JPH02131479A - Pyridylpyrimidine derivative, production thereof and agricultural and horticultural germicide containing the same as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R1 is lower alkyl, lower alkoxy, lower haloalkyl, lower haloalkoxy or halogen; n is 0-3; R2 is lower alkoxy or lower haloalkoxy; R3 is lower alkyl; R4 and R5 are H or R3). EXAMPLE:2-(4-Methoxy-6-o-methylphenyl-2-pyridyl)-4-methylpyrimidine. USE:An active ingredient of agricultural and horticultural germicides capable of exhibiting excellent preventive and treating effects on disease injuries in wide fields of rice plant, wheats or barleys, fruit trees and vegetables and further sufficient controlling effects even on germs resistant to various existing germicides. PREPARATION:A picolinamidine derivative expressed by formula II or salt thereof is reacted with a beta-oxoacetal derivative expressed by formula III (R6 is R3) in a solvent, such as methanol, in the presence of a base, such as CH3 ONa, to afford the compound expressed by formula I (R5 is H).

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a novel pyridylpyrimidine derivative, a method for producing the same, and an agricultural and horticultural fungicide containing the same as an active ingredient.

Problems to be Solved by the Prior Art and the Invention In recent years, the safety of agricultural chemicals has become a problem due to environmental pollution, residue in crops, etc. Therefore, it is desired to develop new agricultural chemicals that have low toxicity and do not accumulate in animals or plants or in soil. Many studies have been done on ways to achieve this, but
In the case of fungicides, for example, the development of highly active or broad-spectrum compounds is considered an effective approach.

<Means for Solving the Problems> As a result of intensive studies to find a highly active and broad-spectrum fungicide, the present inventors found that the general formula R2 [wherein R1 may be the same or different] , lower alkyl group, lower alkoxy group, lower haloalkyl group,
Represents a lower haloalkoxy group or a halogen atom, n
represents 0, 1, 2 or 8, R represents a lower alkoxy group or a lower haloalkoxy group, R. a represents a lower alkyl group, and R4 and R5 may be the same or different and represent a hydrogen atom or a lower alkyl group. ] The biridylpyrimidine derivative (hereinafter referred to as the compound of the present invention) shown in the formula (hereinafter referred to as the compound of the present invention) is an excellent preventive agent for various diseases in a wide range of fields such as rice and wheat, which are important crops. The inventors have discovered that they exhibit efficacy and therapeutic efficacy, and also exhibit sufficient control efficacy against bacteria resistant to various existing fungicides, leading to the present invention.

Examples of the compounds of the present invention include the following compounds,
It is not necessarily limited to these compounds.

2-(4-methoxy6-phenyl-2-biridyl)-
4-Methylpyrimidine 2-(4-ethoxy6-phenyl-2-pyridyl)-
4-Methylpyrimidine 4-ethyl-2-(4-methoxy6-phenyl-2-
pyridyl)pyrimidine 2-(4-methoxy6-phenyl-2-pyridyl)-
4-propylbyrimidine 2-(4-difluoromethoxy-6-phenyl-2-biridyl)-4-methylpyrimidine 4-methyl-2-(6
-Phenyl-4-trifluoromethoxy-2-pyridyl)pyrimidine 2-(4-methoxy-6101methylphenyl-2-pyridyl)-4-methylpyridine2-(4
-ethoxy-6-0-methylphenyl-2-pyridyl)
-4-Methylpyrimidine 4-ethyl-2-(4-methoxy-6-methylphenyl-2-pyridyl)pyridine 2-(4-difluoromethoxy6-0-methylphenyl-2-pyridyl)- 4-Methylpyrimidine 2-(4-methoxy6-m-methylphenyl-2-pyridyl)-4-methylpyrimidine 2-(4-methoxy-
6-1) 1-methylphenyl-2-pyridyl)-4-methylpyrimidine 2-( 6-0-chlorophenyl-4-methoxy-2-pyridyl)-4-methylpyrimidine 2-(
6-0-chlorophenyl-4-ethoxy-2-pyridyl)-4-methylpyrimidine 2-(6-o-chlorophenyl-4-difluoromethoxy-2-pyridyl)-4-methylpyrimidine 2-(6-o-chlorophenyl -4-trifluoromethoxy-2-pyridyl)-4-methylpyrimidine 2-(6-o-chlorophenyl-4-(1.1.2.2
-tetrafluoroethoxy)-2-pyridyl)-4-methylpyrimidine 2-(6-m-chlorophenyl-4-methoxy-2-pyridyl)-4-methylpyrimidine 2-(6-p-chlorophenyl-4-methoxy -2-pyridyl)-4-methylpyrimidine2-(6-0-fluorophenyl-4-methoxy-2-pyridyl)-4-methylpyrimidine2-(6
-o-promophenyl-4-methoxy-2-pyridyl)
-4-Methylpyrimidine 2-(6-(2.4-dimethylphenyl)-4-methoxy-2-pyridyl)-4-methylpyrimidine 2-(6-(2.6-dimethylphenyl)-4-methoxy- 2-pyridyl)-4-methylpyrimidine 2-(6-(4-chloro-2-methylphenyl)-4-
methoxy2-pyridyl)-4-methylpyrimidine2-(4-methoxy6-0-}lifluoromethylphenyl-2-pyridyl)-4-methylpyrimidine2-(6-0-difluoromethoxyphenyl-4-methoxy -2-pyridyl)-4-methylpyridine 2-(4-methoxy6-0-(1.1.2.2-tetrafluoroethoxyphenyl)-2-pyridyl)-4
-Methylpyrimidine 2-(4-methoxy6-o-trifluoromethoxyphenyl-2-pyridyl)-4-methylpyrimidine 2-(6-1-difluoromethoxyphenyl-4-methoxy-2-pyridyl)-4- Methylpyrimidine 2-(4-methoxy6-1)-trifluoromethoxyphenyl-2-pyridyl)-4-methylpyrimidine 2-(5-methoxy6-phenyl-2-pyridyl)-
4-Methylpyrimidine 4-methyl-(6-phenyl-5-trifluoromethoxy-2-pyridyl)pyrimidine 2-(5-methoxy-6
-0-methylphenyl-2-pyridyl)-4-methylpyrimidine2-(6-o-chlorophenyl-5-methoxy-2-pyridyl)-4-methylpyrimidine2-(6-o
-chlorophenyl-5-trifluoromethoxy-2-pyridyl)-4-methylpyrimidine 2-(6-o-chlorophenyl-5-difluoromethoxy-2-pyridyl)-4-methylpyrimidine 2-(5-ethoxy 6-phenyl-2-pyridyl)-
4-Methylpyrimidine 2-(6-0-chlorophenyl-5-ethoxy-2-biridyl)-4-methylpyrimidine 4-methyl-2-(6
-phenyl-5-(1.1.2.2-tetrafluoroethoxy)-2-pyridyl)pyrimidine 2-(6-0-fluorophenyl-5-methoxy-2-
pyridyl)-4-methylpyrimidine 2-(5-ethoxy10-fluorophenyl-2-pyridyl)-4-methylpyrimidine 2-(4-methoxy-6-(2.4.6-trimethylphenyl) )-2-Biridyl)-4-methylpyrimidine 2-(6-0-ethylphenyl-4-methoxy-2-biridyl)-4-methylpyrimidine 2-(4-methoxy-
6-0-methoxyphenyl-2-pyridyl)-4-methylpyrimidine 2-(4-methoxy-6-p-methoxyphenyl-2-pyridyl)-4-methylpyrimidine 2
-(6-p-ethoxyphenyl-4-methoxy-2-pyridyl)-4-methylpyrimidine 2-(4-methoxy-
6-(0-2.2.2-trifluoroethoxyphenyl)-2-pyridyl)-4-methylpyrimidine 2-(4-methoxy6-o-}cyclomethoxyphenyl-2-pyridyl)-4-methyl Pyrimidine 4,5-dimethyl-2-(4-methoxy-6=phenyl-2-pyridyl) Pyrimidine 4,5-dimethyl-2-(
5-methoxy-6-phenyl-2-biridyl)pyrimidine 2-(6-o-difluoromethoxyphenyl-4-methoxy-2-biridyl)-4,5-dimethylpyrimidine 4,5-dimethyl-2-(4- Methoxy-6o (
1 + 1 + 2 + 2-tetrafluoroethoxyphenyl)-2-pyridyl)pyrimidine 5-ethyl-2
-(4-methoxy-6-phenyl-2-biridyl)-4
-Methylpyrimidine 4.5-dimethyl-2-(4-methoxy-610-methylphenyl-2-bilidyl)pyrimidine 2-(6-o-chlorophenyl-4-methoxy2-bilidyl)-4.5-dimethyl Pyrimidine 4,6-dimethyl-2-(4-methoxy-6-phenylene-2-pyridyl) Pyrimidine 4,6-dimethyl-2-(
6-methoxy-6-phenyl-2-pyridyl)pyrimidine 2-(6-0-difluoromethoxyphenyl-4-methoxy-2-pyridyl) -4. 6-dimethylpyrimidine 4.6-dimethyl-2-(4-methoxy-6-O-(1
．． 1,2,2-tetrafluoroethoxyphenyl)-2
-pyridyl)pyrimidine 6-ethyl-2-(4-methoxy-6-phenyl-2-pyridyl)-4-methylpyrimidine 4.6-dimethyl-2-(4-methoxy-610-
Methylphenyl-2-pyridyl)pyrimidine 2-(6-0-chlorophenyl-4-methoxy-2-pyridyl)-4.6-dimethylpyrimidine 4.6-diethyl-2-(4-methoxy-6-phenyl-2-pyridyl )-pyrimidine 2-(4-methoxy-6
-phenyl-2-pyridyl)-4.5.6-}rimethylpyrimidine, or their hydrochlorides, hydrobromides, sulfates, nitrates, and the like.

Plant diseases that can be controlled by the compounds of the present invention include rice blast (Pyricularia oryza).
e), sesame leaf blight (Cochliobolus mi
yabeanus), sheath blight (Rhizoctoni
a solani), powdery mildew of wheat (Ery
sphe graminis f. sp. hord
ei, E. g. f. sp. tritici)
, Pyrenophora gramin
ea), Pyrenophorate
res), Fusa-rium ni
vale), Rust (Puccinia stri)
iformis, P. graminis, P. r
econdita, P. hordei), Pseudocercosporella herer
potrichoides), Rhynch
osporium secalis), leaf blight (S
eptoria tritici), Lep blight (Lep
tosphaeria nodorum), citrus black spot (Diaporthe citri), scab (Elsinoe fawcetti),
Powdery mildew of apples ( Podosphaera le
ucotricha), leaf spot disease (Alte-rna
ria mali), scab (Venturia
inaequalis), pear scab (Vent
uria nashicola), black spot disease (Alt
ernaria kikuchiana), peach sclerosis (Sclerotinia cinerea),
Grape black rot (Elsinoe ampelin)
a), late rot disease (Glomorel lacing)
ulata), powdery mildew (Uncinula n.
ecator), cucurbit anthracnose (Colleto
trichum lagenarium), powdery mildew (Sphaerotheca fuliginea)
), tomato ring spot disease ( Alternaria sol
ani), Phytophthora i
nfestans), eggplant brown spot disease (Phomo
psisvexans), black spot of cruciferous vegetables (
Alternaria japonica), vitiligo disease (Cercosporella brassica)
e), allium rust (Puccinia allii)
), soybean purpura (Cercospora ki
kuchii), black disease (Elsinoegl)
ycines), common bean anthracnose (COI le
totrichum1indemuthianum)
, groundnut black astringent disease (Myc osphaere)
lla personum), brown spot (Ce
rcospora arachidicola), pea powdery mildew (Erys-iphe pisi)
, summer blight of potatoes ( Alternariasol
ani), brown spot of sugar beet (Cercospor
a bet-iCO1a), rose scab (Dip
locarpon rosae), powdery mildew (S
phaerotheca pannosa), gray mold (Botrytis ciner) on various crops
ea), Sclerotinia scle
rotiorum), etc.

Next, the method for producing the compound of the present invention will be explained in detail.

Among the compounds of the present invention, those having the general formula R2 [where n, Rl, Rs+, Rs and R
4 represents the same meaning as above, and R6' represents a hydrogen atom. ] The pyridylpyrimidine derivative represented by the general formula (KIJn [wherein Rl, R! and n represent the same meanings as above]) and the bicolinamidine crocodile conductor or its salt represented by the general formula R4 ■ RaCOCHCH ( ORs ) ! (N) [
In the formula, R3 and R4 represent the same meanings as above, and Rs
represents a lower alkyl group. ] in the presence of a base.

Examples of the salts of picolamidine derivatives include hydrochloride, hydrobromide, acetate, and formate.

In the above reaction, the reaction temperature is typically 50-15
The 0° C1 reaction time is 1 to 6 hours.

Further, the number of reagents used in the reaction is 1 to 1 equivalent of the β-oxoacetal regulator represented by the general formula (IV) per 1 equivalent of the picolinamidine derivative represented by the general formula (II) or its salt. .5 equivalents, and the base has a catalytic amount of ~2.5
This is the first one.

In the above reaction, although a reaction solvent is not necessarily required, it is generally carried out in the presence of a solvent. Examples of solvents that can be used include lower alcohols such as methanol and ethanol, cyclic ethers such as dioxane and tetrahydrofuran, pyridine, and N,N-dimethylformamide.

Examples of the base include alkali metal alkoxides such as sodium methoxide, and organic bases such as triethylamine and N,N-diethylaniline. Note that it is usually preferable to react with sodium methoxide or sodium ethoxide in methanol or ethanol.

After the reaction is completed, the reaction solution is subjected to usual post-treatments such as concentration under reduced pressure, and if necessary, the target compound is obtained by operations such as chromatography.

Furthermore, among the compounds of the present invention, pyridylpyrimidine derivatives represented by the general formula [wherein nsRl, R2, Rs and R4 represent the same meanings as above, and Re'' represents a lower alkyl group] are represented by the general formula R2 [formula In the formula, n, R+, R2, Rl1 and R4 have the same meanings as above, and X represents a halogen atom.
OORs ) t C■] [In the formula, R7 represents a hydrogen atom or a lower alkyl group, and R8 represents a lower alkyl group. It is obtained by reacting the malonic acid diester derivative represented by ] in the presence of a base, followed by hydrolysis and further decarboxylation.

In the reaction between the octoropyrimidine conductor represented by the general formula ([) and the malonic acid diester derivative represented by the general formula cvi), the base used in the reaction includes, for example, an alkali metal hydride such as sodium hydride. class, n-
Examples include alkyllithiums such as butyllithium, lithium dialkylamides such as lithium diisobrobylamide (LDA), alkali metal alkoxides such as sodium methoxide, and alkali metal hydroxides such as sodium hydroxide.

In the above reaction, the reaction temperature is typically 0 to 150°C, the reaction time is 80 minutes to 24 hours, and the amount of reagent used in the reaction is usually the halobyrimidine represented by the above general formula [■]. For one derivative fi+, the general formula [■
] The malonic acid diester derivative and the base each have 1 to 2 equivalents.

In the above reaction, although a reaction solvent is not necessarily required, it is generally carried out in the presence of a solvent. Usable solvents include lower alcohols such as methanol and ethanol, nitriles such as acetonitrile, ethers such as diethyl ether and tetrahydrofuran, halohydrocarbons such as chloroform, and aromatic hydrocarbons such as benzene and toluene. , haloaromatic hydrocarbons such as chlorobenzene,
Examples include ketones such as acetone and methyl isobutyl ketone, esters such as ethyl acetate, yellowing compounds such as dimethyl sulfoxide and sulfolane, and mixtures thereof.

After the above reaction is completed, the target compound can be obtained by hydrolysis and decarboxylation. Typically, 2.1 to 5 equivalents of a base, such as an alkali metal hydroxide such as sodium hydroxide, or an alkali metal carbonate such as sodium carbonate, per equivalent of the halobyrimidine derivative represented by the general formula (V[) above. Aqueous solution of salt etc. or methanol
A mixed solution of a lower alcohol such as alcohol, ethanol, etc. and an aqueous solution of the base is added to carry out an alkaline hydrolysis reaction at a reaction temperature of 10 to 100°C and a reaction time of 10 minutes to 24 hours. Next, 2.6 to 6 equivalents of an acid, for example, an inorganic acid such as sulfuric acid or an organic acid such as acetic acid, per equivalent of the halopyrimidine derivative represented by the above general formula [■] is added to the reaction solution, and the reaction temperature is 20. The decarboxylation reaction is carried out at ~150°C for a reaction time of 10 minutes to 24 hours.

After the reaction is complete, alkali metal hydroxides such as sodium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, alkali metal carbonates such as sodium carbonate, alkali metal hydrogen carbonates such as sodium hydroxide, triethylamine, etc. After neutralizing the reaction solution with an organic base, etc., the target compound can be obtained by performing usual post-treatments such as concentration under reduced pressure and extraction, and if necessary, subjecting it to operations such as recrystallization and column chromatography. can.

The compound of the present invention represented by the general formula CI) can be converted into the respective salt by reacting it with a strong acid such as hydrogen chloride, hydrogen bromide, sulfuric acid, or nitric acid according to a conventional method. can.

When producing these salts, the compound of the present invention represented by the general formula CI) is dissolved in a solvent, 1 equivalent of acid is added as a gas or aqueous solution under water cooling or at room temperature, and the mixture is left for 10 minutes to 1 hour. Post-processing such as vacuum concentration is performed, and if necessary, recrystallization is performed.

Reaction solvents include lower alcohols such as methanol and ethanol, aromatic hydrocarbons such as toluene and benzene, ethers such as ethyl ether, tetrahydrofuran, and dioxane, halogenated hydrocarbons such as chloroform, ketones such as acetone, Examples include esters such as ethyl acetate, hydrocarbons such as hexane, water, and mixtures thereof.

Next, the halopyrimidine derivative represented by the general formula (Vi) and the picolinamidine derivative represented by the general formula (III), which are raw materials for producing the compound of the present invention, are:
For example, it can be synthesized using the following synthesis route.

[■]

[Expletive] [In the formula, n, Rl, Rg%Rs and R4 represent the same meanings as above, M represents an alkali metal atom, and R9
and Rto represents a lower alkyl group. ] In other words, J. Org. Chem. ．． 48. 1
875-1877 (1988), etc., by reacting the cyanopyridine derivative represented by the general formula [■] with the alkoxide represented by the general formula (IX). By reacting the imidate derivative with an ammonium salt, a picolinamidine conductor represented by general formula (III) is obtained.

Next, by reacting the thus obtained picolinamidine derivative or its salt with a β-oxocarboxylic acid ester represented by general formula tII) in the presence of a base, a hydroxypyrimidine represented by general formula [■] is obtained. A derivative is obtained, and by reacting the hydroxypyrimidine derivative with a halogenating agent, a halopyrimidine cross-conductor represented by general formula (Vl) is obtained.

The above manufacturing method will be explained in detail below.

In the reaction between the cyanopyridine derivative represented by the general formula [■] and the alkoxide represented by the general formula CIK),
Examples of the alkali metal atom of the alkoxide used include sodium atom and potassium atom.

In addition, in this reaction, the reaction temperature is typically 10 to 50°C.
The reaction time for C1 is 1 to 48 hours, and the amount of the reagent used for the reaction is 0.1 equivalent of the alkoxide represented by the general formula (IX) per equivalent of the cyanopyridine derivative represented by the general formula [X1]. 1 to 1 equivalent.

In the above reaction, although a reaction solvent is not necessarily required, it is generally carried out in the presence of a solvent.

Examples of solvents that can be used include lower alcohols corresponding to R9 of the alkoxide represented by the general formula (I!), such as methanol, ethanol, n-propyl alcohol, isobropyl alcohol, n-butyl alcohol, etc.
Preferred are methanol and ethanol.

After the reaction is completed, the reaction solution is neutralized with an acid, concentrated under reduced pressure, dissolved in an organic solvent, the insoluble alkali metal salt is removed, the P solution is concentrated under reduced pressure, and if necessary, distilled etc. Through this operation, the desired imidate derivative represented by general formula (1) can be obtained.

Next, in the reaction between the imidate derivative represented by the general formula (J) obtained above and an ammonium salt, examples of the ammonium salt used include ammonium salts such as hydrochloric acid, hydrobromic acid, acetic acid, and formic acid. .

In addition, in this reaction, the reaction temperature is typically 80 to 10
0'C, the reaction time is 80 minutes to 5 hours, and the amount of reagent used in the reaction is usually 1 to 1.1 ammonium salt per equivalent of the imidate derivative represented by general formula (1).
Island in equivalent quantity.

Although a solvent is not necessarily required in the above reaction, it is generally carried out in the presence of a solvent.

Examples of the solvent that can be used include lower alcohols, preferably a mixed solvent of ethanol and water.

After completion of the reaction, the reaction solution is subjected to normal treatment such as vacuum condensation, and if necessary, recrystallization or other operations are performed to obtain the general formula (ill
) It is possible to obtain salts of the bicolamidine derivatives represented by hydrochloric acid, hydrogen bromides, acetic acid, formic acid, etc.

The salt thus obtained is decomposed by a conventional method such as neutralization with an inorganic base such as sodium hydroxide or potassium hydroxide or an alkali metal alkoxide such as sodium methoxide or sodium ethoxide. By doing so, a bicolinamidine derivative represented by the general formula (1[1)] can be obtained.

Alternatively, the salt can be directly subjected to the reaction in the next step, and the salt can be decomposed within the reaction system.

Next, in the reaction of the bicolamidine derivative represented by the general formula CIII) obtained above with the β-oxocarboxylic acid ester represented by the general formula (XI), the reaction temperature is typically 50 to 50°C. The temperature was 150°C, the reaction time was 1 to 24 hours, and the amount of the reagent used for the reaction was based on the general formula (III).
The β-oxocarboxylic acid ester represented by the general formula CIO is usually used in an amount of 1 to 1.5 equivalents, and the base is used in a catalytic amount to 1.5 equivalents per equivalent of the bicolamidine derivative or its salt represented by the formula CIO.
It is 5 equivalents. Although a solvent is not necessarily required in the above reaction, it is generally carried out in the presence of a solvent.

Examples of solvents that can be used include lower alcohols such as methanol and ethanol, cyclic ethers such as dioxane and tetrahydrofuran, pyridine, N,N-dimethylformamide, water, etc., and mixtures thereof. For example, inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, alkali metal alkoxides such as sodium methoxide, triethylamine,
Examples include organic bases such as N,N-diethylaniline.

After the completion of the reaction, salts are removed from the reaction solution by filtration, if necessary, and ordinary post-treatments such as concentration under reduced pressure are carried out, and if necessary, the desired general formula [
(2) A hydroxypyrimidine derivative represented by [2] can be obtained.

Next, in the reaction of the hydroxypyrimidine conductor represented by the general formula [■] obtained above with a halogenating agent,
Examples of the halogenating agent used include thionyl chloride, phosgene, phosphorus oxychloride, phosphorus pentachloride, phosphorus oxybromide, and phosphorus tribromide.

In the above reaction, the reaction temperature is typically 50 to 150
℃, the reaction time is 1 to 10 hours, and the amount of the reagent used in the reaction is usually 1 to 10 equivalents of the halogenating agent per equivalent of the hydroxypyrimidine derivative represented by the general formula.

Although a solvent is not necessarily required in the above reaction, it is generally carried out in the presence of a solvent.

Examples of solvents that can be used include aromatic hydrocarbons such as benzene and toluene, and halogenated hydrocarbons such as chlorobenzene.

After the reaction is completed, the reaction solution is concentrated under reduced pressure, neutralized with an inorganic base such as sodium hydroxide, and subjected to usual post-treatments such as organic solvent extraction and concentration.If necessary, chromatography, recrystallization, etc. By the operation, the desired halopyrimidine derivative represented by the general formula (Vl) can be obtained.

When the compound of the present invention is used as an active ingredient of a fungicide for agriculture and horticulture, it may be used as it is without adding any other ingredients, but it is usually used as a solid carrier, liquid carrier, surfactant, or other pharmaceutical agent. Mixed with auxiliary agents, emulsions, perpetuators, suspension agents,
It is used in formulations such as granules and powders.

These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 0.1 to 99%, preferably 0.2 to 96%.

Solid carriers include fine powders or granules such as kaolin clay, attapulgite clay, bentonite, acid clay, pie phyllite, talc, diatomaceous earth, calcite, corn cob powder, walnut shell powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide. Liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as isopropanol, ethylene glycol, and cellosolve, ketones such as acetone, cyclohexanone, and isophorone, and soybean oil and cottonseed oil. Vegetable oil, dimethyl sulfoxide, acetonitrile, water, etc. are mentioned.

Surfactants used for emulsification, dispersion, wet spreading, etc. include alkyl sulfate salts, alkyl (aryl)
Anionic surfactants such as sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymers Silvitan Examples include nonionic surfactants such as fatty acid esters and polyoxyethylene sorbitan fatty acid esters.

As formulation adjuvants, lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC
(carboxymethylcellulose), PAP (isoprobyl acid phosphate), and the like.

These preparations can be used as they are, or diluted with water and sprayed on foliage, treated with seeds, sprinkled or granulated on the soil, mixed, or applied to the soil. In addition, by mixing with other agricultural and horticultural fungicides,
It can also be expected to increase the pesticidal efficacy. Furthermore, it can be used in combination with insecticides, acaricides, nematicides, herbicides, plant growth regulators, fertilizers, soil conditioners, and the like.

When the compound of the present invention is used as an active ingredient of a fungicide for agriculture and horticulture, the amount to be treated depends on weather conditions, formulation form, treatment time,
Although it varies depending on the method, location, target disease, target crop, etc., it is usually 0.5 to 200 knots per are, preferably 1
~100F, and when applying emulsions, wettable powders, suspensions, etc. diluted with water, the application concentration is 0.005~0.
6%, preferably 0.01 to 0.2%, and granules, powders, etc. are applied as they are without any dilution.

Effects of the Invention The compounds of the present invention have excellent effects against plant diseases caused by various plant pathogenic bacteria, and therefore can be used in various applications as active ingredients of agricultural and horticultural fungicides.

Examples> The present invention will be explained in more detail below using production examples, reference examples, formulation examples, and test examples, but the present invention is not limited only to these examples.

First, a manufacturing example will be shown.

Production Example 1 (Compound (5}) 4-Methoxy6-0-methylphenyl-2-picolinamidine hydrochloride 1f was dissolved in methanol 50-
% sodium methylate in methanol solution 0.91, 1.
1-dimethoxy-8-butanone 0.56F was added and heated under reflux for 1 hour.

After cooling the reaction solution, it was concentrated under reduced pressure, and the resulting residue was added with 50% water.
, 100 ml of dichloromethane was added for extraction, and the layers were separated.

The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the resulting crystalline residue was washed with hexane to give 2-(4
-methoxy-6101methylphenyl-2-pyridyl)
-4-methylpyrimidine 0. 9 4 f was obtained.

m. p. 128.0℃ PMR CDCls δppm 2.89 (s. 8H, -CHa) 2.60
(S. 8H. 1 action) 8.94 (s. 8H, -QC}ro) 8.70 (
d. IH. Pyrimidine-I{', J=5.4Hz) Production Example 2 (Compound (6)) 1.6f of diethylmalonic acid and 0.40f of 60% oily sodium hydride were added to 80ml of tetrahydrofuran, and 4-chloro -2-(4-methoxy-6-0-methylphenyl-2-bilidyl)-6-methylpyrimidine 2.8
Added l. After heating under reflux for 80 minutes after the addition, 0.85F of sodium hydroxide was mixed with 10-10% of water and 10% of methanol.
A mixed solution dissolved in the above was added to the mixture, and the mixture was further heated and cooled for 20 minutes.

After cooling to room temperature, 1.41 g of sulfuric acid was added, and the mixture was further heated under reflux for 80 minutes.The mixture was made neutral by adding an aqueous solution of IN sodium carbonate, and concentrated under reduced pressure.

? The residue was treated with silica gel column chromatography (hexane:acetone = 2:1) to obtain 4,6-dimethyl-2-(4-methoxy-610-methylphenyl-2).
-pyridyl)pyrimidine 1.71 was obtained.

m-p. 87.5℃ PMR CDCla δppm 2.88 (s,8H,-CHa) 2.49 (s.6H.2 Zhangichi ■a) 8.86 (
s. 8H, -OCHa) 7.88 (d, IH, pyridine-H".J=2.4Hz) Next, Table 1 shows some of the compounds of the present invention that can be produced by such a production method.

\, Table 1～ゝ～, \\ Next, the raw material compound picolamidine derivative ((I
I) O and halopyrimidine derivative (Vl) 17) ml preparation examples are shown as reference examples.

Reference example 1 Production of picolamidine derivative (III) 2
- Dissolve 10f of cyano-4-methoxy-6-0-methylphenylpyridine in 20ml of methanol, and add 28ml of
% sodium methylate methanol solution was added. After stirring for 6 hours, 1.84 f of acetic acid was added and concentrated under reduced pressure. Ether 200- was added to the obtained residue, and the insoluble matter was removed by P.
After removal, the solution was concentrated to obtain methyl 4-methoxy-6-0-methylphenyl-2-picolidate. Then ξ
To this was added 100 d of ethanol, and then a solution of 2.89 N ammonium chloride dissolved in 80 ml of water was added, and the mixture was heated under reflux for 80 minutes.

The opposite solution was sufficiently concentrated under reduced pressure, and the resulting crystalline residue was washed with acetone to obtain 11.2N of 4-methoxy-6-01 methylphenyl-2-picolinamidine hydrochloride.

m. p. 105.8°C Reference Example 2 Production of halopyrimidine derivative [■] Add 5f of 4-methoxy-6-0-methylphenyl-2-picolinamidine hydrochloride to 50-methanol, and add 4.2f of 28% sodium methylate methanol solution to this. and 2.61 g of ethyl acetoacetate were added thereto, and the mixture was heated under reflux for 1 hour. After cooling,
Acetic acid was added to the reaction solution to make it neutral, and the mixture was concentrated under reduced pressure. The resulting residue was washed with water and then with hexane to obtain 5.1 g of 4-hydroxy-2-(4-methoxy-6101methylphenyl-2-pyridyl)-6-methylpyrimidine. .

Next, 100 ml of toluene was added to 5.1 g of the obtained hydroxypyrimidine, 5 f of phosphorus oxychloride was added thereto, and the mixture was heated under reflux for 1 hour. After cooling, the mixture was neutralized with an aqueous sodium carbonate solution and separated.

The toluene layer was washed with water, dried over anhydrous sodium sulfate, and then concentrated under reduced pressure. The resulting residual liquid was washed with hexane,
4-chloro-2-(4-methoxy6-o-methylphenyl-2-biridyl)-6-methylpyrimidine 4.8f
I got it.

m. I). 189.0℃ PMR CDCls δppm 2.45 (s.8H, -CHs) 2.68 (s.8H, -CHa) 8.98 (s,8H, -0 (j low) 7.08
(d, IH, pyridi:/-H'.J=2.4Hz)7
．． 94 (d.IH.Pyridine-H".J=2.4
Hz) Next, a formulation example will be shown. The compounds of the present invention are indicated by compound numbers in Table 1, and parts are parts by weight.

Formulation Example 1 50 parts each of the compounds of the present invention (1) to (10), 8 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate, and 45 parts of synthetic hydrous silicon oxide were thoroughly ground and mixed to form a hydrating agent for each of the compounds of the present invention. get.

Formulation Example 2 25 parts each of the compounds (1) to (10) of the present invention, 8 parts polyoxyethylene sorbitan monooleate, 69 parts CMCa, and 69 parts water were mixed and wet-pulverized until the particle size of the active ingredient became 5 microns or less. A suspension of each of the compounds of the present invention is obtained.

Formulation Example 8 2 parts each of the compounds (1) to (10) of the present invention, 88 parts of kaolin clay, and 10 parts of talc are thoroughly ground and mixed to obtain a powder of each of the compounds of the present invention.

Formulation Example 4 20 parts each of the compounds (1) to (10) of the present invention, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, and 60 parts of xylene
The components are thoroughly mixed to obtain an emulsion of each compound of the present invention.

Formulation Example 5 2 parts each of the compounds (1) to (10) of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 80 parts of bentonite and 66 parts of kaolin clay are thoroughly ground and mixed, and water may be added. After kneading, the mixture is granulated and dried to obtain granules of each compound of the present invention.

Next, test examples will show that the compounds of the present invention are useful as fungicides. The compounds of the present invention are indicated by the compound numbers in Table 1, and the compounds used for comparison are indicated by the compound symbols in Table 2.

Table 2 The control efficacy is determined by visually observing the disease state of the test plants at the time of investigation, that is, the degree of bacterial flora and lesions on leaves, stems, etc., and if no bacterial flora or lesions are observed, the rating is ``5''; If around 10% is recognized, it is ``4'', if around 80% is recognized, it is r8J, if around 50% is recognized, it is ``2'', if around 70% is recognized, it is ``1''.
If there is no difference from the disease onset state when the compound is not tested, it will be evaluated as "0" and evaluated on a 6-level scale, with 5, 4, 8, 2.1, and G, respectively.

Test Example 1 Rice blast control test (preventive effect) A plastic pot was filled with sandy loam, and rice (Kinki No. 88) was sown and grown in a greenhouse for 20 days. A test drug prepared as a suspension according to Formulation Example 2 was diluted with water to a predetermined concentration, and the solution was sprayed on the foliage of rice seedlings so as to sufficiently adhere to the leaf surface.

After spraying, the plants were air-dried and then sprayed and inoculated with a spore suspension of the blast fungus. After inoculation, the plants were left at 28° C. in the dark and humid for 4 days, and then the pesticidal efficacy was investigated.

The results are shown in Table 8.

Table 8 Test Example 2 Rice blast control test (therapeutic effect) A plastic pot was filled with sandy loam, and rice (Kinki No. 88) was sown in the dish and grown in a greenhouse for 20 days. Young rice seedlings were inoculated with a spore suspension of the blast fungus. After wetting, 28°C
1. After being left in a dark and humid environment for 16 hours, the test drug made into a permanent agent according to Formulation Example 1 was diluted with water to a predetermined concentration, and sprayed on the leaves so as to sufficiently adhere to the leaf surface. After spraying,
The plants were grown for 8 days at 28°C in darkness and high humidity, and their pesticidal efficacy was investigated. The results are shown in Table 4.

I [Table 4] Sprayed on foliage and foliage as shown in Table 4. After spraying, the seeds were grown in a greenhouse at 28°C for 7 days, and their control efficacy was investigated. The results are shown in Table 6.

Table 5 Test Example 8 Wheat powdery mildew control test (therapeutic effect) Plastic pots were filled with sandy loam and wheat (Norin No. 78)
were sown and grown in a greenhouse for 10 days. Young wheat plants were inoculated with powdery mildew. After inoculation and growing for 8 days at 28°C, the test drug made into a wettable powder according to Formulation Example 1 is diluted with water to a predetermined concentration, and it is sufficiently adhered to the leaf surface.Test Example 4 Wheat dwarf Disease control test (preventive effect) Plastic pots were filled with sandy loam, and wheat (Norin No. 78) was sown and grown in a greenhouse for 8 days. Formulation Example 1 for wheat seedlings
A test chemical made into a permanent agent according to the above was diluted with water to a predetermined concentration, and then sprayed on the leaves so that it would adhere sufficiently to the leaf surface.

? After wrapping, the plants were air-dried and then sprayed with a spore suspension of the blight fungus. After inoculation, incubate for 1 day at 15°C in darkness and high humidity.
The plants were then grown under illumination at 16° C. for 10 days, and the control efficacy was investigated. The results are shown in Table 6.

No. 6 The test chemical used as a surface agent was diluted with water to a predetermined concentration, and was sprayed on stem vegetables so that it would sufficiently adhere to the leaf surface.

After spraying, the plants were air-dried and then sprayed with a spore suspension of the net spot fungus and inoculated. After inoculation, the plants were left at 15°C in the dark and humid for 8 days, and then grown at 20°C and under light for an additional 14 days, and the control efficacy was investigated. The results are shown in Table 7.

Table 7 Test Example 5 Barley net spot disease control test (preventive effect) A plastic pot was filled with sandy loam, barley (Akashinriki) was sown, and grown in a greenhouse for 14 days. To young barley fungi,
Milk test example 6 Barley cloud disease control test (preventive effect) According to Formulation example 4, sandy loam was filled in a plastic pot, barley (Akashinriki) was sown, and grown in a greenhouse for 14 days.

A test drug prepared as an emulsion according to Formulation Example 4 was diluted with water to a predetermined concentration and sprayed on barley seedlings so as to sufficiently adhere to the leaf surface.

After spraying, the plants were air-dried and inoculated by spraying with a spore suspension of the fungus. After inoculation, the plants were left in a 15°C1 dark and humid environment for 1 day, and then grown for another 14 days under a 20"C1 light, and their pesticidal efficacy was investigated. The results are shown in Table 8.

Table 8 Test Example 7 Wheat eye spot disease control test (therapeutic effect) A plastic pot was filled with sandy loam, and wheat (Norin No. 78) was sown and grown in a greenhouse for 10 days. Wheat seedlings were sprayed and inoculated with a spore suspension of the eyelid fungus. After inoculation, 15'
C. After being left in a dark and humid environment for 2 days, the test drug made into a wettable powder according to Formulation Example 1 was diluted with water to a specified concentration, and sprayed on the leaves so that it would fully adhere to the leaf surface. . After spraying,
The plants were grown for 14 days under light and high humidity, and their pesticidal efficacy was investigated.

The results are shown in Table 9.

Table 9 After inoculation, the plants were left at 15°C under humid conditions for 4 days, and then grown under light for 15 days, and their control efficacy was investigated. The results are shown in Table 10.

Table 10 Test Example 8 Apple Scotch Disease Control Test (Preventive Effect) Plastinum scab was filled with crushed soil, apples were sown, and grown in a greenhouse for 20 days. A test drug prepared as an emulsion according to Formulation Example 4 was diluted with water to a predetermined concentration and sprayed on apple seedlings so as to sufficiently adhere to the leaf surface. After spraying, a spore suspension of apple scab was sprayed and inoculated.

Test Example 9 Cucumber Gray Mold Control Test (Preventive Effect) A plastic pot was filled with sandbox soil, and cucumbers (Sagami Hanshiro) were sown and grown in a greenhouse for 14 days. A test chemical prepared as a permanent agent according to Formulation Example 1 was diluted with water to a predetermined concentration and sprayed on cucumber seedlings so as to sufficiently adhere to the leaf surface. After spraying, the plants were air-dried and inoculated with MBC-resistant Botrytis hyphae. After inoculation, the plants were kept at 15° C. in the dark and humid for 8 days, and then the pesticidal efficacy was investigated. The results are shown in Table 11.

No. 11 surface liquid was sprayed and inoculated. After inoculation, the plants were left at 28° C. in the dark and humid for 4 days, and then the pesticidal efficacy was investigated.

The results are shown in Table 12.

Table 12 Test Example 10 Rice sheath blight control test (preventive effect) A plastic pot was filled with sandy loam, and rice (Kinki No. 88) was sown and grown in a greenhouse for 28 days. A test chemical prepared as a permanent agent according to Formulation Example 1 was diluted with water to a predetermined concentration, and was sprayed onto rice young so that it would sufficiently adhere to the leaf surface.

After spraying, the plants were air-dried and the sheath blight fungus was suspended in agar containing bacteria Test Example 1
1 Wheat leaf blight control test (preventive effect) Plastic pots were filled with sandy loam, wheat (Norin No. 78) was sown, and grown in a greenhouse for 8 days. Formulation Example 4 for wheat seedlings
A test drug prepared as an emulsion according to the above was diluted with water to a predetermined concentration, and then sprayed on the foliage to ensure sufficient adhesion to the leaf surface.

After air-drying, a spore suspension of leaf blight fungus was spray inoculated.

After cooling, leave it at 15℃, darkness, and high humidity for 8 days, and then leave it for 2 more days.
The plants were grown for 14 days under illumination at 8°C, and their pesticidal efficacy was investigated. The results are shown in Table 14.

Table 14

Claims (1)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. represents an alkoxy group or a halogen atom, n represents 0, 1, 2 or 3, R_2 represents a lower alkoxy group or lower haloalkoxy group, R_3 represents a lower alkyl group, R_4 and R_5 are the same or different; They may be different and represent a hydrogen atom or a lower alkyl group. ] A pyridylpyrimidine derivative or a salt thereof. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 may be the same or different and represents a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower haloalkoxy group, or a halogen atom, and n is 0 , 1, 2 or 3, and R_2 represents a lower alkoxy group or a lower haloalkoxy group. ] Picolinamidine derivative or its salt represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R_3 represents a lower alkyl group, R_4 represents a hydrogen atom or a lower alkyl group, and R_6 represents a Represents a lower alkyl group. [In the formula, n, R_1, R_2, R_3 and R_4 are the same as above] They have the same meaning, and R_5' represents a hydrogen atom. ] A method for producing a pyridylpyrimidine derivative. (3) General formula ▲ Numerical formula, chemical formula, table, etc. where n represents 0, 1, 2 or 3, R_2 represents a lower alkoxy group or lower haloalkoxy group, R_3 represents a lower alkyl group, R_4 represents a hydrogen atom or a lower alkyl group, and X represents a halogen represents an atom. ] A halopyrimidine derivative represented by the general formula R_7CH(COOR_8)_2 [wherein R_7 represents a hydrogen atom or a lower alkyl group, and R_8 represents a lower alkyl group. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, n, R_1, R_2, R_3 and R_4 have the same meanings as above, and R_5'' represents a lower alkyl group.] A method for producing a pyridylpyrimidine derivative represented by (4) the pyridylpyrimidine derivative or a salt thereof according to claim 1. An agricultural and horticultural fungicide characterized by containing it as an active ingredient.