693-23-2Relevant academic research and scientific papers
Direct and Selective Synthesis of Adipic and Other Dicarboxylic Acids by Palladium-Catalyzed Carbonylation of Allylic Alcohols
Beller, Matthias,Ge, Yao,Huang, Weiheng,Jackstell, Ralf,Liu, Jiawang,Neumann, Helfried,Yang, Ji
supporting information, p. 20394 - 20398 (2020/09/21)
A general and direct synthesis of dicarboxylic acids including industrially important adipic acid by palladium-catalyzed dicarbonylation of allylic alcohol is reported. Specifically, the combination of PdCl2 and a bisphosphine ligand (HeMaRaphos) promotes two different carbonylation reactions with high activity and excellent selectivity.
PROCESS FOR THE CO-PRODUCTION OF LONG CHAIN AMINO ACIDS AND DIBASIC ACIDS
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Paragraph 0058-0061, (2019/02/01)
There is disclosed a process for the co-production of long chain ω-amino acid and long chain dibasic acid, comprising: (1) reacting long chain ketoacid derivative with hydroxylamine or subjecting ketoacid derivative to an ammoximation to yield oxime derivative; (2) subjecting oxime derivative to Beckmann rearrangement to yield a mixture of mixed amide derivatives; (3) hydrolyzing the mixed amide derivatives to produce long chain ω-amino acid and long chain dibasic acid.
Process for producing long chain amino acids and dibasic acids
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Page/Page column 9, (2018/09/21)
There is disclosed a process for the production of long chain amino acid and long chain dibasic acid, comprising: (1) reacting long chain keto fatty acid with hydroxylamine or subjecting keto fatty acid to an ammoximation reaction to yield an oxime fatty acid; (2) subjecting the oxime fatty acid to the Beckmann rearrangement to yield a mixture of two amide fatty acids; (3) hydrolyzing the mixed amide fatty acids to produce long chain amino acid, long chain dibasic acid, short chain alkylamine, and alkanoic acid.
Bio-based α,ω-Functionalized Hydrocarbons from Multi-step Reaction Sequences with Bio- and Metallo-catalysts Based on the Fatty Acid Decarboxylase OleTJE
Bojarra, Samiro,Reichert, Dennis,Grote, Marius,Baraibar, álvaro Gómez,Dennig, Alexander,Nidetzky, Bernd,Mügge, Carolin,Kourist, Robert
, p. 1192 - 1201 (2018/02/13)
OleT from Jeotgalicoccus sp. ATCC 8456 catalyzes the decarboxylation of ω-functionalized fatty acids to the corresponding alkenols, which can themselves serve as starting material for the synthesis of polymers and fine chemicals. To show the versatility of possible reactions, a series of in vitro reaction cascades was developed where an alkenol produced by the decarboxylation of ω-hydroxy fatty acids can be further converted into alkenylamines and diols. By coupling OleT with an alcohol dehydrogenase or alcohol oxidase as well as an amino-transaminase, an oxidative decarboxylation followed by the oxidation of the terminal alcohol and a subsequent reductive transamination could be carried out. By using different cofactors or electron sources, the reactions could be performed sequentially or simultaneously. The combination of enzymatic decarboxylation with a ruthenium catalyst in a chemo-enzymatic cascade provides a novel way to synthesize long-chain diols.
Fatty Acid Chain Shortening by a Fungal Peroxygenase
Olmedo, Andrés,Río, José C. del,Kiebist, Jan,Ullrich, René,Hofrichter, Martin,Scheibner, Katrin,Martínez, Angel T.,Gutiérrez, Ana
supporting information, p. 16985 - 16989 (2017/11/27)
A recently discovered peroxygenase from the fungus Marasmius rotula (MroUPO) is able to catalyze the progressive one-carbon shortening of medium and long-chain mono- and dicarboxylic acids by itself alone, in the presence of H2O2. The mechanism, analyzed using H218O2, starts with an α-oxidation catalyzed by MroUPO generating an α-hydroxy acid, which is further oxidized by the enzyme to a reactive α-keto intermediate whose decarboxylation yields the one-carbon shorter fatty acid. Compared with the previously characterized peroxygenase of Agrocybe aegerita, a wider heme access channel, enabling fatty acid positioning with the carboxylic end near the heme cofactor (as seen in one of the crystal structures available) could be at the origin of the unique ability of MroUPO shortening carboxylic acid chains.
Method for synthesizing muscone by utilizing beta-monomethyl methylglutarate
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Paragraph 0023; 0024, (2017/12/05)
The invention discloses a method for synthesizing muscone by utilizing beta-monomethyl methylglutarate. According to the method, beta-monomethyl methylglutarate and alpha,omega-dodecanedioic acid monomethyl ester respectively prepared through a heteropoly acid catalytic transesterification method are used as raw materials, and Kolbe electrolysis, acyloin condensation and reduction reaction are performed to prepare the muscone. The method of the present invention has advantages of high raw material utilization rate, mold condition, easy control and environmental protection, and is suitable for industrial production .
Preparation of 1,12-twelve carbon b acid method
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Paragraph 0032; 0033, (2017/03/08)
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of 1, 12-lauryl binary acid. Under light irradiation light irradiation, cyclohexanone and a aqueous hydrogen peroxide solution carry out a photochemical reaction under the condition of zero organic solvents and zero catalysts so as to obtain the 1, 12-lauryl binary acid, an irradiation light source is ultraviolet light, visible light or the mixing light of the ultraviolet light and the visible light of 100-800nm. The preparation method of the 1, 12-lauryl binary acid has the advantages that the process is simple, organic solvents are not used, no metal ions are remained, the production efficiency is high, less three wastes are generated, and the cost is low.
Single-step access to long-chain α,ω-dicarboxylic acids by isomerizing hydroxycarbonylation of unsaturated fatty acids
Goldbach, Verena,Falivene, Laura,Caporaso, Lucia,Cavallo, Luigi,Mecking, Stefan
, p. 8229 - 8238 (2017/09/26)
Dicarboxylic acids are compounds of high value, but to date long-chain α,ω-dicarboxylic acids have been difficult to access in a direct way. Unsaturated fatty acids are ideal starting materials with their molecular structure of long methylene sequences and a carboxylate functionality, in addition to a double bond that offers itself for functionaliza-tion. Within this paper, we established a direct access to α,ω-dicarboxylic acids by combining isomerization and selective terminal carbonylation of the internal double bond with water as a nucleophile on unsaturated fatty acids. We identified the key elements of this reaction: a homogeneous reaction mixture ensuring sufficient contact between all reactants and a catalyst system allowing for activation of the Pd precursor under aqueous conditions. Experiments under pressure reactor conditions with [(dtbpx)Pd(OTf)2] as catalyst precursor revealed the importance of nucleophile and reactant concentrations and the addition of the diprotonated diphosphine ligand (dtbpxH2)(OTf)2 to achieve turnover numbers >120. A variety of unsaturated fatty acids, including a triglyceride, were converted to valuable long-chain dicarboxylic acids with high turnover numbers and selectivities for the linear product of >90%. We unraveled the activation pathway of the PdII precursor, which proceeds via a reductive elimination step forming a Pd0 species and oxidative addition of the diprotonated diphosphine ligand, resulting in the formation of the catalytically active Pd hydride species. Theoretical calculations identified the hydrolysis as the rate-determining step. A low nucleophile concentration in the reaction mixture in combination with this high energetic barrier limits the potential of this reaction. In conclusion, water can be utilized as a nucleophile in isomerizing functionalization reactions and gives access to long-chain dicarboxylic acids from a variety of unsaturated substrates. The activity of the catalytic system of hydroxycarbonylation ranks as one of the highest achieved for isomerizing functionalizations in combination with a high selectivity for the linear product.
ENHANCED DIACID PRODUCTION WITH GENETICALLY MODIFIED MICRO-ORGANISMS
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Page/Page column 28, (2016/12/12)
The present invention relates to a field of diacids, and more precisely to a method of producing diacids. The invention further relates to recombinant microorganisms comprising omega-oxidation and increased diacid production, and uses and methods related thereto.
TRANSFORMATION OF PEROXYACETAL INTERMEDIATE
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, (2015/06/03)
A method for transforming a compound of formula IIa: to a compound of formula III: 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.
