141-03-7Relevant articles and documents
Biomass-derived dibasic acids to diesters with inorganic ligand-supported catalyst: synthesis, optimization, characterization
Chen, Zhe,Han, Sheng,Lu, Deli,Xu, Yumeng
, (2021/08/23)
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.
Biobased compositions
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Page/Page column 14-15, (2021/08/05)
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.
Reduction of Activated Alkenes by PIII/PV Redox Cycling Catalysis
Longwitz, Lars,Werner, Thomas
supporting information, p. 2760 - 2763 (2020/02/05)
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.
Synthesis of Esters from Stable and Convenient Sulfoxonium Precursors under Catalyst- And Additive-Free Conditions
Wu, Xiao-Feng,Yuan, Yang
, p. 1820 - 1824 (2019/09/09)
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.
Method for preparing succinate by double carbonylation of acetylene
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Paragraph 0027-0038, (2019/12/02)
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.
Exceptionally active and reusable nanobiocatalyst comprising lipase non-covalently immobilized on multi-wall carbon nanotubes for the synthesis of diester plasticizers
Szelwicka, Anna,Boncel, S?awomir,Jurczyk, Sebastian,Chrobok, Anna
, p. 41 - 47 (2019/02/07)
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.
Method for preparing 1,4-butanediol and/or sec-butyl alcohol
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Paragraph 0038-0066, (2018/03/24)
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.
A novel hydrogen-bonded silica-supported acidic ionic liquid: An efficient, recyclable and selective heterogeneous catalyst for the synthesis of diesters
Fareghi-Alamdari, Reza,Niri, Mehri Nadiri,Hazarkhani, Hassan
, (2018/05/28)
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.
Synthesis and characterization of a new hydroxyl functionalized diacidic ionic liquid as catalyst for the preparation of diester plasticizers
Fareghi-Alamdari, Reza,Nadiri Niri, Mehri,Hazarkhani, Hassan
, p. 153 - 160 (2016/12/30)
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.
BIOFUELS PRODUCTION FROM BIO-DERIVED CARBOXYLIC-ACID ESTERS
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Paragraph 0053; 0056, (2017/04/11)
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.
