- Oxidation of cycloalkanones with hydrogen peroxide: an alternative route to the Baeyer-Villiger reaction. Synthesis of dicarboxylic acid esters
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The acid-catalyzed oxidation of cycloalkanones C5-C8 and C12 with hydrogen peroxide in alcohols was performed, and dicarboxylic acid esters were obtained as the major products in 53-70% yields. In the first step, geminal bishydroperoxides are generated from five-to-seven-membered cyclic ketones. The Baeyer-Villiger reaction is a side process accompanied by the formation of ω-hydroxycarboxylic acid esters.
- Terent'ev, Alexander O.,Platonov, Maxim M.,Kashin, Alexey S.,Nikishin, Gennady I.
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- The synthesis of di-carboxylate esters using continuous flow vortex fluidics
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A vortex fluidic device (VFD) is effective in mediating the synthesis of di-esters at room temperature. Processing under ambient conditions allows for a simple and efficient synthesis, whilst operating under continuous flow addresses scalability. The rotational speed of the sample tube and the flow rate were critical variables during reaction optimization, and this relates to the behaviour of the fluid flow at a molecular level. Whilst at specific rotational speeds the tube imparts a vibrational response into the fluid flow, the flow rate dictates residence time and the ability to maintain high levels of shear stress. The combination of mechanically induced vibrations, rapid micromixing, high levels of shear stress and water evaporation results in yields up to 90% for 3.25 minutes or less residence time. These results are key for devising greener and more efficient processes both mediated by the VFD and other continuous flow platforms.
- Britton, Joshua,Dalziel, Stuart B.,Raston, Colin L.
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- Synergism of microwaves and immobilized enzyme catalysis in synthesis of adipic acid esters in nonaqueous media
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Low-energy microwave irradiation leads to enhancement by a factor of up to 2.63 in comparison with conventional heating in immobilized lipase-catalyzed esterification of adipic acid with various alcohols and this effect is due to the greater frequency of collision, without any change in activation energy of the two modes of heating. Copyright Taylor & Francis, Inc.
- Yadav, Ganapati D.,Lathi, Piyush S.
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- Assisted Tandem Catalytic Conversion of Acrylates into Adipic Esters
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A ruthenium-catalyzed tail-to-tail dimerization of acrylates followed by hydrogenation results in the synthesis of adipic esters in one pot. An imine-ligated ruthenium complex that has good catalytic reactivity for tail-to-tail dimerization of methyl acrylate can be readily converted to a hydrogenation catalyst resulting in the assisted tandem catalytic conversion of methyl acrylate to methyl adipate.
- Maity, Pradip K.,Tunge, Jon A.
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- Zirconia-supported rhenium oxide as an efficient catalyst for the synthesis of biomass-based adipic acid ester
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Synthesis of adipic acid, a key monomer of nylon-66 and polyurethane, from biomass is highly attractive for establishing green and sustainable chemical processes. Here, we report that zirconia-supported rhenium oxide (ReOx/ZrO2) efficiently catalyses the deoxydehydration of cellulose-derived d-glucaric acid, offering adipic acid ester with a yield of 82% by combining with a Pd/C catalyst in subsequent reactions.
- Lin, Jinchi,Song, Haiyan,Shen, Xiaoru,Wang, Binju,Xie, Shunji,Deng, Weiping,Wu, Deyin,Zhang, Qinghong,Wang, Ye
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- Synthesis of carboxylic acid esters in the presence of micro- and mesoporous aluminosilicates
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The catalytic properties of zeolites HY, HBeta, and HZSM-12 and of mesoporous amorphous aluminosilicate in liquid-phase esterification of aliphatic (monobasic C1-C18, dibasic C6, C10) and aromatic (benzoic, trimellitic, phthalic) carboxylic acids with butanol were studied. Zeolite HBeta appeared to be the most active catalyst. Procedures were developed for preparing esters in the presence of zeolitic catalyst HBeta, ensuring 100% selectivity of ester formation at 90-98% conversion of the acid.
- Grigor'Eva,Suleimanova,Agliullin,Kutepov
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- Approaches for scale-up of microwave-promoted reactions
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In this report, we look at a range of classes of reaction involving microwave heating and show how different processing techniques can be used to address scale-up needs. We look at both batch and continuous-flow processing. We have shown that when using batch methodologies working using an open reaction vessel offers operational advantages while still giving good yields of desired products. In cases where open-vessel conditions are not amenable or where particularly volatile or toxic reagents are used, parallel sealed vessels can offer an alternative approach. For continuous-flow processing, homogeneity of the reaction mixture is key. When the mixture is homogeneous, it is possible to move from small-scale sealed-vessel conditions to the continuous-flow apparatus without any modification of reaction conditions or loss in product yield. When either the starting materials or the product mixture contains particulate matter, continuous processing can prove a challenge, but reoptimization of reaction conditions as well as reduction of the concentration may allow these difficulties to be overcome.
- Bowman, Matthew D.,Holcomb, Jennifer L.,Kormos, Chad M.,Leadbeater, Nicholas E.,Williams, Victoria A.
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- Ionic liquid-mediated deoxydehydration reactions: Green synthetic process for bio-based adipic acid
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A novel recyclable Re-catalyzed deoxydehydration (DODH) reaction was developed with an ionic liquid (IL) as a reaction medium for an efficient synthesis of adipic acid (1), one of the commercially important dicarboxylic acids, from biomass galactaric acid. The carefully designed solubility of ILs allowed a homogeneous DODH reaction to produce muconate 3 in excellent yields, a key intermediate for 1. Use of the IL also enabled an efficient separation of the DODH product 3 from the reaction mixture by simple decantation. The recovered IL layer containing the expensive Re catalyst was reused up to four times, yielding 3 without much decrease in yields. The target compound 1 was also produced in an excellent yield with the catalytic hydrogenation of 3 followed by the acidic hydrolysis. Thus, the overall process for bio-based adipic acid would become much more cost-effective, eco-friendly, and industrially viable, which could be applied to various biomass conversions.
- Shin, Nara,Kwon, Sohyun,Moon, Sojeong,Hong, Chae Hwan,Kim, Young Gyu
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- Convenient selective monoesterification of α, ω-dicarboxylic acids catalyzed by ion-exchange resins
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Symmetric dicarboxylic acids, ranging from pentanedioic acid to tetradecanedioic acid, gave selectively the corresponding monoesters in high yields in the transesterification catalyzed by strongly acidic ion-exchange resins in ester/octane mixtures.
- Saitoh, Masahiko,Fujisaki, Shizuo,Ishii, Yasuhiro,Nishiguchi, Takeshi
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- Synthesis of esters of dioxane alcohols and their performance as plasticizers for polyvinyl chloride compounds
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A procedure was developed for preparing a plasticizer for polyvinyl chloride compounds from the fraction of dioxane alcohols. The main physicochemical properties of the new plasticizer were determined. Items prepared from formulations containing the new plasticizer were fabricated and tested in laboratory.
- Glazko,Gur'yanova,Levanova,Kozlova,Neiman
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- 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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- Method for catalyzing esterification reaction of low-carbon alcohol by using ionic liquid
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The invention discloses a method for catalyzing low-carbon alcohol esterification reaction by ionic liquid, which comprises the following steps: mixing dianhydride or diacid, fatty alcohol and ionic liquid, heating to 100-160 DEG C by microwave, and reacting for 0.5-2 hours to obtain diester; wherein the ionic liquid is [Ps2TMEDA] [HSO4] 2 and/or [Ps2BPy] [HSO4] 2, the molar ratio of the ionic liquid to the dianhydride or diacid is 0.005-0.04, and the molar ratio of the dianhydride or diacid to the fatty alcohol is 1-5. The method is simple in process, mild in condition, convenient to operate, environment-friendly, high in double esterification degree, high in ionic liquid activity and easy to separate.
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Paragraph 0041-0048
(2021/07/24)
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- Method for preparing diacid diester compound under catalysis of deep eutectic solvent
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The invention belongs to the technical field of organic synthesis, and discloses a method for preparing a diacid diester compound through catalysis of a deep eutectic solvent, wherein the deep eutectic solvent takes ammonium salt and ferric salt as hydrogen acceptors, takes p-toluenesulfonic acid as a hydrogen donor, takes diacid or anhydride of the diacid and an alcohol compound as raw materials, and adopts a one-pot method to prepare the diacid diester compound; and under the catalysis of the deep eutectic solvent, the esterification reaction is performed to generate the diester product. The selected deep eutectic solvent has characteristics of environmental protection, easy preparation, cheap components and easy recovery; the preparation method has characteristics of simple operation, simple separation, no water-carrying agent, repeated use of the deep eutectic solvent, and high diester yield.
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Paragraph 0063-0066
(2021/05/19)
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- Ruthenium-catalysed oxidative coupling of vinyl derivatives and application in tandem hydrogenation
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The first ruthenium-catalyzed oxidative homo- and cross-coupling of exclusive vinyl derivatives giving highly valued 1,3-diene building blocks is reported. The catalytic system is based on readily available reagents and it mainly delivers the E,E isomer. This methodology also enables the synthesis of adipic acid ester derivatives in a one-pot fashion after in situ ruthenium-catalyzed hydrogenation.
- Abuhafez, Naba,Bruneau, Christian,Gramage-Doria, Rafael,Kamaraj, Raghu,Ruffin, Hervé
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p. 5772 - 5776
(2021/09/10)
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- Diphosphine compound, catalyst system containing diphosphine compound and application of diphosphine compound
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The present invention provides a diphosphine compound, a catalyst system containing the same, and applications of the diphosphine compound, the diphosphine compound has a structure represented by a formula I or a formula II, a phosphorus atom and a benzene ring are connected through methylene, and a nitrogen-containing heteroaryl structure is matched, such that carbon monoxide can be easily activated after phosphorus and a metal are coordinated, and an alkoxy carbonylation reaction is facilitated. The catalyst system comprises a bimetallic catalyst and the diphosphine compound, and when the catalyst system is used for catalyzing conjugated olefin to prepare 1, 6-dicarboxylic ester compounds, the conversion rate of raw materials can be effectively improved, and the yield and regioselectivity of products are improved.
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Paragraph 0108-0109; 0121-0122
(2021/03/13)
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- Efficient Palladium-Catalyzed Carbonylation of 1,3-Dienes: Selective Synthesis of Adipates and Other Aliphatic Diesters
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The dicarbonylation of 1,3-butadiene to adipic acid derivatives offers the potential for a more cost-efficient and environmentally benign industrial process. However, the complex reaction network of regioisomeric carbonylation and isomerization pathways, make a selective and direct transformation particularly difficult. Here, we report surprising solvent effects on this palladium-catalysed process in the presence of 1,2-bis-di-tert-butylphosphin-oxylene (dtbpx) ligands, which allow adipate diester formation from 1,3-butadiene, carbon monoxide, and methanol with 97 % selectivity and 100 % atom-economy under scalable conditions. Under optimal conditions a variety of di- and triesters from 1,2- and 1,3-dienes can be obtained in good to excellent yields.
- Yang, Ji,Liu, Jiawang,Ge, Yao,Huang, Weiheng,Ferretti, Francesco,Neumann, Helfried,Jiao, Haijun,Franke, Robert,Jackstell, Ralf,Beller, Matthias
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supporting information
p. 9527 - 9533
(2021/03/08)
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- Preparation method for catalytic synthesis of adipic acid dialkyl ester by heteropolyacid
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The invention relates to a preparation method for catalytic synthesis of adipic acid dialkyl ester by heteropolyacid. The method specifically comprises the following steps: 1) mixing adipic acid, alcohol and heteropolyacid, uniformly stirring, and carrying out esterification reaction; and 2) after the esterification reaction is finished, standing and filtering to remove heteropoly acid, adding a sodium carbonate aqueous solution to obtain an organic phase and a water phase, taking the organic phase, concentrating and drying to obtain the product adipic acid dialkyl ester. Compared with the prior art, the raw materials are easy to obtain, the preparation method is simple, the preparation method is economical and environmentally friendly, and the adopted catalyst has the advantages of beinghigh in reaction activity, easy to recycle and the like.
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Paragraph 0032-0033
(2021/01/15)
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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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- Preparation method of dicarboxylic acid di-alcohol ester
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The invention relates to a preparation method of a dicarboxylic acid di-alcohol ester. The method comprises the following steps: carrying out a contact reaction of an aliphatic dicarboxylic acid and amonohydric alcohol in the presence of a catalyst, and simultaneously removing water formed by the reaction; and the catalyst is a bulk catalyst containing silicon, tin and oxygen and containing the Sn-O-Si bond. The method has high conversion rate and selectivity, less circulating materials and relatively strong atomic economy.
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Paragraph 0133-0148
(2019/08/30)
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- Direct synthesis of adipic acid esters via palladium-catalyzed carbonylation of 1,3-dienes
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The direct carbonylation of 1,3-butadiene offers the potential for a more cost-efficient and environmentally benign route to industrially important adipic acid derivatives. However, owing to the complex reaction network of regioisomeric carbonylation and isomerization pathways, a selective practical catalyst for this process has thus far proven elusive. Here, we report the design of a pyridyl-substituted bidentate phosphine ligand (HeMaRaphos) that, upon coordination to palladium, catalyzes adipate diester formation from 1,3-butadiene, carbon monoxide, and butanol with 97% selectivity and 100% atom-economy under industrially viable and scalable conditions (turnover number > 60,000). This catalyst system also affords access to a variety of other di- and triesters from 1,2- and 1,3-dienes.
- Yang, Ji,Liu, Jiawang,Neumann, Helfried,Franke, Robert,Jackstell, Ralf,Beller, Matthias
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p. 1514 - 1517
(2020/01/08)
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- Method for preparing di-n-butyl adipate
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The invention relates to a method for preparing di-n-butyl adipate, and the method comprises the following steps: (1), esterification, to be more specific, pouring adipic acid, n-butyl alcohol and concentrated sulfuric acid into a reaction kettle, mixing, slightly vacuumzing, heating to boil for reaction, and keeping in the boiling reflux state for separation of water; (2) water washing, to be more specific, adding water into a mixture after the esterification, mixing evenly, standing for layering, and removing a water layer; (3) dealcoholizing, to be more specific, dealcoholizing the mixture after the water washing to obtain crude di-n-butyl adipate; (4) purification and (5) filtration. The method is convenient to operate, is simple and practical, facilitates realization of industrial production, and improves production efficiency.
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Paragraph 0027; 0029; 0030; 0031; 0032; 0033; 0034-0038
(2017/05/13)
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- Preparation method for refining dibutyl adipate
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The invention relates to a preparation method for refining dibutyl adipate. The preparation method comprises the following steps: (1) an esterification reaction step; (2) a washing step; (3) a dealcoholization step; (4) a refining step: adding a refining agent into a crude product obtained after dealcoholization and carrying out stirring and refining for one hour, wherein the refining agent is prepared by mixing calcium hydrate, magnesium hydroxide, active carbon and magnesium sulfate according to a weight ratio of 1: 1: 2: 1.5; and (5) a filtering step: filtering a refined mixed solution so as to obtain a dibutyl adipate product. In the refining step, the product obtained after treatment by the refining agent has a lighter color and can be sold without high-vacuum refining, and the quality of the prepared product completely meets requirements of technical indexes. The preparation method omits the step of high-vacuum refining, so a high-vacuum pump is not needed; thus, equipment investment is saved, production cost is lowered, and the market competitiveness of the product is improved.
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Paragraph 0027-0038
(2017/06/29)
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- PLASTICIZER COMPOSITION WHICH COMPRISES DIESTERS OF ALIPHATIC DICARBOXYLIC ACIDS AND DIALKYLESTERS OF TEREPHTHALIC ACID
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The present invention relates to a plasticizer composition which comprises at least one diester of aliphatic dicarboxylic acids and at least one dialkylester of terephthalic acid, to molding compositions which comprise a thermoplastic polymer or an elastomer and this plasticizer composition, and to the use of these plasticizer compositions and molding compositions.
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Paragraph 0178
(2016/10/08)
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- Expanding the scope of biomass-derived chemicals through tandem reactions based on oxorhenium-catalyzed deoxydehydration
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New modes of DODH: Oxorhenium compounds act as deoxydehydration(DODH)/acid dual-purpose catalysts to transform biomass-derived diol substrates into a variety of commodity chemical precursors. The power of this approach is highlighted by a tandem [1,3]-OH shift/DODH of 2-ene-1,4-diols and 2,4-diene-1,6-diols, and by a DODH/esterification sequence of sugar acids to unsaturated esters for the production of polymers and plasticizers. Copyright
- Shiramizu, Mika,Toste, F. Dean
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p. 12905 - 12909
(2014/01/06)
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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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- A facile, catalytic and environmentally benign method for esterification of carboxylic acids and transesterification of carboxylic esters with nearly equimolar amounts of alcohols
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A practical and green chemical process for the esterification of carboxylic acids with alcohols and transesterification of carboxylic esters in good to excellent yields by using K5CoW12O14· 3H2O (0.1 mol%) as catalyst is reported. The catalyst exhibited remarkable reusable activity. Georg Thieme Verlag Stuttgart.
- Bose, D. Subhas,Satyender, Apuri,Das, A. P. Rudra,Mereyala, Hari Babu
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p. 2392 - 2396
(2008/02/08)
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- Cobalt-catalyzed dimerization of alkenes
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In the presence of CoX2(PPh3)2/3 PPh 3 and zinc metal conjugated alkenes (CH2CHCOOR, CH 2CHCN, CH2CHSO2Ph and CH 2CHCONEt2) undergo reductive tail-to-tail dimerization to yield the corresponding saturated linear products. Under similar reaction conditions, vinylarenes (ArCHCH2) give stereoselective head-to-tail dimerization products, trans-1,3-diarylbut-1-ene, in good to excellent yields.
- Wang, Chun-Chih,Lin, Pao-Shun,Cheng, Chien-Hong
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p. 6203 - 6206
(2007/10/03)
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- Selective monoesterification of dicarboxylic acids catalysed by ion-exchange resins
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Symmetrical dicarboxylic acids with 4-14 carbon atoms gave selectively the corresponding monoesters in high yields in the transesterification catalysed by strongly acidic ion-exchange resins in ester-hydrocarbon mixtures. It was found that the rate of the esterification of the dicarboxylic acids is much higher than that of the monocarboxylic acids formed. This result can explain the high selectivity for the monoester formation and can also be explained by the existence of an aqueous layer on the surface of the resins. This method of selective esterification is quite simple and practical. The Royal Society of Chemistry 1999.
- Nishiguchi, Takeshi,Ishii, Yasuhiro,Fujisaki, Shizuo
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p. 3023 - 3027
(2007/10/03)
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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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