JPS61229860A - Production of phenyl chlorothioformate - Google Patents

Abstract

PURPOSE:To obtain the titled compound by introducing sulfur dioxide to a mixed solution of a phenol, perchloromethylmercaptan, an organic solvent and water, removing a water layer form the reaction solution and adding a dehydrohalogenating agent to the organic layer. CONSTITUTION:A penol (e.g., 5,6,7,8-tetrahydro-2-naphthol) and >= an equimolar amount based on the phenol of perchloromercaptan are added to a mixed solvent of an organic solvent (e.g., carbon tetrachloride) and water. An equimolar amount -20 times mols based on perchloromethylmercaptan of sulfur dioxide is introduced to the mixed solution, then a water layer is removed from the reaction solution, a dehydrohalogenating agent (e.g., aqueous solution of NaOH) is added to the organic layer, and the reaction is carried out at -10 deg.C - room temperature, to give the aimed substance. USE:An intermediate for synthesizing drugs and agricultural chemicals. EFFECT:The titled substance is obtained simply and safely with avoiding storing and transportation of a large amount of thiophosgene.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing phenyl chlorothiopolmates. Phenyl chlorothiopolmates are extremely useful as intermediates for pharmaceuticals and agricultural chemicals.

[Conventional technology]

It is known that phenyl chlorothiopolmates can be produced by the reaction of phenols and thiophosgene in the presence of a dehydrogenating agent.

[Problems to be solved by the invention]

Thiophosgene is highly toxic and must be handled with great care. Considering abnormal situations such as leakage, it is desirable to avoid storing or moving large quantities as much as possible.

An object of the present invention is to avoid the storage or transfer of large amounts of thiophosgene and to easily and safely produce phenylchlorothioformates.

[Means that the invention solves]

As a result of various tests and intensive studies, the inventors of the present invention found that after blowing sulfur dioxide into a mixed solution of phenol verchlormethyl mercaptan in an organic solvent and water, the aqueous layer was removed from the reaction solution, and the organic layer was dehalogenated. The present invention was completed by discovering that phenylchlorothioformates can be produced from K by adding a hydrogenation reagent.

[Effect]

Next, the method of implementing the present invention will be described in detail.

Phenols and phenol I [perchlormethyl mercaptan in an amount equal to or more than the same mole are added to a mixed solvent of an organic solvent and water.

Phenols include unsubstituted 7-enol, methylphenol, ethylphenol, alkyl-substituted phenol such as tert-butylphenol, β-naphthol or 5.4″18-tetrahydro-2-su7
Condensed phenols such as toll can be used.

Examples of the organic solvent include chlorinated hydrocarbons such as chloroform, dichloromethane, and carbon tetrachloride, and aromatic hydrocarbons such as benzene, toluene, and xylene. It is desirable to use water at least twice the mole of perchloromethyl mercaptan. A small amount of alkali metal iodide can be added to facilitate the reaction. Iodium difluoride is blown into the mixed solution in an amount equivalent to 20 times the mole of perchloromethyl mercaptan, then the aqueous layer is removed from the reaction solution, and a dehydrohalogenation reagent is added to the organic layer.

Examples of dehydrohalogenation reagents include inorganic bases such as alkali metal hydroxides, alkaline earth metal hydroxides, and alkali metal carbonates, and organic bases such as triethylamine, pyridine, quinoli, and isoquinoline. Use the same mole for that.

These dehydrohalogenating reagents can usually be used in the form of a solution, and the concentration of the dehydrohalogenating reagent in the solution and the yield of phenyl chlorothiopolmates are closely related. That is, when a highly concentrated dehydrohalogenation reagent solution is used, the yield of phenyl chlorothiopolmates decreases due to the by-product of diphenylthiocarbohydrate esters. If a dehydrohalogenation reagent solution with a concentration lower than necessary is used, a large reactor must be used, which is disadvantageous.

Therefore, it is preferred to use a solution of about 5-20% dehydrohalogenation reagent.

The reaction temperature is usually about -10°C to room temperature, and the reaction takes place at 2
It can be completed within 4 hours.

〔Effect of the invention〕

Phenols, perchloromethyl mercaptan.

After bubbling sulfur dioxide into a mixed solution of an organic solvent and water, removing the aqueous layer from the reaction solution and adding a dehydrohalogenation reagent to the organic layer, phenyl chlorothiopolmates can be easily, neatly and safely produced. Can be manufactured.

〔Example〕

Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited only to these Examples.

Example 1 11 with stirrer, thermometer and 300 ILt dropping funnel
5.6.7.8-Tetrahydro-2 in a three-bottle flask.
-su7toll659. Perchloromethyl mercaptan 8
1.79. 200au of carbon tetrachloride, 200au of water, and
2 g of potassium iodide was taken and the flask was cooled on ice.

Then, sulfur dioxide 859 was bubbled into the above solution while stirring. The temperature inside the flask was maintained at 0-10°C.

After blowing in sulfur dioxide, the aqueous layer was removed from the reaction solution, and the remaining organic layer was hydroxylated with 8% VC) IJium aqueous solution 220
d was dropped. After the dropwise addition, the mixture was further stirred for 2 hours. After the reaction is completed, the organic layer is separated from the reaction solution and distilled. 5.47.
754 g of 8-tetrahydro-2-su7tyl chlorothioformate was obtained. 5.6.7.8-Tetrahydro-2-su7tyl chlorothioformate yield is 5
．． 6.7.7 based on 8-tetrahydro-2-naphthol
It was 5%.

Examples 2 to 4 The phenols shown in Table 1 were placed in the same reaction apparatus as in Example 1, and the reaction was carried out under the reaction conditions shown in Table 1.
Phenyl chlorothiopolmates were obtained by the same treatment as above.

The results are shown in Table-1.

Procedural amendment August 27, 1985

Claims (1)

[Claims] Phenylchlorothio, which is characterized by blowing sulfur dioxide into a mixed solution of phenols, perchloromethyl mercaptan, an organic solvent, and water, removing the aqueous layer from the reaction solution, and adding a dehydrohalogenating agent to the organic layer. Method for producing formates.