- Biomass-derived dibasic acids to diesters with inorganic ligand-supported catalyst: synthesis, optimization, characterization
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Several attempts have been made to obtain aliphatic dicarboxylic diesters from esterification reaction to develop the biomass-derived platform molecules and green manufacturing processes. In this paper, Na3(H2O)6[AlMo6O18(OH)6], an Anderson-type polyoxometalate, firstly, was reported as a catalyst for diester synthesis from dicarboxylic acid to diester which showed an well productivity and selectivity characterized by 1H and 13C. Response surface methodology (RSM) integrated with the desirability function approach was used to determine the best operative conditions, and the optimal reaction parameters for maximum dipropyl succinate yield (77 ± 2.5%) were identified as 1.19?mol.% catalyst loading, 4.9:1 propanol/succinic acid ratio, 113?°C, and 9.6?h. Three batches of tests were carried for catalyst recycling with 78–75% yield even after 6 cycles of esterification. In addition, the substrate carbon chain was increased for investigation of substrate scope achieving satisfactory results and all products were characterized by 1H and 13C nuclear magnetic resonance spectroscopy.
- Chen, Zhe,Han, Sheng,Lu, Deli,Xu, Yumeng
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- Biobased compositions
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A composition comprised of a component selected from the group consisting of a biobased bis-alkyl succinate and a biobased bis-alkyl sebacate, each derived, for example, from the esterification of biobased diacid such as succinic acid or sebacic acid, and a biobased alcohol and a biobased polyester.
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Page/Page column 14-15
(2021/08/05)
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- Reduction of Activated Alkenes by PIII/PV Redox Cycling Catalysis
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The carbon–carbon double bond of unsaturated carbonyl compounds was readily reduced by using a phosphetane oxide catalyst in the presence of a simple organosilane as the terminal reductant and water as the hydrogen source. Quantitative hydrogenation was observed when 1.0 mol % of a methyl-substituted phosphetane oxide was employed as the catalyst. The procedure is highly selective towards activated double bonds, tolerating a variety of functional groups that are usually prone to reduction. In total, 25 alkenes and two alkynes were hydrogenated to the corresponding alkanes in excellent yields of up to 99 %. Notably, less active poly(methylhydrosiloxane) could also be utilized as the terminal reductant. Mechanistic investigations revealed the phosphane as the catalyst resting state and a protonation/deprotonation sequence as the crucial step in the catalytic cycle.
- Longwitz, Lars,Werner, Thomas
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supporting information
p. 2760 - 2763
(2020/02/05)
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- Exceptionally active and reusable nanobiocatalyst comprising lipase non-covalently immobilized on multi-wall carbon nanotubes for the synthesis of diester plasticizers
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A new method for the synthesis of dicarboxylic acid esters in the presence of a new heterogeneous nanobiocatalyst consisting of Candida antarctica lipase B immobilized on multi-walled carbon nanotubes (MWCNTs) has been developed. Selection and characterization of the support for Candida antarctica lipase B (CALB) was initially performed. Pristine and modified MWCNTs of different geometries, morphologies and surface/core modifications were tested as a lipase carrier and determining that the CheapTubes MWCNTs nanobiocatalyst with a 15.7 wt.% CALB loading was the most active nanobiocatalyst. The model reaction of succinic acid with n-butanol was carried out with a 4-molar excess of alcohol and 150 mg of nanobiocatalyst per 1 mmol of succinic acid at 45 °C in cyclohexane. The di-n-butyl succinate was obtained with 95% yield after 3 h. The activities of the new nanobiocatalysts were compared with the benchmark Novozyme-435 and other acidic catalysts. Recycling studies demonstrated the possibility of utilizing the most active MWCNTs-lipase biocatalyst six times without any significant loss of activity. The main advantage of this study is the superior activity of the new nanobiocatalyst, which resulted in a significant reduction of reaction times as compared to those reported in the literature.
- Szelwicka, Anna,Boncel, S?awomir,Jurczyk, Sebastian,Chrobok, Anna
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- Synthesis of Esters from Stable and Convenient Sulfoxonium Precursors under Catalyst- And Additive-Free Conditions
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A convenient and efficient procedure for the construction of esters from stable sulfoxonium ylides and alcohols has been developed. This protocol presents a broad substrate scope and good yields of the desired esters can be isolated. Notably, no catalyst, oxidant, base or any other additive is required.
- Wu, Xiao-Feng,Yuan, Yang
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p. 1820 - 1824
(2019/09/09)
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- Method for preparing succinate by double carbonylation of acetylene
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The invention provides a method for preparing succinate by double carbonylation of acetylene. Acetylene, carbon monoxide and an alcohol compound are used as raw materials and subjected to the double carbonylation reaction in a solvent under the catalysis of a catalyst, and the succinate compound is obtained. The catalyst is composed of a palladium compound, a lithium halide/acid auxiliary agent and a nitrogen-oxygen ligand, wherein the nitrogen-oxygen ligand is one or more of 2-hydroxypyridine, 3-hydroxypyridine and 2-picolinic acid, and the dosage of the catalyst is 0.0001-1.0% of the total weight of the reaction system; in the reaction system, the molar ratio of acetylene to the alcohol compound is 1:(2-16), and the molar ratio of the alcohol compound to the solvent is 1:(7-35). According to the method, the succinate compounds can be produced by a one-pot method, wherein the process is simple, and the investment cost of an industrial device is low; the reaction conditions in the production process are mild, the catalytic activity of the catalyst is high, the stability is high, the service life is long, the yield can reach 90% or above, and the higher technical competitive advantage is achieved.
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Paragraph 0027-0038
(2019/12/02)
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- A novel hydrogen-bonded silica-supported acidic ionic liquid: An efficient, recyclable and selective heterogeneous catalyst for the synthesis of diesters
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Abstract: In this study, two novel acidic ionic liquids, including a hydroxyl functionalized diacidic ionic liquid [HFDAIL] and a sulfonated diacidic ionic liquid [SFDAIL], were prepared and immobilized on the surface of silica nanoparticles (SNPs) via hydrogen bonding. The materials were characterized by FT-IR, NMR, SEM, nitrogen physisorption measurement, TGA and acid-base titration. The catalytic activity of the prepared catalysts was investigated in the synthesis of phthalate, maleate and succinate diesters under solvent-free conditions. It was found that nanosilica@[HFDAIL] with higher availability of acidic sites and higher hydrophilicity was more efficient compared to the nanosilica@[SFDAIL]. Notably, nanosilica@[HFDAIL] catalyst has also demonstrated excellent selectivity for the diester product while the monoester product was predominant in the case of nanosilica@[SFDAIL] even after prolonged reaction time or higher catalyst loading. In addition, the nanosilica@[HFDAIL] catalyst could be separated by simple filtration and reused several times without any significant loss of catalytic performance, but a remarkable decrease in activity was observed for nanosilica@[SFDAIL] in the next runs. GRAPHICAL ABSTRACT?: SYNOPSIS Two novel acidic ionic liquids, including a hydroxyl functionalized diacidic ionic liquid [HFDAIL] and a sulfonated diacidic ionic liquid [SFDAIL], were prepared and immobilized on the surface of silica nanoparticles via hydrogen bonding. The catalytic activity of the catalysts was investigated in the synthesis of diesters under solvent-free conditions.
- Fareghi-Alamdari, Reza,Niri, Mehri Nadiri,Hazarkhani, Hassan
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- Method for preparing 1,4-butanediol and/or sec-butyl alcohol
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The invention provides a method for preparing 1,4-butanediol and/or sec-butyl alcohol. The method for preparing 1,4-butanediol comprises the steps that (1) butanedioic acid and C2-C6 olefins are subjected to addition reaction; dibutyl succinate is collected; (2) the dibutyl succinate obtained in the step (1) is subjected to hydrogenation reaction; the 1,4-butanediol and/or sec-butyl alcohol is collected. The method provides a high-efficiency and low-cost technical route for 1,4-butanediol and/or sec-butyl alcohol production. The addition reaction and the hydrogenation reaction in the method have high selectivity; the atom utilization rate is very high; an environment-friendly effect is achieved in the preparation process. The method has high butanedioic acid conversion rate and high dibutyl succinate selectivity. The method has the advantages that the acid amount is adjustable; the product selectivity is high; equipment cannot be corroded; catalysts can be cyclically used.
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Paragraph 0038-0066
(2018/03/24)
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- Synthesis and characterization of a new hydroxyl functionalized diacidic ionic liquid as catalyst for the preparation of diester plasticizers
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Two new functionalized diacidic ionic liquids (FDAILs) including hydroxyl functionalized diacidic ionic liquid (HFDAIL) and sulfonated diacidic ionic liquid (SFDAIL) were synthesized and characterized by 1HNMR, 13CNMR and FT-IR. The catalytic activities of these FDAILs were examined in esterification reaction of anhydrides with some alcohols to give corresponding dialkyl plasticizers under solvent-free conditions. The results indicate that HFDAIL, as hydroxyl-bearing catalyst, show better catalytic performance. Under the optimum conditions, using HFDAIL, the conversion of phthalic anhydride was high and diester plasticizers were obtained with good to excellent yields in the presence of only 10?mol% of ionic liquid. All the produced diesters could be easily recovered due to their immiscibility with the ionic liquid. Recycling experiments suggests that these ionic liquids can be reused several times without remarkable loss in their catalytic activity.
- Fareghi-Alamdari, Reza,Nadiri Niri, Mehri,Hazarkhani, Hassan
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p. 153 - 160
(2016/12/30)
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- BIOFUELS PRODUCTION FROM BIO-DERIVED CARBOXYLIC-ACID ESTERS
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A process for producing biofuels compounds directly from carboxylic acid esters recovered from a fermentation system is described. The process involves taking a fermentation broth that has been reduced to a dry powder containing free organic acids; reacting the carboxylic acid in the powder with an alcohol solvent under a CO2-containing atmosphere in substantial absence of any other acid catalyst at a reaction temperature and pressure that corresponds to supercritical, critical or near critical conditions for at least one of the alcohol or CO2 to synthesize an ester, then subjecting the ester to either hydrogenolysis or hydrogenation to form a biofuel.
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Paragraph 0053; 0056
(2017/04/11)
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- A kind of preparation method of succinic acid diester
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Disclosed is a method for preparing succinic acid diester, in which levulinic acid or levulinate esters are used as raw materials, molecular oxygen is used as oxygen source, and succinic acid diester is produced by catalytic selective oxidation and esterification reaction. The levulinic acid or levulinate esters used as raw materials in the method can be obtained from biomass such as cellulose, starch, agricultural and forestry residues or the like. The method is a new route for preparing succinic acid diester that does not rely on fossil resourse. As the reaction condition in the process is moderate and has a high succinic acid diester selectivity, it has important application prospect.
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Paragraph 0063-0066
(2017/01/09)
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- NOVEL PROCESS FOR MAKING OMEGA-AMINOALKYLENIC ALKYL ESTER
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A method for making a compound of formula (V): is provided. The method comprises converting a compound of formula (III): to the compound of formula (V), wherein A is a C6-C10 alkene group having at least one carbon-carbon double bond, B is a C6-C10 alkyl chain; and R1 is an alkyl group, and R3 is an oxygenated functional group.
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-
Paragraph 0184; 0185
(2016/08/17)
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- REDUCTION METHOD USING WATER AS PROTON SOURCE BY MEANS OF N-HETEROCYCLIC CARBENE
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PROBLEM TO BE SOLVED: To provide a reduction method using water as a proton source by means of N-heterocyclic carbene, in which the N-heterocyclic carbene is used actively as a reaction accelerator to realize a hydrogenation reaction by using water as the proton source. SOLUTION: A solution, which is obtained by mixing: a reaction substrate shown at an upper stage of the following formulae; a precursor of the triazole-based N-heterocyclic carbene (NHC) shown at a lower stage; water; and 1,2-dimethoxyethane being a solvent, is reacted at 100°C or higher temperature for 2 hours or more while making the solution to pass through a microwave reaction unit and the reacted solution is subjected to reduced-pressure distillation to obtain a hydrogenated product. The formulae: (EWG1-EWG4 are each an ester group, a cyano group, a ketone group, an amido group or an imido group;R1-R5 are each a 1-20C aliphatic group, a 3-12C alicyclic group or 6-30C aromatic group) SELECTED DRAWING: None COPYRIGHT: (C)2016,JPO&INPIT
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Paragraph 0014; 0015
(2016/10/10)
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- Electroreductive hydrogenation of activated olefins using the concept of site isolation
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Electroreductive hydrogenation of activated olefins was investigated using the concept of site isolation. It was shown by electrochemical measurements as well as preparative electrolyses that the use of silica gel-supported sulfonic acid (Si-SO3H) promotes the protonation step in electroreductive hydrogenation of activated olefins without electroreductive destruction at the cathode. On the basis of the concept of site isolation, electroreductive hydrogenation of several activated olefins was successfully carried out to provide the corresponding hydrogenation products in high yields.
- Tomida, Shinsuke,Tsuda, Ryohei,Furukawa, Shiho,Saito, Marie,Tajima, Toshiki
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- Transfer hydrogenation promoted by N-heterocyclic carbene and water
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N-Heterocyclic carbenes (NHCs) promote the transfer hydrogenation of various activated C=C, C=N, and N=N bonds with water as the proton source. The NHCs act as reducing reagents to be converted into their oxides. A detailed reaction mechanism is proposed on the basis of deuterium-labeling experiments.
- Kato, Terumasa,Matsuoka, Shin-Ichi,Suzuki, Masato
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supporting information
p. 13906 - 13909
(2015/09/07)
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- ACYCLIC ALKENES VIA OZONOLYSIS OF MULTI-UNSATURATED CYCLOALKENES
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A method of making a compound of formula (IIa) by selective ozonolysis of a compound of formula (I) is provided, wherein A is a C6-C10 alkene chain with at least one double bond, R1 is a C1-C10 alkyl, and R3 is an oxygen-containing functional group.
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Paragraph 00152-00153
(2015/02/02)
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- HYDROGENATION PRODUCTS FROM BIOLOGICALLY-DERIVED CARBOXYLIC-ACID ESTERS
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The production of organic acids in low-cost, high-efficiency fermentation system makes available a new route to chemical production from biomass. A process for producing a hydrogenation product involving carboxylic acid esters recovered directly from a fermentation process is described.
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Page/Page column 19
(2014/07/08)
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- Esterification of bio-based succinic acid in biphasic systems: Comparison of chemical and biological catalysts
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Different chemical and biological catalysts were screened for the biphasic esterification of aqueous solutions of succinic acid with 1-octanol. Among them, DBSA, Nafion NR-50 and Novozym 435 were found to be the most attractive catalysts. The pH, the temperature and the catalyst concentration had high impacts on the reaction rates. The optimization of the reaction conditions with a single-variable approach for the chemical catalysts and a Response Surface Methodology for the enzyme allowed an increase of the rates by a factor 1.5 for DBSA, 2.3 for Nafion NR-50 and 1.3 for Novozym 435. Real fermentation broths produced from recombinant Escherichia coli could be successfully esterified with conversions up to 93% for DBSA and 70% for Nafion NR-50 and Novozym 435 as catalysts. Finally, DBSA was selected as the cheapest and most active option. Besides, the esters were isolated with a purity of 83% from fermentation broth solutions. DBSA also catalyzed the esterification of succinic acid from fermentation broth with many alcohols creating a broad spectrum of interesting esters. The esters might then be used as end-product, hydrolyzed back to pure succinic acid or hydrogenated.
- Delhomme, Clara,Goh, Serena L.M.,Kuehn, Fritz E.,Weuster-Botz, Dirk
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experimental part
p. 39 - 47
(2012/09/07)
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- A novel Bronsted acidic heteropolyanion-based polymeric hybrid catalyst for esterification
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A new SO3H-functionalized HPA-based acidic polymeric hybrid was prepared by coupling task-specifically designed SO3H-functionalized polymeric ionic liquid with Keggin-structured heteropolyanion, and characterized by 1H NMR, FT-IR, TG, XRD, BET, Hammett indicator, melting point, and elemental analysis. Its catalytic performance for esterification of alcohols with carboxylic acids was studied under solvent-free conditions. The results demonstrate that the polymeric hybrid is a highly active and selective solid catalyst for various esterifications, and can be easily recovered and steadily reused.
- Leng, Yan,Jiang, Pingping,Wang, Jun
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experimental part
p. 41 - 44
(2012/10/07)
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- Reductive coupling of aldehydes by H2S in aqueous solutions, a C-C bond forming reaction of prebiotic interest
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We report here a novel reductive coupling reaction of conjugated, non- or poorly enolizable aldehydes induced by H2S and operative in aqueous solutions under prebiotically relevant conditions. This reaction leads from retinal to β-carotene, and from benzylic aldehydes to the corresponding diarylethylenes. This novel reaction also opens a new potentially prebiotic pathway leading from glyoxylic acid to various compounds that are involved in the reductive tricarboxylic acid cycle. This C-C bond forming reaction of prebiotic interest might have been operative, notably, in the sulfide-rich environments of hydrothermal vents, which have been postulated as possible sites for the first steps of organic chemical evolution.
- Kajjout, Mohammed,Hebting, Yanek,Albrecht, Pierre,Adam, Pierre
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experimental part
p. 714 - 726
(2012/07/14)
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- Vapor pressures and enthalpies of vaporization of a series of the symmetric linear n -alkyl esters of dicarboxylic acids
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Vapor pressures and the molar enthalpies of vaporization of the linear aliphatic alkyl esters of dicarboxylic acids R-CO2-(CH 2)n-CO2-R with n = (0 to 4) with R = C 2H5, n-C3H7, and n-C 4H9 have been determined using the transpiration method. A linear correlation of enthalpies of vaporization (at T = 298.15 K) of the esters with the number n and with Kovat's indices has been found, proving the internal consistency of measured data.
- Lipp, Svetlana V.,Krasnykh, Eugenii L.,Verevkin, Sergey P.
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body text
p. 800 - 810
(2011/11/05)
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- Atom-economical synthesis of unsymmetrical ketones through photocatalyzed C-H activation of alkanes and coupling with CO and electrophilic alkenes
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A three-component coupling between alkanes, CO, and electron-deficient alkenes in the presence of a catalytic amount of (nBu4N) 4W10O32 (TBADT) has resulted in the efficient formation of unsymmetrical ketones. This process is based on the carbonylation of alkyl radicals photocatalytically generated by C-H activation of alkanes and the subsequent addition to alkenes (see scheme; EWG=electron-withdrawing group).
- Ryu, Ilhyong,Tani, Akihiro,Fukuyama, Takahide,Ravelli, Davide,Fagnoni, Maurizio,Albini, Angelo
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supporting information; experimental part
p. 1869 - 1872
(2011/04/16)
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- Selective hydrogenation by polymer-encapsulated platinum nanoparticles prepared by an easy single-step sonochemical synthesis
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Polypyrrole-encapsulated platinum nanoparticles (PPy/Pt-NPs) prepared by an easy single-step sonochemical synthesis were used as catalysts for the liquid phase hydrogenation of substituted alkenes in methanol or methanol/water mixtures. Polypyrrole (PPy) coatings on the nanoparticles were able to act as nanoscopic filters for substrates molecules, and consequently substrate selectivity could be controlled in the catalytic processes.
- Atobe, Mahito,Okamoto, Mayuko,Fuchigami, Toshio,Park, Jong-Eun
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experimental part
p. 26 - 29
(2010/11/18)
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- Ionic liquids as solvent for efficient esterification of carboxylic acids with alkyl halides
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The selective esterification of carboxylic acid derivatives with a variety of alkyl halides was carried out using ionic liquid as solvent in the presence of triethylamine. The reaction was found to proceed under relatively mild conditions with excellent conversions (up to 99%) and selectivities. The ionic liquid was recycled and reused. TUeBITAK.
- Goek, Yetkin,Alici, Buelent,Cetinkaya, Enginc,OeZdemir, Ismail,Oezeroglu, Ozlem
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experimental part
p. 187 - 191
(2010/09/11)
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- Oxidation of substituted β-diketones with hydrogen peroxide: Synthesis of esters through the formation of bridged 1,2,4,5-tetraoxanes
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Acid-catalyzed oxidation of alkyl- and benzyl-substituted -diketones by hydrogen peroxide at 79-120C in a mixture of an alcohol and a strong acid (sulfuric acid, tetrafluoroboric acid, or perchloric acid) gave the corresponding esters through the formation of bridged 1,2,4,5-tetraoxanes. Georg Thieme Verlag Stuttgart · New York.
- Terentev, Alexander O.,Borisov, Dmitry A.,Yaremenko, Ivan A.,Ogibin, Yuri N.,Nikishin, Gennady I.
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experimental part
p. 1145 - 1149
(2010/06/14)
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- METHOD OF PRODUCING A CARBOXYLIC ALKYL ESTER
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The present invention relates to a novel process for preparing alkyl polycarboxylates from an aqueous solution of an ammonium salt of the polycarboxylic acid by reactive distillation, and to a process for hydrogenating the alkyl carboxylates prepared in this way.
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Page/Page column 8-9
(2009/06/27)
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- Heteropolyanion-based ionic liquids: Reaction-induced self-separation catalysts for esterification
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(Figure Presented) It comes out in the wash: In the esterification of citric acid with n-butanol, heteropolyanion-based ionic liquid (IL) catalysts show high catalytic activity, self-separation, and easy reuse. The good solubility in reactants, nonmiscibility with ester product, and high melting point of the IL catalysts enable the reaction-induced switching from homogeneous (b in the picture) to heterogeneous (c) with subsequent precipitation of the catalyst (d).
- Leng, Yan,Wang, Jun,Zhu, Dunru,Ren, Xiaoqian,Ge, Hanqing,Shen, Lei
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experimental part
p. 168 - 171
(2009/04/18)
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- SELECTIVE MONOETHERIFICATION AND MONOESTERIFICATION OF DIOLS AND DIACIDS UNDER PHASE-TRANSFER CONDITIONS
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Research on the selectivity of etherification reactions of diols and esterification reactions of diacids by alkyl halides under phase-transfer catalysis has shown that under such conditions, selectivity of monoetherification increases in the order prim sec tert diols, though overall yield of monoether decreases from sec to tert diols.Monoesterification of diacids was accomplished with a high degree of selectivity.Optimal extraction of diols and diacids was found to correspond in general to chain lengths of around 5 carbons.This could mean that the complex formed between the catalyst and the anion to react is stabilized for certain carbon lengths by inner solvation in virtue of its spatial conformation.
- Zerda, Jaime de la,Barak, Gabriela,Sasson, Yoel
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p. 1533 - 1536
(2007/10/02)
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- Preparation of succinic acid diesters
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A process for the preparation of succinic acid diesters by carbonylation of acrylic acid esters in the presence of alcohols, using a cobalt carbonyl complex as the catalyst and a heterocyclic nitrogen base as the promoter, at 80°-200° C. and under a carbon monoxide pressure of 60-300 bar, wherein the reaction is carried out in the presence of not less than 20% by weight, based on the amount of all the liquid constituents of the reaction mixture, of an inert liquid and the concentration of the acrylic acid ester is kept, for the predominant part of the reaction time, at below 15% by weight, again based on the amount of all liquid constituents.
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- A Mild, Simple, and Convenient Synthesis of Diesters from Malonyl or Succinyl Dichloride and Alcohols Catalyzed by Potassium Tetracarbonylhydridoferrate, KHFe(CO)4, as a New Catalyst
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A large variety of alcohols react with acyl halides of dicarboxylic acids such as malonyl dichloride and succinyl dichloride in the presence of a catalytic amount of tetracarbonylhydridoferrate at room temperature under carbon monoxide or nitrogen to give the corresponding diesters in good yields.
- Shim, Sang Chul,Huh, Keun Tae,Park, Woo Hyun
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- Process for preparing diesters of dicarboxylic acids
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A process for preparing a diester of a dicarboxylic acid having two more carbon atoms than the unsaturated hydrocarbon used as a starting material, which comprises subjecting an unsaturated hydrocarbon, carbon monoxide and an alcohol to reaction in the presence of a platinum group metal in combination with one or more compounds selected from the group consisting of nitric acid, a nitrogen oxide and an ester of nitrous acid.
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