Xi:Irritant;
110-17-8Relevant articles and documents
Production of Plant Phthalate and its Hydrogenated Derivative from Bio-Based Platform Chemicals
Lu, Rui,Lu, Fang,Si, Xiaoqin,Jiang, Huifang,Huang, Qianqian,Yu, Weiqiang,Kong, Xiangtao,Xu, Jie
, p. 1621 - 1627 (2018)
Direct transformation of bio-based platform chemicals into aromatic dicarboxylic acids and their derivatives, which are widely used for the manufacture of polymers, is of significant importance for the sustainable development of the plastics industry. However, limited successful chemical processes have been reported. This study concerns a sustainable route for the production of phthalate and its hydrogenated derivative from bio-based malic acid and erythritol. The key Diels–Alder reaction is applied to build a substituted cyclohexene structure. The dehydration reaction of malic acid affords fumaric acid with 96.6 % yield, which could be used as the dienophile, and 1,3-butadiene generated in situ through erythritol deoxydehydration serves as the diene. Starting from erythritol and dibutyl fumarate, a 74.3 % yield of dibutyl trans-4-cyclohexene-1,2-dicarboxylate is obtained. The palladium-catalyzed dehydrogenation of the cycloadduct gives a 77.8 % yield of dibutyl phthalate. Dibutyl trans-cyclohexane-1,2-dicarboxylate could be formed in nearly 100 % yield under mild conditions by hydrogenation of the cycloadduct. Furthermore, fumaric acid and fumarate, with trans configurations, were found to be better dienophiles for this Diels–Alder reaction than maleic acid and maleate, with cis configuration, based on the experimental and computational results. This new route will pave the way for the production of environmental friendly plastic materials from plants.
Some aspects of the Knoevenagel-Doebner and Wittig reactions
Aparicio, F. J. Lopez,Herrera, F. J. Lopez
, p. C4 - C7 (1980)
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An efficient and practical system for the catalytic oxidation of alcohols, aldehydes, and α,β-unsaturated carboxylic acids
Grill, Joseph M.,Ogle, James W.,Miller, Stephen A.
, p. 9291 - 9296 (2006)
(Chemical Equation Presented) Upon exposure to commercial bleach (～5% aqueous sodium hypochlorite), nickel(II) chloride or nickel(II) acetate is transformed quantitatively into an insoluble nickel species, nickel oxide hydroxide. This material consists of high surface area nanoparticles (ca. 4 nm) and is a useful heterogeneous catalyst for the oxidation of many organic compounds. The oxidation of primary alcohols to carboxylic acids, secondary alcohols to ketones, aldehydes to carboxylic acids, and α,β- unsaturated carboxylic acids to epoxy acids is demonstrated using 2.5 mol % of nickel catalyst and commercial bleach as the terminal oxidant. We demonstrate the controlled and selective oxidation of several organic substrates using this system affording 70-95% isolated yields and 90-100% purity. In most cases, the oxidations can be performed without an organic solvent, making this approach attractive as a "greener" alternative to conventional oxidations.
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Butkewitsch
, p. 100,104 (1927)
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Purification and characterization of a lyase from the EDTA-degrading bacterial strain DSM 9103 that catalyzes the splitting of [S,S]-ethylenediaminedisuccinate, a structural isomer of EDTA
Witschel, Margarete,Egli, Thomas
, p. 419 - 428 (1997)
The bacterial strain DSM 9103, able to utilize EDTA as a sole source of carbon, nitrogen, and energy, is also capable to grow with [S,S]-ethylenediaminedisuccinate ([S,S]-EDDS), a structural isomer of EDTA. In cell-free extracts of [S,S]-EDDS-grown bacteria, [S,S]-EDDS degradation was observed in the absence of any cofactors. An enzyme was purified 41-fold that catalyzed the non-hydrolytic splitting of [S,S]-EDDS leading to the formation of fumarate and N-(2-aminoethyl) aspartic acid. These data strongly suggest that the enzyme belongs to the group of carbon-nitrogen lyases. The splitting reaction was reversible, and an equilibrium constant of approximately 43.0 10-1 M was determined. Out of the three stereo-isomers of EDDS, [S,S]- and [R,S]-EDDS were accepted as substrates by the lyase, whereas [R,R]-EDDS remained unchanged in assays with both cell-free extracts and pure enzyme. The enzyme catalyzed the transformation of free [S,S]-EDDS and of [S,S]-EDDS-metal complexes with stability constant lower than 10, namely of MgEDDS, CaEDDS, BaEDDS and to a small extent also of MnEDDS; Fe(III)EDDS, NiEDDS, CuEDDS, CoEDDS and ZnEDDS were not transformed.
Microflow photochemistry - A reactor comparison study using the photochemical synthesis of terebic acid as a model reaction
Aida, Shin,Terao, Kimitada,Nishiyama, Yasuhiro,Kakiuchi, Kiyomi,Oelgem?ller, Michael
, p. 5578 - 5581 (2012)
The continuous-microflow photochemical synthesis of terebic acid from maleic acid was investigated in two different microreactor set-ups. The results were subsequently compared to analogue experiments in a conventional chamber reactor. Based on conversion rates, reactor design and energy efficiency calculations, the simple microcapillary reactor showed the best overall performance.
The 3-methylaspartase reaction probed using 2H- and 15N-Isotope effects for three substrates: A flip from a concerted to a carbocationic amino-enzyme elimination mechanism upon changing the C-3 stereochemistry in the substrate from R to S
Gani, David,Archer, Catherine H.,Botting, Nigel P.,Pollard, John R.
, p. 977 - 990 (1999)
The mechanisms of the elimination of ammonia from (2S,3S)-3-methylaspartic acid, (2S)-aspartic acid and (2S,3R)-3-methylaspartic acid, catalysed by the enzyme l-threo-3-methylaspartase ammonia-lyase (EC 4.3.1.2) have been probed using 15N-isotope effects. The 15N-isotope effects for V/K for both (2S,3S)-3-methylaspartic acid and aspartic acid are 1.0246±0.0013 and 1.0390±0.0031, respectively. The natural substrate, (2S,3S)-3-methylaspartic acid, is eliminated in a concerted fashion such that the C(β)-H and C(α)-N bonds are cleaved in the same transition state. (2S)-Aspartic acid appears to follow the same mechanistic pathway, but deprotonation of the conjugate acid of the base for C-3 is kinetically important and influences the extent of 15N-fractionation. (2S,3R)-3-Methylaspartic acid is deaminated via a stepwise carbocationic mechanism. Here we elaborate on the proposed model for the mechanism of methylaspartase and propose that a change in stereochemistry of the substrate induces a change in the mechanism of ammonia elimination. Copyright (C) 1999 Elsevier Science B.V.
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Herasymenko,Tyvonuk
, p. 78 (1930)
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On chemical reactions in the laser-induced breakdown of a liquid
Margulis,Ovchinnikov,Margulis
, p. 986 - 990 (2006)
It is shown experimentally that a laser-induced breakdown of a liquid is accompanied by chemical reactions initiated by radicals and excited species formed in the spark. It is found that, in water, the laser-induced breakdown is accompanied by the dissociation of water and dissolved nitrogen molecules with the formation of HNO2 and HNO3, while, in a FeSO 4 aqueous solution, by the Fe2+ → Fe3+ oxidation reaction. It is assumed that the mechanism of the process is analogous to that of the action of ionizing radiations and the chemical action of ultrasonically induced cavitation (it is proposed that this mechanism of chemical action of a laser-induced spark proposed be termed indirect). Energy yields of these reactions are found to be of the same order of magnitude as for sonochemical redox reactions. It is shown that the laser-induced breakdown of an aqueous solution of maleic acid is accompanied by its stereoisomerization into fumaric acid, a process catalyzed by small amounts of an alkyl bromide. It is established that, for the formation of fumaric acid in a laser-induced spark, the energy yield is about five orders of magnitude higher than that typical of the above-mentioned redox reactions in the laser-induced spark. Nauka/Interperiodica 2006.
N-terminal truncation of a maleate cis-trans isomerase from Rhodococcus jostii RHA1 results in a highly active enzyme for the biocatalytic production of fumaric acid
Liu, Xiangtao,Zhao, Qing,Ren, Jie,Dong, Wenyue,Wu, Qiaqing,Zhu, Dunming
, p. 44 - 50 (2013)
As part of the project to develop an efficient biocatalytic process for the production of fumaric acid, a full-length putative maleate cis-trans isomerase gene from Rhodococcus jostii RHA1 was synthesized and expressed in Escherichia coli Rosetta2 (DE3) pLysS, but the protein was not soluble and showed no catalytic activity. Bioinformatics analysis of the protein sequence indicated that there were two hydrophilic and two hydrophobic amino acid clusters in an alternate arrangement at the N-terminus, and 50 extra amino acid residues at the N-terminus were not present in the known maleate cis-trans isomerases. The alternate hydrophilic and hydrophobic clusters at the N-terminus were thus truncated one by one to evaluate their effect on the gene expression and enzyme activity. Three mutants (MaiR-D41/42-304AA, MaiR-D48/49-304AA and MaiR-D52/53-304AA) without the hydrophilic and hydrophobic clusters were expressed as soluble protein with maleate cis-trans isomerase activity. Among them, MaiR-D48 was purified and its properties were studied. The purified enzyme had a temperature optimum of 40 C and a wide pH range (5.0-9.0) with the optimum pH being 8.0. The whole cells of E. coli expressing MaiR-D48 catalyzed the isomerization of maleic acid to fumaric acid at 1 M substrate concentration, showing its potential for industrial use.
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Ssadikow
, p. 504,508 (1923)
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Study on the Isomerization of Maleic Acid to Fumaric Acid without Catalyst
Gao, Zhuo,Chen, Wangmi,Chen, Xiaoting,Wang, Dali,Yi, Shouzhi
, p. 920 - 924 (2018)
Fumaric acid is an important food additive and industrial intermediate compound. The traditional methods of producing fumaric acid were catalyzed by maleic acid isomerization. In this study, isomerization of maleic acid in water without catalyst was inves
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Ikutani,Y.
, p. 3602 - 3603 (1970)
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Oxidation of aliphatic side chains in anthracene Diels-Alder adducts
McCormick, Frankie A.,Marquardt, Donald J.
, p. 5169 - 5172 (1994)
An efficient oxidation of methyl and primary side chains of anthracene Diels Alder adducts with KMnO4 is reported. The oxidation leaves the bridgehead methines intact providing Diels-Alder adducts of anthracenecarboxylic acids. Retro Diels-Alder reaction allows for the preparation of the parent anthracenecarboxylic acids.
Purification and characterization of fumarase from Corynebacterium glutamicum
Genda, Tomoko,Watabe, Shoji,Ozaki, Hachiro
, p. 1102 - 1109 (2006)
Fumarase (EC 4.2.1.2) from Corynebacterium glutamicum (Brevibacterium flavum) ATCC 14067 was purified to homogeneity. Its amino-terminal sequence (residues 1 to 30) corresponded to the sequence (residues 6 to 35) of the deduced product of the fumarase gene of C. glutamicum (GenBank accession no. BAB98403). The molecular mass of the native enzyme was 200 kDa. The protein was a homotetramer, with a 50-kDa subunit molecular mass. The homotetrameric and stable properties indicated that the enzyme belongs to a family of Class II fumarase. Equilibrium constants (Keq) for the enzyme reaction were determined at pH 6.0, 7.0, and 8.0, resulting in Keq = 6.4, 6.1, and 4.6 respectively in phosphate buffer and in 16, 19, and 17 in non-phosphate buffers. Among the amino acids and nucleotides tested, ATP inhibited the enzyme competitively, or in mixed-type, depending on the buffer. Substrate analogs, meso-tartrate, D-tartrate, and pyromellitate, inhibited the enzyme competitively, and D-malate in mixed-type.
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Taube, H.
, p. 526 - 531 (1943)
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Pompon Dahlia-like Cu2O/rGO Nanostructures for Visible Light Photocatalytic H2 Production and 4-Chlorophenol Degradation
Karthikeyan, Sekar,Ahmed, Kassam,Osatiashtiani, Amin,Lee, Adam F.,Wilson, Karen,Sasaki, Keiko,Coulson, Ben,Swansborough-Aston, Will,Douthwaite, Richard E.,Li, Wei
, p. 1699 - 1709 (2020)
Hierarchical Cu2O nanospheres with a Pompon Dahlia-like morphology were prepared by a one-pot synthesis employing electrostatic self-assembly. Nanocomposite analogues were also prepared in the presence of reduced graphene oxide (rGO). Photophysical properties of the hierarchical Cu2O nanospheres and Cu2O/rGO nanocomposite were determined, and their photocatalytic applications evaluated for photocatalytic 4-chlorophenol (4-CP) degradation and H2 production. Introduction of trace (2O for H2 production from 2.23 % to 3.35 %, giving an increase of evolution rate from 234 μmol.g?1.h?1 to 352 μmol.g?1.h?1 respectively. The AQE for 4-CP degradation also increases from 52 % to 59 %, with the removal efficiency reaching 95 % of 10 ppm 4-CP within 1 h. Superior performance of the hierarchical Cu2O/rGO nanocomposite is attributable to increased visible light absorption, reflected in a greater photocurrent density. Excellent catalyst photostability for >6 h continuous reaction is observed.
Characterization of the cross-linked structure of fumarate-based degradable polymer networks
Timmer, Mark D.,Jo, Seongbong,Wang, Chuanyue,Ambrose, Catherine G.,Mikos, Antonios G.
, p. 4373 - 4379 (2002)
A new method was developed to examine networks formed with linear macromers of fumaric acid and diacrylate cross-linking agents in order to analyze their cross-linked structure. This method involved the accelerated degradation of the networks and the analysis of the degradation products. Two model networks of poly(propylene fumarate) (PPF) cross-linked with poly(propylene fumarate)-diacrylate (PPF-DA) and oligo(poly(ethylene glycol) fumarate) (OPF) cross-linked with poly(ethylene glycol)-diacrylate (PEG-DA) were evaluated with this method to determine the macromer and cross-linking agent conversions, the network cross-linking density, and an estimate of the molecular weight between crosslinks. The validity of the method was confirmed by the analysis of the composition of the un-cross-linked macromers and the correlation of the mechanical properties of the cross-linked polymers with the macromer/cross-linking agent double bond ratio. The results showed that acrylate species had participated more than fumarates in network formation. Furthermore, the structure of PPF/PPF-DA networks was influenced by the amount of cross-linking agent in the polymer formulation, and the OPF/PEG-DA network structure was controlled by the number of repeating fumarate units in the macromer. This method provides a new means to characterize the macromolecular structure of fumarate-based networks.
Ionic liquids breakdown by Fenton oxidation
Munoz, Macarena,Domínguez, Carmen M.,De Pedro, Zahara M.,Quintanilla, Asunción,Casas, Jose A.,Rodriguez, Juan J.
, p. 16 - 21 (2015)
Fenton oxidation has proved to be an efficient treatment for the degradation of ionic liquids (ILs) of different families viz. imidazolium, pyridinium, ammonium and phosphonium, in water. The intensification of the process, defined as the improvement on the efficiency of H2O2 consumption, by increasing the temperature is necessary to avoid high reaction times and the need of large excess of H2O2. In this work, temperatures within the range of 70-90°C have been used, which allowed an effective breakdown of the ILs tested (1 g L-1 initial concentration) with the stoichiometric amount of H2O2 and a relatively low Fe3+dose (50 mg L-1). Under these conditions conversion of the ILs was achieved in less than 10 min, with TOC reductions higher than 60% upon 4 h reaction time, except for the phosphonium IL. The remaining TOC corresponded mainly to short-chain organic acids. The treatment reduced substantially the ecotoxicity up to final values below 0.01 TU in most cases and a significant improvement of the biodegradability was achieved. Upon Fenton oxidation of the four ILs tested hydroxylated compounds of higher molecular weight than the starting ILs, fragments of ILs partially oxidized and short-chain organic acids were identified as reaction by-products. Reaction pathways are proposed.
Dittmar
, p. 2747 (1930)
Preparation method of succinic acid
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Paragraph 0028-0076, (2021/06/22)
The invention discloses a preparation method of succinic acid. The preparation method comprises the following step: with malic acid as a raw material, carrying out one-step reaction in a hydrogen atmosphere in the presence or absence of a non-polar medium and under the action of a metal-solid acid bifunctional catalyst to obtain succinic acid. In the preparation method, the above raw materials can be derived from biomass resources, so dependence on petroleum resources is reduced. By controlling process conditions, succinic acid can be obtained with high yield. The preparation method is simple in process and mild in conditions.
Preparation method of fumaric acid
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Paragraph 0031-0095, (2021/06/22)
The invention discloses a preparation method of fumaric acid. The preparation method is characterized in that malic acid is used as a raw material, and under a solvent-free condition or in a hydrocarbon medium, malic acid is catalyzed to undergo a dehydration reaction so as to generate fumaric acid. The preparation method provided by the invention is simple in reaction process, and the key raw material malic acid can be obtained by fermenting biomass, so the preparation method is a supplement to a existing production route and relieve dependence on fossil resources; and besides, compared with a traditional fumaric acid production method, the method of the invention has the advantages that the use of high-pollution catalysts such as thiourea and oxybromide is avoided, and the method is green and safe since a dehydration reaction can be carried out under a normal-pressure condition. A catalyst used in the invention and a reaction process thereof are efficient and clean.
