- Reusable and efficient polystyrene-supported acidic ionic liquid catalyst for esterifications
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Polystyrene (PS)-supported 1-(propyl-3-sulfonate) imidazolium hydrosulfate acidic ionic liquid (PS-CH2-[SO3H-pIM][HSO4]) catalyst was prepared by supporting the ionic liquid onto highly cross-linked chloromethylated polystyrene (PS-CH2Cl). FT-IR, SEM and TG-DSC were employed to characterize the structure and property of the catalyst. Results suggested that acidic ionic liquid was supported onto the surface of PS-CH 2Cl by covalent bond. The original rough surface of PS-CH 2Cl was covered with acidic ionic liquid, forming a compact and thin surface layer, and its size had no obvious change. Moreover, the PS-CH 2-[SO3H-pIM][HSO4] catalyst showed a better thermal stability than that of PS-CH2Cl support. It also exhibited high catalytic activity for a series of esterifications. After the catalyst was reused for 13 times in the synthesis of n-butyl acetate, the yield only decreased 7.3%. A reaction mechanism of esterification over this new catalyst was proposed as well.
- Xu, Zhenjin,Wan, Hui,Miao, Jinmei,Han, Mingjuan,Yang, Cao,Guan, Guofeng
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- Effect of Hydrogen Bond Donor on the Physical Properties of Benzyltriethylammonium Chloride Based Deep Eutectic Solvents and Their Usage in 2-Ethyl-Hexyl Acetate Synthesis as a Catalyst
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Deep eutectic solvents (DES) containing benzyl triethylammonium chloride (BTEAC) as a hydrogen bond acceptor (HBA) and p-toluene sulfonic acid (PTSA), citric acid (CA), and oxalic acid (OX) as a hydrogen bond donor (HBD) were formed at their respective eutectic points. The physical properties such as pH, ionic conductivity, viscosity, density, and refractive index were measured between 293 and 333 K. Viscosity values as low as 0.21 Pa·s and conductivity values as high as 8 mS/cm were achieved, where the pH values of each DES proved to be extremely low. The effect of HBD on the physical properties was investigated and was found to be very significant. Also, the catalytic application of BTEAC based DES in the esterification reaction of the acetic acid with 2-ethyl-hexanol was studied, and the activation energy was obtained using initial reaction rates. The results showed that very high initial reaction rates and low activation energy can be achieved when catalyzed by DES which was formed using BTEAC and PTSA.
- Taysun, M. Bengi,Sert, Emine,Atalay, Ferhan S.
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- Investigation of steapsin lipase for kinetic resolution of secondary alcohols and synthesis of valuable acetates in non-aqueous reaction medium
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In present study, the application of steapsin lipase (as a biocatalyst) was investigated for kinetic resolution of secondary alcohols (1-phenyl ethanol and their derivatives) using vinyl acetate as an activated acyl donor. The enzymatic protocol was optimized for various reaction parameters such as effect of the molar ratio, solvent, temperature, time and biocatalyst loading to obtain best reaction conditions. On optimization, developed enzymatic methodology provided considerable enantiomeric excess of the product (up to 92% ee) at 55 °C in n-hexane as a solvent. Furthermore using the developed protocol, synthesis of several industrially important acetates was successfully achieved with excellent yield (up to 99%). During acetate synthesis, the biocatalyst was remarkably reused for eight consecutive recycles without any significant loss in its catalytic activity. This revealed the good potential of steapsin lipase for application in organic solvents.
- Dhake, Kishor P.,Deshmukh, Krishna M.,Wagh, Yogesh S.,Singhal, Rekha S.,Bhanage, Bhalchandra M.
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- Cobalt polyoxometalate, CoW12O405- as a new reusable catalyst for the direct, fast, and efficient acetylation of alcohols and phenols under solventless conditions
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Alcohols and phenols were efficiently acetylated with acetic anhydride without solvent in the presence of 0.01 molar equiv. of cobalt polyoxometalate (CoW12O405-).
- Habibi,Tangestaninejad,Mirkhani,Yadollahi
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- Microwave-Assisted Catalytic Acetylation of Alcohols by Gold-Nanoparticle-Supported Gadolinium Complex
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A gold nanoparticle (AuNP)-supported gadolinium complex (RS-Au-L-Gd) catalyst was prepared through simple chelation of GdCl3 to the surface-bound spacer, 1,4,7-tris(carboxymethyl)-10-(11-mercaptoundecyl)-1,4,7,10-tetraazacyclododecane (HSDO3A). This AuNP-supported Gd complex was found to be a highly effective catalyst for the acetylation of various alcohols and phenol in the presence of acetic anhydride. With a loading of 0.4 mol% of RS-Au-L-Gd, the almost complete transformation can be achieved in 60 s under microwave irradiation conditions. This hybrid catalyst was air stable, water soluble, dissolvable in many organic media, and precipitable. It can be readily recycled more than eight times without any significant loss of its catalytic activity. GRAPHICAL ABSTRACT.
- Chang, Tsao-Ching,Yu, Shuchun Joyce
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- Cerium polyoxometalate as a reusable catalyst for acetylation and formylation of alcohols
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Efficient esterification of primary and sterically-hindered secondary or tertiary alcohols with acetic anhydride was achieved in the presence of ammonium decatungestocerate(IV) icosahydrate, (NH4)8[CeW 10O36]·OH2O, as catalyst in high yields. Primary and secondary alcohols were also converted to their corresponding acetates and formates with acetic acid and ethyl formate in the presence of this catalyst. Easy work-up, non-toxicity, reusability, and stability of the catalyst are noteworthy advantages of this method. Springer-Verlag 2004.
- Mirkhani, Valiollah,Tangestaninejad, Shahram,Moghadam, Majid,Yadollahi, Bahram,Alipanah, Ladan
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- Deep eutectic solvent choline chloride·2CrCl3·6H2O: An efficient catalyst for esterification of formic and acetic acid at room temperature
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A highly efficient and selective method for esterification of formic and acetic acid with alcohols has been achieved at room temperature, with the choline chloride (ChCl)/chromium(iii) chloride hexahydrate (CrCl3·6H2O) deep eutectic solvent as a catalyst. High yields and good selectivities of organic esters are obtained using DES [ChCl][CrCl3·6H2O]2 with the molar ratio 5:1 (carboxylic acids:alcohols) at room temperature in 24 h. The ease of recovery and reusability of DES with high catalytic activity makes this method efficient and practical.
- Cao, Jin,Qi, Bin,Liu, Jun,Shang, Yuhan,Liu, Huiwen,Wang, Wenjing,Lv, Jia,Chen, Zhiyan,Zhang, Haibo,Zhou, Xiaohai
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- Acidic ionic liquid based UiO-67 type MOFs: A stable and efficient heterogeneous catalyst for esterification
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A facile strategy for the synthesis of acidic ionic liquid based UiO-67 type MOFs was developed in this study. Br?nsted acids (H2SO4, CF3SO3H and hifpOSO3H (hexafluoroisopropyl sulfuric acid)) were introduced into UiO-67-bpy (bpy = 2,2′-bipyridine-5,5′-dicarboxylic acid) frameworks by reacting with bipyridyl nitrogen to introduce the properties of an acidic ionic liquid into the frameworks. The prepared catalysts, denoted as UiO-67-HSO4, UiO-67-CF3SO3 and UiO-67-hifpOSO3, were characterized by XRD, SEM, FT-IR, EA, TGA and N2 adsorption-desorption studies. The relatively high surface area was still maintained and acidic active groups were uniformly dispersed in the frameworks. The catalytic performance of UiO-67-HSO4, UiO-67-CF3SO3 and UiO-67-hifpOSO3 was evaluated by the esterification of acetic acid with isooctyl alcohol. The prepared catalysts showed good catalytic activities in the esterification, of which UiO-67-CF3SO3 gave the maximum isooctyl alcohol conversion of 98.6% under optimized conditions. The catalyst could be reused five times without a significant decrease in the conversion of isooctyl alcohol, and almost no active species were leached, indicating the excellent stability and reusability of the catalyst. Our study provides one effective way to synthesize heterogeneous acidic ionic liquid catalysts consisting of isolated, well defined acidic groups that will probably attract interest in acid catalyst chemistry.
- Xu, Zichen,Zhao, Guoying,Ullah, Latif,Wang, Meng,Wang, Aoyun,Zhang, Yanqiang,Zhang, Suojiang
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- Synthesis of 2-ethylhexyl acetate by transesterification of methyl acetate with 2-ethylhexanol
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In order to explore a new application field of methyl acetate which is of limited industrial importance, one of the possibilities to obtain the desired products would be the transesterification of methyl acetate with 2-ethylhexanol. The choice of catalyst and the determination of the best experimental conditions for the transesterification were investigated in this paper. Strongly acidic cation-exchange resin NKC-9 was chose as the catalyst in this reaction. The reaction time, the effects of the reaction temperature, the catalyst loading and the molar ratio of methyl acetate to 2-ethylhexyl acetate on the conversion of 2-ethylhexyl acetate were discussed. This paper describes an optimization study on the transesterification reaction based on nine well-planned orthogonal experiments. The maximum conversion of 2-ethylhexanol was found at a NKC-9 catalyst loading of 20 wt. %, a molar ratio of methyl acetate to 2-ethylhexanol of 4:1, a reactive time of 3 h and a reaction temperature of 80 °C. The product yield and the conversion of 2-ethylhexanol under optimal conditions reached 90.90 and 79.64 %, respectively. The structure of the product 2-2-ethylhexyl acetate acetate has been conformed by IR and 1H NMR.
- Yin, Lina,Wang, Dazhi,Qu, Fengzuo,Jia, Lin,Zhang, Shaoyin
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- Catalytic acetylation of alcohols and phenols with potassium dodecatungstocobaltate trihydrate
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Alcohols and phenols are converted to esters in a mild, clean, and efficient reaction with acetic anhydride in the presence of a catalytic amount of potassium dodecatungstocobaltate trihydrate (K5CoW12O40· 3H2O).
- Habibi, Mohammad H.,Tangestaninejad, Shahram,Mirkhani, Valiollah,Yadollahi, Bahram
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- A synthesis of copper based metal-organic framework for O-acetylation of alcohols
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A novel metal-organic framework, Cu-BDC was synthesized by static hydrothermal method using innocuous solvents and characterized by several techniques such as powder XRD, ESR, TG-DTA, elemental analysis, ICP-AES, SEM, EDXS, FT-IR, BET surface area, pore volume and pore size. The catalytic performance of Cu-BDC was explored for O-acetylation of alcohols under solvent-free conditions at room temperature. The catalyst exhibited remarkable activity and reusability affording the desired products in excellent yields.
- Singh, Savita J.,Kale, Sandip R.,Gawande, Manoj B.,Velhinho,Jayaram, Radha V.
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- Synthesis of immobilized Br?nsted acidic ionic liquid on silica gel as heterogeneous catalyst for esterification
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The Br?nsted acidic ionic liquid 1-(propyl-3-sulfonate) vinylimidazolium hydrogen sulfate ([(CH2)3SO 3HVIm]HSO4) was immobilized on the silica gel using tetraethoxysilane (TEOS) as silica source. The properties of samples were characterized by FT-IR, elemental analysis and TG. The results showed that [(CH2)3SO3HVIm]HSO4 had been successfully immobilized onto the silica gel, and the immobilized ionic liquid catalyst (IL/silica gel) had good thermal stability. Moreover, the IL/silica gel exhibited high catalytic activity for a series of esterification and could be separated from the reaction mixture easily. It also remained satisfactory catalytic activity for the synthesis of n-Butyl acetate after 7 times recycling.
- Miao, Jinmei,Wan, Hui,Guan, Guofeng
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- Novel catalytic acetylation and formylation of alcohols with potassium dodecatungstocobaltate trihydrate (K5CoW12O40·3H2O)
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Acetylation and formylation reactions of alcohols with ethyl acetate, acetic acid and ethyl formate were catalyzed with potassium dodecatungstocobaltate trihydrate (K5CoW12O40·3H2O) in a mild, efficient and convenient method with high to excellent yields.
- Habibi, Mohammad H,Tangestaninejad, Shahram,Mirkhani, Valiollah,Yadollahi, Bahram
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- Synthesis of lipase nano-bio-conjugates as an efficient biocatalyst: Characterization and activity-stability studies with potential biocatalytic applications
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In the present study, we have synthesized lipase-nano-bio-conjugates via immobilization of various lipases on multiwall carbon nano-tubes (MCNT), in order to construct an efficient and recyclable biocatalytic system. In a screening study lipase Pseudomonas fluorescens (PFL) acted as an efficient biocatalyst (lipase-nano-bio-conjugates) which showed higher retention of lipase activity and protein loading. Consequently the immobilization support : lipase (MCNT : PFL) composition was screened in which MCNT : PFL (2 : 1) was calculated as a robust biocatalyst composition which showed higher activity retention and protein loading. This nano-bio-conjugate was then characterized in detail with physical and biochemical techniques using SEM, TEM, FTIR, Km, Vmax, catalytic efficiency and (%) water content analysis. This developed biocatalyst was further used for practical biocatalytic applications such as O-acylation reactions. Various reaction parameters were optimized in detail like reactant molar ratio (2 : 3.5), solvent, MCNT : PFL biocatalyst amount (36 mg), temperature (50°C) etc. The developed biocatalytic protocol was then extended to synthesize several (twenty-two) industrially important acylated moieties with an excellent yield, these products are well characterized by 1HNMR, 13CNMR and GCMS analysis. Moreover in the present study, we have reviewed the potential industrial applications of various synthesized compounds. Also, we have studied the thermodynamic aspect which demonstrated more feasibility of use of immobilized MCNT : PFL lipase over free lipase. Interestingly, immobilized MCNT : PFL lipase showed 2.3 fold higher catalytic activity than free PFL. Besides this, the biocatalyst was efficiently recycled for up to five cycles. Thus the present protocol demonstrated, (i) synthesis of nano-bio-conjugates as a bio-catalyst, (ii) detailed physical-biochemical characterization of nano-bio-conjugates, (iii) optimization of the biocatalytic protocol (iv) practical biocatalytic applications along with a mechanistic study (v) a thermodynamic feasibility study and (vi) recyclability study. 2015
- Badgujar, Kirtikumar Chandulal,Sasaki, Takehiko,Bhanage, Bhalchandra Mahadeo
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- A General Catalytic Method for Highly Cost- and Atom-Efficient Nucleophilic Substitutions
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A general formamide-catalyzed protocol for the efficient transformation of alcohols into alkyl chlorides, which is promoted by substoichiometric amounts (down to 34 mol %) of inexpensive trichlorotriazine (TCT), is introduced. This is the first example of a TCT-mediated dihydroxychlorination of an OH-containing substrate (e.g., alcohols and carboxylic acids) in which all three chlorine atoms of TCT are transferred to the starting material. The consequently enhanced atom economy facilitates a significantly improved waste balance (E-factors down to 4), cost efficiency, and scalability (>50 g). Furthermore, the current procedure is distinguished by high levels of functional-group compatibility and stereoselectivity, as only weakly acidic cyanuric acid is released as exclusive byproduct. Finally, a one-pot protocol for the preparation of amines, azides, ethers, and sulfides enabled the synthesis of the drug rivastigmine with twofold SN2 inversion, which demonstrates the high practical value of the presented method.
- Huy, Peter H.,Filbrich, Isabel
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supporting information
p. 7410 - 7416
(2018/04/30)
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- A sun-screening agent to the methoxy cinnamic acid process of isooctyl ester (by machine translation)
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The invention relates to a sun-screening agent to the methoxy cinnamic acid isooctyl (OMC) clean synthetic process. The process adopts a one-pot preparation of methoxy cinnamic acid isooctyl: in a small amount of toluene sulfonic acid under the catalysis of the methyl acetate and isooctanol under isooctyl ester exchange reaction to produce acetic acid, then, in the sodium methoxide under the catalysis of the formaldehyde with the methoxyl condensation reaction, generating to the methoxy cinnamic acid ester. This invention adopts the advanced good ester exchange reaction and then condensation reaction process flow of expensive raw materials to help to improve the utilization rate of the methoxy benzaldehyde, in the process of synthesis does not use any other solvent, no waste water is produced, safety and environmental protection, and the product yield is as high as 97% or more. (by machine translation)
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Paragraph 0024-0033
(2018/04/01)
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- Transformation of amides into esters by the use of chlorotrimethylsilane
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A mild transformation of various amides and imides into the corresponding esters and diesters in good yields by using chlorotrimethylsilane and alcohols at rt are described. Either primary, secondary, or tertiary amide or imide can be used in this transformation. Primary and secondary alcohols gave better yields than tertiary alcohols.
- Xue, Cuihua,Luo, Fen-Tair
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p. 359 - 362
(2015/02/02)
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- Synthesis of C7-C16-Alkyl maltosides in the presence of tin(IV) chloride as a lewis acid catalyst
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The synthesis of C7- to C16-alkyl maltosides in the presence of tin(IV) chloride as Lewis acid catalyst was performed. The characterization of the products and theoretical investigation of the crucial step in the synthesis were carried out. The preparation of the β-maltosides required reaction time of 1 h, and that of the α-maltosides was 72 h. The side products were the α-D-maltosidechloride and 2-hydroxy-β-maltoside, respectively. The PM3 calculation confirmed the formation of the kinetically controlled β-product.
- Markovic, Zoran,Predojevic, Jasmina,Manojlovic, Nedeljko T.
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experimental part
p. 83 - 90
(2012/05/20)
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- Aggregate formation in the intercalation of long-chain fatty acid esters into liposomes
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Various hydrophobic benzenediacetic esters, the corresponding benzenedipropionic esters, and branched alkyl esters were intercalated into DMPC liposomes, where the molar ratio (n/n) of ester:DMPC was 1:5. In the case of the very long-chain derivatives, double carbonyl peaks were observed in the 13C NMR spectrum. This doubling phenomenon was observed only for the carbonyl peaks, whose chemical shift is most sensitive to solvent polarity, and disappeared when the ester:DMPC molar ratio drops below 1:15. This doubling reflects the presence of two populations in these samples: one group includes those molecules which are intercalated within the liposome and feel the polarity corresponding to the liposomal microenvironment; the other consists of aggregates of these long-chain derivatives located in the extra-liposomal aqueous phase.
- Cohen, Yael,Afri, Michal,Frimer, Aryeh A.
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scheme or table
p. 120 - 125
(2009/12/31)
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- Efficient one-step conversion of tetrahydropyranyl ethers into acetates and formates in the presence of potassium dodecatungstocobaltate K 5CoW12O40·3H2O
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Tetrahydropyranyl ethers derived from primary alcohols were directly and efficiently converted into the corresponding acetates and formates by the action of ethyl acetate, acetic acid, acetic anhydride, and ethyl formate in the presence of a catalytic amount of potassium dodecatungstocobaltate K 5CoW12O40 ? 3H2O. Tetrahydropyranyl ethers derived from secondary alcohols and phenols can also be transformed into the corresponding acetates with the use of acetic anhydride, but K5CoW12O40 ? 3H2O was ineffective for esterification with ethyl acetate, acetic acid, and ethyl formate.
- Rafiee,Tangestaninejad,Habibi,Mohammadpoor-Baltork,Mirkhani
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p. 393 - 395
(2007/10/03)
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- Transformation of amides into esters by the use of chlorotrimethylsilane
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A mild transformation of various amides and imides into the corresponding esters and diesters in good yields by using chlorotrimethylsilane and alcohols at rt are described. Either primary, secondary, or tertiary amide or imide can be used in this transformation. Primary and secondary alcohols gave better yields than tertiary alcohols.
- Xue, Cuihua,Luo, Fen-Tair
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p. 359 - 362
(2007/10/03)
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- Method of producing alkoxycinnamic acid ester
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The invention relates to a method of producing alkoxycinnamic acid ester (alkoxy cinnamate) by condensing C5-C8acetic acid esters with C1-C4alkoxybenzaldehyde in the presence of an alkaline and/or alkaline earth C1-C4alcohalate and removing the C1-C4alcohol that is produced by this reaction from the reaction mixture.
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Page column 5
(2008/06/13)
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- Synthesis of C7-C16-alkyl glycosides: Part III - Synthesis of alkyl D-galactopyranosides in the presence of tin(IV) chloride as a Lewis acid catalyst
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The Lewis acid catalyzed glycosylation reaction of β-peracetylated sugar derivative (galactose) with fatty alkanols is used in a synthesis of C7-C16-alkyl galactopyranosides. The process occurs under the influence of tin(IV) chloride as a Lewis acid catalyst.
- Konstantinovi?,Dimitrijevi?,Radulovi?
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p. 598 - 603
(2007/10/03)
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- Mercury-assisted solvolyses of alkyl halides. Simple procedures for the preparation of nitrate esters, acetate esters, alcohols and ethers
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The reactions of a wide variety of alkyl halides with mercury(I) and/or (II) nitrate in 1,2-dimethoxyethane, mercury(II) acetate in acetic acid, aqueous mercury(II) perchlorate, and mercury(II) perchlorate in alcohol solvents have been investigated; as a result, simple high yield procedures for the conversion of alkyl halides into the corresponding nitrate esters, acetate esters, alcohols and ethers have been developed.
- McKillop,Ford
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p. 2467 - 2475
(2007/10/05)
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