- Transacylation. Biomimetic synthesis of esters of acetic acid
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By mixing of β-hydroxypropyl phosphate and acetic acid in ethanol solution, ethyl acetate is produced. As found, acetyl phosphate is first formed, then it reacts with the solvent to give the final ethyl acetate product. By similar procedures, acetates of methanol, n-propanol, and n-butanol are also produced. Propylene oxide serves as a condensing agent.
- Devedjiev, Ivan T.,Ganev, Vesselin G.
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- Hydroisomerization of 1,3-Dioxacycloalkanes to Esters on Platinum. The Role of Hydrogen in the Isomerization.
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Experiments show that the isomerization of 1,3-dioxacycloalkanes to esters proceeds only in the presence of hydrogen, and the selectivity for ester formation can be > 90percent with optimum hydrogen coverage; new data are reported relevant to the mechanism of ester formation and the generalization of the hydroisomerization.
- Bartok, Mihaly,Czombos, Jozsef
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- Isomerization and Hydrogenolysis of 1,3-Dioxacycloalkanes on Metal Catalysts
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The isomerization of 5-, 6-, and 7-membered 1,3-dioxacycloalkanes to esters on various metal catalysts is reported, the hydrogenolysis pattern for this type of compound is determined, and a new reaction mechanism is proposed to interpret these catalytic processes.
- Bartok, Mihaly,Czombos, Jozsef
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- Facile synthesis of mesoporous sulfated Ce/TiO2 nanofiber solid superacid with nanocrystalline frameworks by using collagen fibers as a biotemplate and its application in esterification
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Collagen fibers, one of the most abundant biomass in the natural world, were used as the biomass template to synthesize cerium-doped mesoporous TiO 2 nanofiber (SO42--Cex/TiO 2) solid acid catalysts. The physiochemical properties of the as-prepared catalysts were well characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), N2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy (XPS). The fibrous morphology of native collagen fibers were found to be well preserved in SO42--Ce x/TiO2, and the acid strength and textural property of the SO42--Cex/TiO2 were adjustable by changing the doping amount of Ce and the curing temperature. The catalytic properties of as-prepared catalysts were evaluated in the esterification reactions. It was found that the SO42--Ce x/TiO2 exhibited high activity under mild reaction conditions. When reacted at 90 °C for 45 min with a catalyst amount of 2 wt%, the conversion yields of ethyl acetate, butyl acetate, hexyl acetate and ethyl caproate were 99.9%, 97.06%, 94.29% and 86.75%, respectively. Additionally, the SO42--Cex/TiO2 solid acid catalyst could be reused at least 6 times without significant loss of activity, exhibiting much better reusability as compared with the SO 42--TiO2* catalyst prepared by conventional approach.
- Xiao, Gao,Zhou, Jianfei,Huang, Xin,Liao, Xuepin,Shi, Bi
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- Heterogeneous 1H and 13C Parahydrogen-Induced Polarization of Acetate and Pyruvate Esters
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Magnetic resonance imaging of [1-13C]hyperpolarized carboxylates (most notably, [1-13C]pyruvate) allows one to visualize abnormal metabolism in tumors and other pathologies. Herein, we investigate the efficiency of 1H and 13C hyperpolarization of acetate and pyruvate esters with ethyl, propyl and allyl alcoholic moieties using heterogeneous hydrogenation of corresponding vinyl, allyl and propargyl precursors in isotopically unlabeled and 1-13C-enriched forms with parahydrogen over Rh/TiO2 catalysts in methanol-d4 and in D2O. The maximum obtained 1H polarization was 0.6±0.2 % (for propyl acetate in CD3OD), while the highest 13C polarization was 0.10±0.03 % (for ethyl acetate in CD3OD). Hyperpolarization of acetate esters surpassed that of pyruvates, while esters with a triple carbon-carbon bond in unsaturated alcoholic moiety were less efficient as parahydrogen-induced polarization precursors than esters with a double bond. Among the compounds studied, the maximum 1H and 13C NMR signal intensities were observed for propyl acetate. Ethyl acetate yielded slightly less intense NMR signals which were dramatically greater than those of other esters under study.
- Salnikov, Oleg G.,Chukanov, Nikita V.,Kovtunova, Larisa M.,Bukhtiyarov, Valerii I.,Kovtunov, Kirill V.,Shchepin, Roman V.,Koptyug, Igor V.,Chekmenev, Eduard Y.
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- Kinetics study of propyl acetate synthesis reaction catalyzed by amberlyst 15
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The reaction kinetics of esterification of acetic acid with n-propanol was investigated. The reaction was catalyzed by the commercial cation-exchange resin Amberlyst 15, and the kinetic data were obtained in a batch reactor within the temperature range 338-368 K. The chemical equilibrium constant, Keq, was first determined experimentally; the result shows that Keq is about 20 and slightly temperature dependent. Altogether 14 sets of kinetic data were then measured. The influences of operating parameters such as temperatures, initial molar ratios, and catalyst concentrations were checked. The pseudo-homogeneous (PH), Rideal-Eley (RE), and Langmuir-Hinshelwood-Hougen- Watson (LHHW) kinetic models were developed to interpret the obtained kinetic data. The parameters of the kinetic models were identified by the software DIVA, and the confidence interval of each parameter was also estimated. Both the chemical equilibrium constant and kinetic models were formulated in terms of the liquid phase activity, which was described by the nonrandom two-liquid (NRTL) model. The LHHW model gives the best fitting result, followed by the RE model and the PH model, whereas the confidence intervals rank in the reverse order. In addition, an effective solution was proposed to overcome a convergence problem occurring in the LHHW model parameter identification, which has been reported several times in the literature.
- Huang, Yuan-Sheng,Sundmacher, Kai
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- Heteropolyacid encapsulated in Cu3(BTC)2 nanocrystals: An effective esterification catalyst
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An original synthesis approach to prepare Cu3(BTC)2 (BTC = benzene tricarboxylic acid) encapsulated Keggin phosphotungstic acid (HPW) [HPW/Cu3(BTC)2] involving mixing of reagents at room temperature, quenching in liquid nitrogen and freeze drying has resulted in the formation of nanocrystals. The catalytic properties of the as-synthesized nanocrystalline materials were assessed using a model esterification reaction of acetic acid with 1-propanol. HPW/Cu3(BTC)2 catalyst is partially dissolved in presence of acetic acid. In the esterification reaction the molar ratio of acetic acid to 1-propanol is critical. At high molar ratio of acetic acid to 1-propanol (1:2) leaching of Cu2+ and HPW was observed. However, at low molar ratio of acetic acid to 1-propanol (1:40) leaching of Cu2+ and HPW could be prevented and the catalyst was stable. Nanosized HPW/Cu3(BTC)2 showed higher catalytic activity compared to micron-size Cu3(BTC)2 (HKUST-1), ultrastable Y zeolite and micron-sized HPW/Cu3(BTC)2 catalysts. The stability of the nanosized MOF catalyst in acidic reaction medium after esterification reaction was investigated by powder X-ray diffraction (PXRD), scanning electron microscope (SEM) and N2 adsorption.
- Wee, Lik H.,Janssens, Nikki,Bajpe, Sneha R.,Kirschhock, Christine E.A.,Martens, Johan A.
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- Aluminium triflate as catalyst for epoxide ring-opening and esterification reactions - Mechanistic aspects
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A1(CF3SO3)3 is a highly effective catalyst for the ring opening of epoxides with methanol, as well as for the esterification of carboxylic acids with alcohols. Factors that influence the rate of the ring opening of butene oxide with methanol and the esterification of acetic acid with n-propanol and ethanol were investigated. It was found that low concentrations (e.g., ～5 ppm) of Al(CF3SO3) 3 catalyze the ring-opening reactions, whereas considerably higher concentrations are required for esterification reactions. Molecular modeling studies suggest that these differences can be rationalized in terms of the formation energies of the active intermediates of these reactions.
- Terblans, Yvette M.,Huyser, Johannes J.,Huyser, Michelle,Green, Michael J.,Young, Desmond A.,Sibiya, Mike S.
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- Supported heteropolyacids: Sytnhesis, characterization and effect of supports on esterification reactions
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12-Tungstophosphoric acid supported onto silica was synthesized by impregnation. The supports and synthesized catalysts were characterized for chemical stability, ion exchange capacity, thermogravimetric analysis, differential scanning calorimetry, FT-IR, and BET surface area. The catalytic activity was evaluated for liquid phase esterification reactions. The catalyst was regenerated and reused. The best catalyst was cal- cined at different temperatures and its catalytic activity was also evaluated for esterification reactions under optimized conditions. Further, obtained results are compared with l2-tungstophosphoric acid supported onto zirconia in order to see effect of acidic nature of support on catalytic activity as well as thermal stability of the catalyst. Pleiades Publishing, Ltd., 2010.
- Brahmkhatri,Patel
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- SYNTHESIS OF ESTERS FROM ACETIC ACID WITH METHANOL, ETHANOL, PROPANOL, BUTANOL, AND ISOBUTYL ALCOHOL CATALYZED BY SOLID SUPERACID
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A solid superacid catalyst, which was obtained by exposing Zr(OH)4 to 1N H2SO4 and then calcining in air at 500-750 deg C, was found to be highly active for the heterogeneous title reactions at 30-45 deg C.The reactions with the used catalyst gave identical results with those using freshly activated catalyst.
- Hino, Makoto,Arata, Kazushi
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- Synthesis, Characterisation, and Determination of Physical Properties of New Two-Protonic Acid Ionic Liquid and its Catalytic Application in the Esterification
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A new ionic liquid was synthesised, and its chemical structure was elucidated by FT-IR, 1D NMR, 2D NMR, and mass analyses. Some physical properties, thermal behaviour, and thermal stability of this ionic liquid were investigated. The formation of a two-protonic acid salt namely 4,4′-trimethylene-N,N′-dipiperidinium sulfate instead of 4,4′-trimethylene-N,N′-dipiperidinium hydrogensulfate was evidenced by NMR analyses. The catalytic activity of this ionic liquid was demonstrated in the esterification reaction of n-butanol and glacial acetic acid under different conditions. The desired acetate was obtained in 62-88 % yield without using a Dean-Stark apparatus under optimal conditions of 10 mol-% of the ionic liquid, an alcohol to glacial acetic acid mole ratio of 1.3: 1.0, a temperature of 75-100°C, and a reaction time of 4 h. α-Tocopherol (α-TCP), a highly efficient form of vitamin E, was also treated with glacial acetic acid in the presence of the ionic liquid, and O-acetyl-α-tocopherol (Ac-TCP) was obtained in 88.4 % yield. The separation of esters was conducted during workup without the utilisation of high-cost column chromatography. The residue and ionic liquid were used in subsequent runs after the extraction of desired products. The ionic liquid exhibited high catalytic activity even after five runs with no significant change in its chemical structure and catalytic efficiency.
- Shahnavaz, Zohreh,Zaharani, Lia,Khaligh, Nader Ghaffari,Mihankhah, Taraneh,Johan, Mohd Rafie
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p. 165 - 172
(2020/10/26)
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- Fully recyclable Br?nsted acid catalyst systems
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Homogeneous and heterogeneous sulfonic acid catalysts are some of the most common catalysts used in organic chemistry. This work explores an alternative scheme using a fully recyclable polymeric solvent (a poly-α-olefin (PAO)) and soluble PAO-anchored polyisobutylene (PIB)-bound sulfonic acid catalysts. This PAO solvent is nonvolatile and helps to exclude water by its nonpolar nature which in turn drives reactions without the need for distillation of water, avoiding the need for excess reagents. This highly nonpolar solvent system uses polyisobutylene (PIB) bound sulfonic acid catalysts that are phase-anchored in solvents like PAO. The effectivenes of these catalysts was demonstrated by their use in esterifications, acetalizations, and multicomponent condensations. These catalysts and the PAO solvent phase show excellent recyclability in schemes where products are efficiently separated. For example, this non-volatile polymeric solvent and the PIB-bound catalyst can be recycled quantitatively when volatile products are separated and purified by distillation. In other cases, product purification can be effected by product self-separation or by extraction.
- Watson, Christopher B.,Kuechle, Adrianna,Bergbreiter, David E.
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p. 1266 - 1273
(2021/02/26)
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- Oxidation of Propane: Influence of the Nature of Catalyst, Cocatalyst, and Coreductant
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Abstract: Variation of the nature of the components of the catalytic systems comprisinga catalyst [Pd/C, Pd(α,α-bipy)Cl2,RhCl3] and a cocatalyst(FeSO4, CuSO4), as well as acoreductant (H2, CO), allows exerting some control overthe selectivity of the process of propane oxidation with oxygen. In particular,the yield of carbonyl compounds such as acetone and propanal in the presence ofthe Pd/C–FeSO4–H2catalytic systemreached 90%, and that of propyl esters in the presence ofRhCl3–CuSO4–CO catalyticsystem was 64.5%. These differences are supposedly attributable to the changesin the process mechanism depending on the composition of the catalyticsystems. [Figure not available: see fulltext.]
- Chepaikin, E. G.,Menchikova, G. N.,Pomogailo, S. I.
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p. 781 - 786
(2021/08/03)
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- A study on the cataluminescence of propylene oxide on FeNi layered double hydroxides/graphene oxide
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In this work, FeNi layered double hydroxides/graphene oxide (FeNi LDH/GO) was prepared, which exhibits excellent selective cataluminescent performance towards propylene oxide. The selectivity and sensitivity of the cataluminescence (CTL) reaction were investigated in detail. Moreover, the catalytic reaction mechanism, including the intermediate products and the conversion of reactants to products, was discussed based on both the experimental and computational results. Furthermore, the proposed FeNi LDH/GO based CTL sensor was successfully applied for the determination of propylene oxide residue in fumigated raisins, which indicates extensive application potential for rapid food safety evaluation.
- Li, Ming,Hu, Yufei,Li, Gongke
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p. 11823 - 11830
(2021/07/11)
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- Alcohol-Activated Vanadium-Containing Polyoxometalate Complexes in Homogeneous Glucose Oxidation Identified with 51V-NMR and EPR Spectroscopy
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Alcoholic solvents, especially methanol, show an activating affect for heteropolyacids in homogenously catalysed glucose transformation reactions. In detail, they manipulate the polyoxometalate-based catalyst in a way that thermodynamically favoured total oxidation to CO2 can be completely supressed. This allows a nearly 100 % carbon efficiency in the transformation reaction of glucose to methyl formate in methanolic solution at mild reaction conditions of 90 °C and 20 bar oxygen pressure. By using powerful spectroscopic tools like 51V-NMR and continuous wave EPR we could unambiguously prove that the vanadate-methanol-complex[VO(OMe)3]n is responsible for the selectivity shift in methanolic solution compared to the aqueous reference system.
- Wesinger, Stefanie,Mendt, Matthias,Albert, Jakob
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p. 3662 - 3670
(2021/06/18)
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- Metal-organic frameworks containing nitrogen-donor ligands for efficient catalytic organic transformations
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Metal-organic framework (MOFs) compositions based on nitrogen donor-based organic bridging ligands, including ligands based on 1,3-diketimine (NacNac), bipyridines and salicylaldimine, were synthesized and then post-synthetically metalated with metal precursors, such as complexes of first row transition metals. Metal complexes of the organic bridging ligands could also be directly incorporated into the MOFs. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.
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Page/Page column 44-47
(2020/06/03)
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- Genome mining reveals new bacterial type I Baeyer-Villiger monooxygenases with (bio)synthetic potential
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Baeyer-Villiger monooxygenases (BVMOs) are oxidorreductases that catalyze the oxidation of ketones in a very selective manner. By genome mining we detected seven putative type I BVMOs in Bradyrhizobium diazoefficiens USDA 110. As we established the phylogenetic relationships among them and with other type I BVMOs, we found out that they belong to different clades of the phylogenetic tree. Thus, we decided to clone and heterologously express five of them. Three of them, each one from a divergent phylogenetic group, were obtained as soluble proteins, allowing us to proceed with their biocatalytic assessment and enzymatic characterization. As to substrate scope and selectivity, we observed a complementary behavior among the three BVMOs. BVMO2 was the more versatile biocatalyst in whole-cell systems while BVMO4 and BVMO5 showed a narrow substrate profile with preference for linear ketones and particular regioselectivity for (±)-cis-bicyclo[3.2.0]hept-2-en-6-one.
- Bianchi, Dario A.,Carabajal, María Ayelén,Ceccoli, Romina D.,Rial, Daniela V.
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- Homogeneous Metal-Complex Catalyst Systems in the Partial Oxidation of Propane with Oxygen
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Abstract: The effect of copper compounds and phosphorus–molybdenum–vanadium heteropoly acids (HPAs) H5PMo10V2O40 and H7PMo8V4O40 used as cocatalysts in the cooxidation
- Chepaikin, E. G.,Menchikova, G. N.,Pomogailo, S. I.
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p. 1260 - 1267
(2020/12/02)
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- Catalytic hydrogenolysis of glycerol into propyl acetate with ruthenium complexes
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Ru complexes have been utilized as catalyst precursors for glycerol hydrogenolysis under mild conditions, which gave propyl acetate (PA) as a major product. Notably, the esterification reaction of acetic acid with glycerol can prevent glycerol from polymerization. In(OTf)3 played a critical role in facilitating esterification of glycerol and sequential dehydration, while the Ru complexes' function was hydrogenation. The promoter (FeCl3) can suppress the reduction of Ru complex to Ru particles, improving the catalytic performance. The present catalytic system can give full glycerol conversion and 57% yield of PA. Finally, the reaction pathway was proposed accordingly.
- Xu, Zichen,Gong, Honghui,Chen, Manyu,Luo, Ruihan,Qian, Wei,Peng, Qingpo,Hou, Zhenshan
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- STABILIZATION OF ACTIVE METAL CATALYSTS AT METAL-ORGANIC FRAMEWORK NODES FOR HIGHLY EFFICIENT ORGANIC TRANSFORMATIONS
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Metal-organic framework (MOFs) compositions based on post?synthetic metalation of secondary building unit (SBU) terminal or bridging OH or OH2 groups with metal precursors or other post-synthetic manipulations are described. The MOFs provide a versatile family of recyclable and reusable single-site solid catalysts for catalyzing a variety of asymmetric organic transformations, including the regioselective boryiation and siiylation of benzyiic C—H bonds, the hydrogenation of aikenes, imines, carbonyls, nitroarenes, and heterocycles, hydroboration, hydrophosphination, and cyclization reactions. The solid catalysts can also be integrated into a flow reactor or a supercritical fluid reactor.
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Paragraph 0338
(2019/01/07)
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- Mechanism of Hydrocarbon Functionalization by an Iodate/Chloride System: The Role of Ester Protection
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Mixtures of chloride and iodate salts for light alkane oxidation achieve >20% yield of methyl trifluoroacetate (TFA) from methane with >85% selectivity. The mechanism of this C-H oxygenation has been probed by examining adamantane as a model substrate. These recent results lend support to the involvement of free radicals. Comparative studies between radical chlorination and iodate/chloride functionalization of adamantane afford statistically identical 3°:2° selectivities (～5.2:1) and kinetic isotope effects for C-H/C-D functionalization (kH/kD = 1.6(3), 1.52(3)). Alkane functionalization by iodate/chloride in HTFA is proposed to occur through H-atom abstraction by free radical species including Cl? to give alkyl radicals. Iodine, which forms by in situ reduction of iodate, traps alkyl radicals as alkyl iodides that are subsequently converted to alkyl esters in HTFA solvent. Importantly, the alkyl ester products (RTFA) are quite stable to further oxidation under the oxidizing conditions due to the protecting nature of the ester moiety.
- Schwartz, Nichole A.,Boaz, Nicholas C.,Kalman, Steven E.,Zhuang, Thompson,Goldberg, Jonathan M.,Fu, Ross,Nielsen, Robert J.,Goddard, William A.,Groves, John T.,Gunnoe, T. Brent
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p. 3138 - 3149
(2018/04/14)
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- Enantiomeric two-fold interpenetrated 3D zinc(ii) coordination networks as a catalytic platform: significant difference between water within the cage and trace water in transesterification
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Self-assembly of Zn(ClO4)2 with 1,1,2,2-tetramethyl-1,2-di(pyridin-3-yl)disilane (L) as a bidentate N-donor gives rise to 3D coordination networks, [Zn(μ-OH)(L)]3(ClO4)3·5H2O (1·5H2O), of unique, 103-a srs net topology. An important feature is that two enantiomeric 3D frameworks, 41- and 43-[Zn(μ-OH)(L)]3(ClO4)3·5H2O, are interpenetrated to form a racemic two-fold 3D network with cages occupied by two water molecules. Another structural characteristic is a C3-symmetric planar Zn3(μ-OH)3 6-membered ring with tetrahedral Zn(ii) ions. The steric hindrance of substrates and trace water effects on transesterification catalysis using the network have been scrutinized. The coordination network acts as a remarkable heterogeneous transesterification catalytic system that shows both the significant steric effects of substrate alcohols and momentous water effects. The substrate activity is in the order ethanol > n-propanol > n-butanol > iso-propanol > 2-butanol > tert-butanol. For the reaction system, solvate water molecules within the cages of the interpenetrated 3D frameworks do not decrease the transesterification activity, whereas the trace water molecules in the substrate alcohols act as obvious obstacles to the reaction.
- Choi, Eunkyung,Ryu, Minjoo,Lee, Haeri,Jung, Ok-Sang
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supporting information
p. 4595 - 4601
(2017/04/11)
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- Metal-Organic Frameworks Stabilize Solution-Inaccessible Cobalt Catalysts for Highly Efficient Broad-Scope Organic Transformations
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New and active earth-abundant metal catalysts are critically needed to replace precious metal-based catalysts for sustainable production of commodity and fine chemicals. We report here the design of highly robust, active, and reusable cobalt-bipyridine- and cobalt-phenanthroline-based metal-organic framework (MOF) catalysts for alkene hydrogenation and hydroboration, aldehyde/ketone hydroboration, and arene C-H borylation. In alkene hydrogenation, the MOF catalysts tolerated a variety of functional groups and displayed unprecedentedly high turnover numbers of ～2.5 × 106 and turnover frequencies of ～1.1 × 105 h-1. Structural, computational, and spectroscopic studies show that site isolation of the highly reactive (bpy)Co(THF)2 species in the MOFs prevents intermolecular deactivation and stabilizes solution-inaccessible catalysts for broad-scope organic transformations. Computational, spectroscopic, and kinetic evidence further support a hitherto unknown (bpy?-)CoI(THF)2 ground state that coordinates to alkene and dihydrogen and then undergoing σ-complex-assisted metathesis to form (bpy)Co(alkyl)(H). Reductive elimination of alkane followed by alkene binding completes the catalytic cycle. MOFs thus provide a novel platform for discovering new base-metal molecular catalysts and exhibit enormous potential in sustainable chemical catalysis.
- Zhang, Teng,Manna, Kuntal,Lin, Wenbin
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supporting information
p. 3241 - 3249
(2016/03/19)
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- Single-Site Cobalt Catalysts at New Zr8(μ2-O)8(μ2-OH)4 Metal-Organic Framework Nodes for Highly Active Hydrogenation of Alkenes, Imines, Carbonyls, and Heterocycles
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We report here the synthesis of robust and porous metal-organic frameworks (MOFs), M-MTBC (M = Zr or Hf), constructed from the tetrahedral linker methane-tetrakis(p-biphenylcarboxylate) (MTBC) and two types of secondary building units (SBUs): cubic M8(μ2-O)8(μ2-OH)4 and octahedral M6(μ3-O)4(μ3-OH)4. While the M6-SBU is isostructural with the 12-connected octahedral SBUs of UiO-type MOFs, the M8-SBU is composed of eight MIV ions in a cubic fashion linked by eight μ2-oxo and four μ2-OH groups. The metalation of Zr-MTBC SBUs with CoCl2, followed by treatment with NaBEt3H, afforded highly active and reusable solid Zr-MTBC-CoH catalysts for the hydrogenation of alkenes, imines, carbonyls, and heterocycles. Zr-MTBC-CoH was impressively tolerant of a range of functional groups and displayed high activity in the hydrogenation of tri- and tetra-substituted alkenes with TON > 8000 for the hydrogenation of 2,3-dimethyl-2-butene. Our structural and spectroscopic studies show that site isolation of and open environments around the cobalt-hydride catalytic species at Zr8-SBUs are responsible for high catalytic activity in the hydrogenation of a wide range of challenging substrates. MOFs thus provide a novel platform for discovering and studying new single-site base-metal solid catalysts with enormous potential for sustainable chemical synthesis.
- Ji, Pengfei,Manna, Kuntal,Lin, Zekai,Urban, Ania,Greene, Francis X.,Lan, Guangxu,Lin, Wenbin
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supporting information
p. 12234 - 12242
(2016/09/28)
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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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p. 21612 - 21616
(2016/03/08)
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- Synthesis, characterization and catalytic performance of a novel picolinic acid-12-molybdophosphoric acid hybrid catalyst
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A novel 12-molybdophosphoric acid (HPM)-based complex (H2 PI)2(H 3 O)[PMo12O 40] [Mo2 O5 (H2 O)2 (PI)2 ]?11H2 O (PI-HPM) was prepared by modification with picolinic acid (HPI) and characterized by the methods of Fourier transform infrared (FTIR) spectroscopy, thermogravimetry (TG), X-ray powder and single crystal diffraction. The complex retained the classical Keggin structure of bulk HPM, there were some strong hydrogen bonds existing between the [PMo12 O40 ]3- polyanion, the [Mo2 O5 (H2 O)2 (PI)2 ] coordination moiety, the protonated HPI and the lattice water molecules. Then PI-HPM was employed as heterogeneous catalyst for esterification reaction to evaluate its acid-catalytic activity. The complex exhibited high activity and good durability in reaction mixtures, indicating that it was a promising heterogeneous acid catalyst for esterification that including the conversion of oleic acid to oleates.
- Liu, Lijun,Wang, Honghong,Gong, Shuwen,Lu, Jing,Zhang, Qian
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p. 1007 - 1013
(2016/06/15)
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- Propyl acetate production method of high efficiency and environmental protection
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The invention discloses a propyl acetate efficient environmentally friendly production method, according to a traditional process method, excess of concentrated sulfuric acid as a catalyst is intermittently added, according to the propyl acetate efficient environmentally friendly production method, concentrated sulfuric acid and methyl sulfonic acid are mixed, the mixture is dissolved in n-propyl alcohol to be used as a mixed liquid catalyst, the mixed liquid catalyst continuously enters into a reactor, and through control of each flow, kettle liquid catalytic effect can be precisely controlled, and the kettle liquid subsequent processing difficulty is reduced so as to achieve the efficient and environmentally friendly purpose. After the implementation of the new production method, compared with the traditional process method, because dilute sulfuric acid content in the reactor decreases, the equipment corrosion situation can be reduced, the equipment maintenance cycle in esterification section is 200%-300% of original process, productivity is enhanced by 10%-20%, the efficiency of the kettle liquid subsequent processing section is increased by 10%-20%, and the economic benefit is obvious.
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Paragraph 0016-0018
(2017/05/03)
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- Efficient Baeyer-Villiger electro-oxidation of ketones with molecular oxygen using an activated carbon fiber electrode in ionic liquid [bmim][OTf]
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A new and efficient method for the synthesis of lactones and esters involving the application of an molecular oxygen-based electro-catalytic oxidation system and ionic liquid [bmim][OTf] as electrolyte has been developed. The reaction between various ketones with molecular oxygen proceeds in a three-electrode cell under constant current conditions in [bmim][OTf] at room temperature to give the corresponding esters and lactones in good to excellent isolated yield. Additionally, the possible mechanism of Baeyer-Villiger oxidation of ketones in the electro-catalytic system is proposed.
- Hu, Yu Lin,Xie, Yi Bi,Li, De Jiang
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p. 297 - 306
(2016/08/05)
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- Ag-Cu nanoparticles as efficient catalysts for transesterification of β-keto esters under acid/base-free conditions
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Transesterification of β-keto esters and alcohols are traditionally catalyzed by acid or basic catalysts. However, these traditional catalysts do not always meet the requirements of modern synthetic chemistry which need to be highly efficient, selective, and environmentally friendly. In this work, Ag-Cu metal sites were first introduced as transesterification catalysts. The effect of the support, Ag:Cu molar ratio, and reaction conditions were investigated. The Ag-Cu metal sites were proved to be active in the β-ketoester transesterification with various alcohols, having yields comparable to the conventional acid- or base-catalysts.
- Yue, Hongmei,Yu, Hao,Liu, Sheng,Xu, Chunli
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p. 19041 - 19051
(2016/03/01)
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- A catalytic conversion method for preparing pyruvate ester of lactic acid (by machine translation)
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A method for preparing pyruvate through catalytic conversion of lactic acid is provided; according to the method, with oxygen or air as an oxidant, alcohol as a solvent, and molybdovanadophosphoric heteropoly acid and/or tungstovanadophosphoric heteropoly acid as a catalyst, and by coupling of a catalytic oxidation reaction and an esterification reaction, lactic acid is converted into pyruvate by one step. The method directly adopts oxygen or air as the oxidant and is green and safe; the used raw material lactic acid is obtained directly from conversion of biomass resources, moreover, the reaction conditions are mild, and the method has important application prospects.
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- Powerful Continuous-Flow Hydrogenation by using Poly(dimethyl)silane-Supported Palladium Catalysts
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We developed poly(dimethyl)silane-supported Pd catalysts that are readily prepared from Pd(OAc)2, poly(dimethyl)silane, and Al2O3. The immobilization was achieved for the first time with a support that does not contain benzene rings. The Pd catalyst thus prepared was found to have higher hydrogenation activity than Pd/C. Furthermore, the catalyst was used in continuous-flow hydrogenation with various substrates, including simple liquid substrates (neat) and dissolved solid substrates. Vegetable oils, squalenes, and phosphatidylcholine were successfully hydrogenated on gram to kilogram scales.
- Kobayashi, Shu,Okumura, Mikiko,Akatsuka, Yuichi,Miyamura, Hiroyuki,Ueno, Masaharu,Oyamada, Hidekazu
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p. 4025 - 4029
(2015/12/26)
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- Continuous flow Fischer esterifications harnessing vibrational-coupled thin film fluidics
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Rapid Fischer esterification reactions occur under solventless, continuous flow conditions in dynamic thin films. This methodology uses limited catalyst, require no additional heat input and occurs within the confinements of an inexpensive vortex fluidic device (VFD). The associated mechanoenergy is primarily delivered from two types of vibration, which are manifested in sharp increases in the yield of the reactions. These vibrations promote the existence of Faraday waves that alter the instantaneous shear rates of the reactants within the rotating tube. Tuning the rotational speed of the device allows harmonic vibrations to be utilized in the synthesis of alkyl-based esters within both a high and low contact angle NMR tube. This journal is
- Britton, Joshua,Dalziel, Stuart B.,Raston, Colin L.
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p. 1655 - 1660
(2015/02/02)
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- Efficient and convenient oxidation of aldehydes and ketones to carboxylic acids and esters with H2O2 catalyzed by Co4HP2Mo15V3O62 in ionic liquid [TEBSA][BF4]
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A simple, efficient, and eco-friendly procedure for the oxidation of aldehydes and ketones to carboxylic acids and esters with H2O2 catalyzed by Co4HP2Mo15V3O62 in ionic liquid [TEBSA][BF4] has been developed. This atom-economical protocol affords the target products in good to high yields. The products can be separated by a simple extraction with organic solvent, and the catalytic system can be recycled and reused without loss of catalytic activity. Additionally, the possible mechanism of oxidation in the catalytic system is proposed. This journal is
- Hu, Yu-Lin,Li, De-Jiang,Li, Dong-Sheng
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p. 24936 - 24943
(2015/03/30)
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- CAL-B-Catalyzed Enantioselective Deacetylation of Some Benzylic Acetate Derivatives Via Alcoholysis in Non-aqueous Media
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Enantioselective deacetylation of a set of benzylic acetates via alcoholysis catalyzed by Lipase B from Candida antarctica (CAL-B), under mild conditions is described. A systematic study allows to determine the appropriate combination nucleophile/organic solvent and also to explain the influence of these parameters on the enzymatic catalytic reaction. In all cases, (R)-alcohols are obtained with high ee (up to >99 %) at conversion 36 % 500. The enzymatic reactivity is influenced by the hydrophobicity of solvent and the structure/nature of the nucleophile. Furthermore, CAL-B allows enantio-complementary between transesterifications in non-aqueous media: alcoholysis and acetylation.
- Zadi, Amna,Merabet-Khelassi, Mounia,Aribi-Zouioueche, Louisa
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p. 1054 - 1061
(2015/02/05)
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- Study on the one-pot oxidative esterification of glycerol with MOF supported polyoxometalates as catalyst
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In this work, glycerol was treated under green and mild conditions (water solvent, H2O2 oxidant, 40°C) in an attempt to utilise its additional value. With a metal organic framework (MOF) supported polyoxometallate (POM) as a catalyst, esters were generated as one of the major products which could be useful for various industrial applications. The selectivity of esters formation reached 34.5% in this one-pot oxidative esterification process. Benefiting from the pore limitation effect of the MOF, diffusion was restricted and the original products could be further transformed into esters with the existence of the POM. No other reagents were needed during this process, and all of the intermediates were produced from glycerol itself. The oxidative esterification reaction was studied in detail including the role of the MOF, the influence of pH and the POM type, the mechanism and so on. It was concluded that the POM served as the active site for this oxidative esterification process and H2O2 provided weak acidity in addition to the source of oxygen. Too stronger acidity and oxidizability were unfavourable to the generation of esters. Also, the catalysts could be recovered after reaction, exhibiting good stability and reusability.
- Zhu, Jie,Wang, Peng-Cheng,Lu, Ming
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p. 3383 - 3393
(2015/06/08)
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- Acid-catalyzed oxidation of levulinate derivatives to succinates under mild conditions
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Levulinate derivatives are an attractive platform for the production of renewable chemicals. Here we report on the oxidation of methyl levulinate into dimethyl succinate with peroxides under mild conditions using Br?nsted and Lewis acid catalysts. Selectivities to succinate and acetate derivatives of approximately 60 and 40 %, respectively, were obtained with strong Br?nsted acids in methanol. Although the molecular structure (i.e., carbon-chain length and branching around the C=O group) and the oxidant type affect the product distribution, solvent choice has the strongest impact on changing the location of oxygen insertion into the carbon backbone. Specifically, switching the solvent from methanol to heptane resulted in a decrease in the succinate/acetate ratio from 1.6 to 0.3. In contrast to Br?nsted acids, we demonstrate that the nature of the metal cation is responsible for changing the reaction selectivity of water-tolerant Lewis acidic triflate salts.
- Wang, Yuran,Vogelgsang, Ferdinand,Román-Leshkov, Yuriy
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p. 916 - 920
(2015/03/18)
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- Carboxyl activation of 2-mercapto-4,6-dimethylpyrimidine through n-acyl-4,6-dimethylpyrimidine-2-thione: A chemical and spectrophotometric investigation
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2-Mercapto-4,6-dimethylpyrimidine, as effective carboxyl activating group, has been successfully proved by converting it into respective acyl derivatives and the subsequent conversion to the amides and esters respectively using amines, amino alcohols and alcohols. The aminolysis and esterification were monitored chemically and spectrophotometrically. This paved way to establish that the above mercaptopyrimidine derivative is an efficient carboxyl activating group applicable in solid phase peptide synthesis.
- Rajan
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p. 287 - 291
(2015/01/30)
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- Salicylaldimine-based metal - Organic framework enabling highly active olefin hydrogenation with iron and cobalt catalysts
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A robust and porous Zr metal - organic framework, sal-MOF, of UiO topology was synthesized using a salicylaldimine (sal)-derived dicarboxylate bridging ligand. Postsynthetic metalation of sal-MOF with iron(II) or cobalt(II) chloride followed by treatment with NaBEt3H in THF resulted in Fe- and Co-functionalized MOFs (sal-M-MOF, M = Fe, Co) which are highly active solid catalysts for alkene hydrogenation. Impressively, sal-Fe-MOF displayed very high turnover numbers of up to 145000 and was recycled and reused more than 15 times. This work highlights the unique opportunity of developing MOF-based earth-abundant catalysts for sustainable chemical synthesis.
- Manna, Kuntal,Zhang, Teng,Carboni, Micha?l,Abney, Carter W.,Lin, Wenbin
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supporting information
p. 13182 - 13185
(2015/03/30)
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- A method for esterification reaction rate prediction of aliphatic monocarboxylic acids with primary alcohols in 1,4-dioxane based on two parametrical taft equation
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Esterification reaction rates of aliphatic monocarboxylic acids with primary alcohols in 1,4-dioxane as inert solvent were investigated. Acids were esterified with 1-propanol and alcohols with acetic acid as model reactants at a constant temperature of 60°C, at a fixed ionic strength and pH in a batch reactor with a constant volume. For evaluation of reaction rates, an exact kinetic equation for the equilibrium reaction was applied. Under these conditions and for low reactants, concentrations reaction rate depends only on the structure of reactants and, therefore, can be predicted by a correlation equation with two Taft coefficients (inductive and steric effects). From these equations, it is possible to estimate the esterification reaction rate constant for other acid-alcohol pairs. This methodology may also be suitable for other kinetic systems measured under comparable experimental conditions.
- Vojtko, Jan,Tomcik, Peter
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p. 189 - 196
(2014/02/14)
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- Pseudo-homogeneous kinetic model for esterification of acetic acid with propanol isomers over dodecatungstophosphoric acid supported on montmorillonite k10
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Esterification of acetic acid with propanol isomers such as isopropanol and n-propanol was carried out over dodecatungstophosphoric acid (DTPA), dodecamolybdophosphoric acid ammonium salt hydrate, and sodium tungstate hydrated purified supported on montmorillonite K10, which were characterized by powder X-ray diffraction, Brunauer-Emmett-Teller, and temperature programmed ammonia desorption. A pseudo-homogeneous (P-H) kinetic model was established for esterification of acetic acid with propanol isomers over DTPA supported on montmorillonite K10. Effects of various parameters such as reaction time, speed of agitation, particle size, temperature, percent catalyst loading, molar ratio and mixture of propanol isomer were investigated in detail. The 20% (w/w) DTPA/K10 was found to be an optimum solid catalyst with 82% n-propanol and 53% isopropanol conversion with 100% selectivity toward propyl acetate. The 20% (w/w) DTPA/K10 catalyst was found to be reusable for three cycles. The reaction follows second-order kinetics with activation energies of 25.53-kJ-mol -1 and 28.15-kJ-mol-1 for isopropanol and n-propanol, respectively. Pseudo-homogeneous kinetic model fitted with R2 value of trend line 0.999. This implies that esterification reaction is kinetically controlled owing to high activation energy. Copyright
- Gurav, Hanumant R.,Nandiwale, Kakasaheb Y.,Bokade, Vijay V.
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p. 121 - 127
(2014/02/14)
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- Direct catalytic oxidation of lower alkanes in ionic liquid media
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Immobilization of rhodium (palladium)-copper-chloride catalytic systems in ionic liquids as high-boiling-point solvents affects the distribution of propane oxidation products: the acetone yield increases and the yield of alcohols decreases. Propane is oxidized to acetone, bypassing the isopropanol formation step. Methane is oxidized under more severe conditions than propane, giving methyl trifluoroacetate as the main product. Mechanisms of action of the catalytic systems based on rhodium and palladium are close to each other and likely include oxo or peroxo complexes as intermediates.
- Chepaikin,Bezruchko,Menchikova,Moiseeva,Gekhman
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p. 374 - 381
(2015/02/19)
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- Facile esterification of carboxylic acid using amide functionalized benzimidazolium dicationic ionic liquids
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Herein, we report the synthesis of a new series of amide functionalized dicationic benzimidazolium based ionic liquids (DBimILs) and appraised their efficacy towards perceptive esterification of carboxylic acids with alkyl/allyl/aryl halides in presence of triethylamine. The amide groups present in this new series of DBimILs are expected to form hydrogen bonding with the carboxylic acids and this could facilitate the esterification reactions under mild conditions devoid of any added catalyst or organic solvent. The plausible mechanism for the enhanced catalytic activity in presence of this new series of ILs has been proposed. The corresponding alkyl/allyl/aryl esters isolated from this reaction were of high purity after simple extraction, which wipe out the necessity for further purification. This protocol addresses clean methodology and the efficient recyclability as well as reusability of the catalyst.
- Muskawar, Prashant Narayan,Thenmozhi,Gajbhiye, Jayant M.,Bhagat, Pundlik Rambhau
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p. 214 - 220
(2014/07/08)
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- Vitamin B1 supported on silica-encapsulated γ-Fe 2O3 nanoparticles: Design, characterization and application as a greener biocatalyst for highly efficient acylation
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A new magnetic catalyst was synthesized by the immobilization of vitamin B1 (thiamine hydrochloride) on the surface of silica-encapsulated γ-Fe2O3 nanoparticles. Its capability was evaluated in the acylation of alcohols and phenols with acetic anhydride under solvent-free conditions and afforded the desired products in high yield. This novel magnetic organocatalyst could be separated from the reaction vessel by use of an external magnet and recovered 5 times without a significant loss of its activity. The amount of loaded vitamin B1 on the silica-encapsulated γ-Fe2O3 was assigned by TGA and confirmed by back titration. Availability, cheapness and low toxicity are reasons associated with the utilization of vitamin B1 as a catalyst. The catalyst has been characterized by FT-IR, XRD, SEM, VSM and TG/DTA. The Royal Society of Chemistry.
- Azizi, Kobra,Heydari, Akbar
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p. 8812 - 8816
(2014/03/21)
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- A convenient method for producing mono- and dichlorohydrins from glycerol
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A new method for the transformation of glycerol into mono- and dichlorohydrins has been studied. With trimethylchlorosilane as chlorinating agent and acetic acid as catalyst, mono- and dichlorohydrins have been obtained in high yields and selectivity. In fact, under different reaction conditions, the synthesis of α-monochlorohydrin (3-chloropropan-1,2-diol) or α,γ-dichlorohydrin (1,3-dichloropropan-2-ol) as predominant product has been achieved. This process was also exploited for the valorisation of the crude mixture of glycerol and monochlorohydrin (glyceric mixture), a by-product from an earlier BioDiesel production. A reaction mechanism has been proposed based on investigations on the chlorination of different alcohols.
- Giomi, Donatella,Malavolti, Marino,Piccolo, Oreste,Salvini, Antonella,Brandi, Alberto
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p. 46319 - 46326
(2015/02/19)
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- Expanding ester biosynthesis in Escherichia coli
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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.
- Rodriguez, Gabriel M,Tashiro, Yohei,Atsumi, Shota
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p. 259 - 265
(2014/04/03)
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- Chemoselective palladium-catalyzed oxidation of vinyl ether to acetate using hydrogen peroxide
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A practical and environmental-friendly method was developed to convert vinyl ether into acetate by using a palladium complex with phosphine ligand and hydrogen peroxide. The only by-product is water. Chemoselective oxidation of vinyl ether and tert-enamides to form acetate and N-acetyl amide with hydrogen peroxide in the presence of palladium complex having phosphine ligand was developed under mild reaction conditions. This process is environmentally friendly because it uses hydrogen peroxide as a clean oxidant, with water being the only byprocuct.
- Kon, Yoshihiro,Tanaka, Shinji,Nakashima, Takuya,Sato, Kazuhiko,Shimada, Hiromichi
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p. 749 - 756
(2014/07/22)
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- Synthesis of monoesters and diesters using eco-friendly solid acid catalysts - Cerium(IV) and thorium(IV) phosphates
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In the present endeavour, amorphous cerium phosphate (CP) and thorium phosphate (TP) have been synthesized by sol-gel method and also under microwave irradiation to yield CPM and TPM. CP, TP, CPM and TPM have been characterized for elemental analysis (ICP-AES), spectral analysis (FTIR), thermal analysis (TGA), X-ray diffraction studies, SEM, EDX, surface area (BET) and surface acidity (NH3-TPD). The potential use of these materials as solid acid catalysts has been explored by studying esterification as a model reaction. Monoesters such as ethyl acetate (EA), propyl acetate (PA), butyl acetate (BA), benzyl acetate (BzAc) and diesters such as diethyl malonate (DEM), diethyl succinate (DES), dibutyl phthalate (DBP), dioctyl phthalate (DOP) have been synthesized. Esterification conditions have been optimized by varying several parameters such as reaction time, catalyst amount and mole ratio of reagents. The catalytic activity has been compared and correlated with reference to surface acidity of the catalysts. It is found that catalytic activity of CPM > CP > TP M > TP. The regenerated catalysts could be reused upto two catalytic runs without significant loss in % yields of esters formed. The highlighting feature of the present work is the catalysts CPM and TPM that are synthesized in a much shorter reaction time with higher surface acidity giving good % yield of esters.
- Parangi, Tarun,Wani, Bina,Chudasama, Uma
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p. 430 - 438
(2013/09/23)
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- Design of a highly active silver-exchanged phosphotungstic acid catalyst for glycerol esterification with acetic acid
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A series of highly active, selective, and stable silver-exchanged phosphotungstic acid (AgPW) catalysts were prepared, characterized, and evaluated for bio-derived glycerol esterification with acetic acid to produce valuable biofuel additives. The structures, morphologies, acidities, and water tolerance of these samples were determined by FTIR, Raman, XRD, SEM-EDX, FT-IR of pyridine adsorption, and H2O-TPD. Several typical acidic catalysts were also performed for comparison. Among them, partially silver-exchanged phosphotungstic acid (Ag1PW) presented exceptionally high activity, with 96.8% conversion within just 15 min of reaction time and remarkable stability, due to the unique Keggin structure, high acidity as well as outstanding water-tolerance property. A plausible reaction mechanism was also proposed. In addition, this Ag1PW catalyst exhibited universal significance for esterification, holding great potential for a wide range of other acid-catalyzed reactions.
- Zhu, Shanhui,Gao, Xiaoqing,Dong, Fang,Zhu, Yulei,Zheng, Hongyan,Li, Yongwang
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p. 155 - 163
(2013/09/02)
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- Readily recyclable catalysts of zeolite nanoparticles linked with polymer chains
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Aggregates of zeolite nanoparticles were linked together with polypropylene oxide or polydimethylsiloxane polymer chains, and were used as catalysts for liquid-phase reactions. The polymer-linked catalysts showed high catalytic activity in esterification of acetic acid with 1-propanol and hydrolysis of ethyl acetate, and were readily separated from reaction mixtures by decantation. Moreover, the linkage with the polymer chains enhanced shape selectivity in esterification of acetic acid with cyclohexanol and dehydration of 1-phenylethanol because of passivating the external acid sites of the zeolite with the polymer.
- Okamoto, Masaki,Watanabe, Satoshi,Nitta, Junya
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- Carbodeoxygenation of biomass: The carbonylation of glycerol and higher polyols to monocarboxylic acids
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Glycerol is converted to a mixture of butyric and isobutyric acid by rhodium- or iridium-catalysed carbonylation using HI as the co-catalyst. The initial reaction of glycerol with HI results in several intermediates that lead to isopropyl iodide, which upon carbonylation forms butyric and isobutyric acid. At low HI concentration, the intermediate allyl iodide undergoes carbonylation to give vinyl acetic acid and crotonic acid. Higher polyols CnH n+2(OH)n are carbonylated to the corresponding C n+1 mono-carboxylic acids. Copyright
- Coskun, Timur,Conifer, Christopher M.,Stevenson, Laura C.,Britovsek, George J. P.
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supporting information
p. 6840 - 6844
(2013/07/05)
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- Kinetics on synthesis of propyl acetate catalyzed with expansible graphite
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The reaction for heterogeneous synthesis of propyl acetate catalyzed by expansible graphite was investigated in a stirred batch reactor. By the elimination of internal and external diffusion, the concentration change of acetic acid with reaction time was determined and the parameters of the kinetic model for the reversible second-order reaction were evaluated by the initial reaction rate method. The frequency factor was 5.46 × 107 L/(mol min) and the activation energy was 18.03 kJ/mol under the conditions of 353.2-383.2 K, 101.3 kPa, mass ratio of catalyst is 6-10 % of total mass of acetic arid and propanol. The accuracy of the reaction kinetic equation was testified and the result showed that the calculated values agreed well with the experimental value and the maximum deviation of the calculated value comparing with the experimental results was 10.8 %.
- Pang, Xiu-Yan,Liu, Jin-Huan
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experimental part
p. 5090 - 5092
(2012/10/08)
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- Novel double-SO3h functionalized ionic liquid for acetylation
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Novel double-SO3H functionalized ionic liquid (DFIL) was synthesized and its catalytic activities for acetylation studied. The result showed that the DFIL possess high acidity and was very efficient for the acetylation of alcohols, amines and phenols with good to excellent yields in short reaction times. Operational simplicity, stability to water and air, small amounts needed, low cost, high yields, high acidity, applicability to large-scale reactions and reusability are the key features of the DFIL, which indicated promising applications of DFIL in green chemical processes. Pleiades Publishing, Ltd., 2012.
- Zhu, Lili,Liang, Xuezheng
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p. 684 - 688
(2013/02/23)
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- METHOD FOR PRODUCING n-PROPYL ACETATE
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Provided is a method for producing n-propyl acetate capable of suppressing the deterioration of a hydrogenation catalyst to such an extent that the catalyst can be industrially used, for example, in the case where n-propyl acetate is produced by performing a hydrogenation reaction in the presence of the hydrogenation catalyst using, as a raw material liquid, a liquid containing allyl acetate or the like which has been produced from propylene, oxygen and acetic acid and obtained using a purification process such as distillation. In such a method for producing n-propyl acetate, the concentration of a formyl group-containing compound (such as acrolein, propionaldehyde or 2-methylcrotonaldehyde) and the concentration of an acryloyloxy group-containing compound (such as acrylic acid or allyl acrylate) in the raw material liquid are respectively set to 100 ppm by mass or less. As a result, the deterioration of the hydrogenation catalyst can be suppressed to such an extent that the catalyst can be industrially used.
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Page/Page column 8-9
(2011/04/18)
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- METHOD FOR PRODUCING N-PROPYL ACETATE AND METHOD FOR PRODUCING ALLYL ACETATE
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Provided is a method for producing n-propyl acetate, which is capable of obtaining high-purity allyl acetate with a low amount of coexisting water and is capable of producing n-propyl acetate with a high yield. The method includes an extraction process of subjecting a raw material liquid containing allyl acetate and water to an extraction operation using water as an extraction solvent and separating the extract into an oily phase and an aqueous phase, a distillation process of distilling the oily phase to obtain a distillate containing allyl acetate as a main component, and a hydrogenation process of subjecting the distillate to a hydrogenation reaction.
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Page/Page column 43-44
(2011/10/13)
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- METHOD FOR PRODUCING N-PROPYL ACETATE
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One object of the present invention is to provide a method for producing n-propyl acetate by the hydrogenation reaction with a hydrogenation catalyst, using an allyl acetate containing solution as a raw material, wherein the method can prevent the conversion rate of the substrate (allyl acetate) from decreasing with time and the product quality from deteriorating, and the present invention provides a method for producing n-propyl acetate including a first hydrogenation step in which a raw material solution containing allyl acetate and a hydrogen containing gas are reacted under a pressure P1 of 1.0 MPa G (gage pressure) or more in the presence of a hydrogenation catalyst, to hydrogenate the allyl acetate to produce a hydrogenation reaction product containing n-propyl acetate: a gas-liquid separation step in which the hydrogenation reaction product is gas-liquid separated into to produce a crude n-propyl acetate solution containing n-propyl acetate: and a second hydrogenation step in which non-reacted allyl acetate contained in the crude n-propyl acetate solution is hydrogenated using hydrogen dissolved in the crude n-propyl acetate solution in the presence of a hydrogenation catalyst.
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Page/Page column 34-38
(2011/06/26)
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- Palladium-catalyzed oxidation of vinyl ether to acetate with hydrogen peroxide
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The selective hydrogen peroxide oxidation of vinyl ethers to give acetates was developed using triphenylphosphine palladium and triethyl amine catalysts under mild reaction conditions.
- Kon, Yoshihiro,Chishiro, Takefumi,Imao, Daisuke,Nakashima, Takuya,Nagamine, Takashi,Hachiya, Houjin,Sato, Kazuhiko
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supporting information; experimental part
p. 6739 - 6742
(2011/12/22)
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- Esterification of carboxylate-based ionic liquids with alkyl halides
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A facile reaction of 1-ethyl-3-methylimidazolium acetate ([EMIm]Ac) with dichloromethane at room temperature was observed with esters among the products. This esterification can be exploited for mild solvent-free esterification with a range of other carboxylate-based ionic liquids and alkyl halides. The Royal Society of Chemistry.
- Zhao, Bin,Greiner, Lasse,Leitner, Walter
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scheme or table
p. 2973 - 2975
(2011/04/24)
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