- Method for preparing propionate by ester alcohol exchange
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The invention discloses a method for preparing propionate by ester alcohol exchange, and relates to a method for preparing propionate. According to the invention, the method for synthesizing propionate by ester alcohol exchange of methyl propionate and various alcohols (including monohydric alcohols such as ethanol, propanol, butanol, tert-butanol, isopropanol, cyclohexanol, allyl alcohol and thelike, dihydric alcohols such as 1,3-propylene glycol and the like, glycerol and the like) is adopted, and methyl propionate and the alcohols are used as raw materials to carry out a reaction under catalysis of alkaline ionic liquid, soluble strong alkali or solid alkali to prepare higher propionate and methanol. According to the method, the synthetic route is short, and the reaction product is taken out through azeotropic extraction of the methyl propionate and methanol, so that the reaction is more thorough, and the target product is directly obtained by one step. The product obtained by thereaction only contains propionate and methanol, the whole reaction process is concise and efficient and is free of pollution, no byproducts are generated, and great significance is achieved for large-scale and low-cost production of propionate.
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Paragraph 0038-0039
(2019/07/04)
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- Consecutive addition esterification and hydrolysis of cyclic olefins catalyzed by multi-SO3H functionalized multi heteropolyanion-based ionic hybrids undersolvent-free conditions
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An efficient protocol for the synthesis of cycloalkyl carboxylates and alcohols from cyclic olefins is described. The cyclic olefins were converted to corresponding target molecules under solvent-free conditions catalyzed by two novel multi-SO3H functionalized multi heteropolyanion-based ionic hybrids through one-pot consecutive addition esterification and hydrolysis reactions. This approach has several advantages, including high yield, simple workup and simple purification.
- Zheng, Guocai,Li, Xinzhong
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p. 933 - 941
(2019/03/17)
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- Efficient Palladium-Catalyzed Alkoxycarbonylation of Bulk Industrial Olefins Using Ferrocenyl Phosphine Ligands
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The development of ligands plays a key role and provides important innovations in homogeneous catalysis. In this context, we report a novel class of ferrocenyl phosphines for the alkoxycarbonylation of industrially important alkenes. A basic feature of our ligands is the combination of sterically hindered and amphoteric moieties on the P atoms, which leads to improved activity and productivity for alkoxycarbonylation reactions compared to the current industrial state-of-the-art ligand 1,2-bis((di-tert-butylphosphino)methyl)benzene). Advantageously, palladium catalysts with these novel ligands also enable such transformations without additional acid under milder reaction conditions. The practicability of the optimized ligand was demonstrated by preparation on >10 g scale and its use in palladium-catalyzed carbonylations on kilogram scale.
- Dong, Kaiwu,Sang, Rui,Fang, Xianjie,Franke, Robert,Spannenberg, Anke,Neumann, Helfried,Jackstell, Ralf,Beller, Matthias
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supporting information
p. 5267 - 5271
(2017/04/27)
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- An extremely efficient and green method for the acylation of secondary alcohols, phenols and naphthols with a deep eutectic solvent as the catalyst
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The typical deep eutectic solvent [CholineCl][ZnCl2]3, easily prepared from choline chloride and zinc chloride, is green and useful for the acylation of secondary alcohols, phenols, and naphthols with acid anhydrides. Its efficiency allows the acylation of sterically hindered secondary alcohols and acid anhydrides to proceed in high yield under mild condition. The catalyst is cheap, easy to handle, conveniently synthesized in a single step, and recyclable for several times without significant loss of catalytic activity.
- Nguyen, Hai Truong,Tran, Phuong Hoang
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p. 98365 - 98368
(2016/10/31)
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- Graphite oxide as an efficient solid reagent for esterification reactions
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Esterification of organic acids with alcohols under mild conditions in high yields using graphite oxide, a readily available and inexpensive material, as an effective reagent is described.
- Mirza-Aghayan, Maryam,Rahimifard, Mahshid,Boukherroub, Rabah
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p. 859 - 864
(2014/12/10)
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- Tris(pentafluorophenyl)borane catalyzed acylation of alcohols, phenols, amines, and thiophenols under solvent-free condition
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The acylation of alcohols, phenols, amines, and thiophenols was accomplished with 0.5 mol % of tris(pentafluorophenyl)borane [B(C 6F5)3] at ambient temperature under solvent-free condition. Major advantages of this method include high yield, short reaction time, simple procedure, compatibility with sensitive protecting groups as well as other functional groups, absence of racemization of optical active compounds, and epimerization of sugars.
- Prajapti, Santosh Kumar,Nagarsenkar, Atulya,Babu, Bathini Nagendra
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p. 1784 - 1787
(2014/03/21)
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- Solvent-free transesterification in a ball-mill over alumina surface
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An efficient procedure for transesterification has been developed in a ball-mill in the absence of any solvent, acid/base or metal catalyst. A variety of methyl, ethyl, allyl esters have been transesterified to higher benzyl and other esters in high yields by this procedure.
- Chatterjee, Tanmay,Saha, Debasree,Ranu, Brindaban C.
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experimental part
p. 4142 - 4144
(2012/08/28)
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- Dual behavior of alcohols in iodine-catalyzed esterification under solvent-free reaction conditions
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The dual behavior phenomenon of alcohols in iodine-catalyzed esterification under solvent-free reaction conditions (SFRCs) is described; the governing factor is the stability of the carbonium ion generated from the alcohol; high concentration reaction conditions (HCRCs) or dilute solutions are much less suitable. In the case of benzylic alcohols, loss of optical activity was noted, whereas alkyl alcohols furnished a product with retention of stereochemistry.
- Jereb, Marjan,Vra?i?, Dejan,Zupan, Marko
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scheme or table
p. 2347 - 2352
(2009/09/06)
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- Investigation of the Yamaguchi esterification mechanism. Synthesis of a Lux-S enzyme inhibitor using an improved esterification method
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(Chemical Equation Presented) A one-pot procedure for the regioselective synthesis of aliphatic esters is described. This was a result of a study on mixed aliphatic-aromatic anhydrides. The data suggest that during the Yamaguchi esterification reaction, a symmetric aliphatic anhydride is produced in situ, which upon reaction with an alcohol yields the ester. We confirmed that benzoyl chloride could be used instead of the sterically hindered Yamaguchi acid chloride. This method was successfully applied in the synthesis of Lux-S aspartic acid inhibitor.
- Dhimitruka, Ilirian,SantaLucia Jr., John
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- Steric effects in the uncatalyzed and DMAP-catalyzed acylation of alcohols - Quantifying the window of opportunity in kinetic resolution experiments
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The kinetics of the reaction of several alcohols (benzyl alcohol, ethanol, 1-phenylethanol, cyclohexanol, and 1-methyl-1-phenylethanol) with a selection of anhydrides (acetic anyhydride, propionic anhydride, isobutyric anhydride, isovaleric anhydride, and pivalic anhydride) as catalyzed by 4-(N,N-dimethylamino)pyridine (DMAP)/triethyl amine have been studied in CH 2Cl2 at 20°C. In all cases the reaction kinetics can be described by rate laws containing a DMAP-catalyzed term and an uncatalyzed (back-ground) term. The rate constants for the background reaction respond sensi tively to changes in the steric demand of the alcohol and the anhydride substrates, making the reaction of cyclohexanol with acetic anhydride 526 times faster than the reaction with pivalic anhydride. Steric effects are even larger for the catalyzed reaction and the reactivity difference between acetic and pivalic anhydride exceeds a factor of 8000 for the reaction of cyclohexa nol. There is, however, no linear correlation between the steric effects on the catalyzed and the uncatalyzed part. As a consequence there are substrate combinations with dominating catalytic terms (such as the reaction of benzyl alcohol with isobutyric anhydride), while other substrate combinations (such as the reaction of cyclohexanol with pivalic anhydride) are characterized through a dominating background process. The implications of these findings for the kinetic resolution of alcohols are discussed.
- Fischer, Christian B.,Xu, Shangjie,Zipse, Hendrik
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p. 5779 - 5784
(2008/03/14)
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- Efficient chemoselective liquid phase acylation of amines, alcohols and bifunctional compounds over ZSM-35
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ZSM-35, is a medium pore zeolite, has been synthesized using ethylene diamine as organic template. The catalyst is used in the acylation of different amines, alcohols and bifunctional compounds. This material is found to be active and selective acid catalyst, exhibits not only very good activity but also very high chemo-selectivity towards monoacylation of bifunctional compounds. This material is more reactive for smaller organic compounds because of its pore dimension. In case of bifunctional compounds like amino alcohols, amines are selectively acylated at lower temperature.
- Srivastava,Venkatathri
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p. 888 - 891
(2007/10/03)
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- The thermodynamic properties of cyclohexyl esters in the ideal gas state
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Molecular and spectral data were used to calculate the thermodynamic properties of cyclohexyl formate, cyclohexyl acetate, cyclohexyl propionate, cyclohexyl butyrate, and cyclohexyl valerate in the temperature range 100-1000 K by the method of statistical thermodynamics. The geometry and internal rotation parameters of the molecules were determined by molecular mechanics with the MM3 force field. The frequencies in the vibrational spectra of the molecules were calculated and assigned. The assumption of independent top rotations was found to be too crude for cyclohexyl valerate. The entropies of gaseous cyclohexyl formate, cyclohexyl acetate, and cyclohexyl butyrate calculated at 298.15 K were in close agreement with the experimental values.
- Paulechka,Zaitsau,Kabo,Blokhin
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p. 701 - 706
(2007/10/03)
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- Comprehensive Study of vapor Pressures and Enthalpies of Vaporization of Cyclohexyl Esters
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Vapor pressures and standard molar enthalpies of vaporization Δ lgHmo were determined for five cyclohexyl esters: cyclohexyl formate, cyclohexyl acetate, cyclohexyl propanoate, cyclohexyl butyrate, and cyclohexyl valerate. The data were obtained from the temperature dependence of the vapor pressure measured by the Knudsen and the transpiration methods. Additionally, the standard molar enthalpies of vaporization ΔlgHm o of the same cyclohexyl esters were measured calorimetrically. An analysis of the results obtained from three independent methods has allowed us to improve the determination of the enthalpies of vaporization by the Knudsen effusion method.
- Zaitsau, Dzmitry H.,Verevkin, Sergey P.,Paulechka, Yauheni U.,Kabo, Gennady J.,Viktor M. Sevruk
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p. 1393 - 1400
(2007/10/03)
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- Electronic and steric substituent influences on the conformational equilibria of cyclohexyl esters: The anomeric effect is not anomalous!
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The cyclohexyl esters of a series of carboxylic acids, RCO2H, spanning a range of electronegativities and quotients of steric hindrance for the R substituent (R = Me, Et, iPr, tBu, CF3, CH2Cl, CHCl2, CH2Br, CHBr2, and CBr3) were prepared. Their conformational equilibria in CD2Cl2 were examined by low-temperature 1H NMR spectroscopy to study the axial or equatorial orientation of the ester functionality with respect to the adopted chair conformation of the cyclohexane ring. The ab initio and DFT geometry-optimized structures and relative free energies of the axial and equatorial conformers were also calculated at the HF/ 6-311G**, MP2/6-311G, and B3LYP/ 6-31G** levels of theory, both in the gas phase and in solution. In the latter case, a self-consistent isodensity polarized continuum model was employed. Only by including electron correlation in the modeling calculations for the solvated molecules was it possible to obtain a reasonable correlation between ΔG°calcd and ΔG°exp. Both the structures and the free energy differences of the axial and equatorial conformers were evaluated with respect to the factors normally influencing conformational preference, namely, 1,3-diaxial steric interactions in the axial conformer and hyperconjugation. It was assessed that hyperconjugative interactions, σC-C/σC-H and σC-O*, together with a steric effect - the destabilization of the equatorial conformer with increasing bulk of the R group - were the determinant factors for the position of the conformational equilibria. Thus, because hyperconjugation is held responsible as the mitigating factor for the anomeric effect in 2-substituted, six-membered saturated heterocyclic rings, and since it is also similarly responsible, at least partly, in these monosubstituted cyclohexanes for a preferential shift towards the axial conformer, the question is therefore raised: can the anomeric effect really be construed as anomalous?
- Kleinpeter, Erich,Taddei, Ferdinando,Wacker, Philipp
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p. 1360 - 1368
(2007/10/03)
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- Esterification of alkene with cerium(IV) sulfate in carboxylic acid
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Reaction of alkenes [cyclohexene (1), cycloheptene (2), cyclooctene (3), 1-heptene (4), 1-octene (5), styrene (6), 1,7-octadiene (7), indene (8), and 1,2-dihydronaphthalene (9)] with cerium(IV) sulfate (CS) in carboxylic acids [formic acid, acetic acid, and propionic acid] readily yielded the corresponding carboxylic esters. This addition reaction follows the Markovnikov rule. This reaction provides a new simple method for preparing carboxylic esters from alkenes. It was also found that this method is useful for formylation.
- Horiuchi, C. Akira,Fukushima, Tomoaki,Furuta, Noriyuki,Chai, Wen,Ji, Shun-Jun,Saito, Yoshikazu,Hashimoto, Chikao,Takahashi, T. Tomoyoshi,Sugiyama, Takashi,Muto, Akinori,Sakata, Yusaku,Nozaki, Sukekatsu
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p. 270 - 272
(2007/10/03)
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- Esterification of Carboxylic Acids by Alcohols with 2-Chloro-1,3,5-trinitrobenzene as Condensing Agent
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When mixtures of carboxylic acids or their sodium salts and alcohols were treatment with 2-chloro-1,3,5-trinitrobenzene in the presence of pyridine under mild conditions, the corresponding carboxylic esters were formed.The yields and the rates of the ester formation depended on the types of the acids and the alcohols used.
- Takimoto, Seiji,Inanaga, Junji,Katsuki, Tsutomu,Yamaguchi, Masaru
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p. 1470 - 1473
(2007/10/02)
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