JPH11171864A - 2,6-dichloro-4-pyridine methanol derivative and pesticide - Google Patents

Abstract

(57) [Summary] (Modifications) [PROBLEMS] A novel compound having little effect on phytotoxicity to crops and having an excellent effect of controlling various plant diseases caused by phytopathogenic viruses, bacteria and fungi; 2,
Provided are pesticides, particularly plant disease control agents, containing 6-dichloro-4-pyridinemethanol or a benzoate thereof as an active ingredient. SOLUTION: General formula (1) (W is an optionally substituted alkyl group having 1 to 8 carbon atoms, trifluoromethyl pyridyl group, -C0R ^1, -SO
₂ R ² , -PO (OR ³ ) ₂ , -CONHR ⁴ , -COO
R ¹ is an alkyl group having 1 to 18 carbon atoms which may be substituted, such as R ⁴ and —COCOR ⁴ , and R ² is an alkyl group;
A phenyl group, R ³ is an alkyl group, R ⁴ is an alkyl group or a phenyl group), 2,6-dichloro-4-pyridinemethanol derivative, and 2,6-dichloro-4-pyridinemethanol or a benzoate thereof. Pesticides as active ingredients.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel 2,6-dichloro-4-pyridinemethanol derivative and a pesticide containing the compound as an active ingredient, especially a plant disease controlling agent.

[0002]

2. Description of the Related Art In agricultural production, it is necessary to control various phytopathogenic bacteria, pests, weeds, and the like, and pesticides have conventionally been a useful means for this purpose. However, even if a certain compound has excellent activity as a pesticide, it is not preferable because it causes phytotoxicity to plants, especially crops to be sprayed with pesticide, and even a compound that does not cause phytotoxicity has weak medicinal effect. And thus cannot be put to practical use. Therefore, creation of a compound having excellent medicinal properties and having little phytotoxicity has always been required as an agricultural chemical.

[0003] Japanese Patent No. 2514823 and Japanese Patent Laid-Open No.
No. 3,270 discloses that a 2,6-dichloroisonicotinic acid derivative having a specific structure has an effect of protecting crops from pathogenic microorganisms. However, although these compounds have excellent medicinal properties, they have harmful effects on certain crops.

On the other hand, 2,6-dichloro-4-pyridinemethanol according to the present invention can be synthesized by, for example, starting from 2,6-dichloroisonicotinic acid or an ester thereof and performing a reduction reaction. [J.
Prakt. Chem. 134, 177-187 (1932), West German Patent No. 3,615,293]. However, the 2,6-dichloro-4 of the present invention
A pyridinemethanol derivative or 2,6-dichloro-4
The use of -pyridinemethanol and 2,6-dichloro-4-pyridinemethanol derivatives as pesticides has not been known at all.

[0005]

The problem to be solved by the present invention is to provide a novel compound which is less susceptible to phytotoxicity to crops and has an excellent effect in controlling various plant diseases caused by phytopathogenic viruses, bacteria and fungi. And the compound, 2,
An object of the present invention is to provide a pesticide, particularly a plant disease controlling agent, comprising 6-dichloro-4-pyridinemethanol and / or a benzoate thereof as an active ingredient.

[0006]

Means for Solving the Problems The present inventors have conducted various studies to solve the above problems, and as a result, the 2,6-dichloro-4-pyridinemethanol derivative represented by the general formula (1) has been used as an agricultural chemical. In particular, they have found that the use of a small amount is effective in controlling plant diseases and that there is no concern about chemical damage to plants, and have completed the present invention.

That is, the present invention provides: (a) the following general formula (1)

[0008]

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(Wherein W is unsubstituted or substituted with an alkoxy group, an alkylthio group, a cyano group, a phenyl group, or a pyridyl group optionally substituted with a halogen atom) 8 alkyl group, a trifluoromethyl pyridyl _{^{group, -C0R 1, -SO 2 R 2}} , -PO
(OR ³ ) ₂ , -CONHR ⁴ , -COOR ⁴ , -COCO
R ⁴ or —SiR ⁵ R ⁶ R ⁷

Here, R ¹ is an unsubstituted or substituted alkenyl group, an alkylthio group, a phenyl group which may be substituted by an alkoxy group, a hydroxy group, a phenylalkoxy group, a phenylalkylthio group, an alkyloxycarbonyl group, an alkylcarbonyl group. An amino group or a phenoxy group ", an alkyl group having 1 to 18 carbon atoms which may be substituted by a" phenyl group optionally substituted by an alkoxy group "
An alkenyl group having 1 to 18 carbon atoms which may be substituted with
"A halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted by a halogen atom, an alkoxy group having 1 to 12 carbon atoms which may be substituted by a halogen atom,
3, an alkenyloxy group, a nitro group, an amino group,

A phenyl having at least one substituent selected from the group consisting of an alkylamino group having 1 to 4 carbon atoms, a cyano group, an acetylamino group, a benzoylamino group, an acetyloxy group, a phenyl group and a phenoxy group. A 5- or 6-membered heterocyclic residue which may be substituted with a group or an alkyl group having 1 to 4 carbon atoms and which contains any one of a nitrogen atom, an oxygen atom and a sulfur atom as a ring constituent atom; ² represents an alkyl group having 1 to 12 carbon atoms, or a phenyl group which may be substituted with an alkyl group having 1 to 12 carbon atoms,

R ³ represents an alkyl group having 1 to 4 carbon atoms, R ⁴ represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R ^{5 to} R ⁷ each represent the same or different carbon atoms. Represents an alkyl group of 1 to 4; 2, 6)
A dichloro-4-pyridine methanol derivative;

(B) W in the general formula (1) is unsubstituted or substituted by "an alkoxy group, an alkylthio group, a cyano group, a phenyl group, or a pyridyl group optionally substituted by a halogen atom". An alkyl group having 1 to 8 carbon atoms,
Or a 2,6-dichloro-4-pyridinemethanol derivative according to (a), which is a trifluoromethylpyridyl group;

(C) In the general formula (1), W represents -C0R ¹ , wherein R ¹ is unsubstituted or "phenyl group, hydroxy group which may be substituted by an alkoxy group, an alkylthio group or an alkoxy group. , A phenylalkoxy group, a phenylalkylthio group, an alkyloxycarbonyl group, an alkylcarbonylamino group, or a phenoxy group, a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms or a phenyl group which may be substituted with an alkoxy group. An alkenyl group having 1 to 18 carbon atoms,

A halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted by a halogen atom, an alkoxy group having 1 to 12 carbon atoms which may be substituted by a halogen atom, an alkenyloxy group having 2 to 3 carbon atoms , A nitro group, an amino group, an alkylamino group having 1 to 4 carbon atoms, a cyano group, an acetylamino group, a benzoylamino group, an acetyloxy group, a phenyl group, or a phenoxy group ". A phenyl group having a substituent, or an alkyl group having 1 to 4 carbon atoms,
A 5- or 6-membered heterocyclic residue containing any one of a nitrogen atom, an oxygen atom and a sulfur atom as a constituent atom of a ring,
A 2,6-dichloro-4-pyridinemethanol derivative according to (a),

(D) In the general formula (1), W represents —C0R ¹ , and R ¹ is an unsubstituted or alkenyl group substituted by a “phenyl group optionally substituted with an alkoxy group” ( C) a 2,6-dichloro-4-pyridinemethanol derivative described in

(E) In the general formula (1), W represents -C0R ¹ , and R ¹ is a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted by a halogen atom, or a halogen atom. An alkoxy group having 1 to 12 carbon atoms, an alkenyloxy group having 2 to 3 carbon atoms, a nitro group, an amino group, an alkylamino group having 1 to 4 carbon atoms, a cyano group, an acetylamino group, a benzoylamino group, An acetyloxy group, a phenyl group or a phenoxy group, which is a phenyl group having one or more same or different substituents selected from
A 2,6-dichloro-4-pyridinemethanol derivative according to (c),

(F) In the general formula (1), W represents -C0R ¹ and R ¹ is an alkoxyphenyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom. A 2,6-dichloro-4-pyridinemethanol derivative of

(G) W in the general formula (1) represents --SO ₂ R ² , and R ² is an alkyl group having 1 to 12 carbon atoms, or phenyl which may be substituted with an alkyl group having 1 to 12 carbon atoms. A 2,6-dichloro-4-pyridinemethanol derivative according to (a),

(H) W in the general formula (1) is -PO (O
R ³ ) ₂ , wherein R ³ is an alkyl group having 1 to 4 carbon atoms, (a) the 2,6-dichloro-4-pyridinemethanol derivative according to 1,

(I) W in the general formula (1) is -CONHR
⁴ , -COOR ⁴ or -COCOR ⁴ , wherein R ⁴
Is an alkyl group having 1 to 3 carbon atoms or a phenyl group,
A 2,6-dichloro-4-pyridinemethanol derivative according to (a),

(Nu) W in the general formula (1) is -SiR ⁵ R ⁶ R
⁷ represents, wherein according to R ⁵ to R ⁷ are each the same or different alkyl group of 1 to 4 carbon atoms (b) 2,6
A dichloro-4-pyridine methanol derivative;

(R) an agrochemical containing at least one of the 2,6-dichloro-4-pyridinemethanol derivatives described in any one of (A) to (N) above as an active ingredient;

(E) 2,6-dichloro-4-pyridinemethanol of the formula (1) wherein W is a hydrogen atom, and / or 2,6-dichloro-4-pyridine wherein W is a phenylcarbonyl group An agricultural chemical containing methanol benzoate as an active ingredient;

[0025]

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(A) The pesticide is a plant disease controlling agent.
Or (e) a pesticide,

(F) The plant disease controlling agent comprises the pesticide according to (a), which is a rice blast controlling agent.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION The compound represented by the general formula (1) of the present invention

[0029]

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The substituted or unsubstituted alkyl group having a predetermined number of carbon atoms represented by W and R ^{1 to} R ⁷ is selected from linear, branched or cyclic alkyl groups. , N-propyl, isopropyl, n-butyl, isobutyl, 2-butyl, tert-butyl, n-
Pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-dodecyl, n-octadecyl, n-eicosyl, cyclopropyl, cyclopentyl, cyclohexyl, methoxymethyl, methoxyethyl, butoxybutyl, methoxypentyl, dodecyloxyethyl,

Ethylthioethyl, methylthiopropyl,
Methylthiobutyl, octylthiopropyl, cyanoethyl, cyanopropyl, cyanohexyl, benzyl, phenylethyl, phenylpropyl, ethoxybenzyl, methoxyphenylpropyl, pyridylmethyl, chloropyridylmethyl, hydroxymethyl, hydroxyhexyl,
Benzyloxymethyl, benzylthioethyl, methoxycarbonylbutyl, acetylaminomethyl, phenoxyethyl and the like can be mentioned.

Examples of the alkenyl group represented by R ¹ which may be substituted with an alkoxy group or a phenyl group include, for example, ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptadecenyl, butadienyl,
Pentadienyl, heptadecadienyl, phenylethenyl, phenylpropenyl, methoxyphenylethenyl and the like can be mentioned.

The phenyl group having one or more same or different predetermined substituents represented by R ¹ includes, for example, fluorophenyl, chlorophenyl, bromophenyl, methylphenyl, hexylphenyl, trifluoromethylphenyl, chloromethylphenyl , Methoxyphenyl, hexyloxyphenyl, dodecyloxyphenyl, cyclohexyloxyphenyl, difluoromethoxyphenyl, trifluoroethoxyphenyl, propenyloxyphenyl, nitrophenyl, aminophenyl,
N, N'-dimethylaminophenyl, cyanophenyl,
Acetylaminophenyl, benzoylaminophenyl,
Acetyloxyphenyl, biphenyl, phenoxyphenyl and the like can be mentioned.

It may be substituted with an alkyl group having 1 to 4 carbon atoms represented by R ¹ and contains 5 to 6 carbon atoms containing any one of a nitrogen atom, an oxygen atom and a sulfur atom as a ring-constituting atom.
Examples of the membered heterocyclic residue include furyl, thienyl, pyrrolyl, pyranyl, pyridinyl, methylpyridyl and the like.

Examples of the phenyl group represented by R ² which may be substituted with an alkyl group having 1 to 12 carbon atoms include, for example, methylphenyl, hexylphenyl, dodecylphenyl and the like.

Tables 1 to 10 show specific structures of the compound represented by the general formula (1).
2,6-Dichloro-4-pyridinemethanol in Table 2 and 2,6-dichloro-4-pyridinemethanol benzoate in Table 5 are known compounds, and the other compounds are novel compounds.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

[Table 4]

[0041]

[Table 5]

[0042]

[Table 6]

[0043]

[Table 7]

[0044]

[Table 8]

[0045]

[Table 9]

[0046]

[Table 10]

The compound represented by the general formula (1) of the present invention can be produced by a general method used for producing an ether or an ester. It can be manufactured by the method of (4). However, the production method of the compound of the present invention is not limited to this production method. In addition, W and R ¹ in the reaction formulas (2) to (4) have the same meaning as defined in the formula of the general formula (1), R ⁸ represents an alkyl group having 1 to 4 carbon atoms,
L represents a hydroxyl group or a halogen atom, M represents hydrogen or a metal atom (sodium, potassium, cesium, etc.)
Represents

[0048]

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That is, 2,6-dichloro-4-pyridinemethanol or an alcoholate thereof is dissolved in a suitable solvent, if necessary, in the presence of a dehydrating agent, an acid or a base, to form an alkyl halide derivative, a carboxylic acid derivative, or a carboxylic acid chloride. By reacting with a derivative, a sulfonic acid chloride derivative, a phosphoryl acid chloride derivative, a halogenated formic acid derivative or a halogenated silane derivative, a 2,6-dichloro-4-pyridinemethanol derivative represented by the formula (1) can be obtained. it can.

Further, after leaving a leaving group by reacting 2,6-dichloro-4-pyridinemethanol with an appropriate halogenating agent or arylsulfonic acid or the like, it is reacted with a carboxylic acid derivative, alcohol derivative or the like, A 2,6-dichloro-4-pyridinemethanol derivative represented by the formula (1) can be obtained. Further, the compound represented by the general formula (1) can be obtained by adding 2,6-dichloro-4-pyridinemethanol to an olefin derivative or an isocyanate derivative in the presence of a catalyst such as an acid or a base.

As the reaction solvent, hexane, benzene,
Hydrocarbons such as toluene, alcohols such as methanol and ethanol, polyhydric alcohols and esters such as ethylene glycol and ethylene glycol monoethyl ether, ethers such as diethyl ether and tetrahydrofuran, and halogens such as chloroform and dichloroethane. Hydrocarbons, aprotic polar solvents such as N, N-dimethylformamide, dimethylsulfoxide and the like can be used.

Examples of the base include organic bases such as triethylamine, diisopropylethylamine, pyridine, 4-dimethylaminopyridine and diazabicycloundecene; hydroxides such as sodium hydroxide and potassium hydroxide; potassium carbonate and cesium carbonate. Carbonates and the like can be used. The reaction temperature varies depending on the solvent, base and the like, but is usually from -10 ° C to
It is in the range of boiling point. The reaction time varies depending on the reaction temperature, solvent, base and the like, but is usually 0.1 to 10 hours, preferably 0.5 to 5 hours. Further, 2,6-dichloro-4-pyridinemethanol which is a raw material for synthesizing the compound of the present invention is described in, for example, J. Am. Prakt. Che
m. 134, pages 177-187 (1932).

The novel compound of the present invention is a compound of the formula (1) wherein W is unsubstituted or "pyridyl group optionally substituted with an alkoxy group, alkylthio group, cyano group, phenyl group or halogen atom". Substituted, having 1 to 8 carbon atoms
2,6-dichloro-4-pyridinemethanol derivative, which is an alkyl group or a trifluoromethylpyridyl group,

W in the general formula (1) represents —SO ₂ R ² ,
R ² is an alkyl group having 1 to 12 carbon atoms, or 1 to 1 carbon atoms;
A phenyl group which may be substituted with 2 alkyl groups,
2,6-dichloro-4-pyridine methanol derivative,

In the general formula (1), W represents -PO (OR ³ ) ₂ , and R ³ is an alkyl group having 1 to 4 carbon atoms.
A dichloro-4-pyridine methanol derivative or W of the general formula (1) is -CONHR ⁴ , -COOR ⁴ or -COC
OR ⁴ , wherein R ⁴ is an alkyl group having 1 to 3 carbon atoms or a phenyl group, a 2,6-dichloro-4-pyridinemethanol derivative;

In the general formula (1), W represents --SiR ⁵ R ⁶ R ⁷ , wherein R ^{5 to} R ⁷ are the same or different alkyl groups having 1 to 4 carbon atoms, 2,6-dichloro-4. -Including pyridinemethanol derivatives. Among them, from the viewpoint of the balance between pesticidal activity and phytotoxicity, W in the general formula (1) may be unsubstituted or may be substituted with an "alkoxy group, alkylthio group, cyano group, phenyl group, or halogen atom. A pyridyl group ", an alkyl group having 1 to 8 carbon atoms, or a trifluoromethylpyridyl group,
2,6-Dichloro-4-pyridinemethanol derivatives are preferred.

In the novel compound of the present invention, W in the general formula (1) represents -C0R ¹ , wherein R ¹ is unsubstituted or substituted by an alkoxy group, an alkylthio group or an alkoxy group. A phenyl group, a hydroxy group, a phenylalkoxy group, a phenylalkylthio group, an alkyloxycarbonyl group, an alkylcarbonylamino group, or a phenoxy group '', an alkyl group having 1 to 18 carbon atoms,

An alkenyl group having 1 to 18 carbon atoms which is unsubstituted or substituted by a "phenyl group which may be substituted by an alkoxy group";"an alkyl group having 1 to 6 carbon atoms which may be substituted by a halogen atom or a halogen atom"; Group, an alkoxy group having 1 to 12 carbon atoms which may be substituted with a halogen atom, an alkenyloxy group having 2 to 3 carbon atoms, a nitro group, an amino group, an alkylamino group having 1 to 4 carbon atoms, a cyano group, acetylamino Group, a benzoylamino group, an acetyloxy group, a phenyl group, or a phenoxy group ", a phenyl group having at least one same or different substituent (s) selected from the group consisting of good,
A 5- or 6-membered heterocyclic residue containing any one of a nitrogen atom, an oxygen atom and a sulfur atom as a constituent atom of a ring,
2,6-dichloro-4-pyridinemethanol derivative.

Among these compounds, from the viewpoint of the balance between pesticidal activity and phytotoxicity, R ¹ is an unsubstituted or alkenyl group substituted with a “phenyl group optionally substituted with an alkoxy group”. , 6-dichloro-4-pyridinemethanol derivative, R ¹ is a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or a C ¹ to 12 carbon atom which may be substituted with a halogen atom. An alkoxy group, an alkenyloxy group having 2 to 3 carbon atoms, a nitro group, an amino group, an alkylamino group having 1 to 4 carbon atoms, a cyano group, an acetylamino group, a benzoylamino group, an acetyloxy group, a phenyl group or a phenoxy group " 2,6-dichloro-4-pyridinemethanol derivatives which are phenyl groups having one or more identical or different substituents selected from

Of these, more preferred are 2,6-dichloro-4-pyridinemethanol derivatives in which R ¹ is an alkoxyphenyl group having 1 to 12 carbon atoms which may be substituted with a halogen atom.

The pesticides, particularly the plant disease control agents, comprising the 2,6-dichloro-4-pyridinemethanol derivative according to the present invention as an active ingredient, include various plant diseases caused by phytopathogenic viruses, bacteria and fungi, for example, the main plant diseases of rice. Although it can be applied to blasts and spots of cucumber, which are diseases, it is particularly effective for blasts. It is thought that this drug exerts not only a direct bactericidal action on plant pathogens but also a disease control effect by eliciting a resistance reaction against plant pathogens originally provided in plants.

The drug is the 2,6-dichloro-4 of the present invention.
-It is also possible to use the pyridine methanol derivative alone, but usually used in the formulation of agricultural chemicals, known and commonly used solid and liquid carriers, and dispersants, diluents, emulsifiers, spreading agents, thickeners and the like It can be mixed with an auxiliary agent and formulated into a dosage form such as a wettable powder, a liquid, an oil, a powder, a granule, a sol (a flowable) and used.

Examples of solid and liquid carriers include talc, clay, bentonite, kaolin, diatomaceous earth, montmorillonite, mica, vermiculite, gypsum, calcium carbonate, white carbon, wood powder, starch, alumina, silicate, and sugar polymer. , Waxes, water, alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, ethylene glycol, benzyl alcohol, etc.), petroleum fractions (petroleum ether, kerosene, solvent naphtha, etc.), Aliphatic or alicyclic hydrocarbons (n-hexane, cyclohexane, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, chlorobenzene, cumene, methylnaphthalene, etc.),

Halogenated hydrocarbons (chloroform, dichloromethane, etc.), ethers (isopropyl ether, ethylene oxide, tetrahydrofuran, etc.), ketones (acetone, ethyl methyl ketone, cyclohexanone, isobutyl methyl ketone, etc.), esters (ethyl acetate, ethyl acetate, etc.) Butyl acetate, ethylene glycol acetate, amyl acetate, etc.), acid amides (dimethylformamide, dimethylacetanilide, etc.), nitriles (acetonitrile, propionitrile, acrylonitrile, etc.), sulfoxides (dimethylsulfoxide, etc.), alcohol ethers ( Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.).

Examples of the auxiliary agent include nonionic surfactants (polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan alkyl ester, sorbitan alkyl ester, etc.),
Anionic surfactants (alkylbenzene sulfonate, alkyl sulfosuccinate, polyoxyethylene alkyl sulfate, aryl sulfonate, etc.),

Cationic surfactants (alkylamines, polyoxyethylene alkylamines, quaternary ammonium salts, etc.), amphoteric surfactants (alkylaminoethylglycine, alkyldimethylbetaine, etc.), polyvinyl alcohol, hydroxy alcohol Examples include propylcellulose, carboxymethylcellulose, gum arabic, tragacanth gum, xanthan gum, polyvinyl acetate, gelatin, casein, sodium alginate and the like.

Further, the present drug can be used for various agricultural and horticultural fungicides,
It can also be used as a mixture with agricultural chemicals such as herbicides, plant growth regulators, insecticides, acaricides, and fertilizers. The active ingredient content of this drug varies depending on the form of preparation, application method and other conditions, but is usually 0.5 to 95% (weight),
Preferably it is 1 to 50% (weight).

The method of applying the present agent includes application to plants (foliage application), application to plant growing soil (soil application),
Application to paddy water (water surface application), application to seeds (seed treatment), and the like are possible.

The application rate of the present drug varies depending on the plant to be applied, the disease to be applied and the like. In the case of foliar application, the active ingredient concentration is 1 to 10000 ppm, preferably 10 to 10 ppm.
It is preferable to apply 50 to 300 L of a solution of 00 ppm per 10 ares, and in the case of soil application and surface application, the amount of the active ingredient is 0.1 to 1000 per 10 ares.
g, particularly preferably from 10 to 100 g. In the case of seed treatment, for 1 kg of seed,
It is preferred to apply from 0.001 to 50 g of the active ingredient.

The 2,6-dichloro-4-pyridinemethanol derivative according to the present invention has no fear of phytotoxicity to plants, is useful as a plant disease controlling agent, and is useful for various plant diseases caused by phytopathogenic viruses, bacteria and fungi. It has an excellent effect on disease control.

[0071]

The present invention will now be described by way of examples, preparation examples and test examples, but the present invention is not limited to these examples.

(Example 1) 0.18 g of 2,6-dichloro-4-pyridinemethanol was dissolved in 5 ml of tetrahydrofuran (hereinafter abbreviated as THF), cooled with ice, and then sodium hydride (oil-based, 60% ) 0.04 g. A solution prepared by dissolving 0.15 g of methyl iodide in 2 ml of THF was added dropwise thereto, and the mixture was stirred at room temperature for 2 hours. Ethyl acetate was added to the reaction solution, and the organic layer was washed with water and dried by adding sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to give 2,6.
-Dichloro-4-methoxymethylpyridine (compound N
o. 1) 0.06 g was obtained.

Nuclear magnetic resonance spectrum (internal standard TMS,
Solvent CDCl ₃ ) (ppm): 3.46 (s, 3H),
4.45 (s, 2H), 7.25 (s, 2H)

Example 2 0.36 g of 2,6-dichloro-4-pyridinemethanol and 0.1 g of triethylamine
Was dissolved in 2 ml of THF, and 0.12 g of acrylonitrile was added thereto at room temperature, followed by stirring for 2 hours. After allowing the reaction solution to stand at room temperature overnight, ethyl acetate was added, the organic layer was washed with water, and sodium sulfate was added and dried. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 0.23 g of 2,6-dichloro-4- (2-cyanoethoxymethyl) pyridine (Compound No. 6).

Melting point: 65.5 ° C. Mass spectrum: 230, 232, 161, 163

Example 3 3.56 g of 2,6-dichloro-4-pyridinemethanol and 4 ml of pyridine were added to THF2
0 ml, a solution of 0.8 ml of thionyl chloride dissolved in 12 ml of dichloromethane was added dropwise, and the mixture was stirred for 2 hours. Then, this was heated and distilled for 1 hour, cooled, and extracted with diethyl ether. The organic layer was washed with water and dried by adding sodium sulfate. Evaporate the solvent,
The residue was purified by silica gel column chromatography to obtain 2.31 g of bis (2,6-dichloro-4-pyridylmethyl) ether (Compound No. 11).

Melting point: 69.1 ° C. Mass spectrum: 337,336,338,161,1
60,162,309

Example 4 0.09 g of 2,6-dichloro-4-pyridinemethanol and 0.51 of triethylamine
g was dissolved in 5 ml of THF.
A solution prepared by dissolving 31 g in 2 ml of THF was added dropwise under ice-cooling, and the mixture was stirred for 2 hours. After leaving the reaction at room temperature overnight,
Ethyl acetate was added, and the organic layer was washed with water, dried over sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain acetic acid (2,6-
Dichloro-4-pyridinyl) methyl ester (Compound N
o. 13) 0.10 g was obtained.

Example 5 0.36 g of 2,6-dichloro-4-pyridinemethanol and 0.3 of 4-methylbenzoic acid
To 0 g, 0.5 ml of THF and 2 ml of dichloromethane were added and dissolved, and 0.44 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 4-ml
0.56 g of dimethylaminopyridine was added, and the mixture was stirred for 2 hours. After allowing the reaction solution to stand at room temperature overnight, ethyl acetate was added, the organic layer was washed with water, and sodium sulfate was added and dried. The solvent was distilled off, and the residue was purified by silica gel column chromatography to give 4-methylbenzoic acid (2,6-
Dichloro-4-pyridinyl) methyl ester (Compound N
o. 45) 0.36 g was obtained.

Example 6 1.4 g of 2,6-dichloro-4-pyridinemethanol was dissolved in 5 ml of pyridine and cooled with ice. To this, 1.5 g of 2-nitrobenzoyl chloride prepared from 2-nitrobenzoic acid and thionyl chloride was added dropwise. After stirring the reaction solution at room temperature for 2 hours, dichloromethane was added, the organic layer was washed with water, and sodium sulfate was added and dried. The solvent was distilled off, and the residue was purified by silica gel column chromatography to give 2-nitrobenzoic acid (2,2).
1.4 g of 6-dichloro-4-pyridinyl) methyl ester (Compound No. 69) was obtained.

Example 7 0.36 g of 2,6-dichloro-4-pyridinemethanol and 0.40 of triethylamine
g was dissolved in 4 ml of THF and cooled with ice. 0.42 g of 4-methylbenzenesulfonic acid chloride monohydrate
Was dissolved in 2 ml of THF. After stirring the reaction solution at room temperature for 2 hours, diethyl ether was added, the organic layer was washed with water, and sodium sulfate was added and dried. The solvent was distilled off, and the residue was purified by silica gel column chromatography to give 4-methylbenzenesulfonic acid (2,6-
Dichloro-4-pyridinyl) methyl ester (Compound N
o. 89) 0.43 g was obtained.

Example 8 0.25 g of 2,6-dichloro-4-pyridinemethanol was dissolved in 1 ml of pyridine.
Ice cooled. To this, phenyl isocyanate 0.15m
1 was added dropwise. After stirring the reaction solution at room temperature for 2 hours, dichloromethane was added, the organic layer was washed with water, and sodium sulfate was added and dried. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 0.20 g of phenylcarbamic acid (2,6-dichloro-4-pyridinyl) methyl ester (Compound No. 93).

Example 9 0.35 g of 2,6-dichloro-4-chloromethylpyridine, 0.31 of benzoylformic acid
g and 0.19 g of sodium bicarbonate were added to 5.0 ml of dimethylformamide, and the mixture was heated and stirred at 70 ° C. for 4 hours. After cooling, ethyl acetate was added to the reaction solution, and the organic layer was washed with water, dried over sodium sulfate. Evaporate the solvent,
The residue was purified by silica gel column chromatography to obtain 0.18 g of benzoylformic acid (2,6-dichloro-4-pyridinyl) methyl ester (Compound No. 95).

(Reference Example) Production of 2,6-dichloro-4-chloromethylpyridine 5.0 g of 2,6-dichloro-4-pyridinemethanol and 2.5 ml of pyridine were suspended in 10 ml of toluene. Cooled in the bath. This is followed by thionyl chloride 2.7
of the reaction solution at 110 ° C. for 3 hours.
Stirred for hours. After cooling, water was added and extracted with diethyl ether. The organic layer was washed with water, dried by adding sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 5.0 g of 2,6-dichloro-4-chloromethylpyridine.

Example 10 0.30 g of 2,6-dichloro-4-chloromethylpyridine and 0.25 g of tert-butyldimethylsilyl chloride were added to 4.0 ml of dimethylformamide and dissolved. This was cooled in an ice bath, and 0.14 g of imidazole was added.
Stirred for hours. Ethyl acetate was added to the reaction solution, and the organic layer was washed with water, dried over sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain 0.41 g of 2,6-dichloro-4-((1,1-dimethylethyl) dimethylsilyl) oxymethylpyridine (Compound No. 96). Obtained.

Examples 11 to 96 In the same manner as in Examples 1 to 10, the compounds Nos. 2-5, N
o. Nos. 7 to 10; 12, No. 14 to 44;
46 to 68; 70 to 88; 90-92 and No. 94 was obtained.

[0087]

[Table 11]

[0088]

[Table 12]

[0089]

[Table 13]

[0090]

[Table 14]

[0091]

[Table 15]

[0092]

[Table 16]

[0093]

[Table 17]

[0094]

[Table 18]

[0095]

[Table 19]

[0096]

[Table 20]

[0097]

[Table 21]

[0098]

[Table 22]

[0099]

[Table 23]

[0100]

[Table 24]

[0101]

[Table 25]

[0102]

[Table 26]

[0103]

[Table 27] In Table 27, compounds 97 and 98 are known compounds.

(Formulation Example 1) Dust Compound No. 2,6-dichloro-4 represented by 1 to 98
-2 parts by weight of the pyridinemethanol derivative were each mixed and pulverized with 98 parts by weight of clay to obtain a powder.

(Formulation Example 2) Wetting agent Compound No. 2,6-dichloro-4 represented by 1 to 98
20 parts by weight of a pyridinemethanol derivative were mixed and pulverized with 68 parts by weight of clay, 8 parts by weight of white carbon and 4 parts by weight of polyoxyethylene nonylphenyl ether to obtain a wettable powder.

(Formulation Example 3) Granules Compound No. 2,6-dichloro-4 represented by 1 to 98
5 parts by weight of a pyridinemethanol derivative were mixed and pulverized with 90 parts by weight of an equal mixture of bentonite and talc and 5 parts by weight of sodium alkylbenzenesulfonate to form granules.

(Test Example 1) Rice Blast Control Test (Soil Application) Described in (Formulation Example 2) in a 2-leaf stage rice (variety: Aichi Asahi) bred in a pot (diameter 6 cm, height 5.5 cm). Each of the wettable powders was diluted with water and applied to soil (0.01 mg / pot of active ingredient). Fourteen days later, a spore suspension of rice blast (Pyricularia oryzae) was sprayed and inoculated, left in a moist chamber at 25 ° C for 24 hours, then allowed to develop disease in a greenhouse, and 10 days after inoculation of the spore suspension, the number of lesions was counted. investigated.

As a control drug, probenazole granules commercially available as a rice blast control agent (active ingredient 8%)
And 2,6-dichloroisonicotinic acid (Patent No. 2514)
No. 823) and the amount of the active ingredient was the same, and the test was carried out in the same manner. The control value was calculated by the following formula. In addition, leaf wilt and plant growth inhibition were observed as phytotoxicity. The results are shown in Table 28. A minus (-) in the table indicates that no phytotoxicity occurred, and a plus (+)
Indicates that phytotoxicity has occurred.

Control value (%) = [(number of lesions in untreated area−number of lesions in treated area) / number of lesions in untreated area] × 100

[0110]

[Table 28]

[0111]

[Table 29]

[0112]

[Table 30]

(Test Example 2) Cucumber Spot Bacterial Disease Control Test Four-leaf stage cucumber (variety: Tokiwa Shinjuku) bred in pots (diameter 10 cm, height 9 cm) was subjected to each of the preparations described in (Formulation Example 2). A chemical solution having an active ingredient concentration of 200 ppm prepared by diluting a wettable powder with water was sprayed on foliage. Seven days later, the pathogenic bacterial suspension was inoculated by spraying, left in a moist chamber at 25 ° C for 48 hours, and then allowed to develop disease in the greenhouse. Seven days after the pathogenic bacterial suspension was inoculated, the number of lesions in the lower four leaves was examined. The control value was calculated in the same manner as in (Test Example 1). As a result, compound N
o. The compounds of 1 to 98 showed a control value of 75 to 100%. As a control drug, 2-chloro-6-hydroxyisonicotinic acid was tested in the same manner, and showed a control value of 60%.

[0114]

The present invention provides a novel 2,6-dichloro-4-
A pyridine methanol derivative, an agrochemical containing the compound as an active ingredient, and an agrochemical containing 2,6-dichloro-4-pyridinemethanol and / or a benzoate thereof as an active ingredient, particularly without fear of harm to plants. And a plant disease controlling agent having a sufficient effect,
In particular, a rice blast control agent can be provided.

Claims (14)

[Claims] 1. The following general formula (1): (Wherein, W is an alkyl having 1 to 8 carbon atoms which may be unsubstituted or substituted with “an alkoxy group, an alkylthio group, a cyano group, a phenyl group, or a pyridyl group optionally substituted with a halogen atom”) group, trifluoromethyl pyridyl _{^{group, -C0R 1, -SO 2 R 2}} , -PO (OR 3) 2,
-CONHR ⁴ , -COOR ⁴ , -COCOR ⁴ , or-
Represents SiR ⁵ R ⁶ R ⁷ , wherein R ¹ is unsubstituted or “a phenyl group, a hydroxy group, a phenylalkoxy group, a phenylalkylthio group, an alkyl group which may be substituted with an alkoxy group, an alkylthio group, or an alkoxy group; An oxycarbonyl group, an alkylcarbonylamino group, or a phenoxy group "
An alkyl group having 8 carbon atoms, an alkenyl group having 1 to 18 carbon atoms which may be substituted with a “phenyl group optionally substituted with an alkoxy group”, and a “halogen atom, having 1 to 6 carbon atoms optionally substituted with a halogen atom. An alkyl group, an alkoxy group having 1 to 12 carbon atoms which may be substituted with a halogen atom, an alkenyloxy group having 2 to 3 carbon atoms, a nitro group, an amino group, an alkylamino group having 1 to 4 carbon atoms, a cyano group , An acetylamino group, a benzoylamino group, an acetyloxy group, a phenyl group or a phenoxy group ", a phenyl group having at least one same or different substituent (s) selected from the group consisting of And any one of a nitrogen atom, an oxygen atom and a sulfur atom
Represents a 5- or 6-membered heterocyclic residue containing a carbon atom as a ring constituent atom, and R ² represents an alkyl group having 1 to 12 carbon atoms or a phenyl group which may be substituted with an alkyl group having 1 to 12 carbon atoms. R ³ represents an alkyl group having 1 to 4 carbon atoms, R ⁴ represents an alkyl group having 1 to 3 carbon atoms or a phenyl group, and R ^{5 to} R ⁷ each have the same or different carbon atoms. Represents an alkyl group of 1 to 4; 2,6)
-A dichloro-4-pyridinemethanol derivative. 2. In the general formula (1), W is unsubstituted or substituted by “an alkoxy group, an alkylthio group, a cyano group, a phenyl group, or a pyridyl group optionally substituted by a halogen atom”. The 2,6-dichloro-4-pyridinemethanol derivative according to claim 1, which is an alkyl group having 1 to 8 carbon atoms or a trifluoromethylpyridyl group. 3. In the general formula (1), W represents —C0R ¹ , wherein R ¹ is unsubstituted or “an phenyl group, a hydroxy group which may be substituted by an alkoxy group, an alkylthio group, an alkoxy group, A phenylalkoxy group, a phenylalkylthio group, an alkyloxycarbonyl group, an alkylcarbonylamino group, or a phenoxy group, an alkyl group having 1 to 18 carbon atoms, an unsubstituted or phenyl group which may be substituted with an alkoxy group "An alkenyl group having 1 to 18 carbon atoms substituted with", a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, and 1 to 1 carbon atoms which may be substituted with a halogen atom.
12 alkoxy groups, alkenyloxy groups having 2 to 3 carbon atoms, nitro group, amino group, alkylamino group having 1 to 4 carbon atoms, cyano group, acetylamino group, benzoylamino group, acetyloxy group, phenyl group, or A phenyl group having one or more same or different substituents selected from “phenoxy group”, or any one of a nitrogen atom, an oxygen atom and a sulfur atom, which may be substituted with an alkyl group having 1 to 4 carbon atoms. Containing 5 as a ring constituent atom
Or a 2,6-membered heterocyclic residue.
Dichloro-4-pyridine methanol derivative. 4. The formula (1), wherein W represents —C0R ¹ , and R ¹ is an unsubstituted or alkenyl group substituted with a “phenyl group optionally substituted with an alkoxy group”. Item 4. A 2,6-dichloro-4-pyridinemethanol derivative according to item 3. 5. In the general formula (1), W represents —C0R ¹ , wherein R ¹ is a halogen atom, an alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or a halogen atom. C1-C12 alkoxy group, C2-C3 alkenyloxy group, nitro group, amino group, C1-C4 alkylamino group, cyano group, acetylamino group, benzoylamino group, acetyl The 2,6-dichloro-4-pyridinemethanol derivative according to claim 3, which is a phenyl group having one or more same or different substituents selected from "oxy group, phenyl group, and phenoxy group". 6. In the general formula (1), W represents —C0R ¹ , and R ¹ has 1 carbon atom which may be substituted with a halogen atom.
The 2,6-dichloro-4-pyridinemethanol derivative according to claim 5, which is an alkoxyphenyl group of 1 to 12. 7. In the general formula (1), W represents —SO ₂ R ² , wherein R ² is an alkyl group having 1 to 12 carbon atoms or 1 carbon atom.
The 2,6-dichloro-4-pyridinemethanol derivative according to claim 1, which is a phenyl group which may be substituted with an alkyl group of 1 to 12. 8. The 2,6-dichloro-4 according to claim 1, wherein W in the general formula (1) represents —PO (OR ³ ) ₂ and R ³ is an alkyl group having 1 to 4 carbon atoms. -Pyridinemethanol derivatives. 9. W in the general formula (1) is -CONHR ⁴ ,
It represents -COOR ⁴ or -COCOR ^4, wherein R ⁴ is an alkyl group or a phenyl group having 1 to 3 carbon atoms, 2,6-dichloro-4-pyridinemethanol derivative according to claim 1. 10. W in the general formula (1) is —SiR ⁵ R ⁶ R ⁷
Wherein R ^{5 to} R ⁷ are the same or different alkyl groups having 1 to 4 carbon atoms, respectively.
6-dichloro-4-pyridine methanol derivative. 11. An agricultural chemical comprising one or more of the 2,6-dichloro-4-pyridinemethanol derivatives according to claim 1 as an active ingredient. 12. The compound of the formula (1) wherein W is a hydrogen atom, 2,6-dichloro-4-pyridinemethanol and / or W is a phenylcarbonyl group. A pesticide containing methanol benzoate as an active ingredient. General formula (1) 13. The method according to claim 1, wherein the pesticide is a plant disease controlling agent.
13. The pesticide according to 1 or 12. 14. The pesticide according to claim 13, wherein the plant disease controlling agent is a rice blast controlling agent.