JPS62120358A - Production of phenyl chlorothioformate - Google Patents

Abstract

PURPOSE:To obtain the titled substance, by blowing chlorine gas into a mixture solution of carbon disulfide and hydrochloric aid, removing an aqueous layer, adding water and a iodide, blowing sulfur dioxide gas and adding a phenol and dehydrohalogenating reagent. CONSTITUTION:Chlorine gas is blown into a mixture solution of carbon disulfide and hydrochloric acid and an organic solvent, e.g. carbon tetrachloride, etc., is added to remove an aqueous layer. Water and iodine or an iodide are added and sulfur dioxide gas is blown into the organic layer. A phenol and dehydrohalogenating reagent, e.g. alkali metal hydroxide, etc., are then added to the above-mentioned reaction solution and reacted at -10 deg.C - room temperature for <=24hr to afford the aimed substance. EFFECT:The aimed substance is readily and safely obtained. USE:A synthetic intermediate for medicines and agricultural chemicals.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing phenyl chlorothiopolmates. Phenyl chlorothiopolmates are used as pharmaceuticals,
Very useful as an intermediate for agricultural chemicals.

[Conventional technology]

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

[Problems to be solved by the invention]

Thiophosgene is highly toxic and must be handled with great care. Therefore, in consideration of abnormal situations such as leakage, it is desirable to avoid storing or transferring large amounts of thiophosgene as much as possible. Therefore, the present inventors first developed perchloromethyl mercaptan. A method for producing phenyl chlorothiopolmates by blowing sulfur dioxide gas into a mixed solution of an organic solvent and water, removing the water layer from the reaction solution, and adding phenols and then a dehydrohalogenation reagent to the organic layer. Proposed.

The raw material, perchlormethyl mercaptan, is highly toxic, although not as toxic as thiophosgene, and therefore, like thiophosgene, it is desirable to avoid storing or moving large quantities as much as possible.

That is, an object of the present invention is to avoid storing or transferring large amounts of perchloromethyl mercaptan and thiophosgene, and to easily and safely produce phenyl chlorothiopolmates.

[Means and effects to be solved by the invention] The present inventors,
As a result of various tests and intensive studies, we found that after blowing chlorine gas into a mixed solution of carbon disulfide and hydrochloric acid, we added an organic solvent.
Remove the water layer.

Next, after adding water and iodide, sulfur dioxide gas was blown into the reactor, and then phenols and a dehydrohalokenating agent were added, thereby discovering that phenyl chlorothiopolmates could be produced, and the present invention was completed.

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

Blowing chlorine gas into a mixed solution of carbon disulfide and hydrochloric acid.

When the hydrochloric acid concentration is low, the reaction rate is low, and on the other hand, when the hydrochloric acid concentration is high, the selectivity of the chlorine adduct decreases. Therefore 5-20
A hydrochloric acid concentration of wt% is chosen.

After blowing in chlorine gas in an amount 5 times or more mole relative to carbon disulfide, an organic solvent is added and the aqueous layer is removed. Chloroform and dichloromethane are used as organic solvents.

Halogenated hydrocarbons such as carbon tetrachloride, benzene.

Examples include aromatic hydrocarbons such as toluene and xylene.

Next, freshly blown into water and hydrogen iodide disulfide such as iodine, sodium iodide, potassium iodide, and hydriodic acid (L2~1 vt%).The sulfur dioxide gas is It is used in an equimolar to 5-fold molar amount relative to the sulfurized hydrocarbon.

Further, phenols and a dehydrohalogenating agent are added to the reaction solution to produce phenyl chlorothiopolmates. Preferably phenols.

Remove the aqueous layer before adding the dehydrohalogenation reagent.

Phenols are used in an amount equal to -1 times the mole of carbon disulfide.

As dehydrohalogenation reagents, there are no alkali metal hydroxides, alkaline earth metal hydroxides, or alkali metal carbonates! Examples include organic bases such as 1 base, triethylamine, pyridine, quinoline, and isoquinoline, and are used in about an equimolar amount to the phenol. 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 chlorothioesters decreases due to the by-product of diphenylthiocarbonate esters. However, when using a dehydrohalogenation reagent solution with an unnecessarily low concentration, a large-capacity reactor must be used, which is disadvantageous.

Therefore, a 5 to 20 wt % dehydrohalogenation reagent solution is preferred.

The reaction temperature is usually selected from -10°C to room temperature, and the reaction can usually be completed within 24 hours.

〔Effect of the invention〕

By using the method of the present invention, phenylchlorothiopolmates can be produced simply and safely.

〔Example〕

Next, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 53g of carbon disulfide and 594μ of 20% hydrochloric acid were placed in a 1 ton 5-bottle flask equipped with a stirrer, thermometer and condenser, and the flask was cooled. Chlorine gas 2509 was blown into the reactor while maintaining the temperature inside the reactor at 10 to 15°C. After blowing in chlorine gas, 140 d of carbon tetrachloride was added and the aqueous layer was separated and removed. Next, add water 280- and potassium iodide 1.09-
After cooling with water, 989 sulfur dioxide gas was blown into the reactor.

The temperature inside the reactor was maintained at 0-10°C.

After blowing in iodine dioxide, the aqueous layer was separated and the remaining organic layer was added with 5-tart-butylphenol 852 and an additional 10%
240 ml of sodium hydroxide was added dropwise and stirred for 2 hours to react.

After the reaction is completed, the organic layer is separated from the reaction solution and subjected to distillation.
) 3-tart-butylphenyl chlorothioformate 12 [149 was obtained. The yield of 5-tert-butylphenyl chlorothioformate was 93% based on 5-t@rt-butylphenol.

Examples 2 to 4 The raw materials shown in Table IK were placed in the same reactor as in Example 1, reacted under the reaction conditions in Table 1, and treated in the same manner as in Example 1 to produce phenyl chlorothioformates. I got it.

The results are shown in Table-1.

Procedural Amendment (1948, 21)] 5th, Director General of the Patent Office, Uga Michibu, 1.1 [Indication of Showa 0 (IT't; 1 Revised Application No. 258439; ) 4 Production method of small lumates 3
Relationship between the name 11 and the name 11 of the name 11i1- Soda T Industry Co., Ltd. (Information Department Telephone number (505) 4471) 4. Date of drawing order 5. Target of amendment ``Detailed explanation column of the invention in the specification'' 6. Contents of amendment (11. In the 5th line from the bottom of page 4, "approximately equal mole" is corrected to "approximately equal mole."

Claims (1)

[Claims] After blowing chlorine gas into a mixed solution of carbon disulfide and hydrochloric acid, add an organic solvent and remove the aqueous layer, then add water and iodide, blow in sulfur dioxide gas, and then add phenols and a dehydrohalogenation reagent. A method for producing phenyl chlorothioformates, characterized by: