrophenoxylation of unactivated internal alkynes. Both carbene and phosphine-ligated compounds were screened as part of this work, and the most efficient catalysts contained either JohnPhos or IPr/SIPr. Phenols bearing either electron-withdrawing or electron-donating groups were efficiently added using these catalysts. No silver salts, acids, or solvents were needed for the catalysis, and either microwave or conventional heating afforded moderate to excellent yields of the vinyl ethers. PMID:24204410

  2. Phase Transfer Catalyzed Synthesis of Thiosemicarbazide Derivatives of 2-ethoxybenzoic Acid

    WEI; TaiBao


    A series of 1,4-disubstitued thiosemicarbazides and their related heterocyclic compounds have been found to possess important biological activities[1]. Some thiosemicarbazides have been found to be useful as herbicides, insecticides and plant-growth regulators [1]. In view of these and in continuation of our earlier work on the synthesis and biological activity of thiosemicarbaides derivatives [2], we now report a convenient and efficient method for the preparation of thiosemicarbazides derivatives of 2-ethoxybenzoic acid under the condition of solid-liquid phase transfer catalysis using PEG-400 as the catalyst.  ……

  3. Phase Transfer Catalyzed Synthesis of Thiosemicarbazide Derivatives of 2-ethoxybenzoic Acid

    WEI TaiBao; ZHANG YouMing; WU JiaWei


    @@ A series of 1,4-disubstitued thiosemicarbazides and their related heterocyclic compounds have been found to possess important biological activities[1]. Some thiosemicarbazides have been found to be useful as herbicides, insecticides and plant-growth regulators [1]. In view of these and in continuation of our earlier work on the synthesis and biological activity of thiosemicarbaides derivatives [2], we now report a convenient and efficient method for the preparation of thiosemicarbazides derivatives of 2-ethoxybenzoic acid under the condition of solid-liquid phase transfer catalysis using PEG-400 as the catalyst.

  4. The acid-catalyzed hydrolysis of an α-pinene-derived organic nitrate: kinetics, products, reaction mechanisms, and atmospheric impact

    Rindelaub, Joel D.; Borca, Carlos H.; Hostetler, Matthew A.; Slade, Jonathan H.; Lipton, Mark A.; Slipchenko, Lyudmila V.; Shepson, Paul B.


    data, product identification confirms that a unimolecular specific acid-catalyzed mechanism is responsible for organic nitrate hydrolysis under acidic conditions. The free energies and enthalpies of the isobutyl nitrate hydrolysis intermediates and products were calculated using a hybrid density functional (ωB97X-V) to support the proposed mechanisms. These findings provide valuable information regarding the organic nitrate hydrolysis mechanism and its contribution to the fate of atmospheric NOx, aerosol phase processing, and BSOA composition.

  5. N-heterocyclic carbene-assisted, bis(phosphine)nickel-catalyzed cross-couplings of diarylborinic acids with aryl chlorides, tosylates, and sulfamates.

    Ke, Haihua; Chen, Xiaofeng; Zou, Gang


    Efficient bis(phosphine)nickel-catalyzed cross-couplings of diarylborinic acids with aryl chlorides, tosylates, and sulfamates have been effected with an assistance of N-heterocyclic carbene (NHC) generated in situ from N,N'-dialkylimidazoliums, e.g., N-butyl-N'-methylimidazolium bromide ([Bmim]Br), in toluene using K3PO4·3H2O as base. In contrast to bis(NHC)nickel-catalyzed conventional Suzuki coupling of arylboronic acids, mono(NHC)bis(phosphine)nickel species generated in situ from Ni(PPh3)2Cl2/[Bmim]Br displayed high catalytic activities in the cross-couplings of diarylborinic acids. The structural influences from diarylborinic acids were found to be rather small, while electronic factors from aryl chlorides, tosylates, and sulfamates affected the couplings remarkably. The couplings of electronically activated aryl chlorides, tosylates, and sulfamates could be efficiently effected with 1.5 mol % NiCl2(PPh3)2/[Bmim]Br as catalyst precursor to give the biaryl products in excellent yields, while 3-5 mol % loadings had to be used for the couplings of non- and deactivated ones. A small ortho-substitutent on the aromatic ring of aryl chlorides, tosylates, and sulfamates was tolerable. Applicability of the nickel-catalyzed cross-couplings in practical synthesis of fine chemicals has been demonstrated in process development for a third-generation topical retinoid, Adapalene.

  6. Effect of polyvinylpyrrolidone on mesoporous silica morphology and esterification of lauric acid with 1-butanol catalyzed by immobilized enzyme

    Zhang, Jinyu; Zhou, Guowei; Jiang, Bin; Zhao, Minnan; Zhang, Yan


    Mesoporous silica materials with a range of morphology evolution, i.e., from curved rod-shaped mesoporous silica to straight rod-shaped mesoporous silica, were successfully prepared using polyvinylpyrrolidone (PVP) and triblock copolymer as dual template. The effects of PVP molecular weight and concentration on mesoporous silica structure parameters were studied. Results showed that surface area and pore volume continuously decreased with increased PVP molecular weight. Mesoporous silica prepared with PVP K30 also possessed larger pore diameter, interplanar spacing (d100), and cell parameter (a0) than that prepared with PVP K15 and PVP K90. In addition, with increased PVP concentration, d100 and a0 continuously decreased. The mechanism of morphology evolution caused by the change in PVP concentration was investigated. The conversion rate of lauric acid with 1-butanol catalyzed by immobilized Porcine pancreatic lipase (PPL) was also evaluated. Results showed that PPL immobilized on amino-functionalized straight rod-shaped mesoporous silica maintained 50% of its esterification conversion rate even after five cycles of use with a maximum conversion rate was about 90.15%.

  7. Kinetics and Mechanism of Iridium(Ⅲ)-Catalyzed Oxidation of Ethanol Amine by Cerium(Ⅳ) in Sulfuric Acid Media

    ZHAI Yong-qing; LIU Hong-mei; YANG Lin; YANG Guo-zhong; SONG Wen-yu; LIU Yu-kai


    In this study, the kinetics and mechanism of the iridium(Ⅲ)-catalyzed oxidation of ethanol amine(EAN) by cerium(Ⅳ) in a sulfuric acid medium was investigated using titrimetric technique of redox in a temperature range of 298-313 K. It was found that the reaction is of first order with respect to Ce(Ⅳ) and Ir(Ⅲ), and a positive fractional order with respect to EAN. It was also found that the pseudo-first-order([EAN](》)[Ce(Ⅳ)]) rate constant kobs decreases with the increase of [H+] and [HSO-4]. Under the protection of nitrogen gas, the reaction system can initiate the polymerization of acrylonitrile, indicating the generation of free radicals. On the basis of the experimental results, a suitable mechanism was proposed. From the dependence of kobs on the concentration of hydrogen sulfate, Ce(SO4)2 was found to be the kinetically active species. The rate constants of the rate-determining step together with the activation parameters were evaluated.




    Full Text Available


    In the present study, a kinetic model for the biocatalytic synthesis of esters using Rhizopus oryzae resting cells is proposed. The kinetic study has been made in a range of 30-50 °C and atmospheric pressure. The Influence of operating variables, water content, pH, amount of mycelium was studied. Different values of temperature, initial mycelium concentration and acid/alcohol molar ratio were tested. Initial rates were estimated from the slope of the concentration of palmitic acid, or their corresponding ester at conversions of less than 10%, versus time and reported as mmol l-1 min -1. The values of kinetic constants were computed using the freeware program SIMFIT (http:\\

    Key words: bound lipase, esterification, fungal resting cells, Rhizopus oryzae, palmitic acid, propanol.


    En el presente estudio, un modelo cinético para la síntesis de esteres usando Rhizopus oryzae resting cells es propuesto. El estudio cinético fue realizado en un rango de temperatura de 30-50 ºC a presión atmosférica reducida. La influencia de las variables de operación tales como temperatura, pH y contenido de agua fueron estudiadas. Diferentes valores de concentración de micelio y relación molar de ácido/alcohol son ensayadas, Las velocidades iníciales se estimaron de la curva de concentración de acido palmítico, y su correspondiente conversión a ester en menos del 10%, frente a tiempo y reportadas en mmol I-1 min -1. Los valores de las constantes cinéticas fueron calculados usando el programa freeware SIMFIT (http:\\

    Palabras clave: Lipasas, esterificación, resting cells, Rhizopus oryzae, acido palmítico, propanol.

  9. Optimization of oligoglycerol fatty acid esters preparation catalyzed by Lipozyme 435

    Wan, F. L.


    Full Text Available Oli goglycerol fatty acid esters (OGEs are an important kind of polyglycerol fatty acid esters (PGEs which have been widely used as emulsifiers in food, medicine and cosmetic industries. The aim of this study was to investigate the preparation of OGEs by the esterification of olig oglycerol with linoleic acid in a solvent- free system using Lipozyme 435 as the catalyst. The effects of substrate molar ratio, reaction time, reaction temperature, enzyme dosage, and water addition on the efficiency of esterification (EE were studied. Single factor experiments and response surface methodology (RSM were employed to optimize the reaction parameters. The optimum conditions were obtained as follows: reaction time 4.52 h, reaction temperature 90 °C, enzyme dosage 2 wt% (based on the total substrate mass, the molar ratio of oligoglycerol to linoleic acid 1.59:1 and no water addition. Under these conditions, the experimental EE (95.82±0.22% fitted well with that predicted by RSM (96.15%. Similar results were obtained when the process was scaled up to a production of 500 g in a pilot bubble column reactor (BCR. The enzyme maintained 98.2% of the relative activity after 10 batches of reaction in the BCR. Electro spray ionization mass spectrum was employed to rapidly analyze the esterification products, and most species of OGEs have been identified.Los ésteres grasos de oligoglicerol (OGEs son una clase importante de ésteres de ácidos grasos de poliglicerol (PGE que han sido ampliamente utilizados como emulsionantes en alimentación, medicina y en la industria cosmética. El objetivo de este estudio fue investigar la preparación de OGEs mediante la esterificación de oligoglicerol con ácido linoleico en un sistema libre de disolvente utilizando Lipozyme 435 como catalizador. Se estudiaron los efectos en la eficiencia de esterificación (EE de la relación molar de sustratos, de los tiempos de reacción, las temperaturas de reacción, la dosis de la

  10. Unsaturated Fatty Acid Esters Metathesis Catalyzed by Silica Supported WMe5

    Riache, Nassima


    Metathesis of unsaturated fatty acid esters (FAEs) by silica supported multifunctional W-based catalyst is disclosed. This transformation represents a novel route towards unsaturated di-esters. Especially, the self-metathesis of ethyl undecylenate results almost exclusively on the homo-coupling product whereas with such catalyst, 1-decene gives ISOMET (isomerization and metathesis olefin) products. The olefin metathesis in the presence of esters is very selective without any secondary cross-metathesis products demonstrating that a high selective olefin metathesis could operate at 150 °C. Additionally, a cross-metathesis of unsaturated FAEs and α-olefins allowed the synthesis of the corresponding ester with longer hydrocarbon skeleton without isomerisation.

  11. Ozone toxicity: hormone-like oxidation products from arachidonic acid by ozone-catalyzed autoxidation

    Roycroft, J.H.; Cunter, W.B.; Menzel, D.B.


    The effects of peroxidation by ozone on the activity of arachidonic acid (AA) with and without vitamin E, on the initiation of human platelet aggregation, and on the contraction of superfused smooth muscle strips, are described. AA was rapidly oxidized by a stream of air containing 2 ppm of ozone to peroxides having biological activity similar to prostaglandin endoperoxides. Ozone-formed AA peroxides contracted both rabbit aortic strips and rat fundus strips in the presence of indomethacin and vasoactive hormones at doses comparable to naturally formed prostaglandin endoperoxides. Vitamin E had no effect on the activity of AA peroxides once formed. Ozone-formed AA peroxides also aggregated human platelets in platelet rich plasma, but this activity was blocked by the addition of indomethacin. (2 diagrams, 3 graphs, 8 references)

  12. Biomimetic Fenton-catalyzed lignin depolymerization to high-value aromatics and dicarboxylic acids.

    Zeng, Jijiao; Yoo, Chang Geun; Wang, Fei; Pan, Xuejun; Vermerris, Wilfred; Tong, Zhaohui


    By mimicking natural lignin degradation systems, the Fenton catalyst (Fe(3+), H2O2) can effectively facilitate lignin depolymerization in supercritical ethanol (7 MPa, 250 °C) to give organic oils that consist of mono- and oligomeric aromatics, phenols, dicarboxylic acids, and their derivatives in yields up to (66.0±8.5) %. The thermal properties, functional groups, and surface chemistry of lignin before and after Fenton treatment were examined by thermogravimetric analysis, pyrolysis-gas chromatography-mass spectrometry, (31)P NMR spectroscopy, and X-ray photoelectron spectroscopy. The results suggest that the Fenton catalyst facilitates lignin depolymerization through cleavage of β-ether bonds between lignin residues. The formation of a lignin-iron chelating complex effectively depresses lignin recondensation; thus minimizing charcoal formation and enhancing the yield of liquid products.

  13. Synthesis of 5-hydroxymethylfurfural (HMF) by acid catalyzed dehydration of glucose-fructose mixtures

    Pedersen, Asbjørn Toftgaard; Ringborg, Rolf Hoffmeyer; Grotkjær, Thomas


    -products: soluble humins, glucose dimers, anhydroglucose, and formic acid. The reaction conditions in four different reactor configurations were optimized and compared using the kinetic model. It was found that a recirculating reactor setup is preferable, where the equilibrium controlled by-products (anhydroglucose...... a detailed experimental investigation a reaction network was proposed, and subsequently the corresponding kinetic model was fitted to experimental data in order to obtain estimates of the reaction kinetic parameters. The kinetic model is capable of predicting the formation of HMF along with the important by...... and glucose dimers) are recirculated to the dehydration reactor. The model predicts an HMF selectivity of close to 70% in a recirculating reactor at conditions where HMF degradation is avoided....

  14. Efficient Lewis Acids Catalyzed Aza-Michael Reactions of Enones with Carbamates

    XIA Chun-Gu; XU Li-Wen


    The a-amino carbonyl functionality is not only a segment of biologically important natural products but also a versatile intermediate for the synthesis of nitrogen-containing compounds.1 The development of novel synthetic methods leading to a-amino ketone, a-amino acids or their derivatives has attracted much attention in organic synthesis.2 Among the traditional methods for generating a-amino carbonyl compounds, Mannich-type reaction is one of the classical and powerful methods.3 However, the classic Mannich reaction presents serious disadvantages, for example, there is still a drawback in that the silyl enolates have to be prepared from the corresponding carbonyl compounds. Alternatively, aza-Michael additions can be used to create carbon-heteroatom bonds by reaction of a,a-unsaturated carbonyl compounds with amines. Although recent advances have made this route more attractive, development of cheaper, simpler, and more efficient metal catalyst, especially which can be applied to chalcone, is highly desirable.In this paper, we demonstrated that the first aza-Michael reaction of chalcone with a less nucleophilic carbamates can be accomplished on Me3SiCFFeCl3 catalyst system under very mild conditions. Apart from experimental simplicity, the advantages of this methodology are the use of a very cheap Lewis acid catalyst and the insensitivity of the reaction mixture towards air and moisture.catalyst for aza-Michael reaction of chalcone and cyclic enones with carbamates. And with the cyclic enones with carbamates in dichloromethane at room temperature were also investigated. In this conjugate addition reaction, good to excellent yields of a-amino ketones were obtained with system could also mediates aza-Michael addition of carbamates to chalcone and derivatives.These new strategies opened efficient procedures for the synthesis of a-amino ketones under mild conditions.

  15. Hydrogenation of phenylpyruvic acid to phenylalanine catalyzed by Ni-B/SiO2

    Qunfang Liang; Aiqing Zhang; Lin Li


    Phenylalanine(Phe)is a significant amino acid that cannot be synthesized by human themselves but must be taken from environment.It was initially found that the nanosized amorphous Ni-B/SiO2 alloy prepared by the chemical reduction method was an effective catalyst for the preparation of Phe from phenylpyruvic acid(PPA)by amination and hydrogenation.It has been found that the amorphous Ni-B/SiO2 alloy catalyst exhibits superior activity and selectivity to the traditional catalysts Raney Nj and Urushibara nickel.The effects of reaction time.amounts of catalysts and ammonia solution,reaction temperature,and H2 pressure on the reaction have been investigated systematically.The results indicated that the yield of Phe was 97.9%.and the selectivity for Phe reached 98.9%when the reaction was carried out for 3 h at 333 K and 2.0 Mpa of H2 with m(Cat.):m(PPA)=0.6:1.0 and n(NH3):n(PPA)=3:1.The catalysts were characterized by XRD,AAS,XPS,BET,and TEM.and the relationship between the catalyst structure and the catalytic activity was discussed in detail.It was found that the reason why Ni-B/SiO2 amorphous alloy catalyst was much more active for the preparation of Phe could be accounted for by the presence of electron-rich Ni due to electron donation from alloying B:the smaller size of Ni-B particles,the larger specific surface area of Ni-B/SiO2.

  16. Acetalization of carbonyl compounds with 2,2,4-trimethyl-1,3-pentanedio catalyzed by novel carbon based solid acid catalyst

    Ling Liu; Yuechang Zhao; Shan Gan; Xuezheng Liang; Jianguo Yang; Mingyuan He


    The synthesis of 2, 4-diisopropyl-5,5-dimethyl-1,3-dioxane through the acetalization of isobutyraldehyde with 2, 2,4-trimethyl-1,3-pentanediol (TMPD) catalyzed by the novel carbon based acid was first carried out. High conversion (≥98%) and specific selectivity were obtained using the novel carbon based acid, which kept high activity after it was reused 5 times.Moreover, the catalyst could be used to catalyze the acetalization and ketalization of different aldehydes and ketones with superior yield. The yield of several products was over 90%. The novel heterogeneous catalyst has the distinct advantages of high activity, strikingly simple workup procedure, non-pollution, and reusability, which will contribute to the success of the green process greatly.

  17. Regio-, Diastereo-, and Enantioselective Nitroso-Diels-Alder Reaction of 1,3-Diene-1-carbamates Catalyzed by Chiral Phosphoric Acids.

    Pous, Jonathan; Courant, Thibaut; Bernadat, Guillaume; Iorga, Bogdan I; Blanchard, Florent; Masson, Géraldine


    Chiral phosphoric acid-catalyzed asymmetric nitroso-Diels-Alder reaction of nitrosoarenes with carbamate-dienes afforded cis-3,6-disubstituted dihydro-1,2-oxazines in high yields with excellent regio-, diastereo-, and enantioselectivities. Interestingly, we observed that the catalyst is able not only to control the enantioselectivity but also to reverse the regioselectivity of the noncatalyzed nitroso-Diels-Alder reaction. The regiochemistry reversal and asynchronous concerted mechanism were confirmed by DFT calculations.

  18. Visible-Light Photoredox-Catalyzed Giese Reaction: Decarboxylative Addition of Amino Acid Derived α-Amino Radicals to Electron-Deficient Olefins

    Millet, Anthony


    A tin- and halide-free, visible-light photoredox-catalyzed Giese reaction was developed. Primary and secondary α-amino radicals were generated readily from amino acids in the presence of catalytic amounts of an iridium photocatalyst. The reactivity of the α-amino radicals has been evaluated for the functionalization of a variety of activated olefins. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

  19. Catalytic Asymmetric Piancatelli Rearrangement: Brønsted Acid Catalyzed 4π Electrocyclization for the Synthesis of Multisubstituted Cyclopentenones

    Cai, Yunfei


    The first catalytic asymmetric Piancatelli reaction is reported. Catalyzed by a chiral Brønsted acid, the rearrangement of a wide range of furylcarbinols with a series of aniline derivatives provides valuable aminocyclopentenones in high yields as well as excellent enantioselectivities and diastereoselectivities. The high value of the aza-Piancatelli rearrangement was demonstrated by the synthesis of a cyclopentane-based hNK1 antagonist analogue.

  20. Directing Group in Decarboxylative Cross-Coupling: Copper-Catalyzed Site-Selective C-N Bond Formation from Nonactivated Aliphatic Carboxylic Acids.

    Liu, Zhao-Jing; Lu, Xi; Wang, Guan; Li, Lei; Jiang, Wei-Tao; Wang, Yu-Dong; Xiao, Bin; Fu, Yao


    Copper-catalyzed directed decarboxylative amination of nonactivated aliphatic carboxylic acids is described. This intramolecular C-N bond formation reaction provides efficient access to the synthesis of pyrrolidine and piperidine derivatives as well as the modification of complex natural products. Moreover, this reaction presents excellent site-selectivity in the C-N bond formation step through the use of directing group. Our work can be considered as a big step toward controllable radical decarboxylative carbon-heteroatom cross-coupling.

  1. Nickel-Catalyzed Cross Couplings of Benzylic Ammonium Salts and Boronic Acids: Stereospecific Formation of Diarylethanes via C–N Bond Activation

    Maity, Prantik; Shacklady-McAtee, Danielle M.; Yap, Glenn P. A.; Sirianni, Eric R.; Watson, Mary P.


    We have developed a nickel-catalyzed cross coupling of benzylic ammonium triflates with aryl boronic acids to afford diarylmethanes and diarylethanes. This reaction proceeds under mild reaction conditions and with exceptional functional group tolerance. Further, it transforms branched benzylic ammonium salts to diarylethanes with excellent chirality transfer, offering a new strategy for the synthesis of highly enantioenriched diarylethanes from readily available chiral benzylic amines. PMID:23268734

  2. Palladium-Catalyzed Synthesis of (Hetero)Aryl Alkyl Sulfones from (Hetero)Aryl Boronic Acids, Unactivated Alkyl Halides, and Potassium Metabisulfite.

    Shavnya, Andre; Hesp, Kevin D; Mascitti, Vincent; Smith, Aaron C


    A palladium-catalyzed one-step synthesis of (hetero)aryl alkyl sulfones from (hetero)arylboronic acids, potassium metabisulfite, and unactivated or activated alkylhalides is described. This transformation is of broad scope, occurs under mild conditions, and employs readily available reactants. A stoichiometric experiment has led to the isolation of a catalytically active dimeric palladium sulfinate complex, which was characterized by X-ray diffraction analysis. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Chiral Phosphorus-Olefin Ligands for the Rh(I) -Catalyzed Asymmetric Addition of Aryl Boronic Acids to Electron-Deficient Olefins.

    Chen, Qian; Li, Liang; Zhou, Guangli; Ma, Xiaoli; Zhang, Lu; Guo, Fang; Luo, Yi; Xia, Wujiong


    New chiral phosphorus-olefin hybrid ligands derived from the rigid "privileged" l-proline have been conveniently prepared and applied in the rhodium-catalyzed asymmetric arylation of electron-deficient olefins with arylboronic acids at room temperature; this reaction provides the desired products in excellent yields and high enantioselectivities. The origin of observed stereoselectivity has been investigated by density functional theory (DFT) calculations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Ruthenium-Catalyzed Selective Hydrogenation of bis-Arylidene Tetramic Acids. Application to the Synthesis of Novel Structurally Diverse Pyrrolidine-2,4-diones

    Olga Igglessi-Markopoulou


    Full Text Available Catalytic hydrogenation of 3,5-bis-arylidenetetramic acids, known for their biological activity, has been developed. The chemoselective ruthenium-catalyzed reduction of the exocyclic carbon-carbon double bonds on pyrrolidine-2,4-dione ring system, containing other reducible functions, has been investigated. Depending on the substrate the yield of the hydrogenation process can reach up to 95%. The structural elucidation has been established using NMR and HRMS spectral data.

  5. Lewis acid-catalyzed in situ transesterification/esterification of microalgae in supercritical ethanol.

    Jin, Binbin; Duan, Peigao; Xu, Yuping; Wang, Bing; Wang, Feng; Zhang, Lei


    The activities of several Lewis acid catalysts such SnCl2, FeCl3, ZnCl2, AlCl3, and NbCl5 for the in situ transesterification/esterification of lipid contained within a microalga (Chlorella pyrenoidosa) in ethanol at 350°C were examined to identify the most suitable catalyst in term of crude biodiesel (CBD) yield. Of those catalysts tested, ZnCl2 showed the highest performance toward the CBD production. Using ZnCl2 as catalyst, effects of reaction temperature (200-370 °C), time (0-120 min), ethanol to microalga ratio (EtOH:MA) (5/5-40/5), catalyst loading (0-30 wt.%), and algae moisture (0-80 wt.%) on the yields of product fractions and the properties of CBD were studied. The presence of ZnCl2 not only promoted the production of CBD but also showed activities toward the deoxygenation and denitrogenation of CBD. The moisture content in the starting material is the most influential factor affecting the yield and properties of CBD. Copyright © 2014 Elsevier Ltd. All rights reserved.

  6. Reaction kinetics for synthesis of sec-butyl alcohol catalyzed by acid-functionalized ionic liquid

    Ting Qiu; Wenli Tang; Chenggang Li; Chengming Wu; Ling Li


    The acid-functionalized ionic liquid ([HSO3Pmim]HSO4) was synthesized by a two-step method. Nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FT-IR) show that the synthesis method is feasible and high purity of ionic liquid can be obtained. Using [HSO3Pmim]HSO4 as the catalyst, we studied the reaction kinetics of synthesizing sec-butyl alcohol from sec-butyl acetate and methanol by transesterification in a high-pressure batch reactor. The effects of temperature, initial molar ratio of methanol to ester, and catalyst concentration on the conversion of sec-butyl acetate were studied. Based on its possible reaction mechanism, a ho-mogeneous kinetic model was established. The results show that the reaction heatΔH is 10.94 × 103 J·mol−1, so the reaction is an endothermic reaction. The activation energies Ea+and Ea−are 60.38 × 103 and 49.44 × 103 J·mol−1, respectively.

  7. Synthesis of acetals and ketals catalyzed by tungstosilicic acid supported on active carbon

    YANG Shui-jin; DU Xin-xian; HE Lan; SUN Ju-tang


    Catalytic activity of activated carbon supported tungstosilicic acidin synthesizing 2-methyl-2-ethoxycarbonylmethyl1,3-dioxolane, 2,4-dimethyl-2-ethoxycarbonylmethyl-l,3-dioxolane, cyclohexanone ethylene ketal, cyclohexanone 1,2-propanediol ketal, butanone ethylene ketal, butanone 1,2-propanediol ketal, 2-phenyl-1,3-dioxolane, 4-methyl-2-phenyl-1,3-dioxolane,2-propyl-1,3-dioxolane, 4-methyl-2-propyl-1,3-dioxolane was reported. It has been demonstrated that activated carbon supported tungstosilicic acid is an excellent catalyst. Various factors involved in these reactions were investigated. The optimum conditions found were: molar ratio of aldehyde/ketone to glycol is 1/1.5, mass ratio of the catalyst used to the reactants is 1.0%, and reaction time is 1.0 h. Under these conditions, the yield of 2-methyl-2-ethoxycarbonylmethyl-l,3-dioxolane is 61.5%, of 2,4-dimethyl2-ethoxycarbonylmethyl-1,3-dioxolane is 69.1%, of cyclohexanone ethylene ketal is 74.6%, of cyclohexanone 1,2-propanediol ketal is 80.1%, of butanone ethylene ketal is 69.5%, of butanone 1,2-propanediol ketal is 78.5%, of 2-phenyl-1,3-dioxolane is 56.7%, of 4-methyl-2-phenyl- 1,3-dioxolane is 86.2%, of 2-propyl-1,3-dioxolane is 87.5%, of 4-methyl-2-propyl-1,3-dioxolane is 87.9%.

  8. Activated carbon catalyzed persulfate oxidation of Azo dye acid orange 7 at ambient temperature.

    Yang, Shiying; Yang, Xin; Shao, Xueting; Niu, Rui; Wang, Leilei


    Persulfate (PS) oxidative degradation of azo dye acid orange 7 (AO7) in an aqueous solution was studied in the presence of suspended granular activated carbon (GAC) at ambient temperature (e.g., 25°C). It was observed that there existed a remarkable synergistic effect in the GAC/PS combined system. Higher PS concentration and GAC dosage resulted in higher AO7 degrading rates. Near-neutral was the optimal initial pH. Adsorption had an adverse effect on AO7 degradation. AO7 had not only a good decolorization, but a good mineralization. The decomposition of PS followed a first-order kinetics behavior both in the presence and in the absence of AO7. Radical mechanism was studied and three radical scavengers (methanol (MA), tert-butanol (TBA), phenol) were used to determine the kind of major active species taking part in the degradation of AO7 and the location of degradation reaction. It was assumed that the degradation of AO7 did not occur in the liquid phase, but in the porous bulk and boundary layer on the external surface of GAC. SO(4)(-•) or HO•, generated on or near the surface of GAC, played a major role in the AO7 degradation. Finally, the recovery performance of GAC was studied through the GAC reuse experiments.

  9. Preparation and structural characterization of poly-mannose synthesized by phosphoric acid catalyzation under microwave irradiation.

    Wang, Haisong; Cheng, Xiangrong; Shi, Yonghui; Le, Guowei


    Poly-mannose with molecular weight of 2.457 kDa was synthesized using d-mannose as substrate and phosphoric acid as catalyst under the condition of microwave irradiation for the first time. The optimum reaction conditions were microwave output power of 900 W, temperature 115°C, proton concentration 2.5 mol/L, and microwave irradiation time 5 min. The actual maximum yield was 91.46%. After purified by Sepherdex G-25 column chromatography, the structural features of poly-mannose were investigated by high-performance anion-exchange chromatography (HPAEC), high-performance gel-permeation chromatography (HPGPC), infrared (IR) spectroscopy, methylation analysis and NMR spectroscopy analysis ((1)H, (13)C, COSY, TOCSY, HMQC, and HMBC). HPAEC analysis showed that the composition of synthetic polysaccharides was d-mannose, its purity was demonstrated by HPGPC as a single symmetrical sharp peak, and additionally IR spectra demonstrated the polymerization of d-mannose. Methylation analysis and NMR spectroscopy revealed that the backbone of poly-mannose consisting of (1→3)-linked β-d-Manp, (1→3)-linked α-d-Manp, and (1→6)-linked α-d-Manp residues, and the main chain were branched at the O-2, O-3, O-4, O-6 position.

  10. Glutamate 190 is a general acid catalyst in the 6-phosphogluconate-dehydrogenase-catalyzed reaction.

    Karsten, W E; Chooback, L; Cook, P F


    Site-directed mutagenesis was used to change E190 of sheep liver 6-phosphogluconate dehydrogenase to A, D, H, K, Q, and R to probe its possible role as a general acid catalyst. Each of the mutant proteins was characterized with respect to the pH dependence of kinetic parameters. Mutations that eliminate a titrable group at position 190, result in pH-rate profiles with no observable pK on the basic side of the V/K6PG profile. Mutations that change the pK of the group at position 190 result in the expected pK perturbations in the V/K6PG profile. Kinetic parameters obtained at the pH optimum in the pH-rate profiles are consistent with a rate-limiting tautomerization of the 1,2-enediol of ribulose 5-phosphate consistent with the proposed role of E190. Data are also consistent with some participation of E190 in an isomerization required to form the active Michaelis complex.

  11. Human CYP4Z1 catalyzes the in-chain hydroxylation of lauric acid and myristic acid.

    Zöllner, Andy; Dragan, Calin-Aurel; Pistorius, Dominik; Müller, Rolf; Bode, Helge B; Peters, Frank T; Maurer, Hans H; Bureik, Matthias


    Overexpression of human CYP4Z1, a cytochrome P450 enzyme, has been correlated with poor prognosis in human cancer. However, its catalytic properties are not yet known. We expressed this P450 in Schizosaccharomyces pombe and demonstrate by whole-cell biotransformation assays CYP4Z1-dependent in-chain hydroxylation of lauric and myristic acid, which in both cases leads to the formation of four different monohydroxylated products at positions omega-2, omega-3, omega-4, and omega-5, respectively. The CYP4Z1-expressing fission yeast should be a new valuable tool for testing cancer drugs or for the development of new prodrug strategies.

  12. Optimization of Two-Step Acid-Catalyzed Hydrolysis of Oil Palm Empty Fruit Bunch for High Sugar Concentration in Hydrolysate

    Dongxu Zhang


    Full Text Available Getting high sugar concentrations in lignocellulosic biomass hydrolysate with reasonable yields of sugars is commercially attractive but very challenging. Two-step acid-catalyzed hydrolysis of oil palm empty fruit bunch (EFB was conducted to get high sugar concentrations in the hydrolysate. The biphasic kinetic model was used to guide the optimization of the first step dilute acid-catalyzed hydrolysis of EFB. A total sugar concentration of 83.0 g/L with a xylose concentration of 69.5 g/L and a xylose yield of 84.0% was experimentally achieved, which is in well agreement with the model predictions under optimal conditions (3% H2SO4 and 1.2% H3PO4, w/v, liquid to solid ratio 3 mL/g, 130°C, and 36 min. To further increase total sugar and xylose concentrations in hydrolysate, a second step hydrolysis was performed by adding fresh EFB to the hydrolysate at 130°C for 30 min, giving a total sugar concentration of 114.4 g/L with a xylose concentration of 93.5 g/L and a xylose yield of 56.5%. To the best of our knowledge, the total sugar and xylose concentrations are the highest among those ever reported for acid-catalyzed hydrolysis of lignocellulose.

  13. Catalytic Enantioselective Synthesis of Tetrahydocarbazoles and Exocyclic Pictet-Spengler-Type Reactions

    Hansen, Casper Lykke; Ohm, Ragnhild Gaard; Olsen, Lasse Bohn;


    A synthetic strategy for the synthesis of chiral tetrahydrocarbazoles (THCAs) has been developed. The strategy relies on two types of 6-exo-trig cyclization of 3-substituted indole substrates. Enantioselective domino Friedel-Crafts-type reactions leading to THCAs can be catalyzed by chiral phosph...

  14. Purification, molecular cloning, and expression of 2-hydroxyphytanoyl- CoA lyase, a peroxisomal thiamine pyrophosphate-dependent enzyme that catalyzes the carbon-carbon bond cleavage during à-oxidation of 3- methyl-branched fatty acids

    Foulon, V; Croes, K; Waelkens, E


    Purification, molecular cloning, and expression of 2-hydroxyphytanoyl- CoA lyase, a peroxisomal thiamine pyrophosphate-dependent enzyme that catalyzes the carbon-carbon bond cleavage during à-oxidation of 3- methyl-branched fatty acids

  15. Amino acid-catalyzed seed regrowth synthesis of photostable high fluorescent silica nanoparticles with tunable sizes for intracellular studies

    Shahabi, Shakiba; Treccani, Laura, E-mail:; Rezwan, Kurosch [University of Bremen, Advanced Ceramics (Germany)


    Size-controlled fluorescence silica nanoparticles (NPs) are widely used for nanotoxicological studies, and diagnostic and targeted therapies. Such particles can be easily visualized and localized within cell environments and their interactions with cellular components can be monitored. We developed an amino acid-catalyzed seed regrowth technique (ACSRT) to synthesize spherical rhodamine-doped silica NPs with tunable sizes, low polydispersity index as well as high labeling efficiency and enhanced fluorescence photostability. Via ACSRT, fluorescent silica NPs can be obtained by introducing the fluorophore in seed formation step, while a precise control over particle size can be achieved by simply adjusting the concentration of reactants in the regrowth step. Unlike the conventional methods, the proposed ACSRT permits the synthesis of fluorescent silica NPs in a water-based system, without the use of any surfactants and co-surfactants. By this approach, additional linkers for covalent coupling of the fluorophore to silica matrix can be omitted, while a remarkable doping efficiency is achieved. The suitability of these particles for biomedical application is demonstrated by in vitro tests with normal and malignant bone cells. We show that the particles can be easily and unambiguously visualized by a conventional fluorescence microscope, localized, and distinguished within intracellular components. In addition, it is presented that the cellular uptake and cytotoxic profile of silica NPs are strongly correlated to the particle size, concentration, and cell line. The results of in vitro experiments demonstrate that tunable fluorescent silica NPs synthesized with ACSRT can be potentially used for toxicological assessments and nanomedical studies.

  16. Amino acid catalyzed bulk-phase gelation of organoalkoxysilanes via a transient co-operative self-assembly.

    Shen, Shukun; Hu, Daodao; Sun, Peipei; Zhang, Xiaoru; Parikh, Atul N


    We report acceleration in the rate of bulk phase gelation of an organoalkoxysilane, 3-methacryloxypropyltrimethoxysilane (MAPTMS), in the presence of an amphiphilic additive, N-phenyl glycine (NPG). The MAPTMS gelation occurs within 30 min in the presence of 0.5 wt % NPG, which took several months in the absence of NPG. Using a combination of ATR-FT IR, (29)Si NMR, (1)H NMR, viscosity analysis, SEM, UV-vis, and pi-A isotherm measurements, we elucidate the molecular-level details of the structural changes during NPG-catalyzed MPTMS gelation rate. On the basis of these results, we propose a gelation mechanism in which a transient cooperative self-assembly process fosters hydrolysis and retards early condensation thereby promoting the formation of extended three-dimensionally cross-linked gels. Specifically, the amphiphilic character of the hydrolysis product of MAPTMS, consisting of a hydrophobic tail R = -CH(2)CH(2)CH(2)O(CO)C(CH(3)) horizontal lineCH(2) and a hydrophilic Si-OH headgroup, promotes micelle formation at high MAPTMS/water ratio. NPG readily inserts within these micelles thus retarding the topotactic condensation of silanols at the micellar surface. This in turn allows for a more complete hydrolysis of Si-OCH(3) groups prior to condensation in MAPTMS. With increased silanol concentration at the micellar periphery, a delayed condensation phase initiates. This formation of a covalently bonded Si-O-Si framework (and possibly also the formation of the methanol byproduct) likely destabilizes the micellar motif thus promoting its transformation into condensed mesophases (e.g., lamellar microstructure) upon gelation. Because of the generality of this transient and co-operative organic-inorganic self-assembly between hydrolyzed amphiphilic organoalkoxysilanes and surfactant-like amino acid additives, we envisage applications in controlling bulk phase gelation of many chain-substituted organoalkoxysilanes.

  17. Iridium-catalyzed ortho-selective C-H silylation of aromatic compounds directed toward the synthesis of π-conjugated molecules with Lewis acid-base interaction.

    Wakaki, Takayuki; Kanai, Motomu; Kuninobu, Yoichiro


    We successfully developed an iridium-catalyzed ortho-selective C-H silylation of aromatic compounds. The reaction exhibited a wide substrate scope, and a variety of π-conjugated molecules were synthesized in good to excellent yields, even in gram scale. Several silyl groups could also be introduced into the products. The experimental results indicated that the regioselectivity could be controlled by a Lewis acid-base interaction between the Lewis acidic silicon atoms of fluorinated hydrosilanes and the Lewis basic nitrogen atoms of aromatic compounds.

  18. Low-temperature Rh-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds.

    Korenaga, Toshinobu; Ko, Aram; Shimada, Kazuaki


    Rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds was achieved at temperatures below 0 °C using a Rh/MeO-F12-BIPHEP catalyst. The reaction of cyclohexenone or N-R-maleimide with arylboronic acids proceeded even at -80 °C in the presence of the Rh catalyst. In the latter case, high enantioselectivity was observed because a low-temperature method was used, regardless of the type of substituent on maleimide.

  19. Kinetics and mechanism of OsOsub(4) catalyzed oxidation of chalcones by Cesub(4) in aqueous acetic sulfuric acid media

    Srinivasulu, P.V.; Adinarayana, M.; Sethuram, B.; Rao, T.N. (Osmania Univ., Hyderabad (India). Dept. of Chemistry)


    Kinetics of OsOsub(4) catalyzed oxidation of chalcones by Cesup(4+) was studied in aqueous acetic-sulfuric acid medium in the temperature range 313 to 338 K. The order in oxidant is zero while the order with respect to substrate and catalyst are each fractional. The rate of the reaction decreased with increase in percentage of acetic acid while (Hsup(+)) had practically no effect on the rate. The rates of various substituted chalcones are given. A mechanism in which formation of a cyclic ester between chalcone and OsOsub(4) in a fast step followed by its decomposition in a rate-determining step is envisaged.

  20. 氨基磺酸催化合成脂肪酸丁酯的研究%Synthesis of fatty acid butyl ester catalyzed by amino sulfonic acid

    程正载; 龚凯; 张卫星; 高松; 雷锐; 颜晓潮; 从野


    The fatty acid butyl ester was respectively synthesized by the esterification of oleic acid with bu-tanol and the transesterification of rapeseed oil with butanol catalyzed by amino sulfonic acid. The fatty acid butyl ester product was analyzed by GC and its structure was characterized by FT-IR. The effects of molar ratio of butanol to oil ( oleic acid or rapeseed oil) , catalyst dosage, reaction temperature and reac-tion time on the conversion rates of oleic acid and rapeseed oil were investigated. The results showed that the optimal esterification conditions were obtained as follows: molar ratio of butanol to oleic acid 3∶1 , catalyst dosage 0. 8% (based on the mass of oleic acid), reaction temperature 110℃and reaction time 1. 5 h. Under these conditions, the conversion rate of oleic acid and the yield of fatty acid butyl ester reached 88. 6% and 83. 5%, respectively. The optimal transesterification conditions were obtained as follows:molar ratio of butanol to rapeseed oil 10∶1, catalyst dosage 1. 0% (based on the mass of rapeseed oil), reaction temperature 115℃ and reaction time 2. 0 h. Under the optimal conditions, the conversion rate of rapeseed oil and the yield of fatty acid butyl ester achieved 85. 6% and 80. 1%, respectively.%以氨基磺酸为催化剂,油酸及菜籽油与正丁醇分别进行酯化反应与酯交换反应制备脂肪酸丁酯。并利用气相色谱及红外光谱对产物进行分析及结构表征。考察了醇(正丁醇)油(油酸及菜籽油)摩尔比、催化剂用量、反应温度和反应时间对油酸及菜籽油转化率的影响。结果表明,油酸酯化反应的最佳工艺条件为:醇油摩尔比3∶1,催化剂用量为油酸质量的0.8%,反应温度110℃,反应时间1.5 h,此时油酸转化率达到88.6%,产品收率为83.5%;菜籽油酯交换反应的最佳工艺条件为:醇油摩尔比10∶1,催化剂用量为菜籽油质量的1.0%,反应温度115℃,反应时间2.0 h,

  1. Nickel-catalyzed cross-coupling of functionalized difluoromethyl bromides and chlorides with aryl boronic acids: a general method for difluoroalkylated arenes.

    Xiao, Yu-Lan; Guo, Wen-Hao; He, Guo-Zhen; Pan, Qiang; Zhang, Xingang


    Transition-metal-catalyzed difluoroalkylation of aromatics remains challenging despite the importance of difluoroalkylated arenes in medicinal chemistry. Herein, the first successful example of nickel-catalyzed difluoroalkylation of aryl boronic acids is described. The reaction allows access to a variety of functionalized difluoromethyl bromides and chlorides, and paves the way to highly cost-efficient synthesis of a wide range of difluoroalkylated arenes. The notable features of this protocol are its high generality, excellent functional-group compatibility, low-cost nickel-catalyst, and practicality for gram-scale production, thus providing a facile method for applications in drug discovery and development. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Efficient production of fermentable sugars from oil palm empty fruit bunch by combined use of acid and whole cell culture-catalyzed hydrolyses.

    Li, Qingxin; Ng, Wei Ting; Puah, Sze Min; Bhaskar, Ravindran Vijay; Soh, Loon Siong; MacBeath, Calum; Parakattil, Pius; Green, Phil; Wu, Jin Chuan


    Empty fruit bunch (EFB) of oil palm trees was converted to fermentable sugars by the combined use of dilute acids and whole fungal cell culture-catalyzed hydrolyses. EFB (5%, w/v) was hydrolyzed in the presence of 0.5% H2 SO4 and 0.2% H3 PO4 at 160 °C for 10 Min. The solid fraction was separated from the acid hydrolysate by filtration and subjected to enzymatic hydrolysis at 50 °C using the whole cell culture of Trichoderma reesei RUT-C30 (2%, w/v), which was prepared by cultivation at 30 °C for 7 days to reach its maximal cellulase activity. The combined hydrolyses of EFB gave a total sugar yield of 82.0%. When used as carbon sources for cultivating Escherichia coli in M9 medium at 37 °C, the combined EFB hydrolysates were shown to be more favorable or at least as good as pure glucose for cell growth in terms of the higher (1.1 times) optical density of E. coli cells. The by-products generated during the acid-catalyzed hydrolysis did not seem to obviously affect cell growth. The combined use of acid and whole cell culture hydrolyses might be a commercially promising method for pretreatment of lignocellulose to get fermentable sugars.

  3. Zirconium phosphate nanoparticles as a remarkable solid acid catalyst for selective solvent-free alkylation of phenol

    Abdol R. Hajipour; Hirbod Karimi


    A facile synthesis of α-zirconium phosphate (ZP) nanoparticles as an effective, eco-friendly, and recyclable solid acid catalyst is reported. Polyvinylpyrrolidone (PVP) and polyvinyl alcohol (PVA) were used as organic matrix as dispersing agents and served as a template for the nanoparticles. Hydrogen bonds between ZP and PVA or PVP, along the polymer chains, appear to play an im-portant role for improving the dispersion of in situ formed ZP. Following calcination of PVA/ZP or PVP/ZP, pure hexagonal ZP nanoparticles were obtained. The catalysts were characterized by ni-trogen sorption, inductively coupled plasma optical emission spectroscopy, X-ray diffraction, Fouri-er transform infrared spectroscopy (FTIR), scanning electron microscopy, and transmission elec-tron microscopy. Pyridine-FTIR and temperature-programmed desorption of NH3 suggest the presence of Brönsted acid sites. The acidic properties of the catalyst were studied in Friedel-Crafts alkylation of phenol by tert-butanol, producing 2-tert-butylphenol, 4-tert-butylphenol, and 2,4-di-tert-butylphenol. The alkylation reaction was performed in the presence of catalysts P2O5/Al2O3, P2O5/SiO2, α-ZrP (prepared in the absence of the polymers), and various ionic liquids. The use of the hexagonal ZP nanoparticle catalyst afforded an excellent phenol conversion (86%) and selectivity towards 4-tert-butylphenol (83%) under optimized reaction conditions. The catalyst was easily recovered from the reaction mixture, regenerated, and reused at least four times without significant loss in the catalytic activity.

  4. cis-Diastereoselective synthesis of chroman-fused tetralins as B-ring-modified analogues of brazilin.

    Gogoi, Dimpee; Devi, Runjun; Pahari, Pallab; Sarma, Bipul; Das, Sajal Kumar


    We have synthesized a series of cis-6a,7,8,12b-tetrahydro-6H-naphtho[2,1-c]chromen-6a-ols as B-ring-modified analogues of (±)-brazilin. A completely regio- and cis-diastereoselective intramolecular Friedel-Crafts epoxy-arene cyclization of 1-tetralone-derived glycidyl ethers catalyzed by Brønsted acids was used as the key step. Our worries concerning the formation of cis-trans product mixtures and their probable conversion to naphthopyran derivatives via dehydration of the tertiary hydroxy group were laid to rest. Additionally, the angular hydroxy group of one of the synthesized products has been reductively removed by a diastereoselective method which should be useful in future for preparing libraries of chroman-fused tetralins with trans-stereochemistry at the ring junction.

  5. Rh-catalyzed enantioselective conjugate addition of arylboronic acids with a dynamic library of chiral tropos phosphorus ligands.

    Monti, Chiara; Gennari, Cesare; Piarulli, Umberto


    A library of 19 chiral tropos phosphorus ligands, based on a free-to-rotate (tropos) biphenol unit and a chiral P-bonded alcohol (11 phosphites, 1-P(O)(2)O to 11-P(O)(2)O) or secondary amine (8 phosphoramidites, 12-P(O)(2)N to 19-P(O)(2)N), were screened, individually and in combinations of two, in the rhodium-catalyzed asymmetric conjugate addition of arylboronic acids to enones and enoates. High enantioselectivities (up to 99 % ee) and excellent yields were obtained in the addition to either cyclic or acyclic substrates. The flexible biphenolic P ligands outperformed the analogous rigid binaphtholic P ligands. Variable-temperature (31)P NMR studies revealed that the biphenolic ligands are tropos even at low temperature. Only below 190 K was a coalescence observed; upon further cooling, two atropisomers were detected. The Rh homocomplexes ([Rh(L(a))(2)](+)) were also studied: in general, a single doublet (P-Rh coupling) was observed in the case of the biphenolic phosphite ligands, over the temperature range 380-230 K, demonstrating their tropos nature in the rhodium complexes even at low temperatures. On the other hand, the phosphoramidites showed different behaviors depending on the structure of the ligand and on the nature of the rhodium source. The spectrum at 230 K of the mixture of [Rh(acac)(eth)(2)] (eth=C(2)H(4)) with phosphite 6-P(O)(2)O and phosphoramidite 19-P(O)(2)N (the most enantioselective ligand combination in the conjugate addition reaction) revealed the presence of four homocomplexes (total approximately 40 %: [Rh{6-P(O)(2)O}(2)], [Rh{(aR)-19-P(O)(2)N}(2)], [Rh{(aS)-19-P(O)(2)N}(2)], [Rh{(aR)-19-P(O)(2)N}{(aS)-19-P(O)(2)N}]) and one heterocomplex, [Rh{6-P(O)(2)O}{(aR)-19-P(O)(2)N}] (approximately 60 %) In the heterocomplex, the biphenol-derived phosphite is free to rotate (tropos) while the biphenol-derived phosphoramidite shows a temperature-dependent tropos/atropos behavior (coalescence temperature=310 K).

  6. Hydrolysis of cellooligosaccharides catalyzed by organic acid%有机酸催化水解纤维低聚糖的研究

    马淑玲; 彭红


    The order of catalytic activity of organic acids for hydrolysis of cellooligosaccharides is oxalic acid>maleic acid>malonic acid>acetic acid>formic acid>butanedioic acid. Butanedioic acid could not catalyze the hydrolysis of cellooligosaccharides. The catalytic activity of biatomic acids is relative to their acidity. The acid with higher acidity resulted in higher conversion of cellooligosaccharides. The hydrolysis of cellooligosaccharides catalyzed by organic acid processed step by step,glucose and cellooligosaccharides with lower degree of polymerization produced first,and the produced oligosaccharides was hydrolyzed further. When cellotriose,cellotetraose,and cellopentaose were hydrolyzed under the conditions of substrate concentration 1.5 mg/mL,oxalic acid dosage 0.05 mmol/mL,reaction time 9 h,and temperature 95℃,the product concentrations of glucose were 0.51, 0.53,and 0.13 mg/mL respectively.%有机酸催化水解纤维低聚糖的能力强弱顺序为:草酸>顺丁烯二酸>丙二酸>乙酸>甲酸>丁二酸,丁二酸不能催化水解纤维低聚糖。二元羧酸水解纤维低聚糖时的能力与其水溶液酸性强弱有关,酸性越强,催化水解能力越大,低聚糖的水解率高。有机酸水解纤维低聚糖是分步进行的,先生成葡萄糖和低一级的低聚糖,低一级的低聚糖再水解生成葡萄糖和更低一级的低聚糖。在初始低聚糖浓度为1.5 mg/mL、水解时间9 h和水解温度95℃的条件下,0.05 mmol/mL草酸分别催化水解纤维三糖、纤维四糖和纤维五糖后产物葡萄糖浓度分别为0.51、0.53和0.13 mg/mL。

  7. The role of the alcohol and carboxylic acid in directed ruthenium-catalyzed C(sp3)-H α-alkylation of cyclic amines.

    Bergman, Sheba D; Storr, Thomas E; Prokopcová, Hana; Aelvoet, Karel; Diels, Gaston; Meerpoel, Lieven; Maes, Bert U W


    A general directed Ru-catalyzed C(sp(3))-H α-alkylation protocol for piperidines (less-reactive substrates than the corresponding five-membered cyclic amines) has been developed. The use of a hindered alcohol (2,4-dimethyl-3-pentanol) as the solvent and catalyst activator, and a catalytic amount of trans-1,2-cyclohexanedicarboxylic acid is necessary to achieve a high conversion to product. This protocol was used to effectively synthesize a number of 2-hexyl- and 2,6-dihexyl piperidines, as well as the alkaloid (±)-solenopsin A. Kinetic studies have revealed that the carboxylic acid additive has a significant effect on catalyst initiation, catalyst longevity, and reverses the reaction selectivity compared with the acid-free reaction (promotes alkylation versus competing alkene reduction).

  8. Thiol-functionalized copolymeric polyesters by lipase-catalyzed esterification and transesterification of 1,12-dodecanedioic acid and its diethyl ester, respectively, with 1-thioglycerol.

    Fehling, Eberhard; Bergander, Klaus; Klein, Erika; Weber, Nikolaus; Vosmann, Klaus


    Copolymeric polyoxoesters containing branched-chain methylenethiol functions, i.e., poly(1,12-dodecanedioic acid-co-1-thioglycerol) and poly(diethyl 1,12-dodecanedioate-co-1-thioglycerol), were formed by lipase-catalyzed polyesterification and polytransesterification of 1,12-dodecanedioic acid and diethyl 1,12-dodecanedioate, respectively, with 1-thioglycerol (3-mercaptopropane-1,2-diol) using immobilized lipase B from Candida antarctica (Novozym 435) in vacuo without drying agent in the reaction mixture. After 360-480 h, both polyoxoesters were purified by extraction from the reaction mixtures followed by solvent fractionation. The precipitate of poly(1,12-dodecanedioic acid-co-1-thioglycerol) demonstrated a M(W) of ~170,000 Da, whereas a M(W) of ~7,100 Da only was found for poly(diethyl 1,12-dodecanedioate-co-1-thioglycerol). Both polycondensates were analyzed by GPC/SEC, alkali-catalyzed transmethylation, NMR- and FTIR-spectrometry.

  9. Synthesis of bio-based methacrylic acid by decarboxylation of itaconic acid and citric acid catalyzed by solid transition-metal catalysts

    Notre, le J.E.L.; Witte-van Dijk, S.C.M.; Haveren, van J.; Scott, E.L.; Sanders, J.P.M.


    Methacrylic acid, an important monomer for the plastics industry, was obtained in high selectivity (up to 84%) by the decarboxylation of itaconic acid using heterogeneous catalysts based on Pd, Pt and Ru. The reaction takes place in water at 200–2508C without any external added pressure, conditions

  10. Synthesis of bio-based methacrylic acid by decarboxylation of itaconic acid and citric acid catalyzed by solid transition-metal catalysts

    Notre, le J.E.L.; Witte-van Dijk, S.C.M.; Haveren, van J.; Scott, E.L.; Sanders, J.P.M.


    Methacrylic acid, an important monomer for the plastics industry, was obtained in high selectivity (up to 84%) by the decarboxylation of itaconic acid using heterogeneous catalysts based on Pd, Pt and Ru. The reaction takes place in water at 200–2508C without any external added pressure, conditions

  11. Synthesis of Isocoumarins from Cyclic 2-Diazo-1,3-diketones and Benzoic Acids via Rh(III)-Catalyzed C-H Activation and Esterification.

    Yang, Cheng; He, Xinwei; Zhang, Lanlan; Han, Guang; Zuo, Youpeng; Shang, Yongjia


    A mild and efficient Rh(III)-catalyzed C-H activation/esterification reaction for the synthesis of isocoumarins has been developed. This procedure uses readily available benzoic acids and cyclic diazo-1,3-diketones as starting materials and involves domino intermolecular C-H activation in combination with intramolecular esterification to give the corresponding isocoumarins in moderate to excellent yields. This process provides a facile approach for the construction of isocoumarins containing various functional groups that does not require any additives.

  12. Copper-catalyzed α-amination of phosphonates and phosphine oxides: a direct approach to α-amino phosphonic acids and derivatives.

    McDonald, Stacey L; Wang, Qiu


    A direct approach to important α-amino phosphonic acids and its derivatives has been developed by using copper-catalyzed electrophilic amination of α-phosphonate zincates with O-acyl hydroxylamines. This amination provides the first example of CN bond formation which directly introduces acyclic and cyclic amines to the α-position of phosphonates in one step. The reaction is readily promoted at room temperature with as little as 0.5 mol % of catalyst, and demonstrates high efficiency on a broad substrate scope.

  13. Palladium-catalyzed air-based oxidative coupling of arylboronic acids with H-phosphine oxides leading to aryl phosphine oxides.

    Fu, Tingting; Qiao, Hongwei; Peng, Zhimin; Hu, Gaobo; Wu, Xueji; Gao, Yuxing; Zhao, Yufen


    We present a novel and highly efficient methodology that allows for the construction of C-P bonds via the palladium-catalyzed air-based oxidative coupling of various commercially available arylboronic acids with easily oxidized H-phosphine oxides leading to valuable aryl phosphine oxides, particularly triarylphosphine oxides, with the use of air as the green oxidant, broad substrate applicability and good to excellent yields. The described catalytic system should be an efficient complement to the Chan-Lam type reaction and be useful in synthetic programs.

  14. Ruthenium Hydride/Brønsted Acid-Catalyzed Tandem Isomerization/N-Acyliminium Cyclization Sequence for the Synthesis of Tetrahydro-β-carbolines

    Hansen, Casper Lykke; Clausen, Janie Regitse Waël; Ohm, Ragnhild Gaard;


    This paper describes an efficient tandem sequence for the synthesis of 1,2,3,4-tetrahydro-β-carbolines (THBCs) relying on a ruthenium hydride/Brønsted acid- catalyzed isomerization of allylic amides to N-acyliminium ion intermediates which are trapped by a tethered indolenucleophile. The methodol...... the Suzuki cross-coupling reaction to the isomerization/N-acyliminium cyclization sequence. Finally, diastereo- and enantioselective versions of the title reaction have been examined using substrate control (with dr >15: 1) and asymmetric catalysis (ee up to 57%), respectively...

  15. Solid State Synthesis of Malonic Acid Monoanilide and Its Cyclization with Eaton′s Reagent or Polyphosphoric Acid%丙二酸单苯酰胺的固相法合成及其在Eaton试剂或多聚磷酸作用下的环化反应

    高文涛; 侯文端; 郑美茹


    Malonic acid monoanilides (1a~1f) were prepared by reactions of aniline and substituted anilines with Meldrum's acid under solid state conditions without using catalyst, the yield was 81.0 %~92.2 %. 4-Hydroxyquinolin-2-one derivatives (2a~2f) were facially synthesized in the yields of 63.2 %~93.8 % and 56.5~81.3 % by the intramolecular Friedel-Crafts reactions of 1a~1f using Eaton's reagent (phosphoric anhydride+methylsulfonic acid) or polyphosphoric acid (PPA) as cyclization reagents. The products were characterized by IR, 1H NMR and elemental analysis.%苯胺及取代的苯胺和Meldrum's acid在固相无催化剂条件下反应,合成了丙二酸单苯酰胺(1a~1f) ,收率81.0 %~92.2 %. 化合物1a~1f在Eaton试剂(五氧化二磷+甲基磺酸)或多聚磷酸为环化试剂的条件下发生Friedel-Crafts分子内环化反应,以63.2 %~93.8 %和56.5 %~81.3 %的收率方便地得到4-羟基喹啉-2-酮衍生物(2a~2f). 产物的结构通过IR, 1H NMR和元素分析得以证实.

  16. Reaction Between U(Ⅳ)and Nitrous Acid Catalyzed by Plutonium%Pu催化HNO2氧化U(Ⅳ)的研究

    王浩文; 周贤明; 李高亮; 兰天; 刘金平; 常尚文; 何辉; 段红卫


    The oxidation of U(Ⅳ)by nitrous acid in the present of plutonium was studied. The influence of the concentration of nitrous acid,nitric acid,plutonium on the oxidation of U(Ⅳ)was investigated.The results show that plutonium can catalyze the reaction between U(Ⅳ)and nitrous acid.And the rate equation of the reaction between U(Ⅳ)and nitrous acid catalyzed by plutonium was obtained:-dc(U(Ⅳ))/dt=kc(U(Ⅳ))c1.3 (HNO3 )c1.3 (NO-2 ), k=(0.69±0.04)L2.6/(mol2.6 ·min)when the temperature was 29 ℃.The mechanism of the oxidation of U(Ⅳ)was discussed.%研究了Pu存在条件下 HNO2氧化 U(Ⅳ)的反应,并考察了 HNO2浓度、反应温度、HNO3浓度、Pu 浓度对 U(Ⅳ)氧化速率的影响。结果表明:Pu对 HNO2氧化 U(Ⅳ)的反应具有显著催化作用;获得了 Pu催化条件下 HNO2氧化 U(Ⅳ)的动力学方程:-dc(U(Ⅳ))/dt=kc(U(Ⅳ))c1.3(HNO3)c1.3(NO-2),得到了29℃时的反应速率常数k=(0.69±0.04)L2.6/(mol2.6·min)。并对反应历程进行了探讨。

  17. CYP703 is an ancient cytochrome P450 in land plants catalyzing in-chain hydroxylation of lauric acid to provide building blocks for sporopollenin synthesis in pollen.

    Morant, Marc; Jørgensen, Kirsten; Schaller, Hubert; Pinot, Franck; Møller, Birger Lindberg; Werck-Reichhart, Danièle; Bak, Søren


    CYP703 is a cytochrome P450 family specific to land plants. Typically, each plant species contains a single CYP703. Arabidopsis thaliana CYP703A2 is expressed in the anthers of developing flowers. Expression is initiated at the tetrad stage and restricted to microspores and to the tapetum cell layer. Arabidopsis CYP703A2 knockout lines showed impaired pollen development and a partial male-sterile phenotype. Scanning electron and transmission electron microscopy of pollen from the knockout plants showed impaired pollen wall development with absence of exine. The fluorescent layer around the pollen grains ascribed to the presence of phenylpropanoid units in sporopollenin was absent in the CYP703A2 knockout lines. Heterologous expression of CYP703A2 in yeast cells demonstrated that CYP703 catalyzes the conversion of medium-chain saturated fatty acids to the corresponding monohydroxylated fatty acids, with a preferential hydroxylation of lauric acid at the C-7 position. Incubation of recombinant CYP703 with methanol extracts from developing flowers confirmed that lauric acid and in-chain hydroxy lauric acids are the in planta substrate and product, respectively. These data demonstrate that in-chain hydroxy lauric acids are essential building blocks in sporopollenin synthesis and enable the formation of ester and ether linkages with phenylpropanoid units. This study identifies CYP703 as a P450 family specifically involved in pollen development.

  18. Transesterification catalyzed by polystyrene-supported chymotrypsin in toluene: the effect of neutralization of basic or acidic groups attaching to polystyrene resins.

    Ohtani, N; Inoue, Y; Kobayashi, A; Sugawara, T


    Crosslinked polystyrene resins containing a low level of either basic or acidic groups were used for supports of alpha-chymotrypsin (CT), which catalyzed the transesterification of N-acetyl-L-phenylalanine ethyl ester (AcPheOEt) with propanol in toluene. With a minimal amount of water, CT was sorbed to the resins, basic or acidic groups of which were partly or fully neutralized by several soluble acids or bases. With an increasing degree of neutralization of basic resins by free acids, the rate of disappearance of AcPheOEt was decreased, whereas the by-product formation of AcPheOH, due to hydrolysis, was considerably suppressed, compared with the ester-exchange product, AcPheOPr. The pK(a) value of the neutralizing acid was also important for both CT activity and reaction selectivity. AcPheOPr was selectively produced at a certain range of pK(a) values. On the other hand, the neutralization of acidic resins with free amines enhanced the CT activity but a strong base promoted the formation of hydrolysis product.

  19. Kinetic and mechanistic investigations of chlorocomplex of Ru(III and Ir(III catalyzed oxidation of d-fructose by N-bromophthalimide in acidic medium

    Neerja Sachdev


    Full Text Available The kinetic and mechanistic studies of Ru(III and Ir(III homogeneously catalyzed oxidation of d-fructose (d-fru by N-bromophthalimide (NBP in the presence of aqueous perchloric acid medium have been made at 303 K using mercuric acetate as Br− ion scavenger. The stoichiometry and the oxidation products in both catalysts were found to be the same. The determined stoichiometric ratio was found to be 1:2 ([d-fru]:[NBP]. Arabinonic and formic acids were obtained as the major oxidized products of both the reactions. The kinetics of the reaction were studied as a function of temperature, ionic strength, concentration of the salt, concentration of the added reaction product, and the dielectric constant of the medium to learn the mechanistic aspects of the reaction. Possible mechanisms are proposed, which are consistent with the kinetics, stoichiometry and products of the reaction.

  20. Development of Stereocontrolled Palladium(II)-Catalyzed Domino Heck/Suzuki β,α-Diarylation Reactions with Chelating Vinyl Ethers and Arylboronic Acids.

    Trejos, Alejandro; Odell, Luke R; Larhed, Mats


    A stereoselective and 1,4-benzoquinone-mediated palladium(II)-catalyzed Heck/Suzuki domino reaction involving metal coordinating cyclic methylamino vinyl ethers and a number of electronically diverse arylboronic acids has been developed and studied. Diastereomeric ratios up to 39:1 and 78 % isolated yields were obtained. The stereoselectivity of the reaction was found to be highly dependent on the nature of the arylboronic acid and the amount of water present in the reaction mixture. Thus, a domino β,α-diarylation-reduction of chelating vinyl ethers can now be accomplished and stereochemically controlled, given that optimized conditions and an appropriate chiral auxiliary are used. To the best of our knowledge, this represents the first example of a stereoselective, oxidative Heck/Suzuki domino reaction in the literature.

  1. Highly Efficient Esterification of an Equimolar Amount of Carboxylic Acids and Alcohols Catalyzed by ZrOCl2·8H2O

    Sun Hong-Bin; Hua Ruimao; Yin Ying-Wu


    Esterification of carboxylic acids with alcohols is one of the most fundamental and useful transformations in organic synthesis. The most common catalysts are H2SO4 and TsOH. However,H2SO4 or TsOH-catalyzed esterification procedure has some problems such as corrosion, side reactions, difficulty in separation. Hence, recently, various solid acid catalysts such as ion-exchanged resins, molecular sieve, and heteropoly acids etc. have been employed for esterification reaction.However, the solid acid catalysts are usually not easily accessible and expensive In addition, for achieving the high yield of esters, it is usually to carry out the esterification reaction by addition of an excess of one of the reactants. Therefore it is still interesting to develop the high activity,cost-effective catalyst system.which is a commercially available and very cheap inorganic salt.The esterification was carried out in the presence of ZrOCl2. 8H2O (0.05 mol %) using equimolar amount of carboxylic acids and alcohols at room temperature or at 50℃. For example, the esterification of propionic acid with methanol at room temperature for 24 h gave methyl propionate in 81% GC yield. A higher yield of esters can be obtained by the removal of water azeotropically.The present esterification procedure has the following advantages:1) Esters can be obtained in high yield with the use of equimolar amount of carboxylic acids and alcohols.2) Esterification proceeds at room temperature, the catalyst system is suitable for the esterification of highly reactive carboxylic acids such as acrylic acid.3) It is easy to isolate and purify the esters, and the catalyst is recyclable. The complete reaction mixture becomes two phases at room temperature, the esters in the organic phase can be separated conveniently by decanting, and the catalyst in the water can be reused without any treatment.

  2. 铑催化乙酸乙酯羰基化合成丙酸的研究%Rh Catalyzed Carbonylation of Ethyl Acetate to Propionic Acid

    凌晨; 黄志军


    以乙酸乙酯为原料,在金属铑催化下与一氧化碳进行羰基化反应,生成丙酸.研究了碘化物添加剂和反应条件对丙酸产率的影响.由于避免了乙醇在酸性条件下的酯化和分子间脱水等副反应,丙酸产率显著提高.乙酸乙酯羰基化具有与甲醇羰基化相似的动力学行为.碘化物添加剂的加入能有效提高反应速率和丙酸选择性.通过优化反应条件,丙酸产率大于95%.%Rhodium was used to catalyze the carbonylation of ethyl acetate with carbon monoxide to propionic acid.The effect of iodide additives and reaction conditions on yield of propionic acid was studied.Because of avoiding the esterification and intermolecular dehydration of ethanol the yield of propionic acid was improved significantly.The kinetic behavior of ethyl acetate carbonylation was similar with methanol carbonylation.The reaction rate and propionic acid selectivity were increased obviously with the introduction of iodide additives.The propionic acid yield is greater than 95% under the optimum conditions.

  3. Mechanism of cooperative catalysis in a Lewis acid promoted nickel-catalyzed dual C-H activation reaction.

    Anand, Megha; Sunoj, Raghavan B


    The mechanism of cooperativity offered by AlMe(3) in a Ni-catalyzed dehydrogenative cycloaddition between substituted formamides and an alkyne is investigated by using DFT(SMD(toluene)/M06/6-31G**) methods. The preferred pathway is identified to involve dual C-H activation, with first a higher barrier formyl C(sp(2))-H oxidative insertion followed by benzylic methyl C(sp(3))-H activation. The cooperativity is traced to be of kinetic origin as evidenced by stabilized transition states when AlMe(3) is bound to the formyl group, particularly in the oxidative insertion step.

  4. Difference analysis of the enzymatic hydrolysis performance of acid-catalyzed steam-exploded corn stover before and after washing with water.

    Zhu, Junjun; Shi, Linli; Zhang, Lingling; Xu, Yong; Yong, Qiang; Ouyang, Jia; Yu, Shiyuan


    The difference in the enzymatic hydrolysis yield of acid-catalyzed steam-exploded corn stover (ASC) before and after washing with water reached approximately 15 % under the same conditions. The reasons for the difference in the yield between ASC and washed ASC (wASC) were determined through the analysis of the composition of ASC prehydrolyzate and sugar concentration of enzymatic hydrolyzate. Salts produced by neutralization (CaSO4, Na2SO4, K2SO4, and (NH4)2SO4), sugars (polysaccharides, oligosaccharides, and monosaccharides), sugar-degradation products (weak acids and furans), and lignin-degradation products (ethyl acetate extracts and nine main lignin-degradation products) were back-added to wASC. Results showed that these products, except furans, exerted negative effect on enzymatic hydrolysis. According to the characteristics of acid-catalyzed steam explosion pretreatment, the five sugar-degradation products' mixture and salts [Na2SO4, (NH4)2SO4] showed minimal negative inhibition effect on enzymatic hydrolysis. By contrast, furans demonstrated a promotion effect. Moreover, soluble sugars, such as 13 g/L xylose (decreased by 6.38 %), 5 g/L cellobiose (5.36 %), 10 g/L glucose (3.67 %), as well as lignin-degradation products, and ethyl acetate extracts (4.87 %), exhibited evident inhibition effect on enzymatic hydrolysis. Therefore, removal of soluble sugars and lignin-degradation products could effectively promote the enzymatic hydrolysis performance.

  5. Ruthenium-catalyzed aerobic oxidative decarboxylation of amino acids: a green, zero-waste route to biobased nitriles.

    Claes, Laurens; Verduyckt, Jasper; Stassen, Ivo; Lagrain, Bert; De Vos, Dirk E


    Oxidative decarboxylation of amino acids into nitriles was performed using molecular oxygen as terminal oxidant and a heterogeneous ruthenium hydroxide-based catalyst. A range of amino acids was oxidized in very good yield, using water as the solvent.

  6. Determination of CYP4A11-catalyzed lauric acid 12-hydroxylation by high-performance liquid chromatography with radiometric detection.

    Crespi, Charles L; Chang, Thomas K H; Waxman, David J


    Lauric acid serves as an endogenous substrate for the cytochrome P450 enzyme CYP4A11. A reverse-phase, high-performance liquid chromatography method is described for the quantification of 12-hydroxylauric acid formed enzymatically by incubation of 14C-labeled lauric acid with cDNA-expressed CYP4A11 or human liver microsomes. Analytical separation is achieved using a C18 column and a gradient of 30% acetonitrile and 2 mM perchloric acid to 100% methanol, using a detection scintillation counter. This method is applicable to enzymatic studies for determination of lauric acid 12-hydroxylation activity.

  7. Preparation of stearoyl lactic acid ester catalyzed by lipases from Rhizomucor miehei and porcine pancreas optimization using response surface methodology.

    Kiran, K R; Karanth, N G; Divakar, S


    The esterification reaction between stearic acid and lactic acid using Rhizomucor miehei lipase and porcine pancreas lipase was optimized for maximum esterification using response surface methodology. The formation of the ester was found to depend on three parameters namely enzyme/substrate ratio, lactic acid (stearic acid) concentration and incubation period. The maximum esterification predicted by theoretical equations for both lipases matched well with the observed experimental values. In the case of R. miehei lipase, stearoyl lactic acid ester formation was found to increase with incubation period and lactic acid (stearic acid) concentrations with maximum esterification of 26.9% at an enzyme/substrate (E/S) ratio of 125 g mol-1. In the case of porcine pancreas lipase, esterification showed a steady increase with increase in incubation period and lactic acid (stearic acid) concentration independent of the E/S ratios employed. In the case of PPL, a maximum esterification of 18.9% was observed at an E/S ratio of 25 g mol-1 at a lactic acid (stearic acid) concentration of 0.09 M after an incubation period of 72 h.

  8. A simple, effective, green method for regioselective 3-acylation of unprotected indoles

    Tran, Phuong Huong; Tran, Hai N.; Hansen, Poul Erik;


    A fast and green method is developed for regioselective acylation of indoles in the 3-position without the need for protection of the NH position. The method is based on Friedel-Crafts acylation using acid anhydrides. The method has been optimized, and Y(OTf)3 in catalytic amounts is found...

  9. Cause analysis of the effects of acid-catalyzed steam-exploded corn stover prehydrolyzate on ethanol fermentation by Pichia stipitis CBS 5776.

    Zhu, Junjun; Yang, Jinlong; Zhu, Yuanyuan; Zhang, Lingling; Yong, Qiang; Xu, Yong; Li, Xin; Yu, Shiyuan


    The prehydrolyzate obtained from acid-catalyzed steam-exploded corn stover (ASC) mainly contains xylose and a number of inhibitory compounds that inhibit ethanol fermentation by Pichia stipitis. In this study, the effects of the ASC prehydrolyzate, specifically those of the carbohydrate-degradation products, lignin-degradation products (which were extracted from ASC prehydrolyzate using ethyl acetate), and six major phenolic compounds (added to pure-sugar media individually or in combination), on ethanol fermentation were investigated. Results indicate that the effects of the carbohydrate-degradation products were negligible (10 h delayed) compared with those of pure-sugar fermentation, whereas the effects of the lignin-degradation products were significant (52 h delayed). Meanwhile, the inhibitory effects of the major phenolic compounds were not caused by certain types of inhibitors, but were due to the synergistic effects of various inhibitors.

  10. Rhodium(III)-Catalyzed ortho C-H Heteroarylation of (Hetero)aromatic Carboxylic Acids: A Rapid and Concise Access to π-Conjugated Poly-heterocycles.

    Qin, Xurong; Li, Xiaoyu; Huang, Quan; Liu, Hu; Wu, Di; Guo, Qiang; Lan, Jingbo; Wang, Ruilin; You, Jingsong


    Rh(III)-catalyzed oxidative C-H/C-H cross-coupling between (hetero)aromatic carboxylic acids and various heteroarenes has been accomplished to construct highly functionalized ortho-carboxy-substituted bi(hetero)aryls. The use of a carboxy group as the directing group obviates tedious steps for installation and removal of extra directing groups, and enables a facile one-step synthesis of ortho-carboxy bi(hetero)aryls. The method provides opportunities for rapid assembly of a library of important fluorene and coumarin-type poly-heterocycles through intramolecular electrophilic substitution or oxidative lactonization. As illustrative examples, the strategy developed herein greatly streamlines accesses to a variety of appealing polyheterocycles such as DTPO (5H-dithieno[3,2-b:2',3'-d]pyran-5-one), CPDTO (cyclopentadithiophen-4-one), and indenothiophenes.

  11. Reusable and Ligand-Free Palladium-Catalyzed Suzuki- Miyaura Cross-Couplings of Aryl Halides with Arylboronic Acids in Tetra-n-butylammonium Bromide

    XIE,Ye-Xiang; WANG,Jian; LI,Jin-Heng; LIANG,Yun


    Ligand-free and reusable palladium-catalyzed Suzuki-Miyaura cross-coupling reaction performed in TBAB (tetra-n-butylammonium bromide) was presented. It was found that the amount of water affected these reactions. Excellent results were obtained when there was w= 1% of water in TBAB. In the presence of 3 mol% of Pd(Oac)2 and 1.5 g of TBAB (containing w= 1% of water), a number of aryl halides were coupled with arylboronic acids smoothly in moderate to excellent yields. Moreover, the Pd(Oac)2/TBAB system among the couplings of aryl bro-mides and activated chlorides could be recovered and reused three times without a loss of catalytic efficiency.

  12. Long-chain ethers as solvents can amplify the enantioselectivity of the Carica papaya lipase-catalyzed transesterification of 2-(substituted phenoxy)propanoic acid esters.

    Miyazawa, Toshifumi; Iguchi, Wakana


    The enantioselectivity of the transesterification of the 2,2,2-trifluoroethyl esters of 2-(substituted phenoxy)propanoic acids, as catalyzed by the lipase from Carica papaya, was greatly improved by using long-chain ethers, such as di-n-hexyl ether, as solvents instead of the conventional diisopropyl ether. Thus, for example, the E value was enhanced from 21 [in diisopropyl ether (0.8 ml)] to 57 [in di-n-hexyl ether (0.8 ml)] in the reaction of 2,2,2-trifluoroethyl(RS)-2-phenoxypropanoate (0.1 mmol) with methanol (0.4 mmol) in the presence of the plant lipase preparation (10 mg); it was also improved from 13 (in diisopropyl ether) to 44 (in di-n-hexyl ether) in the reaction of 2,2,2-trifluoroethyl(RS)-2-(2-chlorophenoxy)propanoate with methanol under the same reaction conditions.

  13. Use of immobilized phospholipase A1-catalyzed acidolysis for the production of structured phosphatidylcholine with an elevated conjugated linoleic acid content

    Baeza-Jimenez, R.; Gonzalez-Rodriguez, J.; Kim, I. H.; Gracia, H. S.; Otero, C.


    Structured phosphatidylcholine (SPC) was successfully produced via immobilized phospholipase A1 (PLA1) catalyzed acidolysis of phosphatidylcholine (PC) with conjugated linoleic acid (CLA). The effects of enzyme loading (2, 5, 10, 15 and 20%, with respect to the weight of substrates), temperature (20, 30, 40, 50 and 60 degree centigrade) and the molar ratio of substrates (1:2, 1:4, 1:6, 1:8 and 1:10, PC/CLA) were evaluated to maximize the incorporation of CLA into PC. The maximum incorporation of CLA achieved was ca. 90% for 24 h of reaction at 50 degree centigrade and 200 rpm, using a 1:4 substrate molar ratio and an enzyme loading of 15%. (Author) 30 refs.

  14. Camphor-10-sulfonic acid catalyzed condensation of 2-naphthol with aromatic/aliphatic aldehydes to 14-aryl/alkyl-14H-dibenzo[a,j]xanthenes

    Kundu Kshama


    Full Text Available (±-Camphor-10-sulfonic acid (CSA catalyzed condensation of 2-naphthol with both aliphatic/aromatic aldehydes at 80°C yielded 14-alkyl/aryl-dibenzoxanthenes as the sole product in high yields. However, the same condensation with benzaldehyde at 25°C afforded a mixture of intermediate 1,1-bis-(2-hydroxynaphthylphenylmethane and 14-phenyl-dibenzoxanthene while the condensation with aliphatic aldehydes at 25°C furnished the corresponding 14-alkyl-dibenzoxanthenes as the sole product. Moreover, condensation of 2-naphthol with aromatic/aliphatic aldehydes with low catalyst loading (2 mol% was greatly accelerated under microwave irradiation to afford the corresponding 14-aryl/alkyl-dibenzoxanthenes as the sole product in high yields.

  15. Conversion of nicotinic acid to trigonelline is catalyzed by N-methyltransferase belonged to motif B′ methyltransferase family in Coffea arabica

    Mizuno, Kouichi, E-mail: [Faculty of Bioresource Sciences, Akita Prefectural University, Akita City, Akita 010-0195 (Japan); Matsuzaki, Masahiro [Faculty of Bioresource Sciences, Akita Prefectural University, Akita City, Akita 010-0195 (Japan); Kanazawa, Shiho [Graduate School of Humanities and Sciences, Ochanomizu University, Otsuka, Bunkyo-ku, Tokyo 112-8610 (Japan); Tokiwano, Tetsuo; Yoshizawa, Yuko [Faculty of Bioresource Sciences, Akita Prefectural University, Akita City, Akita 010-0195 (Japan); Kato, Misako [Graduate School of Humanities and Sciences, Ochanomizu University, Otsuka, Bunkyo-ku, Tokyo 112-8610 (Japan)


    Graphical abstract: Trigonelline synthase catalyzes the conversion of nicotinic acid to trigonelline. We isolated and characterized trigonelline synthase gene(s) from Coffea arabica. - Highlights: • Trigonelline is a major compound in coffee been same as caffeine is. • We isolated and characterized trigonelline synthase gene. • Coffee trigonelline synthases are highly homologous with coffee caffeine synthases. • This study contributes the fully understanding of pyridine alkaloid metabolism. - Abstract: Trigonelline (N-methylnicotinate), a member of the pyridine alkaloids, accumulates in coffee beans along with caffeine. The biosynthetic pathway of trigonelline is not fully elucidated. While it is quite likely that the production of trigonelline from nicotinate is catalyzed by N-methyltransferase, as is caffeine synthase (CS), the enzyme(s) and gene(s) involved in N-methylation have not yet been characterized. It should be noted that, similar to caffeine, trigonelline accumulation is initiated during the development of coffee fruits. Interestingly, the expression profiles for two genes homologous to caffeine synthases were similar to the accumulation profile of trigonelline. We presumed that these two CS-homologous genes encoded trigonelline synthases. These genes were then expressed in Escherichiacoli, and the resulting recombinant enzymes that were obtained were characterized. Consequently, using the N-methyltransferase assay with S-adenosyl[methyl-{sup 14}C]methionine, it was confirmed that these recombinant enzymes catalyzed the conversion of nicotinate to trigonelline, coffee trigonelline synthases (termed CTgS1 and CTgS2) were highly identical (over 95% identity) to each other. The sequence homology between the CTgSs and coffee CCS1 was 82%. The pH-dependent activity curve of CTgS1 and CTgS2 revealed optimum activity at pH 7.5. Nicotinate was the specific methyl acceptor for CTgSs, and no activity was detected with any other nicotinate derivatives, or

  16. Solvent effects in acid-catalyzed dehydration of the Diels-Alder cycloadduct between 2,5-dimethylfuran and maleic anhydride

    Salavati-fard, Taha; Caratzoulas, Stavros; Doren, Douglas J.


    Dehydration of the cycloadduct produced from the Diels-Alder reaction between 2,5-dimethylfuran and maleic anhydride to 3,6-dimethylphthalic anhydride exemplifies an important step in producing platform chemicals from biomass. The mechanisms of dehydration and catalytic effects of Lewis and Brønsted acids are investigated with density functional theory. The uncatalyzed reaction has a very high activation barrier (68.7 kcal/mol) in the gas phase and it is not significantly affected by solvation. With a Lewis acid catalyst, modeled as an alkali ion, the activation barriers are reduced, but intermediates are also stabilized. The net effect in vacuum is that the energetic span, or apparent activation energy of the catalytic cycle, is 77.9 kcal/mol, even higher than the barrier in the uncatalyzed case. In solution, however, the energetic span is reduced by as much as 20 kcal/mol, due to differences in the solvation energy of the transition states and intermediates. In the case of a Brønsted acid catalyst, modeled as a proton, the gas phase transition state energies are reduced even more than in the Lewis acid case, and there is no strong stabilization of the intermediates. The energetic span in vacuum is only 13.8 kcal/mol and is reduced even further in solution. Brønsted acid catalysis appears to be the preferred mechanism for dehydration of this cycloadduct. Since the Diels-Alder reaction that produced the molecule has previously been shown to be catalyzed by Brønsted acids, this suggests that a single catalyst could be used to accelerate both steps.

  17. One-step production of biodiesel from rice bran oil catalyzed by chlorosulfonic acid modified zirconia via simultaneous esterification and transesterification.

    Zhang, Yue; Wong, Wing-Tak; Yung, Ka-Fu


    Due to the high content (25-50%) of free fatty acid (FFA), crude rice bran oil usually requires a two steps conversion or one step conversion with very harsh condition for simultaneous esterification and transesterification. In this study, chlorosulfonic acid modified zirconia (HClSO3-ZrO2) with strong acidity and durability is prepared and it shows excellent catalytic activity toward simultaneous esterification and transesterification. Under a relative low reaction temperature of 120 °C, HClSO3-ZrO2 catalyzes a complete conversion of simulated crude rice bran oil (refined oil with 40 wt% FFA) into biodiesel and the conversion yield keep at above 92% for at least three cycles. Further investigation on the tolerance towards FFA and water reveals that it maintains high activity even with the presence of 40 wt% FFA and 3 wt% water. It shows that HClSO3-ZrO2 is a robust and durable catalyst which shows high potential to be commercial catalyst for biodiesel production from low grade feedstock.

  18. Heterogeneous acid-catalyzed biodiesel production from crude tall oil: a low-grade and less expensive feedstock

    Mkhize, NM


    Full Text Available The present study indicates that solid acid catalysis of crude tall oil (CTO) over a WO3/ZrO2 catalyst is effective in converting the CTO fatty acids components into biodiesel in high yield. Preparation of the catalyst by an impregnation method...


    ZHANGYuehua; HUANGWenqiang; 等


    An improved method is developed by using strongly acidic cation exchange resin(001×1,H+ form) as a catalyst for the synthesis of diphenyl 1-(N-benzyloxycarbonyl-amino) alkanephosphonates and 1-(N-benzyloxycarbonylamino) alkanephenyl phosphinic acids in high yields.


    We report here the first evidence of a possible mechanism for the formation of an azobenzene arsonic acid compound in the environment The compound was formed when 3-amino-4-hydroxyphenylarsonic acid (3-amino-HPAA) was added to aqueous suspensions of smectite clay The 3-amino-HPAA...

  1. Transition metal-catalyzed oxidative double bond cleavage of simple and bio-derived alkenes and unsaturated fatty acids

    Spannring, Peter; Bruijnincx, Pieter C. A.; Weckhuysen, Bert. M.; Klein Gebbink, Bert


    The oxidative cleavage of the C=C double bond in unsaturated fatty acids into aldehydes or carboxylic acids is a reaction of current interest in biomass valorization. The products of this reaction, which is currently being performed on an industrial scale by means of ozonolysis, can be applied for t

  2. 对氨基苯磺酸催化合成水杨酸正丁酯%Synthesis of butyl salicylate catalyzed by p-aminobenzene sulfonic acid

    赵卫星; 姜红波


    以正丁醇与水杨酸为原料,采用对氨基苯磺酸为催化剂,通过酯化反应合成了水杨酸正丁酯.考察了酸醇物质的量比、催化剂用量、反应时间对水杨酸正丁酯化收率的影响.结果表明,在回流条件下,当水杨酸的加入量0.20 mol,正丁醇的加入量0.32 mol,即酸与醇物质的量比为1∶1.6,催化剂对氨基苯磺酸用量为0.70 g(相当于5%的酸),反应4.0h时,水杨酸正丁酯收率可达到72.90%.%Synthesis of butyl salicylate from 2-hydroxybenzoic acid and n-butanol catalyzed by p-aminobenzene sulfonic acid was studied.The effects of the molar ratio of 2-hydroxybenzoic acid to n-butanol,the amount of catalyst and the reaction time on the yield was discussed.The results show that when the molar ratio of 2-hydroxybenzoic acid (0.20 mol) to n-butanol (0.32 mol) was 1 ∶ 1.6;the amount of catalyst was 0.70 g (5%,with respect to 2-hydroxybenzoic acid) and the reaction time was 4.0 h under reflux,the yield of butyl salicylate reached 72.90%.

  3. Aspergillus niger lipase-catalyzed synthesis of high contentlauric acid monoglyceride%黑曲霉脂肪酶合成单月桂酸甘油酯

    邓颖颖; 杨哪; 徐学明


    A lipase from Aspergillus niger has been found with strong catalytic activity and selectivity.In order to prove the lipase high selectivity,it was used to catalyze the fatty acids and glycerin synthetic fatty acid glyceride and optimize the reaction process parameters.The results showed that when the ratio of glycerol to lauric acid 1:1.5,the lipase dosage 0.5%(W/W),the water dosage 3%(W/W)based on the reactant which was employed in the reacting system,the conversion rate of lauric acid could reach 91.2% at 50℃ for 12h reaction.The content of lauric acid monoglycerid was about 70% in the reacting production.%从黑曲霉中提出了一种具有很高催化活性和选择性的脂肪酶,为证明这种脂肪酶的高选择性,用此酶直接催化甘油和月桂酸反应合成单月桂酸甘油酯,并且优化了反应的工艺参数。实验表明,采用甘油月桂酸摩尔比为1∶1.5,脂肪酶与底物质量比为0.5%,水与底物质量比为3%的条件在50℃下反应12h,可使月桂酸转化率达到91.2%,单酯含量高达70%。

  4. Enzyme-catalyzed Transesterification of Unusual Substrate: Synthesis of Acyclovir and L-ascorbic Acid (Vitamin C) Vinyl Esters


    The synthesis of acyclovir and L-ascorbic acid with divinyladipate was performed with alkaline protease from Bacillus subtilis and lipase from Lipozyme (immobilized from Mucor miehei) in different anhydrous organic solvents. Two corresponding derivatives were obtained.

  5. Mass spectrometric identification of an azobenzene derivative produced by smectite-catalyzed conversion of 3-amino-4-hydroxyphenylarsonic acid

    Wershaw, R. L.; Rutherford, D.W.; Rostad, C.E.; Garbarino, J.R.; Ferrer, I.; Kennedy, K.R.; Momplaisir, G.-M.; Grange, A.


    The compound 3-amino-4-hydroxyphenylarsonic acid (3-amino-HPAA) reacts with smectite to form a soluble azobenzene arsonic acid compound. This reaction is of particular interest because it provides a possible mechanism for the formation of a new type of arsenic compound in natural water systems. 3-Amino-HPAA is a degradation product excreted by chickens that are fed rations amended with roxarsone. Roxarsone is used to control coccidial intestinal parasites in most of the broiler chickens grown in the United States. The structure of the azobenzene arsonic acid compound was first inferred from negative-ion and positive-ion low-resolution mass-spectrometric analyses of the supernatant of the smectite suspension. Elemental composition of the parent ion determined by high-resolution positive-ion mass spectrometric measurements was consistent with the proposed structure of the azobenzene arsonic acid compound. Published by Elsevier Science B.V.

  6. Photo-degradation of Acid-red 3B dye catalyzed by TiO2 nanotubes

    JIANG Fang; ZHENG Shou-rong; ZHENG Zheng; XU Zhao-yi; WANG Yan-jin


    TiO2 nanotube precursor was synthesized by the hydrothermal reaction of TiO2 powders with NaOH solution and the properties of the nanotube materials were tuned using different post-treatments. Transmission electron microscopic (TEM) observation revealed that the nanotube could be obtained by either a direct rinse with acid solution or rinse with distilled water followed by acid solution. The results of X-ray diffraction (XRD) and inductively coupled plasma (ICP) analysis indicated that the nanotube material on the post-treatment. The results of the photocatalytic reaction showed that the degradation of Acid-red 3B dye fitted pseudo-zero-order kinetics and TiO2 nanotube prepared under direct rinse with acid solution exhibited a higher catalytic efficiency compared to other catalysts.

  7. Biomimetic Decarboxylation of Carboxylic Acids with PhI(OAc)2 Catalyzed by Manganese Porphyrin [Mn(TPP)OAcl

    GHOLAM REZA Karimipour; ROXANA Ahmadpour


    Manganese(Ⅲ) meso-tetraphenylporphyrin acetate [Mn(TPP)OAc] served as an effective catalyst for the oxidative decarboxylation of carboxylic acids with (diacetoxyiodo)benzene [Phl(OAc)2] in CH2C12-H2O(95:5,volume ratio),The aryl substituted acetic acids are more reactive than the less electron rich linear carboxylic acids in the presence of catalyst Mn(TPP)OAc,In the former case,the formation of carbonyl products was complete within just a few minutes with >97% selectivities,and no further oxidation of the produced aldehydes was achieved under these catalytic conditions,This method provides a benign procedure owing to the utilization of low toxic(diacetoxyiodo)benzene,biologically relevant manganese porphyrins,and carboxylic acids.

  8. Effect of Solvent and Acid-Base on Palladium(ll)-catalyzed Dicarbonylation of Terminal Acetylenes: a General, Efficient andStereoselective Synthesis of Maleic Diesters and Maleic Anhydrides

    JIANG, Huan-Feng; LI, JiN-Heng; CHEN, Ming-Cai


    The productions of maleic diesters and maleic anhydrises depend on the effect of solvint and acid-bade of solvent and acid-base in palladium-catalyzed dicarbonylation of terminal acetylenes. For primaryand secondary alcohol in benzene.only maleic diesters wereobtained stereospecifically from the sicabonylation ofacetylenes in the presence of PdCl2,and NaHCO3.For tERTIARy alcohols,maleic anhydrides were synthesized selectively.

  9. Nickel-Catalyzed Aminoxylation of Inert Aliphatic C(sp(3))-H Bonds with Stable Nitroxyl Radicals under Air: One-Pot Route to α-Formyl Acid Derivatives.

    Wang, Chunxia; Zhang, Luoqiang; You, Jingsong


    Nickel-catalyzed aminoxylation of an unactivated C(sp(3))-H bond with a stable nitroxyl radical has been accomplished for the first time to offer various N-alkoxyamine derivatives, which further enables a one-pot approach to α-formyl acid derivatives. The aminoxylation process reported also provides direct evidence for the oxidative addition of a cyclometallic intermediate with a free radical, which is helpful for the reaction-mechanism study in transition-metal-catalyzed functionalization of inert C(sp(3))-H bonds.

  10. Evolution of Diterpene Metabolism: Sitka Spruce CYP720B4 Catalyzes Multiple Oxidations in Resin Acid Biosynthesis of Conifer Defense against Insects1[C][W][OA

    Hamberger, Björn; Ohnishi, Toshiyuki; Hamberger, Britta; Séguin, Armand; Bohlmann, Jörg


    Diterpene resin acids (DRAs) are specialized (secondary) metabolites of the oleoresin defense of conifers produced by diterpene synthases and cytochrome P450s of the CYP720B family. The evolution of DRA metabolism shares common origins with the biosynthesis of ent-kaurenoic acid, which is highly conserved in general (primary) metabolism of gibberellin biosynthesis. Transcriptome mining in species of spruce (Picea) and pine (Pinus) revealed CYP720Bs of four distinct clades. We cloned a comprehensive set of 12 different Sitka spruce (Picea sitchensis) CYP720Bs as full-length cDNAs. Spatial expression profiles, methyl jasmonate induction, and transcript enrichment in terpenoid-producing resin ducts suggested a role of CYP720B4 in DRA biosynthesis. CYP720B4 was characterized as a multisubstrate, multifunctional enzyme by the formation of oxygenated diterpenoids in metabolically engineered yeast, yeast in vivo transformation of diterpene substrates, in vitro assays with CYP720B4 protein produced in Escherichia coli, and alteration of DRA profiles in RNA interference-suppressed spruce seedlings. CYP720B4 was active with 24 different diterpenoid substrates, catalyzing consecutive C-18 oxidations in the biosynthesis of an array of diterpene alcohols, aldehydes, and acids. CYP720B4 was most active in the formation of dehydroabietic acid, a compound associated with insect resistance of Sitka spruce. We identified patterns of convergent evolution of CYP720B4 in DRA metabolism and ent-kaurene oxidase CYP701 in gibberellin metabolism and revealed differences in the evolution of specialized and general diterpene metabolism in a gymnosperm. The genomic and functional characterization of the gymnosperm CYP720B family highlights that the evolution of specialized metabolism involves substantial diversification relative to conserved, general metabolism. PMID:21994349

  11. FeCl3-Assisted Niobium-Catalyzed Cycloaddition of Nitriles and Alkynes: Synthesis of Alkyl- and Arylpyrimidines Based on Independent Functions of NbCl5 and FeCl3 Lewis Acids.

    Fuji, Maito; Obora, Yasushi


    NbCl5-catalyzed [2 + 2 + 2] cycloaddition of nitriles with alkynes was used to synthesize pyrimidine derivatives. In this reaction, the use of individual Lewis acids, namely NbCl5 and FeCl3, is a key strategy for achieving the reaction using a catalytic amount of NbCl5. The roles of the two Lewis acids were investigated using FT-IR spectroscopy. The results showed that NbCl5 served as an efficient Lewis acid catalyst for nitrile activation, whereas FeCl3 showed stronger Lewis acidity toward pyrimidines, releasing NbCl5 into the catalytic cycle.

  12. Rh(I)-Catalyzed 1,4-Conjugate Addition of Alkenylboronic Acids to a Cyclopentenone Useful for the Synthesis of Prostaglandins.

    Syu, Jin-Fong; Wang, Yun-Ting; Liu, Kung-Cheng; Wu, Ping-Yu; Henschke, Julian P; Wu, Hsyueh-Liang


    An efficient and trans-diastereoselective Rh(I)-catalyzed 1,4-conjugate addition reaction of alkenylboronic acids and a homochiral (R)-4-silyloxycyclopentenone useful for the synthesis of derivatives of prostaglandins E and F is described for the first time. The reaction functions under mild conditions and is particularly rapid (≤6 h) under low power (50 W) microwave irradiation at 30 °C in MeOH in the presence of a catalytic amount of KOH. Under these conditions, 3 mol % of [RhCl(COD)]2 is typically required to produce high yields. The method also functions without microwave irradiation at 3 °C in the presence of a stoichiometric amount of KOH. Under these conditions, only 1.5 mol % of [RhCl(COD)]2 is needed, but the reaction is considerably slower. The method accepts a range of aryl- and alkyl-substituted alkenylboronic acids, and its utility has been demonstrated by the synthesis of PGF2α (dinoprost) and tafluprost.

  13. Lipase-catalyzed preparation of diacylglycerol-enriched oil from high-acid rice bran oil in solvent-free system.

    Song, Zhihua; Liu, Yuanfa; Jin, Qingzhe; Li, Lei; Wang, Xingguo; Huang, Jianhua; Liu, Ruijie


    The ability of immobilized lipase from Rhizomucor miehei (Lipozyme RM IM) to catalyze the reaction of high-acid rice bran oil (RBO) and monoglyceride (MG) for diacylglycerol-enriched rice bran oil (RBO-DG) preparation was investigated. The effects of substrate ratio, reaction temperature, time, and enzyme load on the respective content of free fatty acid (FFA) and DG in the final RBO-DG products was investigated. Enzyme screening on the reaction was also investigated. Response surface methodology (RSM) was used to optimize the effects of the reaction temperature (50-70 °C), the enzyme load (2-6 %; relative to the weight of total substrates), and the reaction time (4-8 h) on the respective content of FFA and DG. Validation of the RSM model was verified by the good agreement between the experimental and the predicted values. The optimum preparation conditions were as follows: MG/RBO, 0.25; temperature, 56 °C; enzyme load, 4.77 %; and reaction time, 5.75 h. Under the suggested conditions, the respective content of FFA and DG was 0.28 and 27.98 %, respectively. Repeated reaction tests indicated that Lipozyme RM IM could be used nine times under the optimum conditions with 90 % of its original catalytic activity still retained.

  14. Synthesis of high molecular weight polylactic acid from aqueous lactic acid co-catalyzed by tin(II)chloride dihydrate and succinic anhydride

    LEI Ziqiang; BAI Yanbin; WANG Shoufeng


    Polylactic acid was synthesized from commercial available cheap aqueous lactic acid (85%―90% w/w) using succinic anhydride and SnCl2·2H2O as catalyst in the absence of organic solvents. As a result, polylactic acid with a molecular weight of 60000 was prepared in 10 h. The new procedure is much simple, cheap and outstanding in that the start material is aqueous lactic acid; the catalytic system is environmentally benign.

  15. Studies of manufacturing controlled-release graphene acid and catalyzing synthesis of chalcone with Claisen-Schmidt condensation reaction

    Li, Jihui; Feng, Jia; Li, Mei; Wang, Qiaolian; Su, Yumin; Jia, Zhixin


    In the paper, graphene acid (GA) was manufactured, using flake graphite as raw material, and the acidity and the structure of GA were characterized as well as. Then, chalcone was synthesized in the presence of GA, using acetophenone and benzaldehyde as the reactant. The results showed that the acidity of GA was for pH = 1.12 in aqueous solution, and it was structured by the graphene sheets with the spaces between the graphene sheet and the graphene sheet and sulfuric acid (H2SO4) and acetic acid (CH3CO2H) inside the spaces. At the same time, the results also exhibited that the chalcone yield was able to reach 60.36% when GA dosage was 5 g, and the chalcone yields could attain apart 60.36, 52.05 and 31.16% when 5 g of GA was used thrice. This shows that GA is not only a high-performance catalyst, but also a controlled-release catalyst.

  16. 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)

  17. Molecular cloning of CYP76B9, a cytochrome P450 from Petunia hybrida, catalyzing the omega-hydroxylation of capric acid and lauric acid.

    Imaishi, Hiromasa; Petkova-Andonova, Mariana


    A cDNA encoding a cytochrome P450 (CYP76B9) was isolated from Petunia hybrida. Northern blot analysis revealed preferential expression of the gene in flowers and leaves. The recombinant yeast microsomes expressing CYP76B9 was allowed to react with capric acid and lauric acid as substrates. One major metabolite was produced from each fatty acid after incubation with yeast microsomes expressing CYP76B9. The metabolites were identified by gas chromatography-mass spectrometry (GC-MS) as omega-hydroxy capric acid and omega-hydroxy lauric acid. The kinetic parameters of the reactions were Km=9.4 microM and Vmax=13.6 mol min(-1) per mol of P450 for capric acid, and Km=5.7 microM and Vmax=19.1 mol min(-1) per mol of P450 for lauric acid. We found that the omega-hydroxy metabolites of capric acid and lauric acid can affect the plant growth of Arabidopsis thaliana. Plants grown in the presence of omega-hydroxy fatty acids exhibited shorter root length than control plants with the corresponding non-hydroxylated fatty acids.

  18. Erbium trifluoromethanesulfonate-catalyzed Friedel–Crafts acylation using aromatic carboxylic acids as acylating agents under monomode-microwave irradiation

    Tran, Phuong Hoang; Hansen, Poul Erik; Nguyen, Hai Truong;


    Erbium trifluoromethanesulfonate is found to be a good catalyst for the Friedel–Crafts acylation of arenes containing electron-donating substituents using aromatic carboxylic acids as the acylating agents under microwave irradiation. An effective, rapid and waste-free method allows the preparation...

  19. Horseradish peroxidase-catalyzed oligomerization of ferulic acid on a template of a tyrosine-containing tripeptide

    Oudgenoeg, G.; Dirksen, E.; Ingemann, S.; Hilhorst, R.; Gruppen, H.; Boeriu, C.G.; Piersma, S.R.; Berkel, W.J.H. van; Laane, C.; Voragen, A.G.J.


    Ferulic acid (FA) is an abundantly present phenolic constituent of plant cell walls. Kinetically controlled incubation of FA and the tripeptide Gly-Tyr-Gly (GYG) with horseradish peroxidase and H2O2 yielded a range of new cross-linked products. Two predominant series of hetero-oligomers of FA linked

  20. Lewis acid catalyzed ring-opening polymerization of natural epoxy oil (Euphorbia oil) in carbon dioxide media

    In an attempt to build up useful application of plant oil based polymers, natural epoxy oil (euphorbia oil-EuO) was polymerized in liquid carbon dioxide in the presence of Lewis acid catalyst [Boron trifluoride diethyl etherate (BF3•OEt2)]. The resulting polymers (RPEuO) were characterized by FTIR ...

  1. Platinum-Catalyzed Selective Hydration of Hindered Nitriles and Nitriles with Acid- or Base-Sensitive Groups

    Jiang, Xiao-bin; Minnaard, Adriaan J.; Vries, Johannes G. de; Feringa, Bernard


    Hindered tertiary nitriles can be hydrolyzed under neutral and mild conditions to the corresponding amides using platinum(II) catalysts with dimethylphosphine oxide or other secondary phosphine oxides (SPOs, phosphinous acids) as ligands. We have found that this procedure also works well for




    The catalytic activity of various strong acid ion-exchange resins on the synthesis of methyl tert-butyl ether (MtBE) from methanol and isobutene has been investigated. Relative to Amberlyst 15, Kastel CS 381 and Amberlyst CSP have similar rate constants, whereas Duolite ES 276 and Amberlyst XE 307 h

  3. Polycondensation of dicarboxylic acids and diols in water catalyzed by surfactant-combined catalysts and successive chain extension.

    Takasu, Akinori; Takemoto, Aki; Hirabayashi, Tadamichi


    Direct dehydration polycondensation of dicarboxylic acids and alcohols was carried out by surfactant-combined Brønsted and Lewis acids. This procedure did not require the removal of water, because the esterification was established at the interface of the emulsion in water. Emulsion polycondensations of 1,9-nonanediol (1,9-ND) and dodecanedioic acid (DDA) (the molar ratio of dicarboxylic acid to diol = 1:1) were carried out at 80 degrees C for 48 h in the presence of 16 wt % DBSA. The corresponding polyester (M(w) = 10.1 x 10(3)) was obtained in an excellent yield (99%). Chain extension in the emulsion was carried out using hexamethylene diisocyanate as the chain extender. SEC measurements indicated the expected shift to higher molecular weight region (M(w) = 11.4 x 10(3), M(w)/M(n) = 3.4) compared with parent polyester (M(w) = 4.5 x 10(3), M(w)/M(n) = 2.2).

  4. N-Arylation of azaheterocycles with aryl and heteroaryl halides catalyzed by iminodiacetic acid resin-chelated copper complex


    Iminodiacetic acid resin-chelated copper(Ⅱ) complex is effective in cross-coupling reactions between azaheterocycles and aryl or heteroaryl halides,providing N-arylated products in good to excellent yields.The copper catalyst is air stable and can be readily recovered and reused with minimal loss of activity for three runs.

  5. Rhodium-catalyzed addition of arylboronic acids to isatins : An entry to diversity in 3-aryl-3-hydroxyoxindoles

    Toullec, Patrick Y.; Jagt, Richard B. C.; de Vries, Johannes G.; Feringa, Ben L.; Minnaard, Adriaan J.


    A general method for the catalytic 1,2-addition of aryl and alkenyl boronic acids to isatins is described using a rhodium(I)/triphenylphosphite catalyst. The application of this transformation allows the synthesis of a variety of 3-aryl-3-hydroxyoxindole building blocks in high yields. An enantiosel

  6. Highly enantioselective aza-Diels-Alder reaction of 1-azadienes with enecarbamates catalyzed by chiral phosphoric acids.

    He, Long; Laurent, Gregory; Retailleau, Pascal; Folléas, Benoît; Brayer, Jean-Louis; Masson, Géraldine


    On demand: A highly enantio- and diastereoselective synthesis of 6-amino- trisubstituted tetrahydropyridine compounds has been developed through the inverse-electron-demand aza-Diels-Alder reaction of N-aryl α,β-unsaturated ketimines with enecarbamates (E)-1. Chiral phosphoric acid catalysts achieve simultaneous activation of both the 1-azadiene and dienophile partners.

  7. The development of copper-catalyzed aerobic oxidative coupling of H-tetrazoles with boronic acids and an insight into the reaction mechanism.

    Liu, Chao-You; Li, Yu; Ding, Jin-Ying; Dong, De-Wen; Han, Fu-She


    The development of a highly efficient and practical protocol for the direct C-N coupling of H-tetrazole and boronic acid was presented. A careful and patient optimization of a variety of reaction parameters revealed that this conventionally challenge reaction could indeed proceed efficiently in a very simple system, that is, just by stirring the tetrazoles and boronic acids under oxygen in the presence of different Cu(I) or Cu(II) salts with only 5 mol % loading in DMSO at 100 °C. Most significantly, the reaction could proceed very smoothly in a regiospecific manner to afford the 2,5-disubstituted tetrazoles in high to excellent yields. A mechanistic study revealed that both tetrazole and DMSO are crucial for the generation of catalytically active copper species in the reaction process in addition to their role as reactant and solvent, respectively. It is demonstrated that in the reaction cycle, the Cu(I) catalyst could be oxidized to Cu(II) by oxygen to form a [CuT2D] complex (T = tetrazole anion; D = DMSO) through an oxidative copper amination reaction. The Cu(II) complex thus formed was confirmed to be the real catalytically active copper species. Namely, the Cu(II) complex disproportionates to aryl Cu(III) and Cu(I) in the presence of boronic acid. Facile elimination of the Cu(III) species delivers the C-N-coupled product. The results presented herein not only provide a reliable and efficient protocol for the synthesis of 2,5-disubstituted tetrazoles, but most importantly, the mechanistic results would have broad implications for the de novo design and development of new methods for Cu-catalyzed coupling reactions. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Lipase-Catalyzed Production of 6-O-cinnamoyl-sorbitol from D-sorbitol and Cinnamic Acid Esters.

    Kim, Jung-Ho; Bhatia, Shashi Kant; Yoo, Dongwon; Seo, Hyung Min; Yi, Da-Hye; Kim, Hyun Joong; Lee, Ju Hee; Choi, Kwon-Young; Kim, Kwang Jin; Lee, Yoo Kyung; Yang, Yung-Hun


    To overcome the poor properties of solubility and stability of cinnamic acid, cinnamate derivatives with sugar alcohols were produced using the immobilized Candida antarctica lipase with vinyl cinnamate and D-sorbitol as substrate at 45 °C. Immobilized C. antarctica lipase was found to synthesize 6-O-cinnamoyl-sorbitol and confirmed by HPLC and (1)H-NMR and had a preference for vinyl cinnamate over other esters such as allyl-, ethyl-, and isobutyl cinnamate as co-substrate with D-sorbitol. Contrary to D-sorbitol, vinyl cinnamate, and cinnamic acid, the final product 6-O-cinnamoyl-sorbitol was found to have radical scavenging activity. This would be the first report on the biosynthesis of 6-O-cinnamoyl-sorbitol with immobilized enzyme from C. antarctica.

  9. Facile, mild and selective silica sulfuric acid catalyzed oxidation of benzylalcohols to benzaldehyde derivatives by potassium peroxodisulfate

    M. K. Mohammadi


    Full Text Available An efficient, facile, and mild oxidation of a variety of primary benzylic alcohols to the corresponding aldehydes with potassium peroxodisulfate in the presence of a catalytic amount of sodium chloride and silica sulfuric acid (SSA in acetonitrile as solvent is reported. It is a renowned fact that potassium peroxodisulfate acts as a powerful oxidizing agent and the control of conditions is difficult. For this purpose, SSA as a mild, efficient and reusable solid acid catalyst was used to afford the carbonyl compounds in excellent yields and short time. The structure of all of the resulting products was confirmed by FT-IR spectroscopy.DOI:

  10. Br(o)nsted acidic ionic liquid catalyzed highly efficient synthesis of chromeno pyrimidinone derivatives and their antimicrobial activity

    Janardhan Banothu; Rajitha Bavanthula


    A series of 8,9-dihydro-2-(2-oxo-2H-chromen-3-yl)-5-aryl-3H-chromeno[2,3-d]pyrimidine-4,6(5H,7H)-diones (5a-j)have been synthesized by the reaction of 2-amino-5,6,7,8-tetrahydro-5-oxo-4-aryl-4H-chromene-3-carbonitrile (4a-j) with coumarin-3-catboxylic acid under neat conditions employing Brφnsted acidic ionic liquid (4-sulfobutyl)tris(4-sulfophenyl)phosphonium hydrogen sulfate as catalyst.Structures of all the compounds were established on the basis of analytical and spectroscopic data.All the compounds were evaluated for their in vitro antimicrobial activity against different bacterial and fungal strains.

  11. Polyene Formation Catalyzed by Phosphotungstic Acid and Aluminum Chloride in Thin Films of Poly(Vinyl Alcohol)

    Tretinnikov, O. N.; Sushko, N. I.; Maly, A. B.


    Formation of linear polyenes -(CH=CH) n - during thermal dehydration of thin layers (9-20 μm) of poly(vinyl alcohol) containing phosphotungstic-acid and aluminum-chloride catalysts was investigated. It was found that the concentration of long-chain ( n ≥ 8) polyenes in films containing phosphotungstic acid increased smoothly with increasing annealing time although the kinetics of the dehydration were independent of the film thickness. The polyene ( n ≥ 8) formation rate in films containing aluminum chloride dropped quickly with decreasing film thickness and increasing annealing time. As a result, long-chain polyenes practically did not form regardless of the annealing time for a film thickness of 11 μm.

  12. Rh(I)-Catalyzed Coupling of Conjugated Enynones with Arylboronic Acids: Synthesis of Furyl-Containing Triarylmethanes.

    Xia, Ying; Chen, Li; Qu, Peiyuan; Ji, Guojing; Feng, Sheng; Xiao, Qing; Zhang, Yan; Wang, Jianbo


    Conjugated enynones can be used as carbene precursors to couple with arylboronic acids in the presence of Rh(I) catalyst. This reaction shows good functional compatibility, and a range of furyl-containing triarylmethanes can be smoothly synthesized from easily available starting materials under mild reaction conditions. Mechanistically, the formation of Rh(I) (2-furyl)carbene species and the subsequent carbene migratory insertion are proposed as the key steps in this reaction.

  13. Arabidopsis cytochrome P450s that catalyze the first step of tryptophan-dependent indole-3-acetic acid biosynthesis

    Hull, Anna K.; Vij, Rekha; Celenza, John L.


    Plants synthesize numerous secondary metabolites that are used as developmental signals or as defense against pathogens. Tryptophan (Trp)-derived secondary metabolites include camalexin, indole glucosinolates, and indole-3-acetic acid (IAA); however, the steps in their synthesis from Trp or its precursors remain unclear. We have identified two Arabidopsis cytochrome P450s (CYP79B2 and CYP79B3) that can convert Trp to indole-3-acetaldoxime (IAOx), a precursor to IAA and indole glucosinolates.

  14. A Facile Aqueous Synthesis of Bis(indol-3-yl)alkanes Cata-lyzed by Dodecylbenzenesulfonic Acid

    PENG,Yi-Yuan; ZHANG,Qiu-Lan; YUAN,Jian-Jun; CHENG,Jin-Pei


    An environmentally friendly synthetic method for bis(indol-3-yl)alkane derivatives has been developed. In the presence of 10 mol% of dodecylbenzenesulfonic acid (DBSA), electrophilic substitution reaction of indoles with aldehydes or ketones proceeded smoothly in water, giving rise to the corresponding bis(indol-3-yl)alkanes in good to excellent yields. The use of inexpensive and easily available catalyst, mild reaction conditions and simple work-up procedure made this protocol practical and economically attractive.

  15. Aza-Michael addition reactions between nitroolefins and benzotriazole catalyzed by MCM-41 immobilized heteropoly acids in water

    Shao-Lei Xie; Yong-Hai Hui; Xiang-Ju Long; Chang-Chun Wang; Zheng-Feng Xie


    MCM-41 supported heteropoly acids (HPAs) catalysts were synthesized,characterized and their catalytic activity was evaluated in an aza-Michael addition reaction between nitroolefins and benzotriazole in water at room temperature.50 wt% PW/MCM-41 showed the highest activity (up to 96% yield).The catalyst was used in six consecutive experiments without obvious loss of activity,confirming the success of the anchoring process and the catalyst stability.

  16. Cu(I)-catalyzed (11)C carboxylation of boronic acid esters: a rapid and convenient entry to (11)C-labeled carboxylic acids, esters, and amides.

    Riss, Patrick J; Lu, Shuiyu; Telu, Sanjay; Aigbirhio, Franklin I; Pike, Victor W


    Rapid and direct: the carboxylation of boronic acid esters with (11)CO(2) provides [(11)C]carboxylic acids as a convenient entry into [(11)C]esters and [(11)C]amides. This conversion of boronates is tolerant to diverse functional groups (e.g., halo, nitro, or carbonyl).

  17. Impact of zeolite aging in hot liquid water on activity for acid-catalyzed dehydration of alcohols

    Vjunov, Aleksei; Derewinski, Miroslaw A.; Fulton, John L.; Camaioni, Donald M.; Lercher, Johannes A.


    The catalytic performance of zeolite in aqueous medium depends on a multitude of factors, such as the concentration and distribution of active sites and framework integrity. Al K–edge extended X–ray absorption fine structure and 27Al MAS NMR spectroscopies in combination with DFT calculations are used to determine the distribution of tetrahedral Al sites both qualitatively and quantitatively for both parent and 48 h 160 ºC water treated HBEA catalysts. There is no evidence of Al coordination modification after aging in water. The distribution and concentration of Al T–sites, active centers for the dehydration of cyclohexanol, do not markedly impact the catalytic performance in water, because the Brønsted acidic protons are present in the form of hydrated hydronium ions and thus have very similar acid properties. The results suggest that all Brønsted acid sites are equally active in aqueous medium. The decrease of zeolite catalytic performance after water treatment is attributed to the reduced concentration of Brønsted acid sites. Increasing the stability of pore walls and decreasing the rate of Si–O–Si group hydrolysis may result in improved apparent zeolite catalytic performance in aqueous medium. Authors thank B. W. Arey (PNNL) for HIM measurements, T. Huthwelker for support during Al XAFS measurements at the Swiss Light Source (PSI, Switzerland), J. Z. Hu and S. D. Burton (PNNL) for support during NMR experiments. This work was supported by the U. S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. MD acknowledges support by the Materials Synthesis and Simulation Across Scales (MS3 Initiative) conducted under Laboratory Directed Research & Development Program at PNNL. HIM imaging and NMR experiments were performed at the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the DOE Office of Science, Office of Biological

  18. Microwave-Assisted Resolution of α-Lipoic Acid Catalyzed by an Ionic Liquid Co-Lyophilized Lipase

    Ning Liu


    Full Text Available The combination of the ionic liquid co-lyophilized lipase and microwave irradiation was used to improve enzyme performance in enantioselective esterification of α-lipoic acid. Effects of various reaction conditions on enzyme activity and enantioselectivity were investigated. Under optimal condition, the highest enantioselectivity (E = 41.2 was observed with a high enzyme activity (178.1 μmol/h/mg when using the ionic liquid co-lyophilized lipase with microwave assistance. Furthermore, the ionic liquid co-lyophilized lipase exhibited excellent reusability under low power microwave.

  19. Three-component Pd/Cu-catalyzed cascade reactions of cyclic iodoniums, alkynes, and boronic acids: an approach to methylidenefluorenes.

    Zhu, Daqian; Wu, Yongcheng; Wu, Baojian; Luo, Bingling; Ganesan, A; Wu, Fu-Hai; Pi, Rongbiao; Huang, Peng; Wen, Shijun


    Linear diaryliodonium salts are widely used as arylating reagents for C-C and C-X bond formation. Meanwhile, synthetic applications of cyclic iodoniums are relatively rare although they offer the opportunity to set up reaction cascades. We demonstrate an atom and step economical three-component reaction involving cyclic diphenyleneiodoniums, alkynes, and boronic acids, resulting in the construction of methylidenefluorenes in a single operation. Our route enables facile access to both symmetrical and unsymmetrical methylidenefluorene derivatives, compounds that have attracted interest due to their optical properties.

  20. Enantioselective Cycloaddition Reactions Catalyzed by BINOL-Derived Phosphoric Acids and N-Triflyl Phosphoramides: Recent Advances.

    Held, Felix E; Grau, Dominik; Tsogoeva, Svetlana B


    Over the last several years there has been a huge increase in the development and applications of new efficient organocatalysts for enantioselective pericyclic reactions, which represent one of the most powerful types of organic transformations. Among these processes are cycloaddition reactions (e.g., [3+2]; formal [3+3]; [4+2]; vinylogous [4+2] and 1,3-dipolar cycloadditions), which belong to the most utilized reactions in organic synthesis of complex nitrogen- and oxygen-containing heterocyclic molecules. This review presents the breakthrough realized in this field using chiral BINOL-derived phosphoric acids and N-triflyl phosphoramide organocatalysts.

  1. The effect of metal ions as co-catalysts on acidic ionic liquid catalyzed single-step saccharification of corn stover in water.

    Wiredu, Bernard; Amarasekara, Ananda S


    The effects of adding Cr(3+), Mn(2+), Fe(3+), Co(2+) Ni(2+), Cu(2+), Zn(2+) and La(3+) chlorides as co-catalysts to 1-(1-propylsulfonic)-3-methylimidazolium chloride acidic ionic liquid catalyzed saccharification of corn stover in aqueous medium was studied at 140-170 °C, by measuring the total reducing sugar (TRS) and glucose yields. The samples with Mn(2+), Fe(3+), Co(2+) as co-catalysts produced higher TRS yields compared to the sample without the metal ions. The Mn(2+) produced the highest catalytic effect enhancements and produced TRS yields of 68.0%, 72.9%, 90.2% and 87.9% at 140, 150, 160 and 170 °C respectively; whereas the corn stover samples without the Mn(2+) produced TRS yields of 42.9%, 52.3%, 54.4% and 53.5% at the same four temperatures. At higher temperatures of 160 and 170 °C, all metal ions studied produced significant enhancements in glucose yields, except Cr(3+). The addition of La(3+) as a co-catalyst produced the highest glucose yield improvement.

  2. Lipase-catalyzed esterification of ferulic acid with lauryl alcohol in ionic liquids and antibacterial properties in vitro against three food-related bacteria.

    Shi, Yu-Gang; Wu, Yu; Lu, Xu-Yang; Ren, Yue-Ping; Wang, Qi; Zhu, Chen-Min; Yu, Di; Wang, He


    Lauryl ferulate (LF) was synthesized through lipase-catalyzed esterification of ferulic acid (FA) with lauryl alcohol in a novel ionic liquid ([(EO)-3C-im][NTf2]), and its antibacterial activities was evaluated in vitro against three food-related bacteria. [(EO)-3C-im][NTf2] was first synthesized through incorporating alkyl ether moiety into the double imidazolium ring. [(EO)-3C-im][NTf2] containing hexane was found to be the most suitable for this reaction. The effects of various parameters were studied, and the maximum yield of LF (90.1%) was obtained in the optimum reaction conditions, in [(EO)-3C-im][NTf2]/hexane (VILs:Vhexane=1:1) system, 0.08mmol/mL of FA concentration, 50mg/mL Novozym 435, 60°C. LF exhibited a stronger antibacterial activity against Gram-negative (25 mm) than Gram-positive (21.5-23.2 mm) bacteria. The lowest MIC value was seen for E. coli (1.25mM), followed by L. Monocytogenes (2.5mM) and S.aureus (5mM). The MBCs for L. Monocytogenes, S.aureus and E. coli were 10, 20 and 5mM.

  3. Selective Oxidation of Glycerol to Glyceric Acid in Base-Free Aqueous Solution at Room Temperature Catalyzed by Platinum Supported on Carbon Activated with Potassium Hydroxide

    Tan, Hua


    Pt supported on KOH-activated mesoporous carbon (K-AMC) was used to catalyze glycerol oxidation under base-free conditions at room temperature. To study the relationship between the carbon surface chemistry and the catalytic performance of the K-AMC-based Pt catalysts, different levels of surface oxygen functional groups (SOFGs) on the AMC supports were induced by thermal treatment at different temperatures under inert or H2 gas. A strong effect of the surface chemistry was observed on AMC-supported Pt catalysts for glycerol oxidation. The presence of carboxylic acid groups impedes the adsorption of glycerol, which leads to the reduction of catalytic activity, whereas the presence of high-desorption-temperature SOFGs, such as phenol, ether, and carbonyl/quinone groups, provide hydrophilicity to the carbon surface that improves the adsorption of glycerol molecules on Pt metal surface, which is beneficial for the catalytic activity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Kinetics of an acid-base catalyzed reaction (aspartame degradation) as affected by polyol-induced changes in buffer pH and pK values.

    Chuy, S; Bell, L N


    The kinetics of an acid-base catalyzed reaction, aspartame degradation, were examined as affected by the changes in pH and pK(a) values caused by adding polyols (sucrose, glycerol) to phosphate buffer. Sucrose-containing phosphate buffer solutions had a lower pH than that of phosphate buffer alone, which contributed, in part, to reduced aspartame reactivity. A kinetic model was introduced for aspartame degradation that encompassed pH and buffer salt concentrations, both of which change with a shift in the apparent pK(a) value. Aspartame degradation rate constants in sucrose-containing solutions were successfully predicted using this model when corrections (that is, lower pH, lower apparent pK(a) value, buffer dilution from the polyol) were applied. The change in buffer properties (pH, pK(a)) from adding sucrose to phosphate buffer does impact food chemical stability. These effects can be successfully incorporated into predictive kinetic models. Therefore, pH and pK(a) changes from adding polyols to buffer should be considered during food product development.

  5. Characteristics of structured lipid prepared by lipase-catalyzed acidolysis of roasted sesame oil and caprylic acid in a bench-scale continuous packed bed reactor.

    Kim, Byung Hee; Akoh, Casimir C


    Structured lipid (SL) was prepared from roasted sesame oil and caprylic acid (CA) by Rhizomucor miehei lipase-catalyzed acidolysis in a bench-scale continuous packed bed reactor. Total incorporation and acyl migration of CA in the SL were 42.5 and 3.1 mol %, respectively, and the half-life of the lipase was 19.2 days. The SL displayed different physical and chemical properties, less saturated dark brown color, lower viscosity, lower melting and crystallization temperature ranges, higher melting and crystallization enthalpies, higher smoke point, higher saponification value, and lower iodine value, in comparison to those of unmodified sesame oil. The oxidative stability of purified SL was lower than that of sesame oil. There were no differences in the contents of unsaponifiables including tocopherols and phytosterols. However, total sesame lignans content was decreased in SL due to the loss of sesamol when compared to sesame oil. Most of the 70 volatiles present in roasted sesame oil were removed from SL during short-path distillation of SL. These results indicate that the characteristics of SL are different from those of original sesame oil in several aspects except for the contents of tocopherols and phytosterols.

  6. Kinetics, reactivity, initial-transition state analysis and thermodynamic parameters of base-catalyzed hydrolysis of coumalic acid in solvents with different polarities

    Ezz A. Abu-Gharib


    Full Text Available Base-catalyzed hydrolysis of coumalic acid (COU in binary aqueous-methanol and aqueous-acetone mixtures has been studied kinetically at a temperature range from 283 to 313 K. Moreover, the change in the activation energy barrier of COU from water to water–methanol and water–acetone mixtures is estimated from the kinetic data. Solvent effects on reactivity trends have been analyzed into initial and transition state components by using transfer chemical potentials of the reactants and kinetic data. The transfer chemical potentials δmμθ for COU− anion are derived from solubility data from its calcium, cerium and lanthanum salts. The decrease in rate constant of the base hydrolysis reaction of COU as the percentage of methanol or acetone increases is dominated by transition state (TS. The base hydrolysis reaction of COU follows a rate law with kobs = k2[OH−] and the reaction mechanism was suggested. The high negative values of entropy of activation support the proposal mechanism, i.e. the investigated reaction takes place via the formation of an intermediate complex. Thus, the ring opening of the intermediate complex would be the rate controlling step.

  7. FAME Production from Jatropha curcas Seed Oil via Calcium Oxide Catalyzed Transesterification and its Purification using Acid Activated Bentonite

    Novizar Nazir


    Full Text Available This paper presents the study of transesterification of Jatropha curcas oil (JCO via environmentally benign process using calcium oxide as heterogeneous catalyst.  Response surface methodology (RSM based on central composite design (CCD was performed to optimize three reaction variables in this study.  The transesterification process variables were reaction time, x1 (60 minutes-120 minutes,   molar ratio of methanol: oil, x2 (5:1 – 13:1, and amount of catalyst,  x3 (0.5 % –1.50 % of mass fraction.  Since water washing method is not suitable to purify CaO synthesized fatty acid methyl esters (FAME,   the purification of as-synthesized FAME with acid-activated bentonites to eliminate the remaining calcium was also investigated.   It was found that the yield of JCO FAME could reach up to 94.35 % using the following reaction conditions: 79.33 minutes reaction time, 10.41:1 methanol:oil molar ratio and 0.99 %  catalyst at reaction temperature 65oC.  Among bentonites used in the purification,   2.5% of H2SO4-activated bentonite shows a good performance as decalcifying agent for FAME purification.  The properties of purified jatropha FAME were comparable to those of diesel and satisfied the international standard.

  8. Synthesis of styrenes by palladium(II)-catalyzed vinylation of arylboronic acids and aryltrifluoroborates by using vinyl acetate.

    Lindh, Jonas; Sävmarker, Jonas; Nilsson, Peter; Sjöberg, Per J R; Larhed, Mats


    One Heck of a reaction: Treatment of arylboronic acids or aryltrifluoroborates with vinyl acetate by using a palladium(II) catalyst gives the corresponding styrenes (see scheme). No palladium reoxidant is needed and the vinylation is performed under non-inert conditionsReactions of aromatic and heteroaromatic boronic acids or aryltrifluoroborate salts with vinyl acetate in the presence of a palladium(II) catalyst give the corresponding styrenes in good yields. This Heck reaction proceeds with microwave heating in less than 30 min at 140 degrees C in the absence of base and tolerates a variety of substituents. No palladium reoxidant is needed and the vinylation is performed under non-inert conditions. Mass spectrometry (electrospray ionization mass spectrometry (ESIMS) and tandem mass spectrometry (MS/MS)) was used to identify cationic palladium-containing complexes in ongoing reactions. The key intermediates that have been detected, together with experiments that used deuterated vinyl acetate, support the existence of catalytically active palladium hydride species, and that it is the arylation of ethylene, not vinyl acetate, which generates the styrene product. The mechanism of the reaction is discussed in terms of the palladium(II) intermediates mentioned above.

  9. Synthesis of 1,8-Dioxo-octahydroxanthene Derivatives Catalyzed by p-Dodecylbenezenesulfonic Acid in Water

    JIN,Tong-Shou; ZHANG,Jian-She; WANG,Ai-Qing; LI,Tong-Shuang


    @@ With the increasing concerns of the environment, more and more chemists are devoted to the research of the "green synthesis" which means that the reagent, solvent and catalyst are environmentally friendly in the organic chemical reactions. The importance of aqueous reaction is now generally recognized, and development of carbon-carbon bond-forming reactions that can be carried out in aqueous media is now one of the most challenging topics in organic synthesis.[1]Herein, we report a clean synthesis of 3,3,6,6-tetramethyl-9-aryl-1,8-dioxo-octahydroxanthene derivatives from aromatic aldehyde and 5,5-dimethyl-1,3-cyclohexadione using p-dodecylbenezenesulfonic acid (DBSA) as the catalyst in water.This method provides several advantages such as high yield, simple work-up procedure and environmental friendliness and water was chosen as a green solvent. All the products were characterized by m.p., 1H NMR, IR and elemental analyses.

  10. Sustainable production of a new generation biofuel by lipase-catalyzed esterification of fatty acids from liquid industrial waste biomass.

    Foukis, Athanasios; Gkini, Olga A; Stergiou, Panagiota-Yiolanda; Sakkas, Vasilios A; Dima, Agapi; Boura, Konstantina; Koutinas, Athanasios; Papamichael, Emmanuel M


    In this work we suggest a methodology comprising the design and use of cost-effective, sustainable, and environmentally friendly process for biofuel production compatible with the market demands. A new generation biofuel is produced using fatty acids, which were generated from acidogenesis of industrial wastes of bioethanol distilleries, and esterified with selected alcohols by immobilized Candida antarctica Lipase-B. Suitable reactors with significant parameters and conditions were studied through experimental design, and novel esterification processes were suggested; among others, the continuous removal of the produced water was provided. Finally, economically sustainable biofuel production was achieved providing high ester yield (<97%) along with augmented concentration (3.35M) in the reaction mixtures at relatively short esterification times, whereas the immobilized lipase maintained over 90% of its initial esterifying ability after reused for ten cycles. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO2 Hydrogenation Processes

    Álvarez, Andrea


    The recent advances in the development of heterogeneous catalysts and processes for the direct hydrogenation of CO2 to formate/formic acid, methanol, and dimethyl ether are thoroughly reviewed, with special emphasis on thermodynamics and catalyst design considerations. After introducing the main motivation for the development of such processes, we first summarize the most important aspects of CO2 capture and green routes to produce H2. Once the scene in terms of feedstocks is introduced, we carefully summarize the state of the art in the development of heterogeneous catalysts for these important hydrogenation reactions. Finally, in an attempt to give an order of magnitude regarding CO2 valorization, we critically assess economical aspects of the production of methanol and DME and outline future research and development directions.

  12. Hydrolysis of p-Nitrophenyl Picolinate Catalyzed by Mono-and Binuclear Transition Metal Complexes with Polyether Bridged Dihydroxamic Acid

    李建章; 李鸿波; 冯发美; 谢家庆; 李慎新; 周波; 秦圣英


    Two polyether bridged dihydroxamic acids and their mono-and binuclear manganese(Ⅱ), zinc(Ⅱ) complexes have been synthesized and employed as models to mimic hydrolase in catalytic hydrolysis of p-nitrophenyl picolinate (PNPP). The reaction kinetics and the mechanism of hydrolysis of PNPP have been investigated. The kinetic mathematical model for PNPP cleaved by the complexes has been proposed. The effects of the different central metal ion, mono-and binuclear metal, the pseudo-macrocyclic polyether constructed by polyethoxy group of the complexes, and reactive temperature on the rate for catalytic hydrolysis of PNPP have been examined. The results showed that the transition metal dthydroxamates exhibited high catalytic activity to the hydrolysis of PNPP, the catalytic activity of binuclear complexes was higher than that of mononuclear ones, and the pseudo-macrocyclic polyether might synergetically activate H20 coordinated to metal ion with central metal ion together and promote the catalytic hydrolysis of PNPP.

  13. Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO2 Hydrogenation Processes


    The recent advances in the development of heterogeneous catalysts and processes for the direct hydrogenation of CO2 to formate/formic acid, methanol, and dimethyl ether are thoroughly reviewed, with special emphasis on thermodynamics and catalyst design considerations. After introducing the main motivation for the development of such processes, we first summarize the most important aspects of CO2 capture and green routes to produce H2. Once the scene in terms of feedstocks is introduced, we carefully summarize the state of the art in the development of heterogeneous catalysts for these important hydrogenation reactions. Finally, in an attempt to give an order of magnitude regarding CO2 valorization, we critically assess economical aspects of the production of methanol and DME and outline future research and development directions. PMID:28656757

  14. Use of immobilized phospholipase A1-catalyzed acidolysis for the production of structured phosphatidylcholine with an elevated conjugated linoleic acid content

    Baeza-Jiménez, R.


    Full Text Available Structured phosphatidylcholine (SPC was successfully produced via immobilized phospholipase A1 (PLA1catalyzed acidolysis of phosphatidylcholine (PC with conjugated linoleic acid (CLA. The effects of enzyme loading (2, 5, 10, 15 and 20%, with respect to the weight of substrates, temperature (20, 30, 40, 50 and 60 °C and the molar ratio of substrates (1:2, 1:4, 1:6, 1:8 and 1:10, PC/CLA were evaluated to maximize the incorporation of CLA into PC. The maximum incorporation of CLA achieved was ca. 90% for 24 h of reaction at 50 °C and 200 rpm, using a 1:4 substrate molar ratio and an enzyme loading of 15%.

    Fosfatidilcolina estructurada (SPC fue producida por acidólisis de fosfatidilcolina (PC y ácido linoleico conjugado (CLA usando fosfolipasa A1 (PLA1 inmovilizada. Los efectos de carga de enzima (2, 5, 10, 15 y 20%, respecto al peso de los sustratos, temperatura (20, 30, 40, 50 y 60 °C y la relación molar de sustratos (1:2, 1:4, 1:6, 1:8 y 1:10, PC/CLA fueron evaluados para alcanzar la más elevada incorporación de CLA en PC. La máxima incorporación de CLA obtenida fue de 90% a 50 °C y 200 rpm, para una relación molar 1:4 con una carga de enzima de 15% después de 24 h.

  15. Studies of reaction variables for lipase-catalyzed production of alpha-linolenic acid enriched structured lipid and oxidative stability with antioxidants.

    Mitra, Kanika; Shin, Jung-Ah; Lee, Jeung-Hee; Kim, Seong-Ai; Hong, Soon-Taek; Sung, Chang-Keun; Xue, Cheng Lian; Lee, Ki-Teak


    Alpha-linolenic acid (ALA) enriched structured lipid (SL) was produced by lipase-catalyzed interesterification from perilla oil (PO) and corn oil (CO). The effects of different reaction conditions (substrate molar ratio [PO/CO 1:1 to 1:3], reaction time [0 to 24 h], and reaction temperature [55 to 65 °C]) were studied. Lipozyme RM IM from Rhizomucor miehei was used as biocatalyst. We obtained 32.39% of ALA in SL obtained under the optimized conditions (molar ratio-1:1 [PO:CO], temperature-60 °C, reaction time-15 h). In SL, the major triacylglycerol (TAG) species (linolenoyl-linolenoyl-linolenoyl glycerol [LnLnLn], linolenoyl-linolenoyl-linoleoyl glycerol [LnLnL]) mainly from PO and linoleoyl-linoleoyl-oleoyl glycerol (LLO), linoleoyl-oleoyl-oleoyl glycerol (LOO), palmitoyl-linoleoyl-oleoyl glycerol (PLO) from CO decreased while linolenoyl-linolenoyl-oleoyl glycerol (LnLnO) (18.41%), trilinolein (LLL) (9.06%), LLO (16.66%), palmitoyl-linoleoyl-linoleoyl glycerol (PLL) (9.69%) were increased compared to that of physical blend. Total tocopherol content (28.01 mg/100 g), saponification value (SV) (192.2), and iodine value (IV) (161.9) were obtained. Furthermore, oxidative stability of the SL was also investigated by addition of 3 different antioxidants (each 200 ppm of rosemary extract [SL-ROS], BHT [SL-BHT], catechin [SL-CAT]) was added into SL and stored in 60 °C oven for 30 d. 2-Thiobabituric acid-reactive substances (TBARS) value was 0.16 mg/kg in SL-CAT and 0.18 mg/kg in SL-ROS as compared with 0.22 mg/kg in control (SL) after oxidation. The lowest peroxide value (POV, 200.9 meq/kg) and longest induction time (29.88 h) was also observed in SL-CAT.

  16. A lipoxygenase from red alga Pyropia haitanensis, a unique enzyme catalyzing the free radical reactions of polyunsaturated fatty acids with triple ethylenic bonds.

    Zhu, Zhujun; Qian, Feijian; Yang, Rui; Chen, Juanjuan; Luo, Qijun; Chen, Haimin; Yan, Xiaojun


    Lipoxygenases (LOXs) are key enzymes to regulate the production of hormones and defensive metabolites in plants, animals and algae. In this research, a full length LOX gene has been cloned and expressed from the red alga Pyropia haitanensis (Bangiales, Rhodophyta) gametophyte (PhLOX2). Subsequent phylogenetic analysis showed that such LOX enzymes are separated at the early stage of evolution, establishing an independent branch. The LOX activity was investigated at the optimal pH of 8.0. It appears that PhLOX2 is a multifunctional enzyme featuring both lipoxygenase and hydroperoxidase activities. Additionally, PhLOX2 exhibits remarkable substrate and position flexibility, and it can catalyze an array of chemical reactions involving various polyunsaturated fatty acids, ranging from C18 to C22. As a matter of fact, mono-hydroperoxy, di-hydroperoxy and hydroxyl products have been obtained from such transformations, and eicosapentaenoic acid seem to be the most preferred substrate. It was found that at least triple ethylenic bonds are required for PhLOX2 to function as a LOX, and the resulting hydroxy products should be originated from the PhLOX2 mediated reduction of mono-hydroperoxides, in which the hydrogen abstraction occurs on the carbon atom between the second and third double bond. Most of the di-hydroperoxides observed seem to be missing their mono-position precursors. The substrate and position flexibility, as well as the function versatility of PhLOXs represent the ancient enzymatic pathway for organisms to control intracellular oxylipins.

  17. Mutational Analysis of a Conserved Glutamic Acid Required for Self-Catalyzed Cross-Linking of Bacteriophage HK97 Capsids▿

    Dierkes, Lindsay E.; Peebles, Craig L.; Firek, Brian A.; Hendrix, Roger W.; Duda, Robert L.


    The capsid of bacteriophage HK97 is stabilized by ∼400 covalent cross-links between subunits which form without any action by external enzymes or cofactors. Cross-linking only occurs in fully assembled particles after large-scale structural changes bring together side chains from three subunits at each cross-linking site. Isopeptide cross-links form between asparagine and lysine side chains on two subunits. The carboxylate of glutamic acid 363 (E363) from a third subunit is found ∼2.4 Å from the isopeptide bond in the partly hydrophobic pocket that contains the cross-link. It was previously reported without supporting data that changing E363 to alanine abolishes cross-linking, suggesting that E363 plays a role in cross-linking. This alanine mutant and six additional substitutions for E363 were fully characterized and the proheads produced by the mutants were tested for their ability to cross-link under a variety of conditions. Aspartic acid and histidine substitutions supported cross-linking to a significant extent, while alanine, asparagine, glutamine, and tyrosine did not, suggesting that residue 363 acts as a proton acceptor during cross-linking. These results support a chemical mechanism, not yet fully tested, that incorporates this suggestion, as well as features of the structure at the cross-link site. The chemically identical isopeptide bonds recently documented in bacterial pili have a strikingly similar chemical geometry at their cross-linking sites, suggesting a common chemical mechanism with the phage protein, but the completely different structures and folds of the two proteins argues that the phage capsid and bacterial pilus proteins have achieved shared cross-linking chemistry by convergent evolution. PMID:19091865

  18. Hydrolysis of palm oil catalyzed by acid%棕榈油的酸催化水解工艺研究

    张玲玲; 王晖


    以棕榈油为原料进行常压酸催化水解工艺研究。考察了反应时间、反应温度、催化剂用量、油水质量比及乳化剂用量对棕榈油水解反应的影响,得出棕榈油一次酸催化水解的最佳反应条件:反应时间7 h,反应温度100℃,催化剂浓硫酸用量7.5%,油水质量比1∶1,乳化剂磺酸用量0.5%;在最佳反应条件下棕榈油水解产物酸值(KOH)为192.77 mg/g,水解率达到91.96%。并研究出一套循环水解的工艺流程,实现油脂水解产物的循环利用,提高了水相中甘油的含量。%The hydrolysis of palm oil catalyzed by acid was studied. The effects of reaction time,reaction temperature,catalyst dosage,mass ratio of oil to water and emulsifier dosage on the hydrolysis of palm oil were investigated. The optimal reaction conditions of palm oil hydrolysis were obtained as follows:reaction time 7 h,reaction temperature 100℃,mass ratio of oil to water 1∶1,dosage of sulfonic acid used as emul-sifier 0. 5% and catalyst( concentrated sulfonic acid) dosage 7. 5%. Under the optimal reaction condi-tions,the acid value of the hydrolysates was up to 192. 77 mgKOH/g and the hydrolysis rate of palm oil was 91. 96%. A circulated hydrolysis process was designed, then the recycling of hydrolysates was real-ized,and the content of glycerin in the aqueous phase increased.

  19. Horseradish peroxidase-catalyzed synthesis of poly(thiophene-3-boronic acid) biocomposites for mono-/bi-enzyme immobilization and amperometric biosensing.

    Huang, Yi; Wang, Wen; Li, Zou; Qin, Xiaoli; Bu, Lijuan; Tang, Zhiyong; Fu, Yingchun; Ma, Ming; Xie, Qingji; Yao, Shouzhuo; Hu, Jiming


    We report here on a facile enzymatic polymerization protocol to prepare enzyme-poly(thiophene-3-boronic acid) (PTBA) polymeric biocomposites (PBCs) for high-performance mono-/bi-enzyme amperometric biosensing. Horseradish peroxidase (HRP)-catalyzed polymerization of thiophene-3-boronic acid (TBA) monomer was conducted in aqueous solution containing HRP (or plus glucose oxidase (GOx)) by either directly added or GOx-glucose generated oxidant H2O2. The mono-/bi-enzyme amperometric biosensors were prepared simply by casting the dialysis-isolated PBCs on Au-plated Au electrode (Auplate/Au), followed by coating with an outer-layer chitosan (CS) film. The boronic acid residues are capable of covalent bonding with enzyme at the glycosyl sites (boronic acid-diols interaction), which should less affect the enzymatic activity as compared with the common cases of covalent bonding at the peptide chains, and UV-vis spectrophotometric tests confirmed that the encapsulated HRP almost possesses its pristine enzymatic specific activity. The enzyme electrodes were studied by cyclic voltammetry, electrochemical impedance spectroscopy and chronoamperometry in the presence of Fe(CN)6(4-) mediator. The CS/HRP-PTBA/Auplate/Au electrode responded linearly to H2O2 concentration from 1 to 300 μM with a sensitivity of 390 μA mM(-1)cm(-2) and a limit of detection (LOD) of 0.1 μM. The bienzyme CS/GOx-HRP-PTBA(H2O2)/Auplate/Au electrode responded linearly to glucose concentration from 5 μM to 0.83 mM with a sensitivity of 75.1 μA mM(-1)cm(-2) and a LOD of 1 μM, and it is found here that the use of Fe(CN)6(4-) that can only efficiently mediate HRP favorably avoids the "unusual amperometric responses" observed when other mediators that can efficiently turn over both HRP and GOx are used.

  20. Enantioselective allylation of imines catalyzed by newly developed (-)-β-pinene-based π-allylpalladium catalyst: an efficient synthesis of (R)-α-propylpiperonylamine and (R)-pipecolic acid.

    Fernandes, Rodney A; Nallasivam, Jothi L


    A newly developed π-allylpalladium with a (-)-β-pinene framework and an isobutyl side chain catalyzed the enantioselective allylation of imines in good yields and enantioselectivities (20 examples, up to 98% ee). An efficient enantioselective synthesis of the (R)-α-propyl piperonylamine part of DMP 777, a human leukocyte elastase inhibitor and (R)-pipecolic acid have been achieved as a useful application of this methodology.

  1. Impact of Biochemical Composition on Susceptibility of Algal Biomass to Acid-Catalyzed Pretreatment for Sugar and Lipid Recovery

    Dong, Tao; Van Wychen, Stefanie; Nagle, Nick; Pienkos, Philip T.; Laurens, Lieve M. L.


    One of the major challenges associated with algal biofuels production in a biorefinery-type setting is improving biomass utilization in its entirety, increasing the process energetic yields and providing economically viable and scalable co-product concepts. We focus on the impact of compositional characteristics of biomass on the susceptibility to pretreatment in order to maximize the valorization of algal biomass conversion for biofuels and bioproducts. The release of monomeric carbohydrates in the aqueous phase and extractability of the lipid fraction was measured based a response surface methodology to find significant explanatory variables and interaction terms. We studied the effect of harvest timing on the conversion yields, using three algal strains; Chlorella vulgaris and Scenedesmus acutus and Nannochloropsis granulata representing three different nutritional metabolic phases. Four cultivation conditions of high (= 90 gallon gasoline equivalent/ton biomass) value for a combined sugar- and lipid-based biofuels process were identified. These four conditions represent either mid or late stage harvest cultivation regimes. The results indicate that acid pretreatment has potential to be applicable for a vast range of biomass samples to obtain high energy yields, but that the exact conditions and optima are dependent on the strain and likely the starting composition of the biomass.

  2. A kinetic study on the Novozyme 435-catalyzed esterification of free fatty acids with octanol to produce octyl esters.

    Chowdhury, Avisha; Mitra, Debarati


    Octyl esters can serve as an important class of biolubricant components replacing their mineral oil counterparts. The purpose of the current work was to investigate the enzymatic esterification reaction of free fatty acids (FFA, from waste cooking oil) with octanol in a solvent-free system using a commercial lipase Novozyme 435. It was found that the esterificaton reaction followed the Ping-pong bi-bi kinetics with no inhibition by substrates or products within the studied concentration range. The maximum reaction rate was estimated to be 0.041 mol L(-1) g(-1) h(-1) . Additionally, the stability of Novozyme 435 in the current reaction system was studied by determining its activity and final conversion of FFA to esters after 12 successive utilizations. Novozyme 435 exhibited almost 100% enzyme activity up to 7 cycles of reaction and gradually decreased (by 5%) thereafter. The kinetic parameters evaluated from the study shall assist in the design of reactors for large-scale production of octyl esters from a cheap biomass source. The enzyme reusability data can further facilitate mass production by curtailing the cost of expensive enzyme consumption.

  3. Catalyzed Ester Synthesis Using Candida rugosa Lipase Entrapped by Poly(N-isopropylacrylamide-co-itaconic Acid Hydrogel

    Nikola Milašinović


    Full Text Available This study reports the synthesis of polymeric matrices based on N-isopropylacrylamide and itaconic acid and its application for immobilization of lipase from Candida rugosa. The lipase was immobilized by entrapment method. Free and immobilized lipase activities, pH and temperature optima, and storage stability were investigated. The optimum temperature for free and entrapped lipase was found to be 40 and 45°C, while the optimum pH was observed at pH 7 and 8, respectively. Both hydrolytic activity in an aqueous medium and esterolytic activity in an organic medium have been evaluated. Maximum reaction rate (Vmax and Michaelis-Menten constants (Km were also determined for immobilized lipase. Storage stability of lipase was increased as a result of immobilization process. Furthermore, the operational stability and reusability of the immobilized lipase in esterification reaction have been studied, and it was observed that after 10 cycles, the residual activity for entrapped lipase was as high as 50%, implying that the developed hydrogel and immobilized system could provide a promising solution for the flavor ester synthesis at the industrial scale.

  4. Advanced Model Compounds for Understanding Acid-Catalyzed Lignin Depolymerization: Identification of Renewable Aromatics and a Lignin-Derived Solvent.

    Lahive, Ciaran W; Deuss, Peter J; Lancefield, Christopher S; Sun, Zhuohua; Cordes, David B; Young, Claire M; Tran, Fanny; Slawin, Alexandra M Z; de Vries, Johannes G; Kamer, Paul C J; Westwood, Nicholas J; Barta, Katalin


    The development of fundamentally new approaches for lignin depolymerization is challenged by the complexity of this aromatic biopolymer. While overly simplified model compounds often lack relevance to the chemistry of lignin, the direct use of lignin streams poses significant analytical challenges to methodology development. Ideally, new methods should be tested on model compounds that are complex enough to mirror the structural diversity in lignin but still of sufficiently low molecular weight to enable facile analysis. In this contribution, we present a new class of advanced (β-O-4)-(β-5) dilinkage models that are highly realistic representations of a lignin fragment. Together with selected β-O-4, β-5, and β-β structures, these compounds provide a detailed understanding of the reactivity of various types of lignin linkages in acid catalysis in conjunction with stabilization of reactive intermediates using ethylene glycol. The use of these new models has allowed for identification of novel reaction pathways and intermediates and led to the characterization of new dimeric products in subsequent lignin depolymerization studies. The excellent correlation between model and lignin experiments highlights the relevance of this new class of model compounds for broader use in catalysis studies. Only by understanding the reactivity of the linkages in lignin at this level of detail can fully optimized lignin depolymerization strategies be developed.

  5. A reactivity-selectivity study of the Friedel-Crafts acetylation of 3,3'-dimethylbiphenyl and the oxidation of the acetyl derivatives

    Titinchi, Salam J.J.; Kamounah, Fadhil S.; Abbo, Hanna S.


    ,3'-dmbp using the Perrier addition procedure in boiling 1,2-dichloroethane was found to be superior to other recipes. The discrimination against the 6-acetyl derivative during monoacetylation seems to reflect a mechanism including an AcCl: AlCl3 complex or larger agglomerates as the electrophile, whereas...

  6. Separation and partial characterization of enzymes catalyzing delta-aminolevulinic acid formation in Synechocystis sp. PCC 6803.

    Rieble, S; Beale, S I


    Formation of the universal tetrapyrrole precursor, delta-aminolevulinic acid (ALA), from glutamate via the five-carbon pathway requires three enzymes: glutamyl-tRNA synthetase, glutamyl-tRNA reductase, and glutamate-1-semialdehyde (GSA) aminotransferase. All three enzymes were separated from extracts of the unicellular cyanobacterium Synechocystis sp. PCC 6803, and two of them, glutamyl-tRNA synthetase and GSA aminotransferase, were partially characterized. After an initial high speed centrifugation and differentiatial ammonium sulfate fractionation of cell extract, the enzymes were separated by successive affinity chromatography on Reactive Blue 2-Sepharose and 2',5'-ADP-agarose. All three enzyme fractions were required to reconstitute ALA formation from glutamate. The apparent native molecular masses of glutamyl-tRNA synthetase and GSA aminotransferase were determined by gel filtration chromatography to be 63 and 98 kDa, respectively. Neither glutamyl-tRNA synthetase nor GSA aminotransferase activity was affected by hemin concentrations up to 10 and 30 microM, respectively, and neither activity was affected by protochlorophyllide concentrations up to 2 microM. GSA aminotransferase was inhibited 50% by 0.5 microM gabaculine. The gabaculine inhibition was reversible for up to 1 h after its addition, if the gabaculine was removed by gel filtration before the enzyme was incubated with substrate. However, irreversible inactivation was obtained by preincubating the enzyme at 30 degrees C either for several hours with gabaculine alone or for a few minutes with both gabaculine and GSA. Neither pyridoxal phosphate nor pyridoxamine phosphate significantly affected the activity of GSA aminotransferase at physiologically relevant concentrations, and neither of these compounds reactivated the gabaculine-inactivated enzyme. It was noted that the presence of pyridoxamine phosphate in the ALA assay mixture produced a false positive color reaction even in the absence of enzyme.

  7. Lipozyme RM IM-catalyzed acidolysis of Cinnamomum camphora seed oil with oleic acid to produce human milk fat substitutes enriched in medium-chain fatty acids.

    Zou, Xian-Guo; Hu, Jiang-Ning; Zhao, Man-Li; Zhu, Xue-Mei; Li, Hong-Yan; Liu, Xiao-Ru; Liu, Rong; Deng, Ze-Yuan


    In the present study, a human milk fat substitute (HMFS) enriched in medium-chain fatty acids (MCFAs) was synthesized through acidolysis reaction from Cinnamomum camphora seed oil (CCSO) with oleic acid in a solvent-free system. A commercial immobilized lipase, Lipozyme RM IM, from Rhizomucor miehei, was facilitated as a biocatalyst. Effects of different reaction conditions, including substrate molar ratio, enzyme concentration, reaction temperature, and reaction time were investigated using response surface methodology (RSM) to obtain the optimal oleic acid incorporation. After optimization, results showed that the maximal incorporation of oleic acid into HMFS was 59.68%. Compared with CCSO, medium-chain fatty acids at the sn-2 position of HMFS accounted for >70%, whereas oleic acid was occupied predominantly at the sn-1,3 position (78.69%). Meanwhile, triacylglycerol (TAG) components of OCO (23.93%), CCO (14.94%), LaCO (13.58%), OLaO (12.66%), and OOO (11.13%) were determined as the major TAG species in HMFS. The final optimal reaction conditions were carried out as follows: substrate molar ratio (oleic acid/CCSO), 5:1; enzyme concentration, 12.5% (w/w total reactants); reaction temperature, 60 °C; and reaction time, 28 h. The reusability of Lipozyme RM IM in the acidolysis reaction was also evaluated, and it was found that it could be reused up to 9 times without significant loss of activities. Urea inclusion method was used to separate and purify the synthetic product. As the ratio of HMFS/urea increased to 1:2, the acid value lowered to the minimum. In a scale-up experiment, the contents of TAG and total tocopherols in HMFS (modified CCSO) were 77.28% and 12.27 mg/100 g, respectively. All of the physicochemical indices of purified product were within food standards. Therefore, such a MCFA-enriched HMFS produced by using the acidolysis method might have potential application in the infant formula industry.

  8. Synthesis of acetylsalicylic acid catalyzed by carbon-based solid acid%碳基固体酸催化合成乙酰水杨酸

    占昌朝; 曹小华; 严平; 王剑波; 余祖进; 江小平


    Carbon-based solid acid catalysts synthesized from starch andp-toluene sulphonic acid were characterized by FTIR, TG, BET, SEM and EDS. Its catalytic activity and effect of conventional heat and microwave heat on yield of acetylsalicylic acid were studied. The better condition was determined with single factor tests, which is as follows: the molar ratio of acetic anhydride to salicylic acid was 1.5 : 1, the weight ratio of carbon-based solid acid to salicylic acid was 5.8%, acylation reaction temperature was 76--80 ~C, reaction time was 25 min under conventional heat. The yield of acetylsalicylic acid was 82.1% and kept 78.2% after used five times under conventional heat. The carbon-based solid acid catalyst has high catalytic activity and retrievability under conventional heat, which are better than that of microwave heat.%以淀粉和对甲苯磺酸为原料合成了碳基固体酸催化剂,并采用FTIR、TG、BET、SEM和EDS对催化剂进行了表征。研究了催化剂对乙酰水杨酸合成反应的催化活性,并比较了常规加热和微波加热方式对反应的影响。通过单因素试验确定了较佳工艺条件为:乙酸酐与水杨酸物质的量比为1.5∶1,催化剂用量为水杨酸质量的5.8%,反应时间25 min,反应温度76~80℃。常规加热条件下收率82.1%,使用5次后,收率仍保持在78.2%。碳基固体酸催化剂在常规加热条件下催化性能和重复使用性能均优于微波加热条件反应。

  9. A Synthetic Route to Chiral 1,4-Disubstituted Tetrahydro-β-Carbolines via Domino Ring-Opening Cyclization of Activated Aziridines with 2-Vinylindoles.

    Sayyad, Masthanvali; Wani, Imtiyaz Ahmad; Babu, Raja; Nanaji, Yerramsetti; Ghorai, Manas K


    A simple and efficient strategy for the synthesis of various 1,4-disubstituted tetrahydro-β-carbolines with excellent stereoselectivity (de, ee up to >99%) via domino ring opening cyclization (DROC) of activated aziridines with 2-vinylindoles is described. The reaction proceeds through LiClO4-catalyzed Friedel-Crafts-type alkylation of 2-vinylindoles with activated aziridines followed by an intramolecular aza-Michael reaction in a domino fashion.

  10. Lewis酸性离子液体催化合成丁二酸二异丙酯%Synthesis of succinic acid diisopropyl ester catalyzed by Lewis acid ionic liquids

    赵地顺; 葛京京; 翟建华; 张娟; 刘猛帅; 李俊盼


    采用两步法制备了9种不同的Lewis酸性离子液体,采用1H NMR、FT-IR对离子液体的结构进行了表征,并系统地考察了其对丁二酸和异丙醇酯化反应的催化性能。结果表明,离子液体随着卤化物用量增加表现出更强的酸性。其中[Bmim]Br-Fe2Cl6催化合成丁二酸二异丙酯效果良好,催化剂用量为丁二酸质量的10.0%,反应温度100℃,反应时间4 h,酸醇摩尔比为1:5,丁二酸二异丙酯收率为88.9%,酯化率达92.7%。离子液体重复使用6次后,产品收率下降1.7%。%Nine kinds of different Lewis acid ionic liquids were synthesized by two-step process and their structures were characterized with 1H NMR and FT-IR. Lewis acid ionic liquids prepared were used to catalyze the esterification reaction of succinic acid and isopropyl alcohol. With the increase of dosage of halide, the ionic liquids showed stronger acidity. [Bmim]Br-Fe2Cl6 had the best catalytic performance, and optimal conditions for the synthesis of succinic acid diisopropyl ester were obtained as follows, amount of catalyst 10.0%(g/g)of succinic acid, reaction temperature 100℃ and reaction time 4 h, succinic acid and isopropyl alcohol ratio 1:5. Under the optimal conditions, the yield of succinic acid diisopropyl ester was up to 88.9%, esterification rate was 92.7%.The catalyst was recycled 6 times, and the yield of succinic acid diisopropyl ester only decreased by 1.7%.

  11. Hydrogen Isotope Measurements of Organic Acids and Alcohols by Pyrolysis-GC-MS-TC-IRMS: Application to Analysis of Experimentally Derived Hydrothermal Mineral-Catalyzed Organic Products

    Socki, Richard A.; Fu, Qi; Niles, Paul B.; Gibson, Everett K., Jr.


    We report results of experiments to measure the H isotope composition of organic acids and alcohols. These experiments make use of a pyroprobe interfaced with a GC and high temperature extraction furnace to make quantitative H isotope measurements. This work compliments our previous work that focused on the extraction and analysis of C isotopes from the same compounds [1]. Together with our carbon isotope analyses our experiments serve as a "proof of concept" for making C and H isotope measurements on more complex mixtures of organic compounds on mineral surfaces in abiotic hydrocarbon formation processes at elevated temperatures and pressures. Our motivation for undertaking this work stems from observations of methane detected within the Martian atmosphere [2-5], coupled with evidence showing extensive water-rock interaction during Mars history [6-8]. Methane production on Mars could be the result of synthesis by mineral surface-catalyzed reduction of CO2 and/or CO by Fischer-Tropsch Type (FTT) reactions during serpentization [9,10]. Others have conducted experimental studies to show that FTT reactions are plausible mechanisms for low-molecular weight hydrocarbon formation in hydrothermal systems at mid-ocean ridges [11-13]. Our H isotope measurements utilize an analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-High Temperature Conversion-Isotope Ratio Mass Spectrometry (Py-GC-MS-TC-IRMS). This technique is designed to carry a split of the pyrolyzed GC-separated product to a Thermo DSQII quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of separated organic compounds, therefore both chemical and isotopic measurements can be carried out simultaneously on the same sample.

  12. Horseradish peroxidase-catalyzed polymerization of L-DOPA for mono-/bi-enzyme immobilization and amperometric biosensing of H2O2 and uric acid.

    Dai, Mengzhen; Huang, Ting; Chao, Long; Xie, Qingji; Tan, Yueming; Chen, Chao; Meng, Wenhua


    Horseradish peroxidase (HRP)-catalyzed polymerization of L-DOPA (vs. dopamine) in the presence of H2O2 (and uricase (UOx)) was exploited to immobilize mono-/bi-enzymes for hydroquinone-mediated amperometric biosensing of H2O2 and uric acid (UA). The relevant polymeric biocomposites (PBCs) were prepared in phosphate buffer solution containing HRP and L-DOPA (or plus UOx) after adding H2O2. The mono-/bi-enzyme amperometric biosensors were prepared simply by casting some of the PBCs on Au-plated Au (Au(plate)/Au) electrodes, followed by coating with an outer-layer chitosan (CS) film for each. UV-vis spectrophotometry, scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy were used for film characterization and/or process monitoring. The HRP immobilized by enzyme catalysis well preserved its bioactivity, as confirmed by UV-vis spectrophotometry. Under optimized conditions, the monoenzyme CS/HRP-poly(L-DOPA) (PD)/Au(plate)/Au electrode potentiostated at -0.1V responded linearly to H2O2 concentration from 0.001 to 1.25mM with a sensitivity of 700μA mM(-1)cm(-2) and a limit of detection (LOD) of 0.1μM, and the bienzyme CS/UOx-HRP-PD/Au(plate)/Au electrode at -0.1V responded linearly to UA concentration from 0.001 to 0.4mM with a sensitivity of 349μA mM(-1)cm(-2) and a LOD of 0.1μM. The mono-/bi-enzyme biosensors based on biosynthesized PD performed better than many reported analogues and those based on similarly biosynthesized polydopamine.

  13. Effect of acid-catalyzed formation rates of benzimidazole-linked polymers on porosity and selective CO2 capture from gas mixtures.

    Altarawneh, Suha; İslamoğlu, Timur; Sekizkardes, Ali Kemal; El-Kaderi, Hani M


    Benzimidazole-linked polymers (BILPs) are emerging candidates for gas storage and separation applications; however, their current synthetic methods offer limited control over textural properties which are vital for their multifaceted use. In this study, we investigate the impact of acid-catalyzed formation rates of the imidazole units on the porosity levels of BILPs and subsequent effects on CO2 and CH4 binding affinities and selective uptake of CO2 over CH4 and N2. Treatment of 3,3'-Diaminobenzidine tetrahydrochloride hydrate with 1,2,4,5-tetrakis(4-formylphenyl)benzene and 1,3,5-(4-formylphenyl)-benzene in anhydrous DMF afforded porous BILP-15 (448 m(2) g(-1)) and BILP-16 (435 m(2) g(-1)), respectively. Alternatively, the same polymers were prepared from the neutral 3,3'-Diaminobenzidine and catalytic amounts of aqueous HCl. The resulting polymers denoted BILP-15(AC) and BILP-16(AC) exhibited optimal surface areas; 862 m(2) g(-1) and 643 m(2) g(-1), respectively, only when 2 equiv of HCl (0.22 M) was used. In contrast, the CO2 binding affinity (Qst) dropped from 33.0 to 28.9 kJ mol(-1) for BILP-15 and from 32.0 to 31.6 kJ mol(-1) for BILP-16. According to initial slope calculations at 273 K/298 K, a notable change in CO2/N2 selectivity was observed for BILP-15(AC) (61/50) compared to BILP-15 (83/63). Similarly, ideal adsorbed solution theory (IAST) calculations also show the higher specific surface area of BILP-15(AC) and BILP-16(AC) compromises their CO2/N2 selectivity.

  14. An alternative reaction for heme degradation catalyzed by the Escherichia coli O157:H7 ChuS protein: Release of hematinic acid, tripyrrole and Fe(III).

    Ouellet, Yannick H; Ndiaye, Cheikh Tidiane; Gagné, Stéphane M; Sebilo, Anne; Suits, Michael D L; Jubinville, Éric; Jia, Zongchao; Ivancich, Anabella; Couture, Manon


    As part of the machinery to acquire, internalize and utilize heme as a source of iron from the host, some bacteria possess a canonical heme oxygenase, where heme plays the dual role of substrate and cofactor, the later catalyzing the cleavage of the heme moiety using O2 and electrons, and resulting in biliverdin, carbon monoxide and ferrous non-heme iron. We have previously reported that the Escherichia coli O157:H7 ChuS protein, which is not homologous to heme oxygenases, can bind and degrade heme in a reaction that releases carbon monoxide. Here, we have pursued a detailed characterization of such heme degradation reaction using stopped-flow UV-visible absorption spectrometry, the characterization of the intermediate species formed in such reaction by EPR spectroscopy and the identification of reaction products by NMR spectroscopy and Mass spectrometry. We show that hydrogen peroxide (in molar equivalent) is the key player in the degradation reaction, at variance to canonical heme oxygenases. While the initial intermediates of the reaction of ChuS with hydrogen peroxide (a ferrous keto π neutral radical and ferric verdoheme, both identified by EPR spectroscopy) are in common with heme oxygenases, a further and unprecedented reaction step, involving the cleavage of the porphyrin ring at adjacent meso-carbons, results in the release of hematinic acid (a monopyrrole moiety identified by NMR spectroscopy), a tripyrrole product (identified by Mass spectrometry) and non-heme iron in the ferric oxidation state (identified by EPR spectroscopy). Overall, the unprecedented reaction of E. coli O157:H7 ChuS provides evidence for a novel heme degradation activity in a Gram-negative bacterium.

  15. Inhibition of lactoperoxidase-catalyzed 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) and tyrosine oxidation by tyrosine-containing random amino acid copolymers.

    Clausen, Morten R; Skibsted, Leif H; Stagsted, Jan


    Oxidation of 2,2'-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) by lactoperoxidase was found to be inhibited by tyrosine-containing random amino acid copolymers but not by tyrosine. Both electrostatic effects and polymer size were found to be important by comparison of negatively and positively charged copolymers of varying lengths, with poly(Glu, Tyr)4:1 ([E 4Y 1] approximately 40) as the strongest competitive inhibitor (EC 50 approximately 20 nM). This polymer did not form dityrosine in the presence of lactoperoxidase (LPO) and peroxide. Furthermore, incubation with tert-butyl hydroperoxide, as opposed to hydrogen peroxide, resulted in a peculiar long lag phase of the reaction between the redox intermediate compound II and [E 4Y 1] approximately 40, indicating a very tight association between enzyme and inhibitor. We propose that interactions between multiple positively charged areas on the surface of LPO and the polymer are required for optimal inhibition.

  16. Palladium-Catalyzed Asymmetric Conjugate Addition of Arylboronic Acids to Five-, Six-, and Seven-Membered β-Substituted Cyclic Enones: Enantioselective Construction of All-Carbon Quaternary Stereocenters

    Kikushima, Kotaro


    The first enantioselective Pd-catalyzed construction of all-carbon quaternary stereocenters via 1,4-addition of arylboronic acids to β-substituted cyclic enones is reported. Reaction of a wide range of arylboronic acids and cyclic enones using a catalyst prepared from Pd(OCOCF(3))(2) and a chiral pyridinooxazoline ligand yields enantioenriched products bearing benzylic stereocenters. Notably, this transformation is tolerant to air and moisture, providing a practical and operationally simple method of synthesizing enantioenriched all-carbon quaternary stereocenters.

  17. Palladium-phosphinous acid complexes catalyzed Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid in water/alcoholic solvents

    Ben Li; Cuiping Wang; Guang Chen; Zhiqiang Zhang


    Highly active,air-stable and water-soluble palladium-phosphinous acid complexes have been applied to Suzuki cross-coupling reaction of heteroaryl bromides under mild conditions in water/alcoholic solvents.Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid occurred efficiently using palladium phosphinous acid complexes (POPd) and phase transfer catalyst (tetrabutylammonium bromide and polyethylene glycol) in water/ethanol mixture,water/propanol mixture and neat water respectively,the corresponding yields of cross-coupling heteroaryl-aryls were satisfied.The tert-butyl substituted ligand di-tert-butylphosphino in combination with POPd was found to be more active than the same family derived catalysts dipalladium complexes POPdl and POPd2,and other two kinds of Pd-catalysts Pd(PPh3)4 and Pd2(dba)3.The mechanism of Suzuki cross-coupling reaction between heteroaryl bromides and phenylboronic acid in water was proposed with respect to the key role of phase transfer catalyst on the transmetallation step.Compared with other solid phase transfer catalysts,TBAB was tested as the ideal one.The alkalinity of base and the molar proportion between POPd and TBAB were investigated in water and alcoholic solvents.Notably,in the presence of TBAB adding alcoholic solvents into water enhanced the yields of target products.However in terms of the liquid phase transfer catalyst of PEGs,mixing water into PEGs could slightly decrease the yields with respect to the water free PEGs bulk phase,which was probably due to the homogenous liquid conditions in pure PEGs and weak interactions between PEGs and heteroaryl bromide molecules in water depending on their molecular chain lengths.

  18. Palladium-phosphinous acid complexes catalyzed Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid in water/alcoholic solvents.

    Li, Ben; Wang, Cuiping; Chen, Guang; Zhang, Zhiqiang


    Highly active, air-stable and water-soluble palladium-phosphinous acid complexes have been applied to Suzuki cross-coupling reaction of heteroaryl bromides under mild conditions in water/alcoholic solvents. Suzuki cross-coupling reaction of heteroaryl bromides with phenylboronic acid occurred efficiently using palladium phosphinous acid complexes (POPd) and phase transfer catalyst (tetrabutylammonium bromide and polyethylene glycol) in water/ethanol mixture, water/propanol mixture and neat water respectively, the corresponding yields of cross-coupling heteroaryl-aryls were satisfied. The tert-butyl substituted ligand di-tert-butylphosphino in combination with POPd was found to be more active than the same family derived catalysts dipalladium complexes POPd1 and POPd2, and other two kinds of Pd-catalysts Pd(PPh3)4 and Pd2(dba)3. The mechanism of Suzuki cross-coupling reaction between heteroaryl bromides and phenylboronic acid in water was proposed with respect to the key role of phase transfer catalyst on the transmetallation step. Compared with other solid phase transfer catalysts, TBAB was tested as the ideal one. The alkalinity of base and the molar proportion between POPd and TBAB were investigated in water and alcoholic solvents. Notably, in the presence of TBAB adding alcoholic solvents into water enhanced the yields of target products. However in terms of the liquid phase transfer catalyst of PEGs, mixing water into PEGs could slightly decrease the yields with respect to the water free PEGs bulk phase, which was probably due to the homogenous liquid conditions in pure PEGs and weak interactions between PEGs and heteroaryl bromide molecules in water depending on their molecular chain lengths.

  19. Catalytic Conversion of Bio-Oil to Oxygen-Containing Fuels by Acid-Catalyzed Reaction with Olefins and Alcohols over Silica Sulfuric Acid

    Qingwen Wang


    Full Text Available Crude bio-oil from pine chip fast pyrolysis was upgraded with olefins (1-octene, cyclohexene, 1,7-octadiene, and 2,4,4-trimethylpentene plus 1-butanol (iso-butanol, t-butanol and ethanol at 120 °C using a silica sulfuric acid (SSA catalyst that possesses a good catalytic activity and stability. Gas chromatography-mass spectrometry (GC-MS, Fourier transform infrared spectroscopy (FT-IR and proton nuclear magnetic resonance (1H-NMR analysis showed that upgrading sharply increased ester content and decreased the amounts of levoglucosan, phenols, polyhydric alcohols and carboxylic acids. Upgrading lowered acidity (pH value rose from 2.5 to >3.5, removed the unpleasant odor and increased hydrocarbon solubility. Water content dramatically decreased from 37.2% to about 7.0% and the heating value increased from 12.6 MJ·kg−1 to about 31.9 MJ·kg−1. This work has proved that bio-oil upgrading with a primary olefin plus 1-butanol is a feasible route where all the original heating value of the bio-oil plus the added olefin and alcohol are present in the resulting fuel.

  20. The Practical Asymmetric Syntheses of Key Chiral Intermediates of Chiral Drug from Four-Carbon Chiral Pool

    MI; AiQiao


    (S)-or (R)-2-Amino-4-phenylbutyric acid and (S)-or (R)-2-hydroxy-4-phenylbutyric acid and their ethyl esters are key chiral intermediates for the preparation of angiotensin converting enzyme inhibitors (ACEI) and other chiral drugs. Their practically asymmetric synthetic methods in large scale from four-carbon chiral pool, commercially available L-aspartic acid and L-malic acid, will be presented (as scheme).  (S)-2-Amino-4-phenylbutyric acid and its ethyl ester hydrochloride were prepared from the easily available L-aspartic acid via activation by forming anhydride hydrochloride, Friedel-Crafts reaction with benzene, hydrogenolysis and esterification with ethanol in the presence of thionyl chloride in overall yield of 80% and 73.6% respectively with 99% ee. We first used amino acid anhydride hydrochloride as the acylating agent in Friedel-Crafts reaction without racemization. [1]……