阅读说明：本技术 一种硫代磷酸酯类化合物的制备方法 (Preparation method of thiophosphate compound ) 是由 张昌源 郭火生 邱云 罗建 徐舒婷 王正平 于 2019-10-16 设计创作，主要内容包括：本发明公开了一种硫代磷酸酯类化合物的制备方法,其步骤如下：在空气中氧气的作用及温度60-80℃的条件下,以铜盐为催化剂,将硫代磺酰化物和二苯基磷氧化合物在有机溶剂中进行反应后,经旋转蒸发处理、硅胶柱层析分离提纯,得到硫代磷酸酯类化合物。本发明采用硫代磺酰化物和二苯基磷氧化物为原料合成硫代磷酸酯类化合物,具有操作简便、催化剂廉价、原料稳定、无污染、效率高等优点。(The invention discloses a preparation method of a thiophosphate compound, which comprises the following steps: under the action of oxygen in the air and at the temperature of 60-80 ℃, copper salt is used as a catalyst, thiosulfonylation compound and diphenyl phosphorus oxide compound are reacted in an organic solvent, and then the reaction product is subjected to rotary evaporation treatment and silica gel column chromatography separation and purification to obtain the thiophosphate compound. The method adopts the thiosulfonylation compound and the diphenyl phosphorus oxide as raw materials to synthesize the thiophosphoric ester compound, and has the advantages of simple and convenient operation, low cost of the catalyst, stable raw materials, no pollution, high efficiency and the like.)

1. A preparation method of a thiophosphate compound is characterized by comprising the following steps: under the action of oxygen in the air and at the temperature of 60-80 ℃, copper salt is used as a catalyst, thiosulfonylation compound and diphenyl phosphorus oxide compound are reacted in an organic solvent, and then the reaction product is subjected to rotary evaporation treatment and silica gel column chromatography separation and purification to obtain the thiophosphate compound.

2. the method of claim 1, wherein: the thiophosphate compound is phenyl thiophosphate, the sulfosulfonyl compound is phenyl thiobenzene sulfonate, and the diphenyl phosphorus oxide compound is diphenyl phosphorus oxide.

3. The method of claim 1, wherein: the organic solvent is any one of acetonitrile, DCM, DCE and THF.

4. The method of claim 1, wherein: the copper salt is a copper halide or cuprous halide.

5. the method of claim 1, wherein the temperature is 80 ℃.

6. The method of claim 1, wherein: the dosage of the copper salt is 10 mol percent of the thiosulfonylate.

7. The method of claim 3, wherein: the organic solvent is acetonitrile.

8. The method of claim 4, wherein: the copper halide is CuCl₂、CuBr₂Any one of them.

9. The method of claim 4, wherein: the cuprous halide is any one of CuCl, CuI and CuBr.

10. The method of claim 9, wherein: the cuprous halide is CuI.

Technical Field

The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of a phosphorothioate compound.

background

thiophosphate is an important organic phosphorus compound and has very wide application in the aspects of biology, medicine, pesticide, materials and the like. In recent years, thiophosphate pesticides are widely used in agriculture, mainly as pesticidesThe common thiophosphate pesticides include: iprobenfos (S-benzyl-O, O-diisopropyl thiophosphate, structure formula) And omethoate (O, O dimethyl S-methyl carbamoyl phosphorothionate, structure formula) And the like.

In the past, phosphorothioate compounds were synthesized mainly by coupling reaction of P (O) -Cl compounds with nucleophiles (alcohols, phenols, etc.), and the reaction formula was as follows:

In the formula, R₁、R₂is any one of alkyl, aryl and alkoxy. Therefore, the traditional synthetic method of the thiophosphate compound uses a phosphorus halide reagent and a sulfur reagent which are high in toxicity and air sensitivity, and has the defects of complicated steps, harsh conditions, low reaction selectivity, great environmental pollution and the like.

In order to overcome the defects of the traditional synthesis process of the thiophosphate compound, chemists are dedicated to research and develop methods with green and environment-friendly synthesis routes and high atom economic benefits, and a method which adopts a stable, cheap and easily-obtained P (O) -H compound as a phosphorylation reagent and can efficiently and selectively synthesize the thiophosphate compound is proposed. However, these methods require expensive transition metal catalysts, oxidizing agents or odorous mercaptans.

therefore, the method for preparing the phosphorothioate compound, which is efficient, simple and environment-friendly, is important to explore.

Disclosure of Invention

The invention aims to: the thiophosphate compound is synthesized by taking the thiosulfonylate and the diphenyl phosphorus oxide as raw materials under the conditions of copper salt catalysis, oxygen action in air and temperature of 60-80 ℃, and has the advantages of stable and easily obtained raw materials, low cost, simple synthesis, high efficiency, mildness and no pollution.

In order to achieve the purpose, the invention adopts the following technical scheme:

A preparation method of a thiophosphate compound comprises the following steps: under the action of oxygen in the air and at the temperature of 60-80 ℃, copper salt is used as a catalyst, thiosulfonylate and diphenyl phosphorus oxygen compound react in an organic solvent for 12 hours, then the organic solvent is removed by rotary evaporation, the residue is dissolved by dichloromethane, and the thiophosphate compound is obtained by silica gel column chromatography separation and purification.

Further, the thiophosphate compound is phenyl thiophosphoryl ester, the sulfosulfonyl compound is phenyl thiobenzene sulfonate, and the diphenyl phosphorus oxide compound is diphenyl phosphorus oxide.

Further, the organic solvent comprises any one of acetonitrile, DCM, DCE and THF, and is preferably acetonitrile.

Further, the copper salt is a copper halide or cuprous halide.

Further, the reaction temperature is preferably 80 ℃.

Further, the copper salt is used in an amount of 10 mol% based on the thiosulfonylate.

Further, the copper halide is CuCl₂、CuBr₂Any one of them.

The cuprous halide is any one of CuCl, CuI, and CuBr, and is preferably CuI.

Compared with the prior art, the invention has the beneficial effects that:

1) The invention adopts diphenyl phosphorus oxide and thiosulfonylation compound as raw materials to synthesize the thiophosphate compound, the raw materials are all stable and easily obtained substances, the cost is saved, and the used catalyst is cheap and easily obtained copper salt, the reaction can be completed under the condition of 60-80 ℃, and the invention has the advantages of low preparation cost, mild reaction and short reaction time;

2) The invention does not use alcohol, phenol and other reagents with large pollution in the synthesis/preparation, has the synthesis yield of 86 percent, is an efficient and pollution-free green and environment-friendly synthesis method, and is beneficial to industrial mass production.

Drawings

FIG. 1 is a thin-layer chromatogram of phenyl thiodiphenyl phosphate prepared according to the present invention;

FIG. 2 is a chart of the H spectrum of phenyl thiodiphenyl phosphate prepared by the present invention;

FIG. 3 is a spectrum of a phenyl thiophenylphosphate P prepared according to the present invention;

FIG. 4 is a spectrum C of phenyl thiophenylphosphate prepared by the present invention;

in the figure, S1 is phenyl thiobenzene sulfonate, S2 is diphenylphosphine oxide, P is a reaction liquid, M is a mixed point of S1, S2 and P, and Rf is a ratio of a distance from the center of a spot to an origin to a distance from a solvent development front to the origin.

Detailed Description

To further illustrate the present invention, embodiments of the present invention are described below with reference to specific examples, but it should be understood that these descriptions are only intended to further illustrate the features and advantages of the present invention and not to limit the patent claims of the present invention.

All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.

All the raw materials of the present invention are not particularly limited in purity, and the present invention preferably employs a purity which is conventional in the field of analytical purification or synthesis of an organophosphorus compound.

The invention provides a preparation method of a thiophosphate compound, which comprises the following steps:

A preparation method of a thiophosphate compound comprises the following steps: under the action of oxygen in the air and at the temperature of 60-80 ℃, copper salt is used as a catalyst, thiosulfonylate and diphenyl phosphorus oxygen compound react in an organic solvent for 12 hours, then the organic solvent is removed by rotary evaporation, the residue is dissolved by dichloromethane, and the thiophosphate compound is obtained by silica gel column chromatography separation and purification.

In the following examples, phenyl thiobenzenesulfonate and diphenylphosphoryl oxide were used as starting materials to prepare phenyl thiodiphenylphosphate, which has the following reaction formula: