JPH02279687A - Silylphenyl carbamate derivative, its production and herbicide containing the same as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (W represents methyne or N; A represents H, halogen, lower alkyl or lower alkoxy; X represents O or S; R1 and R2 represent H or trimethylsilyl, and R2 represents trimethylsilyl when R1 represents H, and R2 represents H when R1 represents trimethylsilyl). EXAMPLE:0-3-Trimethylsilylphenyl N-methyl-N-(6-methoxy-2-methylaminopyridine) thiocarbamate. USE:A herbicide. PREPARATION:A phenol derivative expressed by formula II (Y represents H or halocarbonyl) is reacted with an aromatic amine derivative expressed by formula III (Z represents halocarbonyl when group Y in formula II represents H, and represents H when Y represents halocarbonyl).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel silylphenyl carbamate derivative, a method for producing the same, and a herbicide containing the compound as an active ingredient.

(Prior art) Until now, Japanese Patent Application Laid-Open No. 48-49925,
JP-A-56825, JP-A-61-18752, and the like propose and disclose that specific aryl N-aryl carbamate compounds can be used as herbicides for warm water direct seeding cultivation in rice fields. Also, Japanese Patent Publication No. 61-3067
Publication No. 0, JP-A-62-34002, JP-A-62
It is known that certain arylthiocarbamate compounds can be used as herbicides, as disclosed in Japanese Patent No. 37035 and the like.

(Problems to be Solved by the Invention) Known aryl N-aryl carbamate compounds are not necessarily satisfactory in terms of drug toxicity or efficacy.

(Means for Solving the Problems) In response to this situation, the present inventor has further developed a carbamate derivative that does not cause problematic phytotoxicity to target crops, has sufficient herbicidal effect, and has a high degree of selectivity. As a result of intensive research to develop a compound that has the following properties, the invention was completed.

That is, the present invention relates to the general formula (1) (wherein W represents a methine group or a nitrogen atom, where A
represents a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxy group. X represents an oxygen atom or a sulfur atom. R and R2 represent a hydrogen atom or a trimethylsilyl group. When R1 is a hydrogen atom, R2 represents a trimethylsilyl group, and when R1 is a trimethylsilyl group, R2 represents a hydrogen atom. The present invention provides a method for producing a silyl phenyl carbamate derivative (hereinafter referred to as the compound of the present invention) represented by the formula (hereinafter referred to as the compound of the present invention), and a herbicide containing the same as an active ingredient.

(for production) The present invention will be explained in more detail below.

First, the method for producing the compound of the present invention will be explained.

The silylphenyl carbamate derivative represented by the general formula (1) used in the herbicide of the present invention can be produced according to the following reaction formula.

(n) (m) → General formula (1) ((■) In the formula, Y represents a hydrogen atom or a halocarbonyl group, and R and R represent a hydrogen atom or a trimethylsilyl group. When R1 is a hydrogen atom, R2 is It represents a trimethylsilyl group, and when R1 is a trimethylsilyl group, R2 represents a hydrogen atom.Also, in the formula (III), Z is such that Y in the formula (II) is
When it is a hydrogen atom, it is a halocarbonyl group, and when Y in formula (II) is a halocarbonyl group, it is a hydrogen atom. W represents a methine group or a nitrogen atom. Here, A represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group. ) The above reaction is carried out in the presence of a dehydrohalogenating agent and in the presence or absence of a reaction solvent, usually at temperatures between 0°C and 1°C.
The reaction proceeds at a reaction temperature of 50° C. and is completed in a few minutes to about 48 hours.

Examples of dehydrohalogenating agents include alkali hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth hydroxides such as calcium hydroxide, alkali carbonates such as thorium carbonate and potassium carbonate, and sodium hydride. Examples include metal hydrides, tertiary amines such as triethylamine, dimethylaniline, and pyridine.

As a reaction solvent, water, methanol, ethanol,
Alcohols such as isopropanol, acetone 1, ketones such as methyl ethyl ketone, aromatic hydrocarbons such as benzene, toluene, xylene, ethers such as ethyl ether, tetrahydrofuran, dioxane, chlorobenzene, chloroform, carbon tetrachloride 1, dichloroethane, etc. Polar solvents such as halogenated hydrocarbons, dimethylformamide, and dimethyl sulfoxide are used.

After the completion of the reaction, the reaction solution is added to water and subjected to conventional treatments such as organic solvent extraction and concentration, and if necessary, purification operations such as chromatography, distillation, and recrystallization are carried out to achieve the desired objective. The compound of the present invention is obtained.

Next, the compound of the present invention that can be produced by the above production method is added to the first compound.
Shown in the table.

The compound of the present invention has a herbicidal effect on various weeds that are problematic in the flooding treatment of rice fields, including annual weeds such as field weed, perennial weeds such as fireweed, cyperus, and cyperus, and broad-leaved weeds such as cypress and cyperus. In addition, it has extremely high safety against paddy rice, especially young paddy rice, and is suitable as an active ingredient of herbicides.

When using the compound of the present invention as a herbicide, an appropriate amount of one or more of the compounds shown in the general case (1) above is mixed with an inert carrier, and a wettable powder or emulsion, which is a form of usual agricultural chemical use, is prepared. It is used in the form of single tablets, etc.

Examples of solid carriers include talc, diatomaceous earth, bentonite, kaolin acid clay, white carbon, pumice powder, etc. Examples of liquid carriers include water, alcohol, benzene, toluene, xylene, kerosene, cyclohexane, cyclohexanone, and dimethyl. Formamide, mineral oil, etc. can be used.

Furthermore, surfactants, stabilizers, etc. can be added if necessary for the formulation. The herbicide of the present invention may also be used in other agricultural chemicals such as insecticides used in the same field.

Can be used in combination with fungicides, herbicides, plant growth regulators or fertilizers. In particular, it may be appropriate to add and mix other herbicides in order to reduce the spraying effort or to widen the range of grass species that can be effectively controlled.

Herbicides that can be added include atrazine, simazine, and shiftrin. Triazine herbicides such as promethrin, carbamate herbicides such as Ashram, Bentocarb 1 Molinate, urea herbicides such as Linuron 1 Dimuron, 2
．． 4-D, MCP.

Phenoxy herbicides such as MCPB and nabroanilide, genyl ether herbicides such as nitrophen, chloronitrophenone, and chromethoxyl, heterocyclic herbicides such as oxacyacin, virazolate, and pentacin, and amide herbicides such as alachlor, butachlor, and propanil. Agents, etc. can be mentioned. By judiciously combining one or more of these herbicides, it is possible to provide a mixture that is effective against many grass species.

The amount of the compound of the present invention to be applied varies depending on the application situation, application time, application method, target grass species, etc., but in general, the amount of active ingredient is 1 to 1000 g/10 m.

Preferably, a range of 10 to 500 g/10a is appropriate.

(Examples) Hereinafter, the present invention will be explained in more detail using production examples and test examples, but the present invention is not limited to these examples.

First, a method for producing the active ingredient compound used in the herbicide of the present invention will be specifically explained.

Production example 1 0-3-trimethylsilylphenyl N-methyl-N-
(6-Medoxy 2-methylaminopyridine) thiocarbamate (compound of the present invention Part 1) 11.8 g of 3-trimethylsilylphenol and 9.0 g of thiophosgene were dissolved in 200 ml of carbon tetrachloride, and while stirring under water cooling, 11.8 g of 3-trimethylsilylphenol and 9.0 g of thiophosgene were dissolved.
35 ml of 0% aqueous sodium hydroxide solution was added dropwise. After the dropwise addition was completed, stirring was continued at room temperature for 12 hours. A carbon tetrachloride layer was separated from the reaction solution, dried over anhydrous magnesium sulfate, and then carbon tetrachloride was distilled off under reduced pressure. The residue was distilled under reduced pressure to obtain 13.5 g of chlorothioformate having a boiling point of 78 to 80°C and 10.6 mmHg.

'H-NMR spectrum (CDC13) δ value (ppm
) 7.53~7゜10 (4H, m), 0.27 (9H, s,)! R spectrum (KBr) Wavenumber (cll-') 2950.1565.1470.140ON-Methyl-
N-6-medoxy 2-methylaminopyridine 514s
910 mg of 3-trimethylsilylphenylchlorothioformate and 513 mg of anhydrous potassium chloride were added to 20 ml of acetone, and the mixture was heated under reflux for 15 hours. After the reaction mixture was cooled to room temperature, it was poured into cold water, and the benzene solution of the product 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 to give 0-3-trimethylsilylphenyl N-
Methyl-N-(6-medoxy 2-methylaminopyridine) thiocarbamate was obtained.

This product was recrystallized from methyleneol, with a melting point of 47-48°.
1.26 g of colorless crystals were obtained.

'H-NMR spectrum (CDC13) δ value (ppm) 7.65-6.83 (m, 6H).

6.63-6.42 (dd, IH).

3.87 (s, 3H), 3.68 (s, 3H).

0.2 (s, 9H) IR characteristic absorption wave number (as-') 1585.1460, 1420, 1380° From the mass spectrum, the molecular weight is 346 Production example 2 0-3-trimethylsilylphenyl N-methyl-N-
(6-Medoxy 2-methylaminopyridine) thiocarbamate (invention compound No. 2) 1.66 g of 3-trimethylsilylphenol and 0.8 ml of trichloromethyl chloroformate (TCP) were added to 20 ml of toluene.
dimethylaniline 2 while stirring at room temperature.
ml was added dropwise. After the dropwise addition was completed, stirring was continued at room temperature for 15 hours. A toluene layer was separated from the reaction solution, and toluene was distilled under reduced pressure. The residue was dissolved in 20 ml of carbon tetrachloride, and N
- Add 1.38 g of methyl-N-6-medoxy-2-methylaminopyridine and 1.38 g of anhydrous potassium carbonate,
The mixture was 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 to obtain 0-3
-trimethylsilylphenyl N-methyl-N-(6-
Medoxy 2-methylaminopyridine) carbamate was obtained. This product was recrystallized from methanol and had a melting point of 71.
1.7 g of colorless crystals at ~72°C were obtained.

'H-NMR spectrum (CDC13) δ value (ppm) 7.55-6.92 (m, 6H).

6.58-6.38 (dd, IH).

3,85 (s, 3H), 3.53 (s, 3H).

0.2 (s, 9H) IR characteristic absorption (KBr) Wave number ((to) -1) 1730.1580, 1470, 1355° From the mass spectrum, the molecular weight is 330 Table 2 shows the product manufactured according to the above method. Some of the compounds of the present invention are shown below.

Next, formulation examples of the herbicide of the present invention will be described.

In the formulation examples, "parts" are parts by weight.

Formulation example (wettable powder) - Using 2.10 parts of Compound Magnetic as a carrier material, Sickleite 87
．． 3 parts were mixed and ground together with 1635 parts of Neoperex and 1.35 parts of Tsurpol 800A as surfactants to obtain a 10% wettable powder.

(Emulsion) 1.25 parts of 1 lkL of the compound, 65 parts of benzene, and 10 parts of Tsurpol 800A as a surfactant were mixed and dissolved to obtain a 25% emulsion.

(Granules) Compound kl, 10 parts, 50 parts of bentonite, 35 parts of kunilite, and Tsurupol 800A as a surfactant.
After mixing and pulverizing 5 parts, add 10 parts of water, stir evenly, extrude through a knot hole with a diameter of 0.7 mm, and after impression, 1~
The sample was cut into 2 lengths to obtain 10% granules.

Next, the herbicidal effects of the compounds of the present invention will be explained using test examples.

Test Example Weeding effect test under warm water conditions Paddy soil was placed in a magnetic pot with a diameter of 9011 mm, water was added, and after plowing, weed seeds were sown on the surface layer of the soil. Two plants were planted at a depth of 2. The next day, 2 cm of warm water was poured into the pot, and a predetermined amount of the wettable powder of each compound of the present invention was diluted in 10 ml of water per pot and dropped onto the water surface. Thereafter, the plants were allowed to stand at room temperature, and three weeks after the chemical 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 3.

Display Paddy rice chemical damage Weeding effect 5 Death 100% control (Asakusa rate 0%) 4
Severe death 80% control (Asakusa rate 20%) 3 Medium damage 60% control (Asakusa rate 40%) Minor damage 40% control (
Asakusa rate 60%) Slight damage 20% control (Asakusa rate 80%)
Harmless 0% control (Asakusa grass rate 100%) (Effects of the invention) The compound of the present invention has excellent herbicidal efficacy against various weeds that are a problem in hot water treatment of rice fields, and has high safety against young paddy rice. It was shown that it has high applicability as a herbicide for rice fields.

Claims (2)

[Claims] (1) General formula (I): ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, W represents a methine group or a nitrogen atom. Here, A represents a hydrogen atom, a halogen atom, a lower alkyl group, or , represents a lower alkoxy group.
When 1 is a trimethylsilyl group, R_2 represents a hydrogen atom. ) A silylphenyl carbamate derivative represented by (2) General formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, Y represents a hydrogen atom or a halocarbonyl group,
R_1 and R_2 represent a hydrogen atom or a trimethylsilyl group. When R_1 is a hydrogen atom, R_2 represents a trimethylsilyl group, and when R_1 is a trimethylsilyl group, R_2
indicates a hydrogen atom. ) and the general formula (III): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, Z is a halocarbonyl group when Y in (II) is a hydrogen atom; ) When formula Y is a halocarbonyl group, it is a hydrogen atom. W represents a methine group or a nitrogen atom. Here, A represents a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group. General formula (I) (3) of claim (1) characterized by reacting with an amine derivative (
A herbicide characterized by containing a silylphenyl carbamate derivative represented by the general formula (I) in item 1) as an active ingredient.