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Method for synthesizing S-substituted thiobenzoate derivative by Bunte salt

A technology of benzoic acid thioester and synthesis method, applied in the direction of organic chemistry and the like, can solve the problems of high environmental harm, not conforming to the development direction of green chemistry, increased cost of metal catalysts and surfactants, etc., and achieves less three wastes, simple and safe operation. , the preparation process is reasonable

Active Publication Date: 2017-05-31
NANJING UNIV OF SCI & TECH
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0011] Most of the unavoidable use of thiophenol with bad smell in the prior art, even if thiourea or disulfide is used as the sulfur source, the reaction process will also generate thiophenol or prepare the reaction substrate in advance by thiophenol; in addition, metal catalysts The use of surfactants and surfactants also increases the cost of the reaction, which is harmful to the environment and does not conform to the development direction of green chemistry.

Method used

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  • Method for synthesizing S-substituted thiobenzoate derivative by Bunte salt
  • Method for synthesizing S-substituted thiobenzoate derivative by Bunte salt
  • Method for synthesizing S-substituted thiobenzoate derivative by Bunte salt

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Experimental program
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Effect test

Embodiment 1

[0036] Add 11.3g (50mmol) sodium benzylsulfonate, 107mL (1.06mol) benzaldehyde and 27.6mL (0.15mol) di-tert-butyl peroxide into a 250mL vacuum reaction flask, and fill with nitrogen. The reaction was stirred at 135°C for 12h. After the reaction was completed, the reaction solution was diluted with 100 mL of ethyl acetate, washed three times with saturated brine, the organic layer was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The crude product was separated by column chromatography (the eluent was a mixture of ethyl acetate and petroleum ether, the volume ratio of the two was 50:1) to obtain 9.2 g of S-benzylbenzoic acid thioester with a yield of 81%, and NMR characterization Data are as follows:

[0037] 1 H NMR (500MHz, CDCl 3 )δ:4.32(s,2H),7.23-7.26(m,1H),7.30-7.32(m,2H),7.37-7.38(m,2H),7.41-7.45(m,2H),7.54-7.57( m,1H),7.95-7.97(m,2H);

[0038] 13 C NMR (126MHz, CDCl 3 )δ: 33.49(s), 127.44(s), 128.76(s), ...

Embodiment 2

[0040] Add 11.3g (50mmol) sodium benzylsulfonate, 57mL (0.56mol) benzaldehyde and 9.2mL (50mmol) di-tert-butyl peroxide into a 250mL vacuum reaction flask, and fill with nitrogen. The reaction was stirred at 135°C for 10h. After the reaction was completed, the reaction solution was diluted with 100 mL of ethyl acetate, washed three times with saturated brine, the organic layer was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The crude product was separated by column chromatography (the eluent was a mixture of ethyl acetate and petroleum ether with a volume ratio of 50:1) to obtain 5.1 g of S-benzylbenzoic acid thioester with a yield of 45%.

Embodiment 3

[0042] Add 11.3g (50mmol) sodium benzylsulfonate, 107mL (1.06mol) benzaldehyde and 13.8mL (75mmol) di-tert-butyl peroxide into a 250mL vacuum reaction flask, and fill with nitrogen. The reaction was stirred at 150°C for 8h. After the reaction was completed, the reaction solution was diluted with 100 mL of ethyl acetate, washed three times with saturated brine, the organic layer was separated, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The crude product was separated by column chromatography (the eluent was a mixture of ethyl acetate and petroleum ether, the volume ratio of which was 50:1) to obtain 5.9 g of S-benzylbenzoic acid thioester, with a yield of 52%.

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Abstract

The invention discloses a method for synthesizing a S-substituted thiobenzoate derivative by Bunte salt. The method takes Bunte salt and benzaldehyde or its derivative as raw materials, under existence of a radical initiator di-tert-butyl peroxide, benzaldehyde, ethyl acetate or acetonitrile are taken as solvents, nitrogen protection is carried out, the materials are fully reacted at the temperature of 100-150 DEG C, after the reaction is completed, a reaction solution is separated and purified to obtain the S-substituted thiobenzoate derivative. The process condition of the method is reasonable, operation is easy and safe, usage of substrates such as thiophenol having bad smell is avoided, three wastes are little, the method is environmentally friendly, a free radical principle is used for synthesizing the product, metal catalysis is not required, and the method is a novel application of a carbon hydrogen activation reaction.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, in particular to a method for synthesizing S-substituted benzoic acid thioester derivatives from Bunte salt (organic thiosulfate). Background technique [0002] Thioester derivatives are important synthetic intermediates in the field of organic synthesis, and are widely used in polypeptide coupling, acyl transfer, protection of thiols, and organometallic reactions. Many natural compounds and drugs also have thioester moieties in their structures, and this special structure makes them have better biological activity and pharmacological effects. The sulfur sources used in the reported synthetic methods are mainly thiourea, thiophenol and disulfide. [0003] Document 1 (Xuebin Zhu, et.al.Tetraethylammonium Bromide-Catalyzed OxidativeThioesterification of Aldehydes and Alcohols.Adv.Synth.Catal.2013) Zhu et al. used thiophenols and disulfides to tetraethyl bromide under oxidative conditions...

Claims

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Application Information

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IPC IPC(8): C07C327/26C07C327/32
CPCC07C327/26C07C327/32
Inventor 修健敏易文斌
Owner NANJING UNIV OF SCI & TECH
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