JPH02229163A - N-(2-chloroisonicotinoyl)derivative or fungicide for agricultural and horticultural purposes containing the same - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (X, Y are O, S; R<1> is H, lower alkyl, cyanomethyl, allyl, propargyl, and H, when X is S; R<2> is lower alkyl, cyanomethyl, allyl, propargyl). EXAMPLE:Methyl N-(2-chloroisonicotinoyl)carbamate. USE:Fungicide for agricultural and horticultural purposes. PREPARATION:2-Chloroisonicotinoyl iso(thio)cyanate of formula II is allowed to react with an alcohol or thiol in a solvent or using the alcohol or thiol itself as a solvent to give a compound of formula I wherein R<1> is H. The compounds of formula I where X is O and R<1> is other than H is obtained by reaction of a compound of formula III wherein X is O with a compound of R<1>-Z wherein X is halogen in the presence of a base such as an alkali metal hydride or alkali metal alcoholate.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a novel N-(2-chloroisonicotinoyl) derivative, which can be used as an agricultural and horticultural fungicide in paddy fields, fields, orchards, etc. You can do it by using it.

[Conventional technology]

Although it is described in US Pat. No. 4,148,902 that the formula is useful as an insecticide,
There is no description of N-(2-chloroisonicothiyl)carbamate ester derivatives, and there is no description that they are useful as agricultural or horticultural fungicides.

[Problem that the invention seeks to solve]

Many pesticides have been used to treat plant diseases in agricultural and horticultural crops, but their efficacy is insufficient, their use is limited due to the emergence of drug-resistant bacteria, and their use may be limited due to the emergence of drug-resistant bacteria. , and also has disadvantages such as economical problems.

[Failure to solve the problem]

In order to solve the above problems, as a result of intensive research, it was found that the N-(2-chloroisonicotinoyl) derivative represented by the general formula (1) compensates for the drawbacks of conventional agricultural and horticultural fungicides and exhibits a high pesticidal effect. At the same time, they discovered that the method does not have any adverse effects such as phytotoxicity on plants, leading to the creation of the present invention.

That is, the present invention is based on the general formula [wherein X and Y each independently represent an oxygen atom or a sulfur atom, and R1 is a hydrogen atom when X is an oxygen atom,
When X is a sulfur atom in a lower alkyl group, cyanmethyl group, allyl group or propargyl group, it represents a hydrogen atom, and R
2 represents a lower alkyl group, a cyanmethyl group, or an allyl propargyl group. ] It is an N-(2-chloroisonicotinoyl) derivative.

The compound of general formula (f) of the present invention can be produced by the following method.

Q+) (ffl)
[In the formula, X, Y, and R2 have the same meanings as above. 〕formula(
11) Reacting 2-chloroinnicotinoyl incyanate or 2-chloroinnicotinoyl incyanate with alcohols or thiols in a solvent, or using the alcohols or thiols themselves as a solvent. As a result, a carbamate ester derivative, thiocarbamate ester derivative, or dithiocarbamate ester derivative represented by the general formula (Ill'J (R'=II in general formula (1)) is obtained.One of the reaction components, alcohol Examples of solvents other than thiols include aromatic hydrocarbons such as bene, toluene, and xyleno, halogenated hydrocarbons such as dichloromethano and chloroform, ethers such as diethyl ether and tetrahydrofurano, acetonitrile, Examples include nitriles such as propiotrile, ketones such as aceto 7 and methyl ethyl keto 7, esters such as ethyl acetate, aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide, and mixed solvents thereof.Alcohols. The amount of thiols and thiols to be used is usually an equimolar amount or more with respect to the isocyanate represented by Ill or isothiocyanate, and the reaction is usually -100C to 1000C1, preferably The process is carried out at a temperature of 000 to 60°C and usually takes about 3 minutes to 5 hours to complete.

2-chloroisonicotinoyl incyanate in general formula (II) can be used to convert 2-chloroisonicotinamide into halogenated hydrocarbons such as chloroform, aromatic hydrocarbons such as benzene and toluene, chloroform/
It is obtained by reacting it with phosgene, trichloromethyl chloroformate or oxalyl chloride in an inert solvent such as -logenated aromatic hydrocarbons, usually at 50 to 120°C for 5 to 10 hours.

On the other hand, 2-chloroisonicotinoyl isothiocyanate in general formula (1) is represented by 2-chloroisonicotinic acid chloride, and the formula MSCN CM represents a monovalent cation such as potassium, sodium, or ammonium. Thiocyanate and a halogenated hydrocarbon such as chloroform, an aromatic hydrocarbon such as benzene or toluene, or a nitrile such as acetonitrile as a solvent, usually at 60°C to 120°C for 30 minutes to 6 hours. Obtained by reaction.

Next, a compound in which X is an oxygen atom in - installation (1) and 1 (1 is a group other than a hydrogen atom) can be produced by the following method.

(Kawatsu (IV)
) [In the formula, R1, R2, Y have the same meanings as above, and Z
Ha...loge/does not show atoms. ] General formula In the presence of a base such as an alkali metal carbonate, as a solvent, for example, an ether, an ether such as detrahydrofurano, a nitrile such as acetonylyl, or an aprotic polar bath medium such as dimethylformamide. R'-z (in the formula, II' and Z have the same meanings as above)... rogenated hydrocarbon and usually from -2000 to 80°C, preferably from -10°C By reacting at 60 DEG C. for 1 to 1 hours, a carbamic acid ester derivative or thiocarbamino acid ester derivative represented by -incorporation ([V)] is obtained.

Furthermore, when Y'IJ''=oxygen atom in -setting (1v), it can also be produced by the following method.

(V) (IV')
[In the formula, R', R2, and Z have the same meanings as above. ] The amide derivative represented by the general formula (V) is represented by the formula Z C0
Rodanated formic acid esters represented by 0R2, and 1
By reacting under the same reaction conditions in the presence of the same base as used for the preparation of 1 to 1, the carbamic acid ester derivative represented by (IV') can be prepared.

To isolate the target product from the reaction mixture obtained as described above, extract the residue obtained by distilling off the solvent under reduced pressure or add an organic solvent such as ethyl acetate to the reaction mixture, wash with water, dry, and then It is sufficient to simply distill off the organic solvent under reduced pressure, and if necessary, further purification is performed by recrystallization or column chromatography.

Furthermore, the present invention provides an agricultural and horticultural fungicide characterized by containing an N-(2chloroinnicotinoyl) derivative represented by the general formula (I) as an active ingredient.

When using the compound of the present invention as an active ingredient of a fungicide for agriculture and horticulture, one or more compounds of the present invention may be used.

When the compound of the present invention is used as a fungicide for agricultural and horticultural purposes, depending on the purpose of use, it may be used as is, or it may be mixed with an agrochemical auxiliary agent to enhance or stabilize the effect, using methods commonly used in the field of agrochemical manufacturing. Accordingly, it can be used in the production form of powders, fine granules, granules, wettable powders, flowable preparations, emulsions, etc.

In actual use, these various formulations can be used directly or diluted with water to a desired concentration.

The agrochemical auxiliary agents mentioned herein include carriers (diluents) and other auxiliary agents such as spreading agents, emulsifiers, wetting agents, dispersing agents, fixing agents, and disintegrants.

Examples of liquid carriers include aromatic hydrocarbons such as toluene and quinceline, alcohols such as methanol, butanol, and glycol, ketones such as acetono, amides such as dimethylformamide, sulfoxides such as dimethyl sulfoxide, methylnaphthalene, cyclohexane, animals and plants. Examples include oil, fatty acids, fatty acid esters, etc.

Solid carriers include clay kaolin, Merck, diatomaceous earth,
Examples include calcium carbonate, monomolystomite, bentonite, feldspar, quartz, alumina, and sawdust.

Also, as emulsifiers or dispersants, surfactant '1I4-
Anionic surfactants, cationic surfactants, nonionic surfactants such as higher alcohol sodium sulfate, stearyltrimethylammonium chloride, polyoxyethylene alkylphenyl ether, laurylhetaine, etc. , amphoteric ionic surfactants.

Spreading agents include polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, etc. Wetting agents include polyoxyethylene nonylphenyl ether, dialkyl sulfosuccinate, etc., and fixing agents include carboxymethyl cellulose, polyvinyl alcohol, etc. However, examples of disintegrants include sodium pyrogenin sulfonate and sodium lauryl sulfate.

Not only can each formulation be used alone, but
It can also be used in combination with other agricultural and horticultural fungicides, insecticides, plant growth regulators, and acaricides.

The active ingredient content in the horticultural fungicide of the present invention a is:
It varies depending on the formulation form, method of application, and other conditions, and in some cases only the active ingredient compound may be used, but it is usually in the range of 0.5 to 95 (by weight), preferably 2 to 70 (by weight).

The fungicide of the present invention preferably has an active ingredient placement degree of 10 to 4.
000ppm can be sprayed on the stems and leaves of plants, and when spraying on soil, the amount of active ingredient sprayed is 0.02-10k
g/10a is preferred.

〔Effect of the invention〕

The compound of the present invention has a high control effect on plant fungal diseases such as rice blast, bacterial plant diseases such as rice leaf blight, and chyme bacterial leaf spot when applied to soil, foliar spray, or seed treatment. It is an agricultural and horticultural fungicide that is effective against drug-resistant bacteria and does not have any negative effects on plants, such as phytotoxicity.

〔Example〕

The present invention will be explained below with reference to Examples.

Synthesis Example I Synthesis of methyl N-(2-10 leisonicotinoyl)carbaminoate (Nol): In 180 ml of toluene, 30 g (0,1916 mol) of 2-chloroisonicotinamide, 24 ml of oxalyl chloride
5 ml of the mixture was added and heated under reflux for 7 hours.

Thereafter, it was concentrated under reduced pressure to obtain 34.4 g (yield: 98.3%) of 2-chloroinnicotinoyl isocyaner.

Subsequently, 15 g (0,082 mol) of the above incyaner was added to 60 ml of methanol at room temperature, and 25
After stirring at °C for 4.5 hours, methanol was distilled off under reduced pressure, water was added, and the mixture was extracted with ethyl acetate.

After drying the organic layer over sodium sulfate, the crude crystals obtained by concentrating under reduced pressure were recrystallized from ethyl acetate to obtain 13.3 g (yield 70%) of methyl N(2-10 leisonicotinoyl)carbamate. Obtained.

m, P, 136.5-137.5°C Synthesis Example 2 Synthesis of methyl N-(2-chloroinnicotinoyl)dithiocarbamate (No2): Benzene: 15.1 g of potassium thiocyanate in 50 ml ( 0,156 mol) was added thereto, and 25 g (0,142 mol) of 2-chloroisonicotinic acid chloride was added dropwise thereto at 200C, followed by further heating under reflux for 6 hours. After cooling, remove the inorganic salt,
The residue obtained by concentrating the r liquid under reduced pressure was distilled under reduced pressure to obtain 25.9 g (yield: 92.4%) of 2-chloroinnicotinoyl isothiocyanate.

b, I), 115-11.7 °C 15 mm (isothiocyaner obtained above in -Jg acetonitrile 20 mI)
After adding 3,85 g (0,0195 mol) and blowing in a slight excess of methanethiol over the theoretical amount at 0 °C,
The mixture was stirred at 25°C for 5 hours. The reaction solution was poured into water, extracted with ethyl acetate, the organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure to give 4.73 g of N-(2-chloroisonicotinoyl)dithiocarbami/methyl acid. (
A yield of 98.5%) was obtained.

m, I), 149-150°C Synthesis Example 3 Synthesis of 8-propyl N-(2-chloroisonicotinoyl)thiocarbamate (No 6 ): Ethyl acetate 10
7.3 g (0.04 mol) of 2-chloroincotinoyl isocyanate was added to 0.0 ml of water, and 304 g (0.04 mol) of 1-propanethiol was added dropwise at 20°C.
Thereafter, the mixture was heated under reflux for 2 hours. After cooling, the organic layer was washed with dilute aqueous sodium bicarbonate solution and 1ti+Japanese salt aqueous solution, dried over sodium sulfate, concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain N-(
2-Chloroinnicotinoyl)thiocarbamic acid-8-
6.2 g (yield: 6%) of propyl was obtained.

■η, r), 111-113°C Synthesis Example 4 Synthesis of N-(2-chloroisonicotinoyl)-N-methylthiocarbamate-8-propyl (No. 7) 60% sodium hydride in 20 ml of dimethylformamide , 25 g (0,00625 mol) were added,
At 00C N-(2-chloroisonicotinoinolithiorubami/acid S-propyyb 1.48g (0,00573
mol) in dimethylformamide was added dropwise, and after stirring at the same temperature for 30 minutes, 5 ml of methyl iodide was added dropwise at room temperature. After stirring for 5 hours at 40-500C, the mixture was poured into water and extracted with ethyl acetate. The good organic layer was washed with saturated brine and dissolved in sulfuric acid). After drying with sodium chloride, the residue obtained by concentrating under reduced pressure was purified by silica gel column chromatography to obtain N-(2-chloroisonicotinoyl)N- 1.1 g (yield 70.4%) of 8-propyl methylthiocarbamate was obtained.

n25 1.5626 Synthesis Example 5 Synthesis of isobutyl N-(2-chloroisonicotinoyl)-N cyanmethylcarbaminoate (No. 16) In 20 ml of dimethylformamide, 0.44% thorium hydride was added. g (0,011 mol) and 396 g of N-cyanmethyl-2-chloroisonicotinamide (
A dimethylformamide solution of 0.01 mol) was added dropwise at 0°C, and the mixture was further stirred for 30 minutes at the same temperature. Then 0~
1.50 g of isobutyl chloroformate (0,011
mol) was added dropwise, and after the addition was completed, the mixture was stirred at 25°C for 5 hours.

The reaction solution was poured into water, extracted with ethyl acetate, the organic layer was washed with saturated brine, dried over sodium sulfate, concentrated under reduced pressure, and the resulting residue was purified by silica gel chromatography to obtain N-(2 2.22 g (yield: 7
5.1%).

n Dl , 5173 Next, representative examples of the compound represented by the general formula ([) according to the present invention are shown in Table 1 along with physical property values.

]8 Formulation examples are shown below, but the type and mixing ratio of the pesticide adjuvant are not limited to any one, and can be used in a wide range. Note that "parts" means parts by weight.

Formulation example 1. Powder Compound No. 25.2 parts and 98 parts of clay were mixed and ground to obtain a powder.

Formulation Example 2 19.20 parts of wettable powder compound NO, 775 parts of Kaori, 3 parts of higher alcohol sodium sulfate, and 2 parts of sodium ligninsulfonate are mixed and ground to prepare an aqueous phase agent.

Formulation example 3. Powder Finely ground compound No. 4.8 parts Bentonite 60 parts
After mixing 30 parts of talc and 2 parts of disintegrating agent, add 18 parts of water to evenly moisten the mixture, extrude it through an injection molding machine, granulate it, size it with a sizing machine, and then dry it to obtain a particle size Q. , 5
Form into granules with a size of 1 mm to 1 mm.

Formulation Example 4 Fine granules Compound No. 9, 5 parts are uniformly mixed and pulverized with 1 part of polyvinyl alcohol and 14 parts of clay to form a thick powder. Separately, put 80 parts of non-absorbable mineral coarse powder of 74 to 105μ in a suitable mixer, add 15 parts of water while rotating to moisten it, add the above-mentioned layer thickness powder, cover it and dry it to make fine granules. .

Formulation example 5. Emulsion compound No. 14.30 parts was dissolved in 52 parts of xyleno,
To this was added a mixture of alkylphenol ethylene oxide condensate and calcium alkylbenzenesulfonate (8:2
) are mixed and dissolved to form an emulsion.

Next, the compound of the present invention can be used against various agricultural and horticultural crop diseases.
The fact that it has an excellent pesticidal effect will be explained using an experimental example.

Experimental example 1. Rice blast control test (soil application) fresh 1
Rice (variety: Saitama Mochi No. 10) was grown for two weeks in a plastic pot measuring 1 cm, width 5 cm, and height 10 cm, and grains containing the compound of the present invention prepared by the method of Formulation Example 3 as an active ingredient were added to the rice. A predetermined amount of the agent was applied to the soil, and 7 days later, the rice blast fungus (pyricularia oryza
e) was spray inoculated with the spore suspension and placed in a greenhouse at 23°C for 2 hours.
After being kept for several days, the seeds were allowed to develop in a greenhouse, and 10 days after inoculation, the degree of disease onset was investigated and the control value was calculated. The results are shown in Table 2. As a control drug, IBP granules (active ingredient: S-
Penzyldiisopropylphosphorothiolet) was used.

Severity of disease onset 3 : No lesions observed at all.

: Slight lesions are observed.

: Many lesions are observed.

: Very many lesions and dead leaves. Recognized by Zuka.

:Many dead leaves (observed).

: Very many dead leaves are observed. It will be done.

Table 2 Rice blast control test (soil application) Experimental example 2 Rice blast control test (foliar spraying) Freshly prepared 11
Rice (variety: Saitama Mochi No. 10) was grown for two weeks in a plastic bot measuring [cm, width 5 cm, height] and Q cm, and the compound of the present invention prepared by the method of Formulation Example 2 was added to the rice as an active ingredient. A medicinal solution of a predetermined concentration obtained by diluting an irrigation agent was sprayed on the foliage. After air drying, rice blast fungus (Py
riculariaoryzae) was spray-inoculated and kept in a greenhouse at 25°C for 1 day, the plants were allowed to develop disease in the greenhouse, and 10 days after inoculation, the degree of disease onset was investigated and the control value was calculated. The results are shown in Table 3. As a control drug, a di-BP emulsion (active ingredient: S-benzyldiisoprobyl phosphorothiolet 1-) was used.

0: No lesions observed at all.

1: Slight lesions are observed.

2: Many lesions are observed.

Disease severity: 3: Very many lesions and a few dead leaves are observed.

4: Many dead leaves are observed.

5: Very many dead leaves were observed. It will be done.

Table 3 Rice blast control test (spraying on foliage) Experimental example 3 Rice blast control test (soil application) Fresh 1
Rice (variety: Muzashikogane) was grown for one and a half months in a plastic pot measuring 5 cm in width, 5 cm in width, and 10 cm in height. A predetermined amount of the granules of the compound of the present invention prepared by the method of Formulation Example 3 was applied to the soil to this rice, and two days later, the rice leaves were infected with Xanthomonas campes.
tris p, v, oryzae) was inoculated into the anterior leaf, and 3
The cells were kept in a trench room at 0°C for 24 hours to infect them, and were then allowed to develop in a greenhouse. Lesion length was investigated 21 days after inoculation. The results are shown in Table 4. Note that flobenazole granules (active ingredient: 1,2-benzisothiazole-3-ono 1,1-dioxide) were used as a control drug.

Table 4 Rice blight (soil application)

Claims (2)

[Claims] (1) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, X and Y each independently represent an oxygen atom or a sulfur atom, and R^1 represents hydrogen when X is an oxygen atom. atom, a lower alkyl group, a cyanomethyl group, an allyl group, or a propargyl group; when X is a sulfur atom, it represents a hydrogen atom, and R^2 represents a lower alkyl group, a cyanomethyl group, an allyl group, or a propargyl group. ] N-(2-chloroisonicotinoyl) derivative represented by. (2) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, X, Y, R^1, and R^2 have the same meanings as above. ] An agricultural and horticultural fungicide containing an N-(2-chloroisonicotinoyl) derivative represented by the following as an active ingredient.