JPS59170068A - Carbamate derivative - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (X is O or S; R is halogen or lower alkyl; n is 1 ow 2). EXAMPLE:2-Naphthyl N-(6-methyl-2-pyridyl)-N-methylcarbamate. USE:A herbicide in paddy fields. PREPARATION:A naphtol derivative of formula II (Y is H, halocarbonyl or halothiocarbonyl) is reacted with an aminopyridine derivative of formula III (Z is halocarbonyl or halothiocarbonyl when Y is H, and H when Y is halocarbonyl or halothiocarbonyl) in the presence of a dehydrohalogenating agent, e.g. an alkali hydroxide, alkali carbonate or tertiary amine, at 0-150 deg.C to give the aimed compound of formula I .

Description

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

It is well known that ruthiocarbamate compounds have antibacterial properties as pharmaceuticals. It is also known that aryl N-aryl calcmate compounds can be used as herbicides.

The present inventors previously discovered that certain N-pyridylcano(mate derivatives) have herbicidal activity.

The present inventors further carried out intensive research to develop a compound that has sufficient herbicidal activity and a high degree of selectivity among N-hylysyl carnocomate derivatives, and as a result, the present invention has been completed. completed.

That is, the present invention provides car-(mate derivatives (hereinafter referred to as , referred to as the compound of the present invention), and a herbicide containing the compound as an active ingredient.

The herbicide containing the compound of the present invention as an active ingredient exhibits extremely excellent herbicidal activity against many weeds including field weed, especially in flooded rice fields, and is virtually harmless to transplanted paddy rice. It is suitable as a herbicide for paddy fields.

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

(In the formula, xFi represents an oxygen atom or a sulfur atom, R represents a halogen atom or a lower alkyl group, n represents 1 or 2, and Hat represents a halogen atom). ) 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 ranging from 0°C to 150°C.
The reaction time is from several minutes to about 48 hours.

Examples of dehydrohalogenation agents include alkali hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth hydroxides such as calcium hydroxide, sodium carbonate, potassium carbonate,
Examples include alkali carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, metal hydrides such as sodium hydroxide, and tertiary amines such as triethylamine, dimethylaniline, and pyridine. In reaction formula (2),
The raw material 2-methylaminopyridine derivative can be used as a dehydrohalogenating agent.

As reaction solvents, water and methanol, ethanol,
Alcohols such as isopropanol, ketones such as acetone and methyl ethyl ketone, aromatic hydrocarbons such as benzene, toluene, and xylene, ethyl ether, tetrahydrofuran, dioxane, etc. +7) x-7ols, chlorobenzene, chloroform , halogenated hydrocarbons such as carbon tetrachloride and dichloroethane, and polar solvents such as dimethylformamide and dimethyl sulfoxide.

Next, the present invention will be explained in more detail with reference to Examples.

[Example 1] 2-naphthyl N-(6-methyl-2-pyridyl)-N
-Production method of methyl carbamate (invention compound AI) N-(6-methyl-2-pyridyl)-N-methylcarbamoyl chloride 1.85 g, 2-naphthol 1.44
9 and 1.589 g of anhydrous potassium carbonate were added to 50 ml of methyl ethyl ketone, and the mixture was heated under reflux for 48 hours.

After the reaction mixture was cooled to room temperature, it was poured into cold water and the product was extracted with benzene. Benzene solution in water.

After washing with a saturated aqueous sodium chloride solution and drying over anhydrous magnesium 61 choate, benzene was distilled off under reduced pressure. The residue was purified by column chromatography (silica gel, developed with ethyl acetate/benzene-1,/9 (V/V)) to obtain 2-naphthyl N-(6-methyl-2-pyridyl)-y-methylcarbamate. 639 (yield 90%)
I got it. A part of this material was recrystallized from ethanol, with a melting point of 91~? Colorless crystals at 2.5°C were obtained.

[Example 2] Method for producing 0-2-su7tyl N-(5,6-dimethyl-2-pyridyl)-N-methylthiocarbamate
(Compound A8 of the present invention) 1,569 λ3-dimethyl-6-methylaminopyridine and 1,389 g of anhydrous potassium carbonate were added to 20 g of acetone, and while stirring at room temperature, 2-naphthyl chlorthioforme) 2.237 g
was dissolved in 20 grams of acetone and added. After stirring as it was for 30 minutes, the mixture was heated under reflux for 2 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).

0-2-naphthyl N-(5,6-cymethyl-2-
pyridyl)-N-methylthiocarbame-)2.749(
A yield of 85 cm) was obtained. A portion of this product was recrystallized from ethanol to obtain colorless crystals with a melting point of 108-109°C.

Table 1 shows representative examples and physical constants of the compounds represented by the general formula (1).

In order to use the compound of the present invention as a herbicide, an appropriate amount of one or more compounds represented by the above general formula (I) is mixed with an inert carrier, and the compound is prepared into an aquarium or an emulsion, which is a conventional form of agricultural chemical use. It is used in the form of two tablets, powder, etc.

Talc, clay, diatomaceous earth as solid carriers.

Examples include bentonite, kaolin, acid clay, white carbon, pumice powder, etc., and liquid carriers include water, alcohol, benzene, toluene, and xylene.

Kerosene, cyclohexane, cyclohexanone.

Isophorone, butyl cellosolve, benzyl acetate.

Dimethylformamide, mineral oil, etc. are used.

Furthermore, if necessary, surfactants, stabilizers, etc. can be added during soil excavation. Furthermore, the herbicide of the present invention can be applied in combination with other agricultural chemicals used in the same field, such as insecticides, 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.

As herbicides that can be added, triazine herbicides such as cymetrin and glometrin, and bentiocarb.

Carbamate herbicides such as molinate, urea herbicides such as Daimeron, 2.4-D, MOP.

Examples include phenoxy herbicides such as MC A B and naproanilide, diphenyl erthyl herbicides such as nitrofen, chlornitrophen, and chlormethoxynil, heterocyclic herbicides such as oxacyacin, virazolate, and pentacin, and noamide herbicides such as butachlor and propanil. be able to. By combining one or more of these herbicides, it is possible to provide a mixture that is effective against many grass species.

Next, examples of formulations using the compounds of the present invention will be described.

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

[Example 6] (Wettable powder) 1.10 parts of the compound A of the present invention as a carrier material, 87.3 parts of Zikrite [trade name, manufactured by Kunimine Kogyo ■], as a surfactant, Neoperex [trade name, Kao Atlas] ■Made)
The mixture was mixed and pulverized with 1.55 parts of Tsurupol 800A (trade name, manufactured by Toho Chemical Industries, Ltd.) and 1.65 parts to obtain a 10-chi permanent adhesive.

[Example 4] (Emulsion) 2.25 parts of the compound of the present invention was mixed and dissolved with 65 parts of benzene and 10 parts of Tsurpol 800A as a surfactant.
A 25% emulsion was obtained.

[Example 5] (Granules) 3.10 parts of the compound of the present invention was mixed and pulverized with 50 parts of bentonite, 65 parts of Kunilide [trade name, manufactured by Kunimine Industries C'1], and 5 parts of Tsurupol 800A as a surfactant. Thereafter, 10 parts of water was added, stirred uniformly, extruded through a hole with a diameter of α7, dried, and cut into 1-2 inch lengths to obtain 10% granules.

The compound of the present invention is suitable as a herbicide active ingredient, particularly for waterlogging treatment of rice fields before weed germination. 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 generally the amount of active ingredient is 50 to 100n 9
/10a, good luck 100-5009 /10a
A range of is appropriate.

The herbicidal properties of the compounds of the present invention are that they act particularly strongly during the germination of weeds and strongly suppress their elongation after germination.
The residual effect within the weed body is extremely long.

That is, by killing weeds, stopping their growth, or significantly inhibiting and delaying their growth, weeds lose their ability to compete with crops.

Herbicidal Spectrum is highly effective against the major pests in rice fields, such as the grasshopper and the Japanese cyperus, and is also highly effective against the Japanese grasshopper and Japanese grasshopper.

On the other hand, the safety for paddy rice transplanted from young seedlings is extremely high.
Even with 09/10a, no effect was observed at all, and extremely excellent selective herbicidal activity was obtained.

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

[Example 6] Paddy soil was placed in a porcelain pot with a diameter of 9 cm, water was added, and after plowing, weed seeds were sown on the surface layer of the soil, and paddy rice seedlings (variety, Nipponbare) at the two-leaf stage were placed at a depth of 1 crn. Two plants were planted. The next day, the pots were flooded with water to a depth of 2 cm, and a predetermined amount of each compound of the present invention as an aquarium was diluted in 1° of water per pot and dropped onto the water surface. Thereafter, the plants were left in a greenhouse, and 5 weeks after the chemical solution 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.

Display: Paddy rice damage, weed removal effect

Claims (3)

[Claims] (1) General formula (I): (wherein, X represents an oxygen atom or a sulfur atom, R1'i
It represents a halogen atom or a lower alkyl group, and n represents 1 or Fi2. ) Carbamate derivatives represented by (2) General formula (n): (wherein, Y is a hydrogen atom, a halocarbonyl group, or a halothiocarbonyl group) A naphthol derivative represented by the general formula ((2): (wherein, 2 is ( It) When Y in the formula is a hydrogen atom, it is a halocarbonyl group or a halothiocarbonyl group, and (II)
When Y in the formula is a halocarbonyl group or a no-lotiocarbonyl group, it is a hydrogen atom, R is a halogen atom or a lower alkyl group, and n represents 1 or 2. General formula (■) characterized by reacting with an aminopyridine derivative represented by (): (wherein, X represents an oxygen atom or a sulfur atom, and R represents
It represents a rogene atom or a lower alkyl group, and n represents 1 or 2. ) A method for producing a carbamate derivative represented by (3) General formula (■): (wherein, X represents an oxygen atom or a sulfur atom, R represents a halogen atom or a lower alkyl group, and n represents 1 or 2
shows. A herbicide characterized by containing a carbamate derivative represented by ) as an active ingredient.