- Method for catalytically synthesizing organic carboxylic acid by strong-acidic ion exchange resin
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The invention provides a method for catalytically synthesizing organic carboxylic acid by strong-acidic ion exchange resin. The method comprises the following steps: taking olefin and carbon monoxide as raw materials, taking the organic carboxylic acid as a solvent and taking the strong-acidic ion exchange resin as a catalyst; synthesizing the organic carboxylic acid through a Koch reaction; during the reaction, adding the solvent and the catalyst in one step; keeping system pressure being 2MPa to 8MPa by the carbon monoxide; adding the olefin into liquid in a carbon monoxide pressure keeping process by adopting a constant-pressure dripping or spraying manner and adding gas by adopting a bubbling manner; keeping the temperature being at 10 DEG C to 80 DEG C, wherein the charging time is 0.2h to 2.0h; after charging is finished, keeping the material for 1.0h to 5.0h; after the reaction is finished, obtaining a target product, namely the organic carboxylic acid, through a post-treatment procedure including a hydrolysis process. According to the method provided by the invention, industrial green production is realized.
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Paragraph 0012
(2017/07/18)
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- Mild, single-pot hydrocarboxylation of linear C5-C9 alkanes into branched monocarboxylic C6-C10 acids in copper-catalyzed aqueous systems
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A single-pot method has been developed for the hydrocarboxylation of the liquid C5-C9 alkanes (n-pentane, n-hexane, n-heptane, n-octane, n-nonane and 3-methylhexane) into the branched monocarboxylic C 6-C10 acids bearing one more carbon atom. This method is characterized by a direct, selective and low-temperature (60 °C) hydrocarboxylation reaction of the alkane with carbon monoxide, water (which acts as a reagent besides being a solvent component) and potassium peroxodisulfate, in H2O/MeCN medium. The hydrocarboxylations are markedly enhanced in the presence of a tetracopper(II) triethanolaminate complex as a homogeneous catalyst precursor. Total yields (based on alkane) of carboxylic acids up to 46% (with 97-99% overall selectivity) have been achieved, which are remarkable in the field of alkane functionalization under mild conditions, especially for a C-C bond formation reaction in aqueous acid-solvent-free medium. The regio- and bond selectivity parameters have been determined and a free radical mechanism has been proposed.
- Kirillova, Marina V.,Kirillov, Alexander M.,Pombeiro, Armando J.L.
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experimental part
p. 106 - 113
(2012/04/04)
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- Syntheses of female sex pheromone precursors of pine sawfly species and of some structurally related methyl-branched long-chain 2-alkanols.
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3,7-Dimethyl-2-undecanol, 3,7,9-trimethyl-2-tridecanol, and 3,7, 11-trimethyl-2-tridecanol were synthesized as racemic mixtures in moderate yields. The alcohols are known precursors of the female sex pheromones of the pine sawfly species Diprion nipponica, Macrodiprion nemoralis, and Microdiprion pallipes, respectively. Stereoisomeric mixtures of 3,8,12-trimethyl-2-tridecanol, erythro-(2R,3R, 11R/S)-3,11-dimethyl-2-tetradecanol, 3,5-dimethyl-2-tetradecanol, and 5,7-dimethyl-2-tetradecanol, structurally related to sex pheromone alcohol precursors of pine sawfly species, were also synthesized in moderate yields. The key reaction in the syntheses was the ring opening of gamma-butyrolactones by using different alkyl lithiums as nucleophiles.
- Hedenstroem, Erik,Andersson, Fredrik
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p. 1237 - 1254
(2007/10/03)
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- Process for producing optically active carboxylic acid
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A process for producing an optically active carboxylic acid represented by formula (I): STR1 wherein R1, and R2, and R3 each represents a hydrogen atom, an alkyl group, an alkenyl group, or a phenyl or naphthyl group which may have a substituent, provided that all of R1, R2, and R3 are not simultaneously a hydrogen atom; when R1 and R2 are simultaneously a hydrogen atom, then R3 is not a methyl group; and that when R3 is a hydrogen atom, then R1 and R2 are each a group other then a hydrogen atom, is disclosed, comprising asymmetrically hydrogenating an α,β-unsaturated carboxylic acid represented by formula (II): STR2 wherein R1, R2, and R3 are the same as defined above, in the presence of a ruthenium-optically active phosphine complex as a catalyst. According to the process of the invention, the desired optically active carboxylic acids which can be widely used as raw materials for synthesizing various useful compounds, for example, as intermediates for synthesizing physiologically active substances of natural materials and also as liquid crystal materials can be industrially advantageously produced.
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