JPS6347704B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to O-3-tert-butylphenyl-chlorothioformate and a method for producing the same.

Phenyl chlorothioformates are known as raw materials for thiocarbamates that have excellent antifungal properties. For example, JP-A-57-176952 discloses that thiocarbamates made from O-4-tert-butylphenyl chlorothioformate have excellent effects against filamentous fungal infections of the skin. .

The present inventors used thiocarbamates to kill insects,
As a result of extensive research to develop compounds with bactericidal and herbicidal effects, it was discovered that derivatives with an O-3-tert-butylphenyl group were suitable for this purpose, and based on this knowledge, the present invention was developed. completed.

The O-3-tert-butylphenyl chlorothioformate 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, and the like. For example, by reacting the O-3-tert-butylphenyl chlorothioformate of the present invention with 3-methoxy-N-methylaniline,
-Butylphenyl N-(3-methoxyphenyl)-N-methylthiocarbamate can be produced.

A herbicide containing O-3-tert-butylphenyl N-(3-methoxyphenyl)-N-methylthiocarbamate as an active ingredient can be prepared from the O-3-tert-butylphenyl N-(3-methoxyphenyl)-N-methylthiocarbamate thus obtained.

This product exhibits extremely excellent herbicidal activity against many weeds, including field weeds, and is practically harmless to transplanted paddy rice, making it suitable as a herbicide for paddy fields. In addition, by treating upland soil, weeds of the grass family -
It shows excellent selective weeding effect among broad-leaved crops, and is also applicable as a herbicide for upland fields.

O-3-tert-butylphenyl chlorothioformate of the present invention can be produced by reacting 3-tert-butylphenol and thiophosgene.

The present invention provides a method for producing O-3-tert-butylphenyl chlorothioformate, which is characterized by reacting O-3-tert-butylphenyl chlorothioformate and 3-tert-butylphenol with thiophosgene. It is.

The reaction between 3-tert-butylphenol and thiophosgene proceeds easily in the presence of a dehydrohalogenating agent. For the reaction, there are methods such as adding a dehydrohalogenation reagent to a mixed solution of 3-tert-butylphenol and thiophosgene, or adding a mixed solution of a dehydrohalogenating reagent and 3-tert-butylphenol to a thiophosgene solution. used.

Examples of dehydrohalogenation reagents include inorganic bases such as American metal hydroxides, alkaline earth metal hydroxides, and alkali metal carbonates, and organic bases such as triethylamine, pyridine, quinoline, and isoquinoline. These dehydrohalogenation reagents are usually used after being dissolved in water or a suitable organic solvent, and are used in an equivalent amount to 3-tert-butylphenol like thiophosgene.

It is preferable to use a solvent to facilitate the reaction. As the solvent, chlorinated hydrocarbons such as chloroform, dichloromethane, and carbon tetrachloride, and aromatic hydrocarbons such as benzene, toluene, and xylene are selected.

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

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

Example 1 2 with stirrer, thermometer and 300 ml dropping funnel
Place 64 g of 3-tert-butylphenol, 600 ml of chloroform, and 50 g of thiophosgene in a three-necked flask, and cool the flask on ice.

Then add 20% aqueous sodium hydroxide solution to the dropping funnel.
Take 200ml and while stirring, lower the temperature inside the flask to 5~5.
While maintaining the temperature at 10°C, add aqueous sodium hydroxide solution dropwise from the dropping funnel over 3 hours. After adding the entire amount of the sodium hydroxide aqueous solution dropwise, the mixture is further stirred at room temperature for 10 hours.

After the reaction is complete, transfer the reaction solution to Separatory funnel No. 1,
Separate the chloroform layer and dry with calcium chloride. After filtering off calcium chloride, the filtrate was distilled to obtain 71 g of O-3-tert-butylphenyl chlorothioformate having a boiling point of 123-4°C/4 mmHg.

Infrared absorption spectrum (NaCl) 2950, 1605, 1570, 1490, 1230, 1050 cm ^-1 Nuclear magnetic resonance absorption spectrum (CCl ₄ , internal standard
TMS) 1.29 (s) ppm (9H) 6.74-7.40 (m) (4H) The results of elemental analysis (as C ₁₁ H ₁₃ ClOS) were as follows.

C H Cl S Analytical value (%) 57.69 5.64 15.62 13.96 Theoretical value (%) 57.76 5.73 15.50 14.02 Molecular weight by GC-MS 228 Example 2 Into the same reaction apparatus as Example 1, 64 g of 3-tert-butylphenol and 500 ml of dichloromethane were added. , then take 50 g of thiophosgene and cool the flask on ice.

Then add 200 ml of 15% potassium carbonate aqueous solution to the dropping funnel.
ml and perform the same reaction procedure as in Example 1 to obtain O-
69 g of 3-tert-butylphenyl chlorothioformate was obtained.

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

1.37 g of 3-methoxy-N-methylaniline and the same amount of anhydrous potassium carbonate were stirred in 20 ml of acetone at room temperature, and 2.28 g of O-3-tert-butylphenyl chlorothioformate, which is the target substance of the present invention, was dissolved in 20 ml of acetone. After 30 minutes, the reaction mixture was extracted with benzene, washed with water, dried, and recrystallized.
3-tert-butylphenyl N-(3-methoxyphenyl)-N-methylthiocarbamate 2.63g
I got it.

Melting point: 64-65℃ Put paddy soil in a porcelain pot with a diameter of 9 cm, add water, plow through the soil, sow weed seeds on the soil surface, and
Paddy rice seedlings (variety, Nipponbare) in the leaf stage are planted at a depth of 1 cm.
Two of these plants were transplanted. The next day, 2cm of water was filled and O-3
A wettable powder containing 10% of -tert-butylphenyl N-(3-methoxyphenyl)-N-methylthiocarbamate was diluted in 10 ml of water per pot and dropped onto the water surface. After that, leave it in the greenhouse and treat it with chemical solution 3.
After a week, the weeding effect and the effect on paddy rice were investigated. As a result, there was no chemical damage to paddy rice seedlings with the amount of the test chemical of 125g/10a, and it was found that there was no chemical damage to rice seedlings, and that it was not harmful to rice seedlings.
100% control of Japanese staghorn and staghorn grass.

Claims (1)

[Claims] 1 O-3-tert-butylphenyl-chlorothioformate. 2. A method for producing O-3-tert-butylphenyl-chlorothioformate, which comprises reacting 3-tert-butylphenol and thiophosgene.