103-45-7Relevant articles and documents
Synthesis of 2-phenylethyl acetate in the presence of Yarrowia lipolytica KKP 379 biomass
Bialecka-Florjanczyk, Ewa,Krzyczkowska, Jolanta,Stolarzewicz, Izabela,Kapturowska, Agata
, p. 241 - 245 (2012)
Increasing demand for natural products in the food industry has encouraged significant efforts toward the development of biotechnological processes for the production of flavour compounds. The aim of the present study was to synthesise 2-phenylethyl acetate, an essential aroma component for the food and cosmetic industries, by acetate ester alcoholysis with 2-phenylethanol in the presence of Yarrowia lipolytica KKP 379 biomass. Optimisation of reaction conditions were conducted, inter alia, by selection of the proper acyl donor and determination of optimal permeabilisation conditions for the yeast cell wall. Optimal reaction conditions enabled synthesis of the desired ester with an efficiency comparable to commercial enzymes, but at considerably lower cost.
Facile catalyzed acylation of heteroatoms using BiCl3 generated in situ from the procatalyst BiOCl and acetyl chloride
Ghosh, Rina,Maiti, Swarupananda,Chakraborty, Arijit
, p. 6775 - 6778 (2004)
Acylation of a variety of alcohols, phenols, aliphatic and aromatic amines, a thiol and a thiophenol proceeds efficiently using BiCl3 generated in situ from the procatalyst BiOCl and acetyl chloride in a solvent or under solventless conditions, furnishing the corresponding acylated derivatives in very good to excellent yields.
Expanding ester biosynthesis in Escherichia coli
Rodriguez, Gabriel M,Tashiro, Yohei,Atsumi, Shota
, p. 259 - 265 (2014)
To expand the capabilities of whole-cell biocatalysis, we have engineered Escherichia coli to produce various esters. The alcohol O-acyltransferase (ATF) class of enzyme uses acyl-CoA units for ester formation. The release of free CoA upon esterification with an alcohol provides the free energy to facilitate ester formation. The diversity of CoA molecules found in nature in combination with various alcohol biosynthetic pathways allows for the biosynthesis of a multitude of esters. Small to medium volatile esters have extensive applications in the flavor, fragrance, cosmetic, solvent, paint and coating industries. The present work enables the production of these compounds by designing several ester pathways in E. coli. The engineered pathways generated acetate esters of ethyl, propyl, isobutyl, 2-methyl-1-butyl, 3-methyl-1-butyl and 2-phenylethyl alcohols. In particular, we achieved high-level production of isobutyl acetate from glucose (17.2 g l -1). This strategy was expanded to realize pathways for tetradecyl acetate and several isobutyrate esters.
Alkylchlorotins grafted to cross-linked polystyrene beads by a -(CH 2)n spacer (n-4, 6, 11): Selective, clean and recyclable catalysts for transesterification reactions
Camacho-Camacho, Carlos,Biesemans, Monique,Van Poeck, Manu,Mercier, Frederic A. G.,Willem, Rudolph,Darriet-Jambert, Karine,Jousseaume, Bernard,Toupance, Thierry,Schneider, Uwe,Gerigk, Ursula
, p. 2455 - 2461 (2005)
Insoluble polystyrene grafted compounds of the type (P-H) (1-t)(P-(CH2)nSnBupCl 3-p,}t, (P-H)(1-t){P-(CH2) nSnBuO)t and (P-H)(1-t)[(P-(CH 2)nSnBuCl}2O]t/2, in which (P-H) is a cross-linked polystyrene; n=4, 6, and 11; p=0 and 1; and t the degree of functionalisation, were synthesised from Amberlite XE-305, a polystyrene cross-linked with divinylbenzene. The compounds were characterised by using elemental analysis, and IR, Raman, solid-state 117Sn NMR, and 1H and 119Sn high-resolution MAS NMR spectroscopy. The influence of the spacer length and the tin functionality on the catalytic activity of these compounds, as well as their recycling ability, was assessed in the transesterifica tion reaction of ethyl acetate with various alcohols. These studies showed significant differences in the activity of the catalysts interpreted in terms of changes in the mobility of the catalytic centres. Some of the supported catalysts could be recycled at least seven times without noticeable loss of activity. The residual tin content in the reaction products was found to be as low as 3 ppm.
Organic Reducing Agents. Reduction of Electron Deficient Bromides by 1,2,2,6,6-Pentamethylpiperidine (PMP)/Mercaptoethanol
Amoli, Maryam,Workentin, Mark S.,Wayner, Danial D. M.
, p. 3997 - 4000 (1995)
1,2,2,6,6-pentamethylpiperidine (PMP) is shown to be an effective reducing agent for the radical chain conversion of primary bromoesters in these reactions to the corresponding esters.The problem of inefficient reduction of tertiary bromoesters in these reactions has been overcome by the addition of an alkyl thiol which mediates the hydrogen atom transfer between the two hindered alkyl centers.
Acetylation and formylation of alcohols in the presence of silica sulfuric acid
Shirini, Farhad,Zolfigol, Mohammad Ali,Mohammadi, Kamal
, p. 1617 - 1621 (2003)
Alcohols are converted to esters in a mild, clean, and efficient reaction with acetic and formic acids in the presence of silica sulfuric acid. All reactions were performed under mild and completely heterogeneous conditions in refluxing n-hexane.
A simple and practical method for large-scale acetylation of alcohols and diols using bismuth triflate
Carrigan,Freiberg,Smith,Zerth,Mohan
, p. 2091 - 2094 (2001)
A practical method for large-scale acetylation of 1° and 2° alcohols as well as diols has been developed. The acetylation proceeds smoothly in MeCN with as little as 0.1 mol% bismuth triflate in good yields.
Pentafluorophenylammonium triflate as a mild and new organocatalyst for acylation of alcohols, phenols, and amines under solvent-free condition
Khaksar, Samad,Zakeri, Hasan
, p. 576 - 579,4 (2012)
A simple, inexpensive, environmentally friendly and efficient route for the acylation of a number of alcohols, phenols and amines using pentafluorophenylammonium triflate (PFPAT) as a catalyst is described. PFPAT organocatalyst is air-stable, cost-effective, easy to handle, and easily removed from the reaction mixtures.
Highly Selective Acylation of Alcohols Using Enol Esters Catalyzed by Iminophosphoranes
Ilankumaran, Palanichamy,Verkade, John G.
, p. 9063 - 9066 (1999)
The iminophosphorane bases PhCH2N=P(MeNCH2CH2)3N and PhCH2N=P(NMe2)3 catalyze the acylation of primary alcohols with enol esters in excellent yields and in high selectivity. It was found that acid labile groups such as acetal and epoxide survive under the reaction conditions. Groups such as TBS and disulfide, which undergo cleavage in the presence of Ac2O and the Lewis acid Sc(OTf)3, are also unaffected. Diene, conjugated acetylene, oxazoline, nitro, and benzodioxane groups are also compatible with our catalyst/reagent system. Because secondary alcohols do not react under our conditions, our methodology is attractive for the selective acylation of primary alcohols. Polymer-supported iminophosphorane catalysts are also shown to be useful in these reactions, thus opening the possibility of wider applications.
A facile and efficient one-step conversion of alcohol triphenylmethyl ethers to the corresponding acetates
Kobayashi, Kumiko,Watahiki, Tsutomu,Oriyama, Takeshi
, p. 484 - 486 (2003)
Alcohol triphenylmethyl (trityl) ethers were readily and efficiently transformed into the corresponding acetates by reaction with acetyl bromide. Triphenylmethyl ethers can also be transformed into the corresponding substituted acetates in high yields by the use of various substituted acetyl chlorides combined with sodium iodide.
Bi(III) salts as new catalysts for the selective conversion of trimethylsilyl and tetrahydropyranyl ethers to their corresponding acetates and formates
Mohammadpoor-Baltork,Khosropour
, p. 2433 - 2439 (2002)
Bi(III) salts such as BiCl3, Bi(TFA)3 and Bi(OTf)3 were found to be efficient catalysts for the transformation of trimethylsilyl (TMS) and tetrahydropyranyl (THP) ethers to their corresponding acetates and formates with acetic acid and ethyl formate. Selective acetylation and formylation of TMS and THP ethers of alcohols in the presence of phenolic TMS and THP ethers make this method a useful and practical procedure in organic synthesis.
Efficient approach for the chemoselective acetylation of alcohols catalyzed by a novel metal oxide nanocatalyst CuO-ZnO
Albadi, Jalal,Alihosseinzadeh, Amir,Mardani, Mehdi
, p. 308 - 313 (2015)
A new method has been developed for the chemoselective acetylation of alcohols with acetic anhydride in the presence of phenols using a novel, recyclable CuO-ZnO nanocatalyst. The catalyst was synthesized using the co-precipitation method and characterized by N2 adsorption-desorption, X-ray diffraction, scanning electron microscopy, transmission electron microscopy and energy dispersion scanning analyses. Furthermore, this catalyst could be recycled up to six times without significant loss in its activity.
Synthesis of sulfonic acid containing ionic-liquid-based periodic mesoporous organosilica and study of its catalytic performance in the esterification of carboxylic acids
Elhamifar, Dawood,Karimi, Babak,Moradi, Abbas,Rastegar, Javad
, p. 1147 - 1152 (2014)
A new sulfonic acid containing ionic-liquid-based periodic mesoporous organosilica (PMO-IL-SO3H) material was prepared and its catalytic application was investigated in the esterification of carboxylic acids with alcohols. The PMO-IL-SO3H nanocatalyst was first characterized with diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and nitrogen sorption analysis. Then, the catalytic performance of this material was studied in the esterification of carboxylic acids with short- and long-chain aliphatic alcohols, cyclic alcohols, and benzylic alcohols under solvent-free conditions. The results showed that the catalyst has superior activity for the conversion of several alcohols to afford the corresponding ester products in excellent yields and high purity. Moreover, the catalyst could be recovered and reused several times without a significant decrease in activity and product selectivity. Copyright
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Bertin et al.
, p. 8113 (1974)
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Alcohol acetylation with acetic acid using borated zirconia as catalyst
Osiglio, Lilian,Romanelli, Gustavo,Blanco, Mirta
, p. 52 - 58 (2010)
The use of zirconium oxide doped with boron (borated zirconia) as catalyst in the acetylation of alcohols and phenol was studied. The catalysts were obtained by employing different preparation conditions, in order to observe the effect of the concentration of the precursor in the solution used to obtain the oxide, the concentration of the boron precursor, and the calcination temperature. All the solids showed amorphous characteristics and strong acidity. Boron addition increased the temperature range of the hydrated oxide stability, which depends on the boron concentration in the sample. Besides, the characterization by infrared spectroscopy showed an effect on the boron species present in the solid depending on the added concentration. The three preparation conditions under study affected the textural properties of the catalysts, as well as their acid strength. It was observed that in the acylation of alcohols using acetic acid as acylating agent and toluene as reaction solvent, at reflux temperature, the yield of acetylated product correlated with the acid strength of the catalysts, which depended on the preparation conditions. The best yield was achieved with a catalyst obtained using a high solution concentration of the oxide precursor (0.56 mmoles Zr/cm3), an intermediate boron concentration (15 g B2O3/100 g support) and a relatively low calcination temperature (320 °C).
The effect of solvents on the thermal degradation products of two Amadori derivatives
Li, Rui,Zhang, Shiyi,Zhang, Yudan,Zhao, Mingqin
, p. 9309 - 9317 (2020)
To enrich the flavor additives of the Maillard reaction, two Amadori analogs, N-(1-deoxy-d-fructosyl-1-yl)-l-phenylalanine ester (Derivative 1) and di-O-isopropylidene-2,3:4,5-?-d-fructopyranosyl phenylalanine ester (Derivative 2), were chemically synthes
Facile esterification of alcohols with 2-Acyl-4,5-dichloropyridazin-3(2 H)-ones under Friedel-Crafts conditions
Kim, Bo Ram,Sung, Gi Hyeon,Ryu, Ki Eun,Yoon, Hyo Jae,Lee, Sang-Gyeong,Yoon, Yong-Jin
, p. 1909 - 1915 (2014)
This paper describes the esterification of aromatic and aliphatic alcohols by using 2-acyl-4,5-dichloropyridazin-3(2H)-ones as an acyl source under Friedel-Crafts conditions. Twelve alcohols were reacted with four 2-acyl-4,5-dichloropyridazin-3(2H)-ones in the presence of AlCl3 in tetrahydrofuran at room temperature to give the corresponding esters in moderate to excellent yields. Thus, 2-acylpyridazin-3(2H)-ones serve as good and atom-economic acyl sources for the esterification of aromatic alcohols under Friedel-Crafts conditions, representing a rapid, practical, and efficient method of esterification. Georg Thieme Verlag Stuttgart. New York.
Electron-deficient [TiIV(salophen)(OTf)2]: A new and highly efficient catalyst for the acetylation of alcohols and phenols with acetic anhydride
Yadegari, Maryam,Moghadam, Majid,Tangestaninejad, Shahram,Mirkhani, Valiollah,Mohammadpoor-Baltork, Iraj
, p. 2237 - 2243 (2011)
In the present work, a highly efficient method for acetylation of alcohols and phenols with acetic anhydride catalyzed by high-valent [Ti IV(salophen)(OTf)2] is reported. Under these conditions, primary, secondary and tertiary alcohols as well as phenols were acetylated with short reaction times and high yields. The catalyst was reused several times without loss of its catalytic activity.
Mild and practical acylation of alcohols with esters or acetic anhydride under distannoxane catalysis
Orita, Akihiro,Sakamoto, Katsumasa,Hamada, Yuji,Mitsutome, Akihiro,Otera, Junzo
, p. 2899 - 2910 (1999)
Distannoxane catalysts effect acylation of alcohols by action of esters and acetic anhydride. In particular, use of enol esters provides an extremely useful method. Primary alcohols are acylated in preference to secondary ones as well as phenol. Both acid- and base-sensitive functional groups remain intact. Especially unique is the discrimination of thio function which is completely tolerant under the present reaction conditions. This method is highly practical since operation is quite simple. Esters and solvents can be used without purification and no inert atmosphere is necessary. The products can be isolated simply by column chromatography or distillation without aqueous workup.
Rapid and efficient method for acetylation of alcohols and phenols with acetic anhydride catalyzed by silica sulfate
Jin, Tong-Shou,Zhao, Ying,Liu, Li-Bin,Chen, Zhuo,Li, Tong-Shuang
, p. 1221 - 1227 (2006)
A rapid and efficient method is described for acetylation of a series of alcohols and phenols with acetic anhydride catalyzed by silica sulfate solid acid at room temperature or at refluxing temperature in excellent yield. Copyright Taylor & Francis Group, LLC.
Solvent Effects on the Esterification of 2-Chloroethyl Compounds with Potassium Acetate
Shinoda, Kiyonori,Yasuda, Kensei
, p. 4081 - 4084 (1991)
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Sequence-Based Prediction of Promiscuous Acyltransferase Activity in Hydrolases
Badenhorst, Christoffel P. S.,Becker, Ann-Kristin,Berndt, Leona,Bornscheuer, Uwe T.,Godehard, Simon P.,Lammers, Michael,Müller, Henrik,Palm, Gottfried J.,Reisky, Lukas
, p. 11607 - 11612 (2020)
Certain hydrolases preferentially catalyze acyl transfer over hydrolysis in an aqueous environment. However, the molecular and structural reasons for this phenomenon are still unclear. Herein, we provide evidence that acyltransferase activity in esterases highly correlates with the hydrophobicity of the substrate-binding pocket. A hydrophobicity scoring system developed in this work allows accurate prediction of promiscuous acyltransferase activity solely from the amino acid sequence of the cap domain. This concept was experimentally verified by systematic investigation of several homologous esterases, leading to the discovery of five novel promiscuous acyltransferases. We also developed a simple yet versatile colorimetric assay for rapid characterization of novel acyltransferases. This study demonstrates that promiscuous acyltransferase activity is not as rare as previously thought and provides access to a vast number of novel acyltransferases with diverse substrate specificity and potential applications.
Enhancement of activity and stability of lipase by microemulsion-based organogels (MBGs) immobilization and application for synthesis of arylethyl acetate
Zhang, Wei-Wei,Wang, Na,Zhou, Yu-Jie,He, Ting,Yu, Xiao-Qi
, p. 65 - 71 (2012)
Lipase from Candida rugosa (CRL) was immobilized in microemulsion-based organogels (MBGs) and subsequently applied in large scale synthesis of arylethyl acetate in organic solvents as a more stable and efficient catalyst. Various reaction parameters (solvent, temperature, substrate concentration) were investigated for enhancement of ester production. Thermal and operational stabilities were improved compared with free CRL showing its potential for continuous applications. They were more stable at 50-60 °C and showed good recovery activity, which retained 70% of their initial activity after 16 recycles in organic media and remained constant at that level thereafter. Moreover, the immobilized lipase can maintain high catalytic activity in a variety of organic solvents, while free lipase was easily inactivated in polar solvent. A series of alcohols with different substitution groups were successfully applied in CRL MBGs-catalyzed transesterification, affording higher conversions than those with the free enzyme.
Highly efficient and versatile acetylation of alcohols, phenols and amines catalyzed by methylenediphosphonic acid (MDP) under solvent-free conditions
Xie, Minhao,Wang, Hongyong,Wu, Jun,He, Yongjun,Liu, Yaling,Zou, Pei
, p. 884 - 886 (2011)
Methylenediphosphonic Acid (MDP) was found to be a simple, cheap and reusable heterogeneous catalyst for the acetylation of structurally diverse alcohols, phenols and amines with acetic anhydride under solvent-free conditions at room temperature. This method showed preferential selectivity for the acetylation of the amino group in the presence of hydroxyl group. The method is very mild and the yields were in excellent.
Exploring the catalytic activity of Lewis-acidic uranyl complexes in the nucleophilic acyl substitution of acid anhydrides
Takao, Koichiro,Akashi, Shin
, p. 12201 - 12207 (2017)
The catalytic activities of several uranyl complexes, such as N,N′-disalicylidene-o-phenelyenediaminato(ethanol)dioxouranium(vi) (UO2(salophen)EtOH), bis(dibenzoylmethanato)(ethanol)dioxouranium(vi) (UO2(dbm)2EtOH), pentakis(N,N-dimethylformamide)dioxouranium(vi) ([UO2(DMF)5]2+), and tetrakis(triphenylphosphine oxide)dioxouranium(vi) ([UO2(OPPh3)4]2+), were examined in the nucleophilic acyl substitution of acid anhydrides. Among them, [UO2(OPPh3)4]2+ was the most efficient to give ethyl acetate and acetic acid from acetic anhydride (Ac2O) and ethanol, and was resistant towards decomposition during the catalytic reaction. Several nucleophiles were also subjected to the catalytic acylation reaction using acetic and pivalic anhydride. Kinetic and spectroscopic studies suggested that [UO2(OPPh3)4]2+ interacts with Ac2O to form [UO2(Ac2O)(OPPh3)3]2+. Interaction of this actual catalyst with additional Ac2O determines the rate of the overall nucleophilic acyl substitution reaction.
Bioproduction of Natural Phenethyl Acetate, Phenylacetic Acid, Ethyl Phenylacetate, and Phenethyl Phenylacetate from Renewable Feedstock
Li, Xirui,Li, Zhi,Sekar, Balaji Sundara
, (2022/02/17)
Natural phenethyl acetate (PEA), phenylacetic acid (PAA), ethyl phenylacetate (Et-PA), and phenethyl phenylacetate (PE-PA) are highly desirable aroma chemicals, but with limited availability and high price. Here, green, sustainable, and efficient bioproduction of these chemicals as natural products from renewable feedstocks was developed. PEA and PAA were synthesized from l-phenylalanine (l-Phe) via novel six- and five-enzyme cascades, respectively. Whole-cell-based cascade biotransformation of 100 mm l-Phe in a two-phase system (aqueous/organic: 1 : 0.5 v/v) containing ethyl oleate or biodiesel as green solvent gave 13.6 g L?1 PEA (83.1 % conv.) and 11.6 g L?1 PAA (87.1 % conv.), respectively. Coupled fermentation and biotransformation approach produced 10.4 g L?1 PEA and 9.2 g L?1 PAA from glucose or glycerol, respectively. The biosynthesized PAA was converted to natural Et-PA and PE-PA by esterification using lipases with ethanol or 2-phenylethanol derived from sugar, affording 2.7 g L?1 Et-PA (83.1 % conv.) and 4.6 g L?1 PE-PA (96.3 % conv.), respectively.
ZWITTERIONIC CATALYSTS FOR (TRANS)ESTERIFICATION: APPLICATION IN FLUOROINDOLE-DERIVATIVES AND BIODIESEL SYNTHESIS
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Paragraph 0013; 0028, (2021/01/29)
An amide/iminium zwitterion catalyst has a catalyst pocket size that promotes transesterification and dehydrative esterification. The amide/iminium zwitterions are easily prepared by reacting aziridines with aminopyridines. The reaction can be applied a wide variety of esterification processes including the large-scale synthesis of biodiesel. The amide/iminium zwitterions allow the avoidance of strongly basic or acidic condition and avoidance of metal contamination in the products. Reactions are carried out at ambient or only modestly elevated temperatures. The amide/iminium zwitterion catalyst is easily recycled and reactions proceed in high to quantitative yields.