JPS6221344B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to carbamate derivatives and methods for producing the same. For more details, see the general formula () (In the formula, m is 1 or 2, n is 0, 1 or 2
shows. However, when n is 0, a hydrogen atom is bonded to each of the two carbons to which -(CH ₂ ) _{o -} is bonded in place of -(CH ₂ ) o -. R ₁ represents a hydrogen atom or a halogen atom, and R ₂ represents a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxy group. ) (hereinafter referred to as the compound of the present invention) and a method for producing the same. Conventionally, O-aryl N-arylthiocarbamate compounds are known to have antibacterial properties as medicines, and substituted phenyl N-aryl carbamate compounds can be used as herbicides. The compound of the present invention has not been described in any literature, and no literature suggesting its useful physiological activity is known. The present inventors have conducted intensive research to develop carbamate derivatives with sufficient herbicidal effects and high selectivity, and have found that the compound of the present invention has excellent herbicidal properties against various weeds. The present invention was completed based on the discovery that the compound exhibits activity. The compounds of the present invention are useful as active ingredients in herbicides. The herbicide containing the compound of the present invention as an active ingredient exhibits extremely excellent herbicidal activity against many weeds, including grasshoppers, especially in flooded rice fields, and is harmless to transplanted paddy rice. It is suitable as an agent. In addition, when treated with upland soil, it showed an excellent selective weeding effect between grass weeds and broad-leaved crops, and was recognized to have applicability as a herbicide for upland fields. The compound of the present invention represented by the general formula () can be produced according to the following reaction formula. (In the formula, m is 1 or 2, n is 0.1 or 2.
shows. However, when n is 0, a hydrogen atom is bonded to each of the two carbons to which -(CH ₂ ) _{o -} is bonded in place of -(CH ₂ ) o -. R ₁ represents a hydrogen atom or a halogen atom, and R ₂ represents a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxy group. Hal indicates a halogen atom. ) The above reaction is carried out in the presence of a dehydrohalogenating agent,
Further, the reaction usually proceeds in the presence or absence of a reaction solvent at a reaction temperature of 0°C to 150°C, and the reaction time is about several minutes to 48 hours. Examples of dehydrohalogenation agents include alkali hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth hydroxides such as calcium hydroxide, and alkali carbonates such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate. , metal hydrides such as sodium hydride, and tertiary amines such as triethylamine, dimethylaniline, and pyridine. In reaction formula (2), the aniline derivative as a raw material can be used as a dehydrohalogenating agent. Reaction solvents include water, alcohols such as methanol, ethanol, and isopropanol, ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as benzene, toluene, and xylene, ethers such as ethyl ether, tetrahydrofuran, and dioxane, and chlorine. Halogenated hydrocarbons such as benzene, chloroform, carbon tetrachloride and dichloroethane, polar solvents such as dimethylformamide and dimethyl sulfoxide, and the like are used. Next, the method for producing the compound of the present invention will be specifically explained. Example 1 Method for producing 5-indanyl N-methyl-N-(3-methylphenyl)carbamate (compound
No.1) N-Methyl-N-(3-methylphenyl)carbamoyl chloride 1.84g, 5-indanol
1.34 g and 1.38 g of anhydrous potassium carbonate were added to 50 ml of methyl ethyl ketone and heated under reflux for 15 hours.
After the reaction mixture was cooled to room temperature, it was poured into cold water and the product was extracted with benzene. The benzene solution was washed with water and a saturated aqueous sodium chloride solution in that order, dried over anhydrous magnesium sulfate, and then benzene was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel, developed with benzene) to obtain 5-indanyl N-methyl-
N-(3-methylphenyl)carbamate 1.97g
(yield 70%). A part of this product was recrystallized from n-hexane to obtain colorless crystals with a melting point of 73.5 to 75°C. Example 2 5,6,7,8-tetrahydro-2-naphthyl N-methyl-N-(3-methoxyphenyl)
Method for producing carbamate (compound No. 10) 1.37 g of 3-methoxy-N-methylaniline and 1.52 g of anhydrous potassium carbonate were added to 20 ml of acetone, and while stirring under ice cooling, 5,6,7,8-tetrahydrocarbonate was added. -2-naphthyl chlorformate
2.11 g was dissolved in 20 ml of acetone and added. at room temperature
After stirring for 30 minutes, the reaction mixture was poured into cold water and the product was extracted with benzene. The benzene solution was washed with water and a saturated aqueous sodium chloride solution in that order, dried over anhydrous magnesium sulfate, and then benzene was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel, developed with benzene),
5,6,7,8-tetrahydro-2-naphthyl
2.27 g of N-methyl-N-(3-methoxyphenyl)carbamate (yield 73%, _{oily, n25D} ^:
1.5780) was obtained. Next, representative examples of the compound represented by the general formula (1) and their physical properties are shown in Table 1 below.

【table】

[Table] The compound of the present invention exhibits excellent herbicidal activity against various weeds and does not cause any phytotoxicity to crops such as paddy rice, soybeans, and cotton, and is therefore suitable as an active ingredient in herbicides. In other words, the action of the compound of the present invention is that it kills weeds, stops their growth, or significantly inhibits and retards their growth without causing chemical damage to crops, thereby eliminating growth competition with crops. One example is to make it possible. The compound of the present invention can be used particularly in flooded paddy fields.
Including wild wildflowers, Japanese cypresses, Japanese cypresses,
50 against many weeds such as Kikashigusa and Firefly
It was observed that an extremely excellent herbicidal activity was exhibited at an active ingredient amount of ~500g/10a. On the other hand, it is extremely safe for young rice seedlings, with no effects observed even at an active ingredient amount of 1000g/10a, and has extremely excellent properties as a herbicide for paddy fields. Furthermore, when the compound of the present invention is used as a soil treatment agent after sowing general broad-leaved crops such as soybeans, which are upland crops, it will not cause chemical damage to crops,
It was found that it can effectively control grass weeds such as grasshopper and foxtail grass, and has applicability as a herbicide for upland fields. Next, the herbicidal effects of the compounds of the present invention will be explained using usage examples. Usage example 1 Herbicidal effect test under submerged conditions 10 parts of the compound of the present invention as a carrier material, 87.3 parts of Siegrite [trade name, manufactured by Kunimine Kogyo Co., Ltd.], and as a surfactant, Neopellex [trade name, manufactured by Kao Atlas Co., Ltd.]
[manufactured by Toho Chemical Industry Co., Ltd.] 1.35 parts and Solpol 800A [trade name, manufactured by Toho Chemical Industry Co., Ltd.] 1.35 parts mixed and crushed to 10%
A hydrating agent was obtained. Next, put paddy soil in a porcelain pot with a diameter of 9 cm.
After adding water and puddling, weed seeds were sown on the soil surface, and two two-leaf rice seedlings (variety: Nipponbare) were planted at a depth of 1 cm. The next day, the pots were flooded with water to a depth of 2 cm, and a predetermined amount of the wettable powder of the compound of the present invention obtained as described above was diluted in 10 ml of water per pot and dropped onto the water surface. Thereafter, the mixture was left in a greenhouse, and 20 days after treatment, the herbicidal effect and the effect on paddy rice were investigated. The evaluation was displayed on a 6-level scale, and the specific details are as follows. The results are shown in Table 2.

【table】

【table】

[Table] Usage Example 2 Weeding effect test by field soil surface treatment Field soil was put into a porcelain pot with a diameter of 12 cm, seeds of several types of plants were sown, and the pot was covered with 1 cm of soil. A predetermined amount of the hydrating powder of the compound of the present invention obtained as described above was diluted in 10 ml of water per pot, which was sprayed onto the soil surface, and then left standing in a greenhouse and watered at appropriate times. Three weeks after the chemical solution treatment, the herbicidal effect and the effect on soybeans and cotton were investigated and evaluated according to Use Example 1. The results are shown in Table 3.

【table】

【table】

Claims (1)

[Claims] 1 General formula () (In the formula, m represents 1 or 2, and n represents 0, 1 or 2. However, when n is 0, the two carbons to which -(CH ₂ ) _o - are bonded are -(CH ₂ ) In place of _o -, each hydrogen atom shall be bonded. R ₁ represents a hydrogen atom or a halogen atom, and R ₂ represents a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxy group.) Carbamate derivatives. 2 General formula () (In the formula, X is a hydrogen atom or a halocarbonyl group, m is 1 or 2, and n is 0, 1 or 2. However, when n is 0, _- (CH ₂ ) A phenol derivative represented by _the general formula () is assumed to have a hydrogen atom bonded to each _of the two carbon atoms in (In the formula, Y is a halocarbonyl group when X in formula () is a hydrogen atom, and is a hydrogen atom when X in formula () is a halocarbonyl group. R ₁ represents a hydrogen atom or a halogen atom, and R ₂ represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group.) General formula () (In the formula, m is 1 or 2, and n is 0, 1 or 2. However, when n is 0, the two carbons to which -(CH ₂ ) _o - are bonded are -(CH ₂ ) Instead of _o −,
Assume that hydrogen atoms are bonded to each. R ₁ represents a hydrogen atom or a halogen atom, and R ₂ represents a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxy group. ) A method for producing a carbamate derivative represented by