- Carboxyl Methyltransferase Catalysed Formation of Mono- and Dimethyl Esters under Aqueous Conditions: Application in Cascade Biocatalysis
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Carboxyl methyltransferase (CMT) enzymes catalyse the biomethylation of carboxylic acids under aqueous conditions and have potential for use in synthetic enzyme cascades. Herein we report that the enzyme FtpM from Aspergillus fumigatus can methylate a broad range of aromatic mono- and dicarboxylic acids in good to excellent conversions. The enzyme shows high regioselectivity on its natural substrate fumaryl-l-tyrosine, trans, trans-muconic acid and a number of the dicarboxylic acids tested. Dicarboxylic acids are generally better substrates than monocarboxylic acids, although some substituents are able to compensate for the absence of a second acid group. For dicarboxylic acids, the second methylation shows strong pH dependency with an optimum at pH 5.5–6. Potential for application in industrial biotechnology was demonstrated in a cascade for the production of a bioplastics precursor (FDME) from bioderived 5-hydroxymethylfurfural (HMF).
- Ashbrook, Chloe,Carnell, Andrew J.,Goulding, Ellie,Hatton, Harry,Johnson, James R.,Kershaw, Neil M.,McCue, Hannah V.,Rigden, Daniel J.,Ward, Lucy C.
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supporting information
(2022/02/21)
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- EFFICIENT PROCESS FOR PRODUCING 5-(ALKOXYCARBONYL)-FURAN-2-CARBOXYLIC ACIDS
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A process for preparing 5-(alkoxycarbonyl)furan-2-carboxylic acids (ACFC) by oxidizing various furcates in the presence of a catalyst containing cobalt, manganese, and bromine, and a solvent while simultaneously removing water vapor from the reaction chamber. The process can produce ACFC with high purity and low color, and in high yield.
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Paragraph 0140-0141
(2021/03/13)
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- PROCESS FOR PRODUCING 2,5-FURANDICARBOXYLIC ACID FROM ETHERS OF 5-HYDROXYMETHYLFURFURAL
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Process for producing a carboxylic acid composition comprising 2,5-furandicarboxylic acid, comprising the steps: a) oxidizing an oxidizable compound comprising 5-alkoxymethylfurfural in an oxidation reactor in the presence of a saturated organic acid solvent having from 2 to 6 carbon atoms and a catalyst system comprising cobalt, manganese and bromine using an oxidizing gas at a temperature in the range of 160 to 210 °C to obtain a crude carboxylic acid composition comprising mono alkyl ester of 2,5-furandicarboxylic acid and solid 2,5- furandicarboxylic acid, b) isolating at least a portion of the solid 2,5-furandicarboxylic acid from the crude carboxylic acid composition in a solid-liquid separation zone to generate a solid cake and a mother liquor, c) determining the amount of manganese and/or cobalt in the cake, and d) increasing the amount of one or more controlling acids in the oxidation reactor, if the determined amount of manganese and/or cobalt in the cake exceeds a predefined threshold value, wherein the one or more controlling acids are selected from the group consisting of hydrobromic acid and mono- or dicarboxylic acids having from 2 to 5 carbon atoms and a pKa of less than 3.2, wherein the mother liquor comprises mono alkyl ester of 2,5-furandicarboxylic acid in the range of 0.5 to 7 % by weight with respect to the weight of the mother liquor.
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Page/Page column 19; 20
(2021/06/26)
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- Scalable synthesis of hydroxymethyl alkylfuranoates as stable 2,5-furandicarboxylic acid precursors
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Hydroxymethyl furanoic acid and its derivatives have been synthesized in high yields and purity from gluconolactone. The reaction sequence allows the recovery of reagents and the use of bio-friendly chemicals and solvents, and can easily be scaled up. The reaction product on a >100 gram scale can be purified by a single purification method, such as distillation or precipitation. The overall yield is above 50%.
- Jurys, Arminas,Pedersen, Christian Marcus,Pedersen, Martin J?ger
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supporting information
p. 2399 - 2402
(2020/05/13)
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- NOVEL ESTERIFICATION CATALYST AND USES THEREOF
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Tin (II) glucarate is found to be effective alone and in combination with other tin compounds for catalyzing the reaction of carboxylic acids such as furan-2,5-dicarboxylic acid, terephthalic acid and adipic acid with alcohols such as the C1-C3 alcohols.
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Page/Page column 0026; 0030-0031
(2020/07/07)
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- OXIDATION PROCESS TO PRODUCE 5-(ALKOXYCARBONYL)FURAN-2-CARBOXYLIC ACIDS (ACFC)
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Disclosed herein is a very efficient method to make 5-(alkoxycarbonyl)furan-2-carboxylic acids (ACFC) from feedstocks comprised of furoates. When a feedstock comprised of methyl 5-methylfuran-2-carboxylate (MMFC) is used a product comprised of (5-(methoxycarbonyl)furan-2-carboxylic acid (MCFC) is obtained in high yield.
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Paragraph 0072
(2020/01/12)
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- OXIDATION PROCESS TO PRODUCE 5-(ALKOXYCARBONYL)FURAN-2-CARBOXYLIC ACIDS (ACFC)
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Disclosed herein is a very efficient method to make 5-(alkoxycarbonyl)furan-2-carboxylic acids (ACFC) from feedstocks comprised of furoates. When a feedstock comprised of methyl 5-methylfuran-2-carboxylate (MMFC) is used a product comprised of (5-(methoxycarbonyl)furan-2-carboxylic acid (MCFC) is obtained in high yield.
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Paragraph 0089
(2020/01/12)
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- Aerobic Oxidation and Oxidative Esterification of 5-Hydroxymethylfurfural by Gold Nanoparticles Supported on Nanoporous Polymer Host Matrix
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The aerobic oxidation and oxidative esterification of 5-hydroxymethylfurfural (HMF) catalyzed by gold nanoparticles (AuNPs) supported on a semicrystalline nanoporous multiblock copolymer matrix consisting of syndiotactic poly(styrene)-cis-1,4-poly(butadiene) (sPSB) have been investigated. Depending on the reaction parameters (support nanoporosity, presence of water, solvent, temperature, cocatalyst, oxygen pressure), the conversion of HMF can be finely addressed to the formation of the desired oxidation product, such as 2,5-diformylfuran (DFF), 5-formylfuran-2-carboxylic acid (FFCA), methyl 5-(hydroxymethyl)furan-2-carboxylate (MHMFC), dimethyl furan-2,5-dicarboxylate (DMFC), and furan-2,5-dicarboxylic acid (FDCA), under optimized reaction conditions. The AuNP–sPSB catalyst is highly effective and selective because the polymer support acts as a conveyor and concentrator of the reactants toward the catalytic sites.
- Buonerba, Antonio,Impemba, Salvatore,Litta, Antonella Dentoni,Capacchione, Carmine,Milione, Stefano,Grassi, Alfonso
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p. 3139 - 3149
(2018/09/14)
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- ORGANOTIN CATALYSTS IN ESTERIFICATION PROCESSES OF FURAN-2,5-DICARBOXYLIC ACID (FDCA)
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A method for preparing sugar-based mono and diesters is described. The process entails the esterification of 2,5-furan-dicarboxylic acid (FDCA) with an alcohol in the presence of low loadings of a homogeneous organotin (IV) catalyst.
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Paragraph 0026; 0027; 0028; 0029; 0030; 0031; 0032-0054
(2018/06/06)
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- PROCESS FOR PRODUCING 2,5-FURANDICARBOXYLIC ACID DIALKYL ESTER
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Disclosed herein are processes for producing 2,5-furandicarboxylic acid dialkyl ester. In one embodiment, the process comprises a) contacting 2,5-furan dicarboxylic acid, excess alcohol, and optionally, a catalyst in a reactor at a temperature in the range of from 50°C to 325°C and a pressure in the range of between 1 bar to 140 bar to form a liquid phase composition comprising an ester of 2,5-furan dicarboxylic acid, the alcohol and water; b) lowering the temperature of the liquid phase composition to form a crude crystallized ester of 2,5-furan dicarboxylic acid; c) separating the product of step b) to form a solids phase comprising a purified ester of 2,5-furan dicarboxylic acid and a mother liquor comprising alcohol and water; and d) removing at least a portion of the water from the mother liquor. In one embodiment, the 2,5-furan dicarboxylic acid is contacted with an alcohol source and optionally, a catalyst.
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Page/Page column 26; 27
(2017/02/24)
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- REACTIVE DISTILLATION PROCESS FOR THE ESTERIFICATION OF FURANDICARBOXYLIC ACID
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Disclosed are processes for producing the dialkyl ester of 2,5-furan dicarboxylic acid by contacting a feed containing 2,5-furan dicarboxylic acid and a high boiling solvent with an alcohol in the presence of a solid acid catalyst using reactive distillation.
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Page/Page column 27
(2017/02/24)
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- OLIGOMERS OF FDCA AND GLYCOLS FROM A ONE-POT ESTERIFICATION-TRANSESTERIFICATION PROCESS USING WATER-TOLERANT METAL TRIFLATE CATALYST
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A method for preparing sugar-based oligomers is described. The process involves sequential (one-pot) esterification of 2,5-furan-dicarboxylic acid (FDCA) with an alcohol and transesterification with a glycol, as catalyzed by relatively low amounts of homogeneous water-tolerant Lewis acid catalysts, which can be retained in the product mixture from the esterification through transesterification.
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Paragraph 0049
(2017/09/02)
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- PROCESS FOR PURIFYING AN ACID COMPOSITION COMPRISING 2-FORMYL-FURAN-5-CARBOXYLIC ACID AND 2,5-FURANDICARBOXYLIC ACID
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An acid composition comprising 2-formyl-furan-5-carboxylic acid and 2,5-furandicarboxylic acid is purified in a process which comprises; contacting the acid composition with an alcohol to obtain an esterified composition; and separating the ester of 2-formyl-furan-5-carboxylic acid from the esterified composition to obtain a purified esterified product; and contacting the purified esterified composition with water for saponification or hydrolysis, to obtain a product composition, comprising 2,5-furandicarboxylic acid and a reduced amount of 2-formyl-furan-5-carboxylic acid.
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Page/Page column 14; 15
(2015/03/16)
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- Aerobic oxidation of hydroxymethylfurfural and furfural by using heterogeneous CoxOy-N@C catalysts
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2,5-Furandicarboxylic acid (FDCA) is considered to be a promising replacement for terephthalic acid since they share similar structures and properties. In contrast to FDCA, 2,5-furandicarboxylic acid methyl (FDCAM) has properties that allow it to be easily purified. In this work, we reported an oxidative esterification of 5-hydroxymethylfurfural (HMF) and furfural to prepare corresponding esters over CoxOy-N@C catalysts using O2 as benign oxidant. High yield and selectivity of FDCAM and methyl 2-furoate were obtained under optimized conditions. Factors which influenced the product distribution were examined thoroughly. The CoxOy-N@C catalysts were recycled five times and no significant loss of activity was detected. Characterization of the catalysts could explain such phenomena. Using XPS and TGA, we made a thorough investigation of the effects of ligand and pyrolysis temperature on catalyst activity.
- Deng, Jin,Song, Hai-Jie,Cui, Min-Shu,Du, Yi-Ping,Fu, Yao
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p. 3334 - 3340
(2015/03/03)
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- PROCESS FOR THE PREPARATION OF 2,5-FURAN-DICARBOXYLIC ACID
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2,5-Furandicarboxylic acid and methyl acetate are prepared in a continuous process, comprising -introducing a 5-methoxymethylfurfural-containing feedstock, an oxygen-containing gas, an oxidation catalyst and an acetic acid-containing solvent into a reactor; -allowing 5-methoxymethylfurfural to react with oxygen and acetic acid in the presence of the oxidation catalyst to yield 2,5-furandicarboxylic acid as main product and methyl acetate; -withdrawing 2,5-furandicarboxylic acid-containing product from the reactor and recovering 2,5-furandicarboxylic acid product; and -withdrawing a vaporous stream containing methyl acetate from the reactor.
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Page/Page column 10; 11
(2014/10/18)
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- ESTERIFICATION OF 2,5-FURAN-DICARBOXYLIC ACID
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A method of making a furan dicarboxylate by means of reacting 2,5-furan dicarboxylic acid (FDCA) with an alcohol or mixture of alcohols in a CO2-predominant atmosphere without the presence of any other acid catalyst is described. The reaction is conducted under conditions that correspond to either supercritical, critical or near-critical temperatures and pressures for the alcohol species and/or CO2 gas.
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Page/Page column 11
(2014/07/08)
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- METHOD FOR THE PREPARATION OF 2,5-FURANDICARBOXYLIC ACID AND ESTERS THEREOF
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The application describes a method for the preparation of 2,5-furandicarboxylic acid ("FDCA") and/or an alkyl ester of FDCA comprising the step of contacting a feed comprising a starting material selected from 5-alkoxymethylfurfural, 2,5-di(alkoxymethyl)furan and a mixture thereof with an oxidant in the presence of an oxidation catalyst. The feed may also comprise 5-hydroxymethylfurfural as a further starting material.
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Page/Page column 6; 7; 11
(2011/04/26)
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