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Preparation method of S-aryl phosphorothioate

A technology of aryl phosphorothioate and phosphite, which is applied in the field of preparation of S-aryl phosphorothioate, can solve the problems that the synthetic method cannot meet the requirements of industrial production and the like, achieves convenient operation, wide substrate range, simple craftsmanship

Active Publication Date: 2015-01-21
ZHENGZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] The purpose of the present invention is to provide a kind of preparation method of S-aryl phosphorothioate, solve the problem that existing synthetic method can't meet industrial production requirement

Method used

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  • Preparation method of S-aryl phosphorothioate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] O, the preparation method of O-dimethyl-S-(4-methylphenyl) phosphorothioate comprises the following steps:

[0024] 1) Take 0.06mmol of anhydrous copper acetate, 0.4mmol of p-toluenesulfonyl chloride, and 2.8mmol of dimethyl phosphite, add 2ml of acetonitrile to make a mixture, put the mixture in a 5ml Schlenk tube, and heat it to 140°C After reacting for 24 hours in an oil bath, cool to room temperature to obtain a reaction solution;

[0025] 2) The reaction liquid obtained in step 1) was directly concentrated to obtain a concentrate, and the concentrate was separated by thin-layer chromatography using ethyl acetate / petroleum ether=1 / 3 (v / v) as a developing solvent to obtain 71 mg of the target product.

[0026] The target product yield of the present embodiment is 76%.

[0027] Carry out NMR characterization to target product, as follows: 1H NMR (CDCl 3 ,400MHz,ppm):δ7.43(dd,J=8.0Hz,1.6Hz,2H),7.16(d,J=7.9Hz,2H),3.82(s,3H),3.79(s,3H),2.34 (s,3H).

Embodiment 2

[0029] O, the preparation method of O-diethyl-S-(4-methylphenyl) phosphorothioate comprises the following steps:

[0030] 1) Take 0.06mmol of anhydrous copper acetate, 0.4mmol of p-toluenesulfonyl chloride, and 2.8mmol of diethyl phosphite, add 2ml of acetonitrile to make a mixture, put the mixture in a 5ml Schlenk tube, and heat it to 140°C After reacting for 24 hours in an oil bath, cool to room temperature to obtain a reaction solution;

[0031] 2) The reaction solution obtained in step 1) was directly concentrated to obtain a concentrate, and the concentrate was separated by thin-layer chromatography using ethyl acetate / petroleum ether=1 / 3 (v / v) as a developing solvent to obtain 76 mg of the target product.

[0032] The target product yield of the present embodiment is 73%.

[0033] Carry out NMR characterization to target product, as follows: 1H NMR (CDCl 3 ,400MHz,ppm):δ7.41(dd,J=8.0Hz,1.5Hz,2H),7.13(d,J=7.9Hz,2H),4.23-4.08(m,4H),2.32(s,3H) ,1.28(t,J=7.04Hz,6H).

Embodiment 3

[0035] O, the preparation method of O-dipropyl-S-(4-methylphenyl) phosphorothioate comprises the following steps:

[0036] 1) Take 0.06mmol of anhydrous copper acetate, 0.4mmol of p-toluenesulfonyl chloride, and 2.8mmol of dipropyl phosphite, add 2ml of acetonitrile to make a mixture, put the mixture in a 5ml Schlenk tube, and heat it to 140°C After reacting for 24 hours in an oil bath, cool to room temperature to obtain a reaction solution;

[0037] 2) The reaction solution obtained in step 1) was directly concentrated to obtain a concentrate, and the concentrate was separated by thin-layer chromatography using ethyl acetate / petroleum ether=1 / 3 (v / v) as a developing solvent to obtain 82 mg of the target product.

[0038] The target product yield of the present embodiment is 71%.

[0039] Carry out NMR characterization to target product, as follows: 1H NMR (CDCl 3 ,400MHz,ppm):δ7.42(dd,J=8.2Hz,1.6Hz,2H),7.12(d,J=8.0Hz,2H),4.11-3.98(m,4H),2.31(s,3H) ,1.70-1.61(m,4H),0.90(t,J...

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Abstract

The invention discloses a preparation method of S-aryl phosphorothioate. The preparation method comprises the following steps of (1) adding a copper catalyst, an aryl sulfonyl chloride and phosphite in an organic solvent, reacting for 12-24 h at a temperature of 60-150 DEG C and cooling to a room temperature to obtain a reaction liquid; and (2) concentrating the reaction liquid, separating and purifying to obtain S-aryl phosphorothioate. According to the preparation method of S-aryl phosphorothioate, a one-pot method is adopted; copper is used as the catalyst; economical and easily available aryl sulfonyl chloride and phosphite are used as the raw materials; and a coupling reaction is carried out directly to generate corresponding S-aryl phosphorothioate, without adding alkali in air. A synthetic system has a relatively wide application scope, is compatible with a plurality of groups such as alkoxy, aryl, halogen and acyloxy. The preparation method provided by the invention is simple in process, convenient for operations and mild in reaction conditions, has a wide substrate range and relatively high yield, and is suitable for popularization and application.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a preparation method of S-aryl phosphorothioate. Background technique [0002] S-aryl phosphorothioate is a kind of organic synthesis intermediate with wide application, and has important application value in pharmaceutical production and organic synthesis. There have been some synthetic methods in the prior art to successfully prepare S-aryl phosphorothioate, such as: reaction of phosphite with disulfide or thiophenol, reaction of ammonium salt of phosphorothioate with halide, etc. However, these synthetic methods generally have many problems, such as: reactant odor, complex structure of reactant, harsh reaction conditions, need stoichiometric base, single substrate, etc., which cannot meet the requirements of industrial production. Contents of the invention [0003] The purpose of the present invention is to provide a preparation method of S-aryl phosph...

Claims

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Application Information

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IPC IPC(8): C07F9/18
Inventor 崔秀灵白洁吴养洁
Owner ZHENGZHOU UNIV
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