JPH0649063A - Quinoline derivative having halogen at 5-position of pyrimidine ring and its production and agricultural and horticultural germicide containing the same as active ingredient - Google Patents

Abstract

PURPOSE:To provide a menu compound having an excellent diseasecontrol effect, safe for crops, and useful as an agricultural or horticultural germicide. CONSTITUTION:The compound of formula I (X is 0,5; Y is halogen; Z is halogen; R<1>, R<2> are 1-3C alkoxy; n is 0-2), e.g. 7-chloro-4-(5-bromo-4,6-dimethoxy-2- pyrimidinylthio) quinoline. The compound of formula I is obtained by reacting a 4-chloroquinoline compound of formula II with a pyrimidine compound of formula III in a solvent (e.g. ethanol), if necessary, in the presence of a base (e.g. sodium carbonate) at 10-200 deg.C. The compound of formula I exhibits excellent control effects against wide plant diseases such as cucumber powdery mildew, cucumber anthracnose, tomato powdery mildew, wheat powdery mildew, wheat rust, strawberry anthracnose, apple rust and pear scab.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel quinoline derivative having a halogen at the 5-position of a pyrimidine ring, a method for producing the same, and an agricultural and horticultural fungicide containing the same.

[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 bactericidal activity. 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 only exemplified in 1 to 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 an excellent disease control effect. The present inventors have focused on the fact that pyrimidines have a good affinity for living organisms, and have studied their development into physiologically active substances. Therefore, a compound having a pyrimidinyloxy group or a pyrimidinylthio group at the 4-position of the quinoline ring has not been studied at all until now, and attention was paid to the fact that it was a novel compound, and research was started. For comparison, the compounds described in the above publications were tested for those that are considered to be excellent, and those with a high control effect have phytotoxicity against crops, and those with a low phytotoxicity also have a control effect. Low and not practical.

[0003]

The object of the present invention is to provide a novel quinoline derivative having a halogen at the 5-position of the pyrimidine ring, which is a compound which exhibits an excellent bactericidal effect and is safe for crops. It is intended to provide a method for producing a compound, an agricultural / horticultural fungicide containing these compounds, and a method for applying the fungicide.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve these problems, and as a result, the compound of the present invention has a better controlling effect than conventional compounds, and further, cucumber, tomato, grape and They have found that they also exhibit excellent safety against crops such as wheat, and have completed the present invention. That is, the present invention provides a compound represented by the general formula (1)

[0005]

[Chemical 12] (In the formula, X is an oxygen atom or a sulfur atom, Y is a halogen atom, Z is a halogen atom, R ¹ and R ² are independently of each other a C _{1 to} C ₃ alkyl group or a C _{1 to} C ₃ alkoxy group,
And n represents an integer of 0 to 2), and a quinoline derivative having a halogen at the 5-position of the pyrimidine ring represented by the formula (2)

[0006]

[Chemical 13] (In the formula, Y represents a halogen atom, and n represents an integer of 0 to 2), and 4-chloroquinoline represented by the general formula (3)

[0007]

[Chemical 14] (Wherein X represents an oxygen atom or a sulfur atom, Z represents a halogen atom, R ¹ and R ² independently of each other represent a C _{1 to} C ₃ alkyl group or a C _{1 to} C ₃ alkoxy group). And a general formula (4) in which the pyrimidines are mixed and reacted in a molten state or in the presence of an inert solvent.
(Chemical formula 15)

[0008]

[Chemical 15] (Wherein, X represents an oxygen atom or a sulfur atom, Y represents a halogen atom, and n represents an integer of 0 to 2).
Hydroxy (or mercapto) quinoline is converted to a metal salt, or in the presence of a base, the compound of the general formula (5)
6)

[0009]

[Chemical 16] (In the formula, Z represents a halogen atom, R ¹ and R ² independently represent a C _{1 to} C ₃ alkyl group, a C _{1 to} C ₃ alkoxy group), and reacts with 2-chloropyrimidines Manufacturing method, and further, the compound represented by the general formula (2)

[0010]

[Chemical 17] (In the formula, Y represents a halogen atom, and n represents an integer of 0 to 2) and the general formula (3)
(Chemical formula 18)

[0011]

[Chemical 18] (Wherein, X represents an oxygen atom or a sulfur atom, Z represents a halogen atom, and R ¹ and R ² represent C _{1 to} C ₃ alkyl groups or C _{1 to} C ₃ alkoxy groups which are independent of each other). Produced by reacting the pyrimidines described above in a molten state or in an inert solvent in the presence of a base, and a quinoline derivative having a halogen at the 5-position of the pyrimidine ring represented by the general formula (1) as an active ingredient. It is a fungicide for agricultural and horticultural use.

The compounds of the present invention are represented by the following (A),
It can be produced by the method (B) or (C). Method A: (Chemical formula 19)

[0013]

[Chemical 19]

The compound (1) of the present invention is prepared by mixing the compound represented by the general formula (2) and the compound represented by the general formula (3), which are starting materials, in a molten state or in an inert solvent,
It can be produced by reacting in the presence of a base or without adding a base.

Next, the reaction conditions will be described in detail. In the general formula (3), the compound in which X is a sulfur atom has better reactivity, and the reaction proceeds in the presence of a base or without addition of a base. The reaction temperature is between 10 ° C and 200 ° C, preferably 20 ° C to 90 ° C. The compound in which X is an oxygen atom is slightly inferior in reactivity. In this case, the reaction proceeds in the presence of a base or without addition of a base, but it is generally preferable not to add a base. The reaction temperature is in particular between 100 and 200 ° C., preferably 110
~ 150 ° C. Although the reaction time varies depending on the reaction temperature, it is usually completed in 1 to 10 hours.

Any solvent may be added 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. . As the base to be added, a usual base such as sodium metal, sodium hydride, alkali hydroxide, alkali carbonate, alkali hydrogen carbonate, potassium fluoride and the like can be used.

4-in the general formula (2) which is an intermediate
Chloroquinolines are commercially available or can be produced by any of the methods shown below. (I) Organic Syntheses, Coll. Vol.3, 272 (1955)
It can be produced by the method according to the following reaction formula described in (Chemical Formula 20).

[0018]

[Chemical 20] (Ii) A methoxymethylene Meldrum's acid is used in place of diethyl ethoxymethylenemalonate in the above method (i) to obtain the compound in the same manner as in the following (Chemical Formula 21)

[0019]

[Chemical 21] The pyrimidines represented by the general formula (3), which is another intermediate, can be commercially available products or can be produced by the following method. (Iii) When X is an oxygen atom It can be obtained by diazotizing the corresponding amino compound according to the following formula and then hydrolyzing it. At this time, if HCl is used, a Cl body is also produced. The Cl-form and 0H-form are replaced with N-chlorosuccinimide (NCS) or N-bromosuccinimide (NBS) at the 5-position to replace Cl or B.
Introduce a substituent of r. (Chemical formula 22)

[0020]

[Chemical formula 22] (Iv) When X is a sulfur atom (Chemical formula 23)

[0021]

[Chemical formula 23] Next, another method for producing the compound represented by the general formula (1) will be described.

The compound represented by the general formula (1) can also be produced by the following production method. (Chemical formula 2
4)

[0023]

[Chemical formula 24] In the case of this production method, when the compound of the general formula (4) in which X is an oxygen atom, the target compound of the general formula (1) is obtained in an extremely low yield or is not obtained at all. The compound is mainly obtained. However, when X is a compound having a sulfur atom, the reaction proceeds smoothly, and the desired compound of the general formula (1) is obtained in high yield. This will be described in more detail below. Method B: When X is an oxygen atom When a usual base such as alkali hydroxide, alkali carbonate, sodium hydride or sodium metal is used as a base, the compound of the general formula (6) is usually obtained. It was found that the compound of the general formula (1) can be obtained by converting the compound of 4) into an Ag salt. The Ag salt of the compound of the general formula (4) can be easily obtained as a precipitate by adding AgNO ₃ to the aqueous sodium hydroxide solution of the compound of the general formula (4). After azeotropic dehydration with benzene or toluene, the compound of the general formula (1) is obtained by reacting with 2-chloropyrimidines in a reaction-inert solvent such as dimethylimidazolidinone. Method C: When X is a sulfur atom The desired reaction proceeds in the presence of a base, and an N-substituted product such as the compound of the general formula (6) is not formed. As a base,
Metallic sodium, sodium hydride, alkali hydroxides, alkali carbonates and organic bases such as triethylamine and pyridine can be used. Any solvent can be used as long as it is inert to the reaction, and organic bases such as pyridine can also be used as a solvent. The reaction temperature can range from 0 ° C to the boiling point of the solvent, but a range of 20 to 120 ° C is desirable.

The intermediate 4-mercaptoquinolines can be produced from 4-chloroquinolines and thiourea according to the method described in J Amer. Chem. Soc., 70 , 2190 (1948). . The other 2-chloropyrimidines are simultaneously formed with the 2-hydroxypyrimidines as already described in the explanation of the reaction formula (iii).

The compound represented by the general formula (1) exhibits an excellent bactericidal action. The agricultural and horticultural fungicides containing the compound represented by the general formula (1) of the present invention are cucumber powdery mildew,
Cucumber anthrax, tomato powdery mildew, barley powdery mildew, wheat powdery mildew, wheat leaf rust, strawberry powdery mildew, strawberry anthrax, grape powdery mildew, apple powdery mildew, apple red star disease, apple spot leaf spot , Excellent control effect against a wide range of plant diseases such as 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 means a synthetic or natural inorganic or organic substance 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. . 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.

As the liquid carrier, 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 according to 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 fungicide for agricultural and horticultural use according to the present invention varies depending on the formulation form, but is usually 0.05 to 20% by weight in a dusting agent,
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. Content of auxiliary agent is 0
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, foliage spraying, etc., 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. When a wettable powder, a flowable agent or an emulsion is diluted with water and sprayed, the dilution ratio is suitably 500 to 20,000 times, preferably 1,000 to 10,000 times.

The fungicide for agricultural and horticultural use of the present invention is another fungicide,
Not only can it be used in combination with agricultural chemicals such as insecticides, herbicides and plant growth regulators, soil improvers or fertilizers, but also mixed preparations with these are 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. Examples of the dithiocarbamate fungicides and tetrachloroisophthalonitrile, sulfur and the like, insecticides such as 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.

[0033]

EXAMPLES Next, the production method of the compound of the present invention will be specifically explained with reference to examples. Example 1 7-chloro-4- (5-bromo-4,6-dimethoxy-
Synthesis of 2-pyrimidinylthio) quinoline [Compound No. 1] (Method A) (1) 7-Chloro-4-mercaptoquinoline (intermediate) 25 ml of 4,7-dichloroquinoline in 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 7-chloro-4-mercaptoquinoline of interest as yellow crystals. m. p. 199.8 ~
_{200.5 ℃ NMR (DMSO-d 6} ) δ: 7.29 (1H, d, J = 6.6Hz), 7.46
~ 7.49 (1H, m), 7.71 (1H, d, J = 2.2Hz), 7.88 (1H, d, J = 6.6H
z), 8.66 (1H, d, J = 8.8Hz) (2) 5-Bromo-2-chloro-4,6-dimethoxypyrimidine (intermediate) N, N-dimethylformamide 100 ml of 2-chloro-4,6 5.0 g of -dimethoxypyrimidine and 6.1 g of N-bromosuccinimide were added, and the mixture was heated at 50 ° C for 4 hours. After cooling, the reaction solution is discharged into ice water and extracted with ethyl acetate. The obtained ethyl acetate layer was distilled off under reduced pressure to obtain 6.8 g (yield 93%) of 5-bromo-2-chloro-4,6-dimethoxypyrimidine as white crystals. m. p. 1
78.8-180.0 ° C. (3) 7-chloro-4- (5-bromo-4,6-dimethoxy-2-pyrimidinylthio) quinoline 7-chloro-4-mercaptoquinoline 1.0 g, 5-bromo- 2-chloro-4,6-dimethoxypyrimidine 1.
3 g and 20 ml of pyridine were added and heated at 100 ° C. for 5 hours. After cooling, it was separated by silica gel column chromatography (n-hexane / ethyl acetate = 7/3), and 7-
Chloro-4- (5-bromo-4,6-dimethoxy-2-
Pyrimidinylthio) quinoline was obtained. Yield 1.0 g,
m. p. 160-161 ° C NMR (CDCl ₃ ) δ: 3.60 (6H, s), 7.51 (1H, dd, J = 2.2,
8.8Hz), 7.77 (1H, d, J = 4.4Hz), 8.16 (1H, d, J = 2.2Hz), 8.20
(1H, d, J = 8.8Hz), 8.93 (1H, d, J = 4.4Hz)

Example 2 Synthesis of 5,7-dichloro-4- (5-chloro-4,6-dimethoxy-2-pyrimidinylthio) quinoline [Compound No. 2] 5,7-dichloro-4-mercaptoquinoline 1. 0g,
2,5-dichloro-4,6-dimethoxypyrimidine
0.9 g and 20 ml of pyridine were mixed and heated at 100 ° C. for 4 hours. After cooling, column chromatography (n
-Hexane / ethyl acetate = 7/3) to separate 5,7-
Dichloro-4- (5-chloro-4,6-dimethoxy-2
0.8 g of -pyrimidinylthio) quinoline was obtained. m.
p. 175-176 ° C NMR (CDCl ₃ ) δ: 3.60 (6H, s), 7.62 (1H, d, J = 2.2H
z), 7.78 (1H, d, J = 4.4Hz), 8.11 (1H, d, J = 2.2Hz), 8.86 (1H,
(d, J = 4.4Hz)

Example 3 7-chloro-4- (5-chloro-4,6-dimethoxy-
Synthesis of 2-pyrimidinyloxy) quinoline (Compound No. 3) 4,7-Dichloroquinoline 5.0 g, 5-chloro-4,
4.8 g of 6-dimethoxy 2-hydroxypyrimidine and 20 ml of N, N-dimethylimidazolidinone were mixed and heated at 125 ° C for 4 hours. After cooling, it was separated by column chromatography (n-hexane / ethyl acetate = 7/3) to obtain 5.5 g of 7-chloro-4- (5-chloro-4,6-dimethoxy-2-pyrimidinyloxy) quinoline. It was m. p. 148-149 ° C NMR (CDCl ₃ ) δ: 3.89 (6H, s), 7.30 (1H, d, J = 5.1H)
z), 7.51 (1H, dd, J = 2.2,8.6Hz), 8.04 (1H, d, J = 8.8Hz), 8.20
(1H, d, J = 2.2Hz), 8.94 (1H, d, J = 5.1Hz), Example of compound synthesized by the same method as other examples
They are summarized in the table (Table 1 to Table 9).

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

[Table 3]

[0039]

[Table 4]

[0040]

[Table 5]

[0041]

[Table 6]

[0042]

[Table 7]

[0043]

[Table 8]

[0044]

[Table 9]

Formulation Example and Physiological Test Example 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 No. 1 and 98 parts of clay were uniformly mixed and pulverized to obtain a powder containing 2% of the active ingredient.

Formulation Example 2 (wettable powder) 5 parts of the compound of Compound No. 2, 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. 3, 70 parts of kaolin, 18 parts of white carbon and 2 parts of calcium alkylbenzene sulfonate were 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. 5, 3 parts of calcium alkylbenzene sulfonate, 5 parts of polyoxyethylene nonylphenyl ether and 72 parts of clay were uniformly mixed and ground to obtain 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. 7, 1 part of sodium lignin sulfonate, 5 parts of white carbon and 44 parts of diatomaceous earth were mixed and ground to give a wettable powder containing 50% of the active ingredient. Got

Formulation Example 6 (floating agent) 5 parts of compound No. 8 and 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 the compound of Compound No. 9, 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 compound No. 5 and 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 the compound of Compound No. 3, 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 59.8 parts of water were wet-ground with a sand grinder to obtain a flowable agent.

Test Example 1 Cucumber Powdery Mildew Control Effect Test A first leaf stage seedling of a cucumber (cultivar: Sagamihanjiro) grown in a 7.5 cm diameter plastic pot in a greenhouse was prepared with Formulation Example 2.
The water-dispersible powder prepared according to 1. 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 (Table 10
~ Table 11).

Degree of disease 0: No disease 1: Area of lesion is 5% or less 2: 〃 5 to 25% 3: 〃 25 to 50% 4: 〃 50% or more Moreover, the drug damage standard was judged as follows. Criteria for phytotoxicity −: No phytotoxicity ±: Minor phytotoxicity is found in some seedlings ＋: Minor phytotoxicity is observed in all seedlings ++: Moderate phytotoxicity but recovers ++ ： Non-recoverable phytotoxicity Chemical damage: The growth around the leaves stops and the leaves curve.

[0056]

[Table 10]

[0057]

[Table 11]

Comparative agents 1 and 2 are the following compounds (chemical formula 2)
5) is shown. (The same applies to Test Example 2)

[0059]

[Chemical 25] Comparative agents 1 and 2 are the compounds disclosed in JP-A-1-246263 (the same applies to Test Example 2).

Test Example 2 Control Test for Barley Powdery Mildew A first leaf stage seedling of barley (variety: Azuma Golden) grown in a vinyl pot having a diameter of 7.5 cm in a greenhouse was tested.
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
It shows in a table (Table 12-Table 13).

[0061]

[Table 12]

[0062]

[Table 13]

The results of Test Examples 1 and 2 are obtained by using 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.

[0064]

INDUSTRIAL APPLICABILITY The fungicide for agricultural and horticultural use containing the compound represented by the general formula (1) according to the present invention exhibits a remarkable controlling effect against a disease causing a problem in agriculture and horticulture at a low dose. , 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 1144, Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd. (72) Yuji Yanase, 1144, Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Hitoshi Shimotori Chiba 1144, Togo, Mobara-shi, Mie Prefecture In Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Naofumi Tomura 1144, Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd.

Claims (5)

[Claims] 1. A general formula (1) (Chemical Formula 1) (In the formula, X is an oxygen atom or a sulfur atom, Y is a halogen atom, Z is a halogen atom, R ¹ and R ² are independently of each other a C _{1 to} C ₃ alkyl group or a C _{1 to} C ₃ alkoxy group,
And n represents an integer of 0 to 2), wherein the quinoline derivative has a halogen at the 5-position of the pyrimidine ring. 2. General formula (2) (Chemical formula 2) (Wherein Y represents a halogen atom, and n represents an integer of 0 to 2), and 4-chloroquinolines represented by the general formula (3) (Chemical Formula 3) (Wherein, X is an oxygen atom or a sulfur atom, Z is a halogen atom, R ¹ and R ² are each independently a C _{1 to} C ₃ alkyl group or a C _{1 to} C ₃ alkoxy group). Of the general formula (1), (Chemical Formula 4), wherein the pyrimidines are mixed and reacted in a molten state or in the presence of an inert solvent. (Wherein X, Y, Z, R ¹ , R ² and n have the same meanings as described above), and a process for producing a quinoline derivative having a halogen at the 5-position of the pyrimidine ring. 3. The general formula (4) (formula 5): (Wherein, X represents an oxygen atom or a sulfur atom, Y represents a halogen atom, and n represents an integer of 0 to 2), 4-hydroxy (or mercapto) quinoline is formed into a metal salt, or In the presence of the general formula (5) (Chemical formula 6) (In the formula, Z is a halogen atom, R ¹ and R ² are each independently a C _{1 to} C ₃ alkyl group, or a C _{1 to} C ₃ alkoxy group) and a 2-chloropyrimidine General formula (1) characterized by reacting (Wherein X, Y, Z, R ¹ , R ² and n have the same meanings as described above), and a process for producing a quinoline derivative having a halogen at the 5-position of the pyrimidine ring. 4. General formula (2) (Chemical formula 8) (In the formula, Y represents a halogen atom, and n represents an integer of 0 to 2) and a 4-chloroquinoline represented by the general formula (3)
(Chemical Formula 9) [Chemical Formula 9] (Wherein, X represents an oxygen atom or a sulfur atom, Z represents a halogen atom, and R ¹ and R ² represent a C _{1 to} C ₃ alkyl group or a C _{1 to} C ₃ alkoxy group). Of the general formula (1) (formula 10), characterized in that the compounds are reacted in a molten state or in an inert solvent in the presence of a base. (Wherein X, Y, Z, R ¹ , R ² and n have the same meanings as described above), and a method for producing a quinoline derivative having a halogen at the 5-position of the pyrimidine ring. 5. A compound represented by the general formula (1) (formula 11): (In the formula, X is an oxygen atom or a sulfur atom, Y is a halogen atom, Z is a halogen atom, R ¹ and R ² are independently of each other a C _{1 to} C ₃ alkyl group or a C _{1 to} C ₃ alkoxy group,
And n represents an integer of 0 to 2), which is an agricultural and horticultural fungicide containing a quinoline derivative having a halogen at the 5-position of the pyrimidine ring as an active ingredient.