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Method for preparing carboxylic acid methyl ester catalyzed by metal copper salt

A technology of methyl carboxylate and metal copper salt, which is applied in the field of preparation of methyl carboxylate, can solve problems such as industrial production waste, and achieve the effects of cost reduction and simple preparation method

Inactive Publication Date: 2015-01-14
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

But this reaction is a reversible reaction, so an excess of alcohol or carboxylic acid is needed to make the reaction proceed toward the direction of ester formation, which is relatively wasteful in industrial production

Method used

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  • Method for preparing carboxylic acid methyl ester catalyzed by metal copper salt
  • Method for preparing carboxylic acid methyl ester catalyzed by metal copper salt
  • Method for preparing carboxylic acid methyl ester catalyzed by metal copper salt

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] In a dry Schlenk tube, add 61 mg of benzoic acid and 5.0 mg of cuprous chloride. The test tube was evacuated first, then filled with nitrogen, and repeated three times. Then, 146 mg of tert-butyl peroxide and 1 ml of chlorobenzene were added to the Schlank test tube, and the resulting reaction liquid was stirred at 130° C. for 12 hours. After the reaction, cool to room temperature, filter with a glass funnel, concentrate, pass through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:20), and obtain the product methyl benzoate (CAS number: 93-58-3) 52mg , productive rate 76%, reaction process is shown in the following formula:

[0030]

[0031] Carry out nuclear magnetic resonance analysis to the product that present embodiment prepares:

[0032] 1 H NMR (400MHz, CDCl 3 ):δ8.05(d,J=7.2Hz,2H),7.56(t,J=7.6Hz,1H),7.44(t,J=7.8Hz,2H),3.92(s,3H).

[0033] 13 C NMR (100MHz, CDCl 3 ): δ167.8, 133.6, 130.8, 130.2, 129.0, 52.8.

Embodiment 2

[0035] In a dry Schlenk tube, add 78 mg of p-chlorobenzoic acid and 5.0 mg of cuprous chloride. The test tube was evacuated first, then filled with nitrogen, and repeated three times. Then, 146 mg of tert-butyl peroxide and 1 ml of chlorobenzene were added to the Schlank test tube, and the resulting reaction solution was stirred at 130° C. for 12 hours. After the reaction, cool to room temperature, filter with a glass funnel, concentrate, and pass through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:20) to obtain the product methyl 4-chlorobenzoate (CAS No.: 1126-46- 1) 68mg, yield 80%, the reaction process is shown in the following formula:

[0036]

[0037] Carry out nuclear magnetic resonance analysis to the product that present embodiment prepares:

[0038] 1 H NMR (400MHz, CDCl 3 ):δ7.96(d,J=8.8Hz,2H),7.40(d,J=8.8Hz,2H),3.91(s,3H).

[0039] 13 C NMR (100MHz, CDCl 3 ): δ166.9, 140.0, 131.6, 129.4, 129.2, 52.9.

Embodiment 3

[0041] In a dry Schlenk tube, add 101 mg of p-bromobenzoic acid and 5.0 mg of cuprous chloride. The test tube was evacuated first, then filled with nitrogen, and repeated three times. Then, 146 mg of tert-butyl peroxide and 1 ml of chlorobenzene were added to the Schlank test tube, and the resulting reaction solution was stirred at 130° C. for 12 hours. After the reaction, cool to room temperature, filter with a glass funnel, concentrate, and pass through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:20) to obtain the product 4-bromobenzoic acid methyl ester (CAS number: 619-42- 1) 82mg, yield 76%, the reaction process is shown in the following formula:

[0042]

[0043] Carry out nuclear magnetic resonance analysis to the product that present embodiment prepares:

[0044] 1 H NMR (400MHz, CDCl 3 ):δ7.89(d,J=8.8Hz,2H),7.58(d,J=8.8Hz,2H),3.91(s,3H).

[0045] 13 C NMR (100MHz, CDCl 3 ): δ167.0, 132.4, 131.8, 129.7, 128.7, 53.0.

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Abstract

The invention discloses a method for preparing carboxylic acid methyl ester catalyzed by metal copper salt. In an organic solvent, the metal copper salt is taken as a catalyst; and carboxylic acid is taken as a substrate to react under the effect of peroxide; and the carboxylic acid methyl ester is obtained by post-treatment after the reaction is finished. According to the method disclosed by the invention, the carboxylic acid is directly methylated to synthetize ester; the reaction material is cheap and easily available; the preparation method is simple; the metal copper salt is utilized as the catalyst, and is cheap and easily available; and the cost can be greatly reduced. The method disclosed by the invention can be used for synthetizing a series of carboxylic ester; and the synthetic product is an important organic synthetic midbody.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a method for preparing methyl carboxylate catalyzed by metal copper salts. Background technique [0002] Esters are one of the most important organic structures in chemistry and pharmacy, and are widely used in the production of various valuable compounds such as polymers, perfumes, and fatty acids (Larock, R.C. ComprehensiVe Organic Transformation; VCH: New York, 1999) . Therefore, esterification is one of the most important reactions in organic synthesis. [0003] The traditional method of synthesizing esters is to use activated carboxylic acid derivatives such as acid chlorides, acid anhydrides, etc. to undergo substitution reactions with alcohols. The disadvantage of this method is the acid chloride. Compounds such as acid anhydrides are unstable and environmentally unfriendly. [0004] Another direct way to prepare esters is to condense carboxylic acids with alcohols to ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C69/78C07C67/24C07C205/06C07C201/12C07C255/57C07C253/30C07C69/92C07C69/618C07C69/24
Inventor 陈万芝夏钦钦
Owner ZHEJIANG UNIV