Preparation method of alpha, beta-unsaturated carboxylic acid compounds

A technology of compounds and carboxylic acids, applied in the field of α, can solve problems such as very good, unspecified functional group compatibility effect, narrow substrate range, etc.

Active Publication Date: 2016-05-11
UNIV OF SCI & TECH OF CHINA
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, this method still needs to use the noble metal catalyst palladium, the substrate range...

Method used

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  • Preparation method of alpha, beta-unsaturated carboxylic acid compounds
  • Preparation method of alpha, beta-unsaturated carboxylic acid compounds
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[0035] The present invention provides a kind of α, the preparation method of β-unsaturated carboxylic acid compound, comprising: under the condition that nickel-containing catalyst, phosphine ligand, acid anhydride and organic solvent exist, compound shown in formula (I) and Formic acid reacts to obtain the α shown in formula (II), the β-unsaturated carboxylic acid compound;

[0036]

[0037] where the R 1 with R 2 each independently selected from one of hydrogen, alkyl, substituted alkyl, alkenyl, substituted alkenyl, aryl and substituted aryl.

[0038] The reaction formula for this reaction is as follows:

[0039]

[0040] The present invention has no special limitation on the sources of all raw materials, which can be commercially available.

[0041] Wherein, the nickel-containing catalyst is a nickel-containing catalyst well known to those skilled in the art, and there is no special limitation. In the present invention, nickel chloride, bis(1,5-cyclooctadiene) nic...

Embodiment 1

[0054] Example 1: Preparation of (E)-2,3-diphenyl α, β-unsaturated carboxylic acid

[0055] Reaction formula:

[0056]

[0057] Add di(acetylacetonate)nickel (5mol%, 6.5mg) and 1,2-bis( Diphenylphosphino)benzene (7mol%, 15.6mg), completely replace the air in the tube with argon three times, then add 1ml of toluene, toluene (0.50mmol, 89.2mg), formic acid (1.1mmol, 50.6mg) and pivalic anhydride (20mol%, 0.1mmol, 18.4mg); The reaction system was heated to 100°C under an oil bath and stirred continuously for 24 hours (use IKA magnetic stirrer, RCT basic type, stirring speed 500 rpm / minute). After the reaction was completed, the system was cooled to room temperature. The reaction solution was diluted with ethyl acetate, and then the diluted reaction solution was concentrated by rotary evaporation (BUCHI Co., Ltd., BUCHI rotary evaporator R-3). The concentrated residue was chromatographically separated by a chromatographic column (Beijing Xinweier Glass Instrument Co., Ltd....

Embodiment 2

[0060] Example 2: Preparation of (E)-2,3-di-p-methylphenylacrylic acid

[0061] Reaction formula:

[0062]

[0063] The method is the same as Example 1, the yield is 86%, and the purity is >99%.

[0064] The (E)-2,3-di-p-methylphenylacrylic acid obtained in Example 2 is analyzed by nuclear magnetic resonance, and the results are obtained: 1 HNMR (400MHz, CDCl 3 )δ7.89(s,1H),7.19(d,J=7.8Hz,2H),7.13(d,J=7.9Hz,2H),6.99(s,4H),2.39(s,3H),2.28( s,3H); 13 CNMR (101MHz, CDCl 3 ) δ 172.66, 142.23, 139.83, 137.73, 132.50, 131.65, 130.88, 130.46, 129.59, 129.51, 129.03, 21.38.

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Abstract

The invention provides a preparation method of alpha, beta-unsaturated carboxylic acid compounds. The method is characterized in that compounds represented by formula (I) react with formic acid in the presence of a nickel-containing catalyst, a phosphine ligand and an organic solvent to obtain the alpha, beta-unsaturated carboxylic acid compounds represented by formula (II), wherein R1 and R2 are respectively independently selected from H, C1-C30 alkyl groups, C1-C30 substituted alkyl groups, C1-C30 alkenyl groups, C1-C30 substituted alkenyl groups, C6-C30 aryl groups and C6-C30 substituted aryl groups. Compared with the prior art, the method adopting formic acid as a carboxylation reagent has the advantages of low price, safety, stability, low toxicity, high yield, simple operation, good economy, avoiding of use of precious metal catalysts and toxic gas carbon monoxide, meeting of requirements of environmentally friendly compounds, wide function group compatibility, high conversion rate and industrial synthesis values.

Description

technical field [0001] The invention belongs to the technical field of chemical synthesis, and in particular relates to a preparation method of α, β-unsaturated carboxylic acid compounds. Background technique [0002] Acrylic acid is an important organic raw material for the production of polymer materials such as polyacrylate, polyacrylic acid and its salts, or copolymers formed with other monomers. These materials are used in synthetic resins, synthetic rubbers, synthetic fibers, and coatings, latex, It is widely used in adhesives, leather tanning, papermaking, detergent and other fields. [0003] The important application value of acrylic acid has promoted the development of its synthesis technology. As early as 1843, Josepl Redtenbach obtained acrylic acid for the first time through the oxidation of acrylic acid in the presence of silver oxide. In 1927, American Rohm&Hass Company used chlorohydrin and sodium cyanide as raw materials to produce cyanohydrin, and then dehy...

Claims

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Application Information

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IPC IPC(8): C07B37/02C07C51/353C07C57/42C07C59/64C07C57/60C07C253/30C07C255/57C07C57/03C07C59/68C07C67/293C07C69/767C07C57/52C07C255/23C07F5/02C07C69/74C07C69/753C07C59/74C07D209/08C07D209/48C07D307/54C07C319/20C07C323/54C07C69/618C07C59/90C07D207/327C07C69/716C07C69/75
CPCC07B37/02C07C51/353C07C57/03C07C57/42C07C57/52C07C57/60C07C59/64C07C59/68C07C59/74C07C59/90C07C67/293C07C69/618C07C69/716C07C69/74C07C69/75C07C69/753C07C69/76C07C253/30C07C255/23C07C255/57C07C319/20C07C323/54C07D207/327C07D209/08C07D209/48C07D307/54C07F5/025
Inventor 傅尧付明臣尚睿贺超
Owner UNIV OF SCI & TECH OF CHINA
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