JPH0641117A - Pyrimidinylthioquinoline derivative, its production and agricultural and horticultural fungicide containing the derivative as active component - Google Patents

Abstract

PURPOSE:To provide a new pyrimidinylthioquinoline derivative having excellent blight controlling effect, absolutely free from phytotoxicity to wide variety of crops and useful as an active component of agricultural and horticultural fungicide. CONSTITUTION:The compound of formula I (X is a halogen; (n) is 0-2; R is a straight or branched 1-4C alkyl), e.g. 7-chloro-4-(4,6-dimethoxy-2-pyrimidylthio) quinoline. The compound can be produced by reacting a 4-mercaptoquinoline compound of formula II with a 2-chloropyrimidine compound of formula III after converting the compound of formula II into a metal salt or in the presence of a base. The compound exhibits excellent controlling effect on various plant blights, especially powdery mildew of various crops compared with conventional compound.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel pyrimidinylthioquinoline derivative, a process for producing the same, and an agricultural and horticultural fungicide containing the same as an active ingredient.

[0002]

2. Description of the Related Art Japanese Patent Application Laid-Open No. 1-246263 discloses that quinolines having an aryloxy group or an arylthio group at the 4-position have a controlling effect against various plant diseases such as powdery mildew of wheat. Has been done.

However, the compound described in this publication mainly has a substituted phenyl group as the aryl group. As the heterocyclic group, a pyridyl group, a pyridazyl group, a pyrazole group, and a tetrazole group are merely exemplified by 1-2 points, respectively, and it is described that their disease control effect is very low or not. Therefore, the gist of the invention of this publication is that those having a substituted phenoxy group at the 4-position of the quinoline ring have a controlling effect on powdery mildew of wheat. The inventors of the present invention have focused on the fact that pyrimidines have a good affinity for living bodies, and have studied the development into physiologically active substances. Therefore, a compound having a pyrimidinylthio group at the 4-position of the quinoline ring has never been studied so far, and attention was paid to the fact that it is a novel compound, and research was started. For comparison, when tested from among the compounds described in the above publication, which are excellent, those having a high powdery mildew control effect have phytotoxicity against crops, and those with low phytotoxicity also have a low control effect. It wasn't practical.

[0004]

The object of the present invention is to provide a novel pyrimidinylthioquinoline derivative which is a compound which exhibits a controlling effect against plant diseases and is also safe against crops, and a method for producing this novel compound. And a fungicide for agricultural and horticultural use containing these compounds and a method for applying the fungicide.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies on novel pyrimidinylthioquinoline derivatives in order to solve these problems. As a result, the compound of the present invention has various plant diseases, especially various crops, as compared with conventional compounds. It was found that the present invention has an excellent controlling effect against powdery mildew of No. 1 and also shows no disease at all in a wide range of crops, and has completed the present invention.

That is, the present invention is based on the general formula (1)

[0007]

[Chemical 15]

(In the formula, X is a halogen atom, and n is 0 to 2
Represents the integer. R may be linear or branched C
A pyrimidinylthioquinoline derivative represented by the formula (2)
(Chemical formula 16)

[0009]

[Chemical 16]

(In the formula, X is a halogen atom, and n is 0 to 2
Represents an integer of 4) and is converted to a metal salt of 4-mercaptoquinoline or represented by the general formula (3)

[0011]

[Chemical 17]

## STR1 ## (wherein R represents a C1-C4 alkyl group which may be linear or branched), and a method of producing it by reacting with 2-chloropyrimidines, and a general formula (2) ( 18)

[0013]

[Chemical 18]

(In the formula, X is a halogen atom, n is 0 to 2)
The 4-mercaptoquinoline represented by the general formula (3)

[0015]

[Chemical 19]

2-chloropyrimidines represented by the formula (wherein R represents a C1-C4 alkyl group which may be linear or branched) are mixed and reacted in a molten state or in the presence of an inert solvent. And a general formula (4)
(Chemical formula 20)

[0017]

[Chemical 20]

2-mercaptopyrimidines represented by the formula (wherein R represents a C1-C4 alkyl group which may be linear or branched) are converted into metal salts, or in the presence of a base, Formula (5) (Formula 21)

[0019]

[Chemical 21]

(In the formula, X is a halogen atom, and n is 0 to 2
Of the general formula (4)

[0021]

[Chemical formula 22]

The 2-mercaptopyrimidines represented by the formula (wherein R represents a C1-C4 alkyl group which may be linear or branched) are represented by the general formula (5)

[0023]

[Chemical formula 23]

(In the formula, X is a halogen atom, and n is 0 to 2
Of the pyrimidinylthioquinoline derivative represented by the general formula (1), which is a mixture of 4-chloroquinoline represented by the formula (1) and a reaction in a molten state or in the presence of an inert solvent. The present invention relates to an agricultural and horticultural fungicide contained as.

The compound of the present invention can be produced by the following method (A) (Chemical formula 24).

[0026]

[Chemical formula 24]

The above reaction proceeds in the presence of a base to obtain a compound represented by the general formula (1). As the base, sodium metal, sodium hydride, alkali hydroxides, alkali carbonates and organic bases such as pyridine and triethylamine can be used. Reaction temperature is 0 ℃
To the boiling point of the solvent, but a range of 20 ° C to 100 ° C is desirable.

Usually, the synthesis of an ether bond or a sulfide bond can be obtained by reacting the corresponding halide with a hydroxide or mercaptan in the presence of a base as described above. However, as a result of various studies, the compound of the present invention was prepared by mixing the compound represented by the general formula (2) and the compound represented by the general formula (3), which are starting materials, and heating the mixture, or It was also found that it can be obtained only by adding an inert solvent to give fluidity and heating. The reaction temperature is between room temperature and 200 ° C, but preferably 70
The temperature is from 100 ° C to 100 ° C. Although the reaction time varies depending on the reaction temperature, it is usually completed in 1 to 10 hours in many cases.

The solvent to be added may be any as long as it is inert to the reaction of the present invention and has a boiling point higher than the reaction temperature. Specific examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as dioxane and diglyme, aprotic polar solvents such as dimethylformamide, dimethylimidazolidinone and dimethylsulfoxide, or acetonitrile. .

4- represented by the general formula (2) which is an intermediate
The mercaptoquinolines can be produced by the method shown below (Formula 25).

[0031]

[Chemical 25]

The 4-chloroquinolines used as the starting materials are commercially available or can be produced by any of the following methods.

(1) Organic Syntheses, Col Vol.3,
272 (1955) according to the following reaction formula (Chemical Formula 26).

[0034]

[Chemical formula 26]

(2) A methoxymethylene Meldrum's acid is used in place of diethyl ethoxymethylenemalonate in the above method (1), and a similar production can be carried out according to the following formula (Formula 27).

[0036]

[Chemical 27]

4-mercaptoquinolines are available from J. Amer. C.
4 according to the method described in hem. Soc., 70, 2190 (1948).
It can be prepared from chloroquinolines and thiourea (Chemical Formula 28).

[0038]

[Chemical 28]

The 2-chloropyrimidines used as the other raw material are the 2-aminopyrimidines described in J. Ame.
r. Chem. Soc., 73, 2986 (1951).

[0040]

[Chemical 29]

The compound represented by the general formula (1) can also be produced by the following method (B).

[0042]

[Chemical 30]

The presence or absence of a base, the kind of the base, the reaction temperature, the reaction solvent and the like as the above reaction conditions can be produced by using the conditions according to Method A.

The 2-mercaptopyrimidines represented by the general formula (5), which are intermediates, can be prepared by the method of J. Amer. Chem.
It can be produced from 2-chloropyrimidines according to the method described in c., 70, 2190 (1948) (Chemical Formula 31).

[0045]

[Chemical 31]

The other starting material, 4-chloroquinolines, can be produced by the method described above.

The present invention is an agricultural and horticultural fungicide containing a compound represented by the general formula (1) as an active ingredient.

The agricultural and horticultural fungicides of the present invention are cucumber powdery mildew, cucumber anthracnose, tomato powdery mildew, barley powdery mildew, wheat powdery mildew, wheat red rust, strawberry powdery mildew, strawberry anthracnose, It shows an excellent control effect against grape powdery mildew, apple powdery mildew, apple scab, apple spot foliage, apple scab, pear scab, pear scab, and pear black spot.

When the compound represented by the general formula (1) according to the present invention is used as an agricultural and horticultural fungicide, the raw material may be used as it is for the plant to be treated, but it is generally inactive. It is mixed with various liquid carriers or solid carriers and used as a commonly used formulation such as powders, wettable powders, flowables, emulsions, granules and other commonly used formulations. Further, an auxiliary agent can be added if necessary for formulation.

The term "carrier" as used herein refers to a synthetic or natural inorganic or organic substance which is formulated to help the active ingredient reach the site to be treated and to facilitate the storage, transportation and handling of the active ingredient compound. Means The carrier may be either solid or liquid as long as it is usually used for agricultural and horticultural agents, and is not limited to a particular carrier.

Examples of solid carriers include clays such as montmorillonite and kaolinite, diatomaceous earth, clay, talc, vermiculite, gypsum, calcium carbonate, silica gel, inorganic substances such as ammonium sulfate, soybean powder, sawdust, and wheat flour. And plant-derived organic substances and urea.

Liquid carriers include toluene, xylene,
Aromatic hydrocarbons such as cumene, paraffin hydrocarbons such as kerosene and mineral oil, halogenated hydrocarbons such as carbon tetrachloride, chloroform and dichloroethane, acetone,
Ketones such as methyl ethyl ketone, ethers such as dioxane and diethylene glycol dimethyl ether,
Examples thereof include alcohols such as methanol, ethanol, propanol, and ethylene glycol, dimethylformamide, dimethylsulfoxide, and water.

Further, in order to enhance the efficacy of the compound of the present invention, the following auxiliary agents may be used alone or in combination depending on the purpose in consideration of the dosage form of the preparation, the application scene and the like. . As the auxiliary agent, a surfactant, a binder (for example, ligninsulfonic acid, alginic acid, polyvinyl alcohol, gum arabic, CMC sodium, etc.) usually used in agricultural and horticultural chemicals, a stabilizer (for example, phenol for antioxidant) Compounds, thiol compounds or higher fatty acid esters, phosphates as pH adjusters, and sometimes light stabilizers), etc., can be used alone or in combination as required. Further, in some cases, an industrial bactericidal agent, an antibacterial and antifungal agent, etc. may be added for antibacterial and antifungal agents.

The auxiliary agent will be described in more detail. Emulsification,
Anionic interfaces such as lignin sulfonate, alkylbenzene sulfonate, alkyl sulfate ester salt, polyoxyalkylene alkyl sulfate salt, polyoxyalkylene alkyl phosphate ester salt for the purpose of dispersing, spreading, wetting, binding, stabilizing, etc. Activator, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl aryl ether, polyoxyalkylene alkyl amine, polyoxyalkylene alkyl amide, polyoxyalkylene alkyl amide, polyoxyalkylene alkyl thioether, polyoxyalkylene fatty acid ester, glycerin fatty acid ester, Nonionic surfactant such as sorbitan fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxypropylene polyoxyethylene block polymer Agents, calcium stearate, lubricants such as wax, stabilizers such as isopropyl hydroperoxide diene phosphate, other cellulose, carboxymethyl cellulose, casein, gum arabic, and the like. However, these components are not limited to the above.

The content of the compound represented by the general formula (1) in the agricultural and horticultural fungicide according to the present invention varies depending on the formulation form, but is usually 0.05 to 20% by weight in the case of powder.
The wettable powder is 0.1 to 80% by weight, the emulsion is 1 to 50% by weight, the flowable formulation is 1 to 50% by weight, and the dry flowable formulation is 1 to 80% by weight, and preferably 0.5 for powders. -5% by weight, wettable powder 5-80% by weight, granules 0.5-8% by weight, emulsion 5-20% by weight, flowable formulation 5-30% by weight and dry flowable formulation 5-5% by weight. It is 50% by weight.

The content of the auxiliary agent is 0 to 80% by weight,
The content of the carrier is 100% by weight minus the contents of the active ingredient compound and the auxiliary agent.

Examples of the application method of the composition of the present invention include seed disinfection, foliar application, and the like, but any application method usually used by those skilled in the art is sufficiently effective. The application rate and application concentration vary depending on the target crop, target disease, degree of disease occurrence, compound form, application method and various environmental conditions, but when sprayed, the amount of the active ingredient should be 5 to 500 g per hectare. And preferably 10 to 200 g per hectare. Also, wettable powders and flowable agents (suspended concentra)
When diluted with water, the dilution ratio is suitably 500 to 20,000 times, and preferably 1,000 to 10,000 times.

The agricultural and horticultural fungicides of the present invention can be used not only as a mixture with other fungicides, insecticides, herbicides and plant growth regulators, pesticides, soil improvers or fertilizers, but also with them. Mixed formulations are also possible. Examples of the fungicides include triadimefon, hexaconazole, prochloraz, azole fungicides such as triflumizole, metalaxyl, acylalanine fungicides such as oxadixyl, thiophanate methyl, benzimidazole fungicides such as benomyl, manzeb and the like. Dithiocarbamate fungicides and tetrachloroisophthalonitrile, sulfur and the like,
Examples of insecticides include fenitrothion, diazinon, pyridafenthion, chlorpyrifos, marathon,
Fentate, dimethoate, methylthiomethone, prothiophos, DDVP, acephate, salicione, E
Examples include phosphorus insecticides such as PN, carbamate insecticides such as NAC, MTMC, BPMC, pirimicarb, carbosulfan and mesomil, and pyrethroid insecticides such as etofenprox, permethrin and fenvalerate. It is not something that will be done.

[0059]

EXAMPLES Next, the production method of the compound of the present invention will be specifically described with reference to Examples and Reference Examples. Example 1 Synthesis of 7-chloro-4- (4,6-dimethoxy-2-pyrimidinylthio) quinoline [Compound No. 9] (when Method A base is not used) 7-chloro-4-mercaptoquinoline 1.00 g, 2-
Add 0.89 g of chloro-4,6-dimethoxypyrimidine and 5 ml of N, N-dimethylimidazolidinone and add 1
Heated at 00 ° C. for 5 hours. After the reaction is completed, the reaction liquid is 50 m
It was discharged into 1 l of water and extracted 3 times with 30 ml of ethyl acetate.
After washing with water, the mixture was dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography (elution solvent: n-hexane / ethyl acetate = 7 /
Separated in 3), 0.45 g of the desired 7-chloro-4- (4,6-dimethoxy-2-pyrimidinylthio) quinoline
(Yield 26%) was obtained.

Example 2 Synthesis of 5,7-dichloro-4- (4,6-diethoxy-2-pyrimidinylthio) quinoline [Compound No. 34] (when Method A base is used) N, N-dimethylimidazolidi 0.25 g of 60% sodium hydride and 5,7-chloro-4- in 15 ml of non-
1.18 g of mercaptoquinoline was added, and the mixture was stirred at 60 ° C. for 1 hour. Next, 1.04 g of 2-chloro-4,6-diethoxypyrimidine was added, and the mixture was stirred at 80 ° C. for 2 hours and 30 minutes. After completion of the reaction, the reaction solution was discharged into 100 ml of water and extracted with 50 ml of ethyl acetate three times. After washing with water, the mixture was dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was separated by silica gel column chromatography (elution solvent: n-hexane / ethyl acetate = 7/3), and the target 7-chloro-4- (4,6-diethoxy-2-pyrimidinylthio) quinoline 0.40 g (Yield 20%) was obtained.

Example 3 Synthesis of 5,7-dichloro-4- (4,6-dimethoxy-2-pyrimidinylthio) quinoline [Compound No. 33] (when method A base is used) 5,7-dichloro-4 -Mercaptoquinoline 1.00
g, 2-chloro-4,6-dimethoxypyrimidine 0.7
6 g and 15 ml of pyridine were added and heated at 100 ° C. for 5 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, 50 ml of ethyl acetate was added to the reaction solution, washed with water and then dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was separated by silica gel column chromatography (elution solvent: n-hexane / ethyl acetate = 7/3) to obtain the desired 5,7-
0.70 g (yield 44%) of dichloro-4- (4,6-dimethoxy-2-pyrimidinylthio) quinoline was obtained.

Example 4 Synthesis of 7-iodo-4- (4,6-dimethoxy-2-pyrimidinylthio) quinoline [Compound No. 25] (when Method B base is not used) 4-chloro-7-iodoquinoline 1 0.25 g, 4,6-
0.74 g of dimethoxy-2-mercaptopyrimidine,
Add 10 ml of N, N-dimethylimidazolidinone and
Heated at 00 ° C. for 5 hours. After the reaction is completed, the reaction liquid is 50 m
It was discharged into 1 l of water and extracted 3 times with 30 ml of ethyl acetate.
After washing with water, dehydration was performed with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography (elution solvent: n-hexane / ethyl acetate = 7/3).
Separation was performed to obtain 0.55 g (yield 30%) of 7-iodo-4- (4,6-dimethoxy-2-pyrimidinylthio) quinoline of interest.

Example 5 Synthesis of 7-iodo-4- (4,6-diethoxy-2-pyrimidinylthio) quinoline [Compound No. 26] (when method B is used as base) N, N-dimethylimidazolidinone 15 ml 0.22 g of 60% sodium hydride and 4,6-diethoxy-
Add 0.69 g of 2-mercaptopyrimidine and add 1 at 60 ° C.
Stir for hours. Next, 1.00 g of 4-chloro-7-iodoquinoline was added, and the mixture was stirred at 80 ° C. for 2 hours and 30 minutes. After completion of the reaction, the reaction solution was discharged into 100 ml of water and extracted with 50 ml of ethyl acetate three times. After washing with water, dehydration was performed with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was separated by silica gel column chromatography (eluting solvent: n-hexane / ethyl acetate = 7/3) to obtain the desired 7-iodo-4- (4,6-diethoxy-2-pyrimidinylthio).
0.35 g (yield 22%) of quinoline was obtained.

Reference Example 1 Synthesis of 7-chloro-4-mercaptoquinoline (intermediate) 4,7-dichloroquinoline 25 was added to 250 ml of ethanol.
g was added and the mixture was heated to 50 ° C. Then 9.7 g of thiourea was added. A large amount of crystals were deposited in about 5 minutes. The precipitated crystals were collected by filtration, added to an aqueous sodium carbonate solution and stirred. Orange crystals precipitated. This was collected by filtration, added to 250 ml of a 5% aqueous sodium hydroxide solution, and stirred for a while. The insoluble matter was filtered off, neutralized with acetic acid and the precipitated crystals were collected by filtration and dried to obtain 19.6 g (yield 80%) of the desired 7-chloro-4-mercaptopyrimidine as yellow crystals.

Reference Example 2 2-Chloro-4,6-dimethoxypyrimidine (intermediate)
Synthesis of 2-amino-4,6-dimethoxypyrimidine To 100 g of concentrated amino acid, 435 ml of concentrated hydrochloric acid was added and completely dissolved at room temperature. The reaction solution was kept at -10 ° C and 310 g of a 32% sodium nitrite aqueous solution was added dropwise while stirring. Furthermore, after continuing stirring for 1 hour, 580% sodium hydroxide aqueous solution 580
g was added while the reaction solution was kept at -10 ° C with stirring. 1
After a lapse of time, the reaction solution was discharged into 5000 ml of water and extracted with 400 ml of ethyl acetate four times. The obtained organic layer was washed with water, dehydrated with anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 35 g of the target 2-chloro-4,6-dimethoxypyrimidine (yield 31%).

Reference Example 3 Synthesis of 4,6-dimethoxy-2-mercaptopyrimidine (intermediate) To 250 ml of ethanol was added 5 g of 2-chloro-4,6-dimethoxypyrimidine and the mixture was heated to 50 ° C. Then 2.3 g of thiourea was added. After stirring and refluxing for 6 hours, the reaction solution was evaporated under reduced pressure to remove the solvent, and a 5% aqueous sodium hydroxide solution 7
0 ml was poured and the mixture was thoroughly suspended and filtered. The aqueous layer was neutralized with acetic acid, extracted 3 times with 30 ml of ethyl acetate, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to give the desired 4,6-dimethoxy-2-mercaptopyrimidine 0.8.
g (yield 16%) was obtained.

Other examples of compounds which can be synthesized by the same method as in Examples are shown in Table 1 (Tables 1 to 5).

[0068]

[Table 1]

[0069]

[Table 2]

[0070]

[Table 3]

[0071]

[Table 4]

[0072]

[Table 5]

Next, formulation examples and test examples of the fungicide for agricultural and horticultural use according to the present invention will be shown.

Formulation Example 1 (Dust) 2 parts of the compound of Compound No. 9 and 98 parts of clay were uniformly mixed and ground to obtain a powder containing 2% of the active ingredient.

Formulation Example 2 (wettable powder) 5 parts of the compound of Compound No. 9, 50 parts of diatomaceous earth, 43 of clay
Parts and 2 parts of sodium alkylbenzene sulfonate were uniformly mixed and pulverized to obtain a wettable powder containing 5% of the active ingredient.

Formulation Example 3 (wettable powder) 10 parts of the compound of Compound No. 25, 70 parts of kaolin, 18 parts of white carbon and 2 parts of calcium alkylbenzene sulfonate are uniformly mixed and pulverized to obtain a fine powdery active ingredient having a uniform composition. A wettable powder containing 10% was obtained.

Formulation Example 4 (Wettable powder) 20 parts of the compound of Compound No. 9, 3 parts of calcium alkylbenzene sulfonate, 5 parts of polyoxyethylene nonylphenyl ether and 72 parts of clay were uniformly mixed and pulverized to give a fine composition. A powdery wettable powder containing 20% of the active ingredient was obtained.

Formulation Example 5 (wettable powder) 50 parts of the compound of Compound No. 25, 1 part of sodium lignin sulfonate, 5 parts of white carbon and 44 of diatomaceous earth
The parts were mixed and ground to obtain a wettable powder containing 50% of the active ingredient.

Formulation Example 6 (floating agent) 5 parts of compound No. 25, propylene glycol 7
Parts, 4 parts of sodium lignin sulfonate, 2 parts of sodium salt of dioctylsulfosuccinate, and 82 parts of water were wet pulverized with a sand grinder to obtain a flowable agent.

Formulation Example 7 (floating agent) 5 parts of compound No. 33, propylene glycol 5
Parts, 5 parts of polyoxyethylene oleic acid ester, 5 parts of polyoxyethylene diallyl ether sulfate, 0.2 parts of a silicon-based defoaming agent, and 79.8 parts of water were wet-ground with a sand grinder to obtain a flowable agent.

Formulation Example 8 (floating agent) 10 parts of the compound of Compound No. 9, propylene glycol 7
Part, 2 parts of sodium lignin sulfonate, 2 parts of sodium salt of dioctyl sulfosuccinate, and 79 parts of water were wet pulverized with a sand grinder to obtain a flowable agent.

Formulation Example 9 (floating agent) 25 parts of compound No. 25, 5 parts of propylene glycol, 5 parts of polyoxyethylene oleate, 5 parts of polyoxyethylene diallyl ether sulfate,
0.2 parts of a silicon-based defoaming agent and 59.8 parts of water were wet pulverized with a sand grinder to obtain a flowable agent.

Test Example 1 Cucumber Powdery Mildew Control Effect Test Prepared according to Formulation Example 2 on the first leaf stage seedlings of cucumber (variety: Sagamihanjiro) grown in a vinyl pot having a diameter of 7.5 cm in a greenhouse. The wettable powder was diluted to a predetermined concentration and sprayed at 50 ml per 3 pots. After the drug solution was air-dried, the cucumber powdery mildew spores that had been generated on the cucumber leaves in advance were gently shaken on the leaves to inoculate. Ten days after the inoculation, the area occupied by cucumber powdery mildew lesions per leaf was investigated according to the following index. The results are shown in Table 2 (Tables 6 and 7).

[0084] Moreover, the drug damage standard was judged as follows.

Criteria for phytotoxicity −: No phytotoxicity ±: Slightly phytotoxic to some seedlings ＋: Minor phytotoxicity to all seedlings ++: Moderate phytotoxicity, but recovers +++: Unrecoverable Chemical damage Chemical damage symptoms of cucumber: The growth around the leaves stops and the leaves curve.

[0086]

[Table 6]

[0087]

[Table 7]

Comparative agents 1 and 2 are the following compounds (Chemical Formula 3)
2) is shown. (The same applies to Test Example 2)

[0089]

[Chemical 32]

Comparative agents 1 and 2 are disclosed in JP-A-1-246.
No. 263 publication (same in Test Example 2).

Test Example 2 Control Effect of Barley Powdery Mildew on the first leaf stage seedlings of barley (variety: Azuma Golden) grown in a 7.5 cm diameter vinyl pot in a greenhouse.
A wettable powder prepared according to Formulation Example 3 was diluted to a predetermined concentration and sprayed at 50 ml per 3 pots. On the next day, barley powdery mildew spores that had been previously generated on the barley leaves were lightly shaken onto the leaves for inoculation. Inoculation 10
After one day, the number of barley powdery mildew fungus per leaf was examined, and the control value (%) was calculated by the following formula. The result is the third
The results are shown in Tables (Tables 8 and 9).

[0092]

[0093]

[Table 8]

[0094]

[Table 9]

The results of Test Examples 1 and 2 are the same as those of the general formula (1).
With the compound of the present invention represented by cucumber powdery mildew and barley powdery mildew with excellent control effect,
It is shown to be safe for crops. On the other hand, in this test, the comparative drug 1 had no effect, and the comparative drug 2 had a controlling effect, but showed phytotoxicity against cucumber.

[0096]

INDUSTRIAL APPLICABILITY The fungicide for agricultural and horticultural use containing the compound represented by the general formula (1) according to the present invention shows a remarkable controlling effect against a disease causing a problem in agriculture and horticulture with a low leaf amount. , Especially against powdery mildew. On the other hand, it is extremely safe against crops such as cucumber and wheat.
In view of the situation that resistant bacteria have appeared in recent years against azole fungicides, the present invention provides an excellent agricultural and horticultural fungicide that can replace them.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Nao Maeda 1144 Togo, Mobara-shi, Chiba Prefecture Mitsui Toatsu Chemical Co., Ltd. (72) Hideo Kawashima 1144, Togo, Mobara-shi Chiba Prefecture Mitsui Toatsu Chemical Co., Ltd. ( 72) Inventor Katsutoshi Ishikawa 1900 Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Hitoshi Shimotori 1900 Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Yuji Yanase Chiba 1900 Togo, Mobara-shi, Mie Prefecture Mitsui Toatsu Chemicals, Inc. (72) Inventor Yoko Kuno 1900, Togo, Mobara-shi, Chiba Mitsui Toatsu Chemicals, Inc.

Claims (6)

[Claims] 1. General formula (1) (Chemical formula 1) (In the formula, X represents a halogen atom, n represents an integer of 0 to 2, and R represents a C1-C4 alkyl group which may be linear or branched) and a pyrimidinylthioquinoline derivative. 2. General formula (2) (Chemical formula 2) (Wherein, X represents a halogen atom and n represents an integer of 0 to 2), a 4-mercaptoquinoline represented by the general formula (3) ) [Chemical 3] (Wherein R represents a C1-C4 alkyl group which may be linear or branched) and is reacted with a 2-chloropyrimidine represented by the general formula (1) (Chemical Formula 4) Chemical 4] (In the formula, Xn and R have the same meanings as described above.) A method for producing a pyrimidinylthioquinoline derivative. 3. The general formula (2) (formula 5): (Wherein, X represents a halogen atom, and n represents an integer of 0 to 2), 4-mercaptoquinolines are represented by the general formula (3) (Chemical Formula 6): (Wherein R represents a C1-C4 alkyl group which may be straight-chain or branched) and is mixed with 2-chloropyrimidines and reacted in a molten state or in the presence of an inert solvent. General formula (1) (Formula 7) (In the formula, Xn and R have the same meanings as described above.) A method for producing a pyrimidinylthioquinoline derivative. 4. General formula (4) (Chemical formula 8) (In the formula, R represents a C1-C4 alkyl group which may be linear or branched), a 2-mercaptopyrimidine compound is converted to a metal salt, or in the presence of a base, the compound of the general formula (5 ) (Chemical formula 9) [Chemical formula 9] (Wherein, X is a halogen atom, and n is an integer of 0 to 2) and is reacted with 4-chloroquinolines. (In the formula, Xn and R have the same meanings as described above.) A method for producing a pyrimidinylthioquinoline derivative. 5. The general formula (4) (formula 11): 2-mercaptopyrimidines represented by the formula (wherein R represents a C1-C4 alkyl group which may be linear or branched) are represented by the general formula (5) (Chemical Formula 12): (Wherein, X represents a halogen atom, and n represents an integer of 0 to 2), the compound is mixed with 4-chloroquinoline and reacted in a molten state or in the presence of an inert solvent. (1) (Chemical Formula 13) [Chemical Formula 13] (In the formula, Xn and R have the same meanings as described above.) A method for producing a pyrimidinylthioquinoline derivative. 6. General formula (1) (Chemical formula 14) (Wherein, X represents a halogen atom, n represents an integer of 0 to 2, and R represents a C1-C4 alkyl group which may be linear or branched) as an active ingredient. Agro-horticultural fungicide containing.