JPS59167565A - 3-tert-butylphenylchlorothioformate and its preparation - Google Patents

Abstract

NEW MATERIAL:3-t-Butylphenylchlorothioformate. USE:An intermediate for drugs, agricultural chemicals, etc. PREPARATION:3-t-Butylphenol is reacted with thiophosgene preferably in the presence of a dehydrohalogenating agent [e.g., alkaline (earth) metal hydroxide, triethylamine, etc.], and if necessary, using a solvent such as chloroform, etc. at 5 deg.C- room temperature for <=20hr.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to ro-tert-butylphenyl chlorotheoformate and a method for producing the same.

Chlorophenylthiopolmates are known as raw materials for thiocarbamates that have excellent antifungal effects. For example, in JP-A-57-176, 95.2, 4-
It has been disclosed that thiocarbamates made from tert-butylphenylchlorothioformate have excellent effects on skin fungal infections.

The present inventors used thiocarbamates to kill insects.

As a result of extensive research to develop compounds with bactericidal and herbicidal effects, we discovered that derivatives with a 3-tert-butylphenyl group were suitable for this purpose, and based on this knowledge, we completed this invention. did.

The 3-tert-butylphenylchlorothioformate of the present invention is a novel compound that has not been described in any literature, and is a compound useful as an intermediate for pharmaceuticals, agricultural chemicals, etc.

For example, the 5-tert-butylphenyl chlorotheoformate of the present invention is reacted with 5-methoxy-N-methylarniline to form O-3-tert-butylphenyl N
-(5-methoxyphenyl)-N-methylthiocarbamate can be produced.

From the thus obtained 0-5-tert-butyl 7enyl N-(!l-methoxyphenyl)-N-methylthiocarbamate, a herbicide containing this as an active ingredient can be prepared.

No. 0 exhibits extremely excellent herbicidal activity against many weeds including field weeds, and is virtually harmless to transplanted paddy rice, making it suitable as a herbicide for paddy fields. In addition, it exhibits an excellent selective weeding effect between grass weeds and broad-leaved crops when treated with upland soil, and has applicability as a herbicide for upland fields.

The 3-tert-butylchlorophenyl thioformate of the present invention can be produced by reacting 3-tert-butylphenol and thiophosgene.

The method of the present invention is characterized in that 3-tert-butylphenylchlorothioformate and 3-tert-butylphenol are reacted with thiophosgene.
A method for producing tert-buterphenylchlorothioformate is provided.

The reaction between 3-tert-butylphenol and thiophosgene proceeds easily in the presence of a dehydrohalogenating agent. During the reaction, a dehalogenating reagent is added to a mixed solution of 3-tert-butylphenol and thiophosgene, or a dehalogenating reagent and 3-tert-butylphenol are added to a thiophosgene solution.
A method such as adding a mixed solution of -tert-butylphenol is used.

Examples of dehydrohalogenation reagents include alkali metal hydroxides, alkaline earth metal hydroxides, inorganic bases such as alkali metal carbonates, and triethylamine.

Examples include organic bases such as pyridine, quinoline, and isoquiline. These dehalogenation reagents are usually used after being dissolved in water or a suitable organic solvent, and are used in the same manner as thiophosgene (5
An equivalent amount of -tert-butylphenol is used. A solvent is used to facilitate the reaction. Examples of solvents include chloroform, dichloromethane, chlorinated hydrocarbons such as carbon tetrachloride, and benzene.

Aromatic hydrocarbons such as toluene and xylene are selected.

And the reaction temperature is 5°C to 100°C, preferably 5°C.
~room temperature is suitable and the reaction time is generally within about 20 hours.

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 A 2-ton 6-piece machine equipped with a stirrer, a thermometer, and a 30070 dropping funnel.
Add 64 mL of 3-tert-butylphenol to a double flask and add 600 mL of chloroform. and thiophosgene 509
Remove and cool the flask on ice.

Then add 20% hydroxide to the dropping funnel) IJum aqueous solution 2
00rnl and while stirring, lower the temperature inside the flask to 5~1
While maintaining the temperature at 0°C, aqueous sodium hydroxide solution was added dropwise from the dropping funnel over a period of 3 hours. After dropping the entire amount of the aqueous sodium hydroxide solution, the mixture is further stirred at room temperature for 10 hours.

After the reaction is completed, the reaction solution is transferred to a 1 ton separating funnel, the chloroform layer is separated and dried over calcium chloride. After filtering off calcium chloride, the 0ζ liquid was distilled to a boiling point of 125-4°C/
5-tert-butylchlorophenylthioformate 719 elk at 4 mvtHg.

Infrared absorption spectrum (NacA) 2950.1605, 1570, 1490, 1230.
1050cIn'' nuclear magnetic resonance absorption spectrum (act4
．． Internal standard TMS)' = 9 (s) ppm (9H) &74-7.40 (m) (4H) Elemental analysis (cl
la,,ctos) The results were as follows.

OHC1S analysis value (%) 57.69 5.64 15.
62 1!1h96 theoretical value←) 57.76
5.75 15.50 1.02 Molecular weight by GO-MS 228 Example 2 64 g of 3'' tsrt-butylphenol, 500 g of dichloromethane, and 50 g of thiophosgene were placed in the same reactor as in Example 1, and the flask was cooled on ice.

Next, add 15qI) potassium carbonate aqueous solution 200ml to the dropping funnel.
- was removed and the same reaction procedure as in Example 1 was carried out to obtain 5-te.
69 rt-butylchloro 7-emulthioformate was obtained.

Next, examples of compounds obtained from the compounds of the present invention and their use as herbicides will be shown.

1.379 g of 3-methoxy-N-methylaniline and the same amount of anhydrous potassium carbonate were stirred in 20 g of acetone at room temperature.
Acetone 20rnI! After 30 minutes, the reaction mixture was extracted with benzene, washed with water, dried and recrystallized to give 0-5-tert- Butylphenyl N-(5-methoxyphenyl)-N-methylthiocarbamate 2,. 639 was obtained.

Melting point: 8a5-90℃ Paddy soil is placed in a porcelain pot with a diameter of 9m, water is added, and after puddling, weed seeds are sown on the surface layer of the soil, and two-leaf stage paddy rice seedlings (
Two plants (variety Nipponbare) were transplanted at a depth of 1 crn.

The next day, the pot was flooded to a depth of 2 cm, and 0-3-tert-butylphenyl N-(5-methoxyphenyl)-N-methylthiocarbamate hydrating agent was diluted with 10 ml of water and dropped onto the water surface. Thereafter, the plants were left in a greenhouse and 3 weeks after treatment with the chemical solution, the herbicidal effect and the effect on paddy rice were investigated. As a result, there was virtually no chemical damage to paddy rice seedlings with the amount of the test chemical being 1259/10 a, and there was virtually no chemical damage to rice seedlings, such as wildflowers, cypresses, and fireflies.

Controlled 100 thorns and grasshoppers.

Patent Applicant: Toyo Soda Kogyo Co., Ltd. Proceeding Amendment Minister March 9, 1980 Director General of the Patent Office Mr. Kazuo Genge 1 Notes 1988 Patent Application No. 040610 2 Name of the invention 3 Person making the amendment Relationship with ink Patent applicant telephone number ('585) ro 311 4. 8+1 of the amendment order 5. Number of inventions increased by voluntary 5. amendment 6. Target of amendment ``Column for detailed explanation of the invention in the specification'' 7. Contents of the amendment (1) Description , page 3, line 7, page 5, line 7 from the bottom, page 6, line 5 from the bottom, and page 7, line 3 (-3-tert-butylphenylchlorothioformate) Mate,” he corrected.

(2) Specification; 2-3 lines from the bottom of page 3, 1-2 lines from the bottom of page 3, and 6 lines from the top of page 4, "Dehalogenation reagent" Corrected to [dehydrohalogenation reagent].

Claims (1)

[Claims] (113-t8rt-butylphenylchlorothioformate (2) 3-tert-butylphenol and thiophosgene are reacted.
Method for producing rt-butylphenylchlorothioformate.