WO1993007138A1 - Pyrazole derivative and agrohorticultural bactericide containing same - Google Patents

Abstract

A compound represented by general formula (I), which has an agrohorticultural bactericidal activity, wherein Q represents (a) or (b); Y represents CR6 or N; A represents an optionally substituted aryl or heterocyclic group; and B represents (c), (d) or (e).

Description

 Pyrazole derivatives and fungicides for agricultural and horticultural use

 The present invention relates to a novel pyrazole derivative and a fungicide for agricultural and horticultural use.

 Background technology:

 In the cultivation of agricultural and horticultural crops, a number of control agents are used against crop pests, but their use is limited due to insufficient control effect or the emergence of drug-resistant pathogens and pests. Many of them are not necessarily satisfactory control agents because they are degraded, cause phytotoxicity and contamination of plants, and are highly toxic to humans, livestock and fish. Therefore, there is a strong demand for a drug that can be used safely with few such disadvantages.

 As a compound similar to the compound of the present invention, the following compound having bactericidal activity is described in JP-A-62-404,

(Here, R,, R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are a hydrogen atom, a lower alkyl group, a lower alkenyl group, and R ₂ , R ₅ may further be a halogen atom, and R ₂ may form a lower alkylene group, R ₂ and R ₃ , and R ₅ and R ₆ may form a buta jenylene group.)

Further, the following compound having a bactericidal activity is described in DE 40 24 488 issued on January 30, 1992.

An object of the present invention is to provide a novel compound which can be industrially advantageously synthesized, can be used as a fungicide for agricultural and horticultural use with certain effects and safe use.

 DISCLOSURE OF THE INVENTION:

 The present invention has the general formula (I)

[I]

[Where Q is

Represents

Y represents CR ^S or N,

R ¹ .R ² , R ³ .R ⁴ R ⁶ are the same or different and are each a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted A good alkenyloxy group, an optionally substituted alkynyloxy group, or a hydroxy group, and R ¹ and R ² may together form a ring, W

R ⁵ is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted alkenyloxy group, an optionally substituted alkynyloxy group, Represents a hydroxy group or an optionally substituted alkylthio group; R ⁴ and R ⁵ may be taken together to form a ring;

A represents an optionally substituted aryl group or an optionally substituted heterocyclic group,

B is r ¹ r ³ 1 3

 C-1 C-1 C-1 or 1 C-1 C-1 C-1

r ² r ⁴ — 2 ^ 4 _r 6

^{(Wherein, r 1 r 2 r 3 r} 4 r 5. R 6 are the same or differences connexion, a hydrogen atom, a halogen atom, hydroxy group, an optionally substituted alkyl group, an optionally substituted alkoxy group or optionally substituted Ashiruokishi group, also r ¹ and r ² r ³ and r ^4, or r ⁵ and r ⁶ represents an Okiso group together, further, the r ¹ ~! · ⁶ and R ⁴ And may together form a ring. However, if Q

In the formula, all of R ¹ R ² R ³ R ⁶ are not hydrogen atoms. ]

 The method for producing the compound of the present invention, which is a pyrazole derivative represented by or a salt thereof and a fungicide for agricultural and horticultural use, is as follows.

(1-1) When R ⁵ is a hydroxy group 07138

 Four

[II] [III]

 CI '— 1]

In the formula, R represents an alkyl group, and Y, R ^{1 to} R ⁴ , ^A , and B have the same meanings as described above.

(1-2) When R ⁴ is a hydroxy group

A— & — Awake H ₂ +

 (IV)

 [V]

CI ^r- 1 2) In the formula, R represents an alkyl group, and Y, R ^{1 to} R ³ , R ⁵ , A, and B have the same meanings as described above.

 The reaction of (111) and (1-2) is usually carried out by reacting the general formula (II) and the general formula (III) or the general formula (IV) with the general formula (V) or a salt thereof without a solvent. It is preferably obtained by stirring in a solvent at a reaction temperature of 0 to 150 ° C for 10 minutes to 24 hours. Solvents that can be used include alcohols such as ethanol and methanol, ethers such as getyl ether, tetrahydrofuran, and dioxane; cellosolves such as methyl sorb and ethyl sorb; and aromatic hydrocarbons such as benzene and toluene. Is mentioned. These solvents can be used alone or as a mixture of two or more solvents in various mixing ratios. This reaction does not necessarily require the presence of a catalyst, but the addition of an acid or base may significantly accelerate the reaction. Examples of the acid include organic acids such as formic acid and acetic acid, inorganic acids such as hydrochloric acid and sulfuric acid, and Lewis acids such as titanium tetrachloride and boron trifluoride. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium methacrylate and sodium methylate, and organic bases such as pyridine and triethylamine.

 Hydrazines such as [III] and [IV] may be salts or hydrates with HC1, HBr and the like.

 (2-1) When R is halogen

In the formula, Ha 1 represents a halogen atom, and Y, R ^{1 to} R ⁴ , A, and B have the same meaning as described above.

 (2-2) When R is halogen

Halogenating agent

 CI 'I 2)

CI′-1] In the formula, Ha 1 represents a halogen atom, and Y, R ^{1 to} R ³ , R ⁵ , A, and B have the same meanings as described above.

 In the reactions (2-1) and (2-2), usually 1 to 10 equivalents of a halogenating agent are not necessarily required for a solvent, but the reaction temperature is generally 20 to 15 in the presence of a solvent. (The reaction is performed with TC for 0.5 to 24 hours to synthesize a halogen derivative. Examples of the halogenating agent include phosphorus oxychloride, thionyl chloride, phosphorus pentachloride, phosgene, phosphorus tribromide, thionyl bromide and the like. As the solvent, aromatic hydrocarbons such as benzene and toluene, and haegenated hydrocarbons such as tetrachloroethylene are used.

(3-1) When R ⁵ is hydrogen

 (I'-1)

[I 'one 5] wherein H a 1 represents a halogen ^{atom, Y, R 1 ~ R 4} , A, and B as defined above.

(3-2) When R ⁴ is hydrogen,

Hal

-N,, R'H,

 A-B

 Cat.

(I'-1)

C

In the formula, Ha 1 represents a halogen atom, and Y, R ^{1 to} R ³ , R ⁵ , A, and B have the same meaning as described above.

 In the reaction of (3-1). (3-2), it can be obtained by contacting hydrogen gas in a solvent in the presence of a catalyst at normal pressure or under pressure at room temperature to 50 ° C.

 Examples of the solvent include alcohols such as methanol and ethanol, esters such as ethyl acetate, aromatic hydrocarbons such as benzene and toluene, ethers such as dioxane, water, and mixtures thereof. Examples of the catalyst include palladium carbon and the like, and the hydrogen pressure is preferably 1 to 10 atm. Also preferably, the reaction is carried out in the presence of a dehalogenating hydrogen agent. Examples of the dehydrohalogenating agent include bases such as sodium carbonate, sodium acetate, and triethylamine.

 (4-1) when R is an optionally substituted alkoxy group, an optionally substituted alkenyloxy group, or an optionally substituted alkynyloxy group

 (I'-1 7)

In the formula, r represents an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted alkynyl group, and Y, R ^{1 to} R ⁴ , A, and B have the same meanings as described above. Is shown.

(-2) an alkoxy group wherein R ⁴ is optionally substituted, which may be substituted When an alkenyloxy group or an optionally substituted alkynyloxy group.

[I′-18] In the formula, r represents an alkyl group which may be substituted, an alkenyl group which may be substituted, or an alkynyl group which may be substituted; Y, R ^{1 to} R ³ , R ⁵ , A and B have the same meaning as described above.

In the reaction of (4-1) and (4-2), the general formula [I'1-1] or [I'-2] is converted to sodium hydroxide, hydroxylated lithium, A silver salt of the general formula [I'-1] or [I'1-2] obtained by operating an aqueous solution of silver nitrate at ~ 50 ° C in the presence of a base such as sodium alcohol in a solvent, r—X wherein X represents a leaving group, and r has the same meaning as described above. And room temperature to 150 ° C. for 10 minutes to 24 hours. Examples of the solvent that can be used include ethers such as getyl ether, tetrahydrofuran and dioxane, and aromatic hydrocarbons such as benzene and toluene. The leaving group for X includes a halogen atom such as iodine, bromine and chlorine. Alternatively, the general formula [I'1-1] or [I'1-2] is used in a solvent, and r-X [wherein, r and X represent the same meaning as described above. ] And room temperature to 150 in the presence of silver oxide or silver carbonate It is synthesized by reacting at ° C for 10 minutes to 24 hours. Examples of the solvent that can be used include ethers such as getyl ether, tetrahydrofuran, and dioxane, and aromatic hydrocarbons such as benzene and toluene.

(5) When R ⁵ is an optionally substituted alkyl group

Catalysts such as NiCl ₂ (dppe)

[I′—9] In the formula, A, B, R ^{1 to} R ⁴ , Y, and Hai have the same meaning as described above, and R ⁵ ′ represents an alkyl group which may be substituted.

 This reaction can be obtained by stirring general formula [1'-3], Grignard reagent and general formula [VI] in the presence of a nickel catalyst at -78 ° C to 100 ° C for 10 minutes to 24 hours. .

 Examples of the solvent that can be used include ethers such as getyl ether, tetrahydrofuran, and 1,2-dimethoxetane, and aromatic hydrocarbons such as benzene and toluene.

Examples of the catalyst include a Ni (II) complex represented by Nir ₂ L ₂ (Χ ′ = halogen, L ₂ = 2PPh ₃ , dppe, dppp, bpy, etc.). Here, dppe = Ph ₂ P (CH ₂ ) ₂ PPh ₂ and dppp = Ph ₂ P (CH ₂ ) ₃ PPh ₂ xbpy = 2,2′-bipyridyl are shown. (6-1) When R ⁵ is combined with an optionally substituted alkyl group or R ⁴ to form a ring,

NHNH ₂

 (VII) (III)

In the formula, A, B, R ¹ R ⁴ and Y have the same meaning as described above. R ⁵ 〃 shows the connexion ring such with an alkyl group or R ⁴ be substituted.

(6-2) When R ⁴ is combined with an alkyl group or R ⁵ to form a ring,

In the formula, A, B, R ^{1 to} R ³ , R ⁵ and Y have the same meaning as described above.

R ⁴ ″ represents a ring together with an alkyl group which may be substituted or R ^5. (6-1). The reaction of (6-2) is usually carried out by the general formula [VII] and the general formula [III Or a mixture of the general formula [IV] and the general formula [ν ′] or a salt thereof in a solvent-free solvent, preferably in a solvent, at a reaction temperature of 0 to 150 ° C. for 10 minutes to 24 hours. Solvents that can be used include alcohols such as ethanol and methanol, ethers such as getyl ether, tetrahydrofuran, and dioxane; cellosolves such as methyl sorb and ethyl sorb; and aromatic hydrocarbons such as benzene and toluene. These solvents can be used alone or as a mixture of two or more solvents in various mixing ratios.The presence of a catalyst is not essential in this reaction, but an acid or a base may be used. The acid may be an organic acid such as formic acid or acetic acid, an inorganic acid such as hydrochloric acid or sulfuric acid, or a Lewis acid such as titanium tetrachloride or boron trifluoride. Examples include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium ethylate, and sodium methylate, and organic bases such as pyridine and triethylamine.

 The hydrazines of [III] and [IV] may be salts or hydrates with HC1, HBr and the like.

 (7)

A— CH ₂

CI '—12] In the formula, A ′ represents a nitrogen-containing hetero ring, L represents a halogen atom or a leaving group such as a methanesulfonyloxy group, and R ^{1 to} R ⁵ and Y have the same meaning as described above. This reaction can be obtained by reacting at 0 to 150 ° C for 10 minutes to 24 hours without a solvent, preferably in a solvent, in the presence of a base.

 Examples of the solvent include aromatic hydrocarbons such as DMF, DMSO, benzene, and toluene, ethers such as dioxane and tetrahydrofuran, acetonitrile, pyridine, water, and the like, and mixtures thereof.

 Examples of the base include alkali metal hydrides such as sodium hydride, alkyllithiums such as n-butyl lithium, alkali metal alkoxides such as sodium methoxide, carbonated sodium, sodium hydroxide and the like. Examples thereof include inorganic bases, organic bases such as triethylamine and pyridine. Depending on the type of the nitrogen-containing hetero ring, it can also serve as a solvent or a base.

 (8)

In the formula, L, Y, R ^{1 to} R ⁵ , A and B have the same meanings as described above.

 In this reaction, the general formula (X) and the general formula (XIV) are stirred without a solvent, preferably in a solvent, in the presence of a deoxidizing agent such as a base at a reaction temperature of 0 to 150 ° C for 10 minutes to 2 hours. It is obtained by doing so. Solvents that can be used include ketones such as acetone and 2-butanone, ethers such as ether and tetrahydrofuran, aromatic hydrocarbons such as benzene and toluene, acetonitrile, N, N-dimethylformamide, and dimethyl. Sulfoxide, sulfolane and the like.

 Organic bases such as pyridine, triethylamine, dimethylaniline, DBU, etc. (these can also be used as solvents in some cases), sodium hydroxide, sodium hydroxide, lithium carbonate, sodium carbonate, hydrogenation And inorganic bases such as sodium.

The starting compound of the general formula [XIV] can be synthesized, for example, as follows. When R ⁴ = H,

CXIV] (9)

KM _n 0 an oxidizing agent such as ₄

 A-

[I

Appropriate modification of carbonyl group

 CI '—15]

In the formula, A, R ^{1 to} R ⁵ , Y, r ¹ and r ² have the same meaning as described above.

 This reaction is obtained by stirring with potassium permanganate in an aqueous solvent for 10 minutes to 24 hours at 20 to 100 ° C.

 It can also be obtained by using an oxidizing agent such as selenium dioxide, manganese dioxide or chromic anhydride described in ACS Monograph 186 "Oxidations in Organic Chemistry" 1990, 103-104.

Also, by appropriate modification of the carbonyl group obtained in this reaction, it can be converted to various functional groups such as alcohol derivatives and halogen derivatives. In the present invention, examples of the salt include salts such as hydrochloric acid and hydrobromic acid.

 In any case, after completion of the reaction, the desired product can be obtained by performing ordinary post-treatment.

 The structure of the compound of the present invention was determined from IR, NMR, MASS and the like.

 When a hydroxy group is substituted on the pyrazole ring in the compound of the present invention, a tautomer represented by the following formula may exist.

BEST MODE FOR CARRYING OUT THE INVENTION

 Next, the present invention will be specifically described with reference to examples.

 Example 1

 3- (4-benzyl benzyl) 1-5-hydroxyl 1 (6-methyl-2-pyridyl) virazole (Compound No. 1-13)

3.0 g of (6-methyl-2-pyridyl) hydrazine was dissolved in 5 Oml of anhydrous ethanol, and 5.9 g of ethyl 4-phenylphenylacetyl acetate was added thereto, followed by heating under reflux for -5 hours. After cooling the reaction solution to room temperature, a sodium ethoxide ethanol solution prepared from 15 ml of ethanol and 0.56 g of sodium metal was added thereto, followed by stirring at room temperature for 3 hours. The reaction solution was poured into ice water, and acetic acid was added thereto for neutralization. The precipitated crystals were filtered, washed with cold water, washed with n-hexane and then with ether to obtain 5.5 g of the desired product (mp. 103-104 ° C).

Example 2

 3- (4-cyclobenzyl) -1-5-methoxy-11- (6-methyl-2-pyridyl) pyrazole (Compound No. 1-13)

3- (4-chlorobenzyl) -1-5-hydroxy-11- (6-methyl-2-pyridyl) pyrazole 2.86 g of sodium hydroxide 0.38 g aqueous solution 15 ml and metafur 1 5 ml was added and dissolved, and thereto was added dropwise an aqueous solution (1.5 ml) of silver nitrate (1.70 g) at room temperature with stirring. After stirring at room temperature for 30 minutes, the precipitated silver salt was filtered, washed with water, and sufficiently dried. This was suspended in 40 ml of tetrahydrofuran (THF), 2.0 g of methyl iodide was added, and the mixture was heated under reflux for 4 hours. After removing the insoluble matter by filtration, the filtrate was concentrated under reduced pressure, and the obtained oily residue was purified by silica gel column chromatography (eluent; hexane: ethyl acetate = 1: 1 (VZV)) to obtain the desired product. 1.87 g (n _D ⁶ 1.55863) of the product were obtained. Example 3

 5-chloro-3- (4-cyclobenzyl) -1-1 (6-methyl-2-pyridyl) virazole (Compound No. 1-155)

3- (4-chlorobenzyl) -1-5-hydroxy-1- (6-methyl-12-pyridyl) birazol 4.4 g of phosphorus oxychloride 9.O g was added to N, N-dimethylaniline 1.8 g was added, and the mixture was heated under reflux for 6 hours. After allowing to cool, the reaction solution was further cooled with ice water, ice water and chloroform were added thereto, and a 1N aqueous solution of sodium hydroxide was added to adjust the pH to 9, followed by separation. The formal layer was washed with water and saturated brine, and then dried over anhydrous magnesium sulfate. This was concentrated under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (eluent; hexane: ethyl acetate = 3: 1 (V / V)) to obtain 2.6 g of the desired product (n _D ²⁵ 1. 6059).

 Example 4

3- (1-cyclobenzyl) 1-1- (4,6-dimethyl-2-pyrimidinyl) virazole (Compound No.1-178)

5-Chloro-3- (4-chloro benzyl) 1-11 (4,6-dimethyl-2-pyrimidinyl) pyrazole 0.6 g was dissolved in ethanol 5 ml and toluene 1 Oml c sodium carbonate 0.2 Then, 0.1 g of 10% palladium on carbon was added, and the mixture was brought into contact with hydrogen gas at room temperature for 2.5 hours. After the catalyst was removed by filtration using celite, toluene and water were added to the filtrate, and the mixture was separated. After the toluene layer was washed with saturated brine, it was dried over anhydrous magnesium sulfate. This was concentrated under reduced pressure, and the obtained white crystal residue was washed with n-hexane to obtain 0.56 g (mp. 109-111 ° C) of the desired product.

 Example 5

1-Benzyl-1-hydroxy-3- (6-methyl-2-pyridyl) pyrazol (Compound No. VI-2)

Dissolve 4.4 g of benzylhydrazine dihydrochloride, 4.7 g of ethyl 3- (6-methyl-2-pyridyl) -3-oxopropionate and 3.7 g of anhydrous sodium acetate in 30 ml of acetic acid, The mixture was stirred at room temperature for 2 hours. The reaction solution was poured into ice water, ethyl ether was added, and the mixture was neutralized with an aqueous sodium hydrogen carbonate solution. This was separated, and the ethyl acetate layer was washed with saturated saline and dried over anhydrous magnesium sulfate. This was concentrated under reduced pressure, and the obtained crystalline residue was washed with n-hexane to obtain 3.4 g of the desired product (mp. 163-165 ° C).

 Example 6

1-benzyl-1-5-methoxy-3- (6-methyl-2-pyridyl) pyrazole (Compound No. VI-3)

1 Benzyl-5-hydroxy-3- (6-methyl-2-pyridyl) villa, 1.0 g was dissolved in 0.15 g of sodium hydroxide in 5 ml of an aqueous solution. A 67 g aqueous solution (5 ml) was added dropwise with stirring at room temperature. After stirring at room temperature for 30 minutes, the precipitated silver salt was filtered, washed with water, and sufficiently dried. This was suspended in 15 ml of tetrahydrofuran, 0.8 g of methyl iodide was added, and the mixture was heated under reflux for 2 hours. After removing the insoluble matter by filtration, the filtrate was concentrated under reduced pressure, and the obtained oily residue was purified by silica gel column chromatography (eluent; hexane: ethyl acetate = 4: 1 (V / V)) to obtain the target compound. 0.82 g (n _D ²⁵ 1.592) was obtained.

Reference example 1

 4-Methoxy-1- 3- (6-methyl-2-pyridyl) virazole

3- (N, N-dimethylamino) -12-methoxy-11- (6-methyl-2-pyridyl) -12-propen-1-one 0.5 g is dissolved in 1 Oml of ethanol, and hydrazine hydrate 0 .17 g was added, and the mixture was heated under reflux for 2 hours. After the reaction solution was concentrated under reduced pressure, chloroform and water were added to separate the solution. The porthole form layer was washed with saturated saline and dried over anhydrous magnesium sulfate. This was dried under reduced pressure, and the obtained crystalline residue was washed with hexane to obtain 0.37 g of the desired product (mp. 171-173 ° C).

 2.53 (s, 3H), 3.92 (s, 3H), 7.01 (d, 1H), 7.43 (s, 1H), 7.60 (t, 1H), 7.72 (d, 1H)

 Reference example 2

 3-(N, N-dimethylamino) 1-2-methoxy 1-1 (6-methyl-2-pyridyl) 1-2-propene 1-one

Difficult ₃ ) ₂

1.0 g of 2- (methoxymethyl) carbonyl 6-methylpyridine and 1.8 g of N, N-dimethylformamide dimethyl acetal were dissolved in 1 Oml of toluene, and the mixture was heated under reflux for an entire period of time. After cooling, the reaction solution was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography (eluent; ethyl acetate: methanol = 9: 1 (V / V)) to obtain 0.5 g of the desired product.

^ NMR (CDC 13) 5 pm P / JP9201303

 twenty three

2.58 (s, 3H), 3.14 (s, 6H), 3.72 (s, 3H), 7.17 (d, 1H), 7.47 (s, 1H), 7.58 (d, 1H), 7.65 (t, 1H)

 Example 7

 1- (4-cyclohexyl) 1-4-methoxy 3- (6-methyl-2-pyridyl) pyrazole (Compound No. VI-17)

Dissolve 0.37 g of 4-methoxy-3- (6-methyl-2-pyridyl) pyrazole in 5 ml of N, N-dimethylformamide and add 0.41 g of potassium carbonate, 0.40 benzyl bromide 0.44 g was added and stirred at room temperature for 17 hours. The reaction solution was poured into ice water and extracted with ethyl acetate. This was washed with a saturated saline solution and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the obtained crude product was purified by silica gel column chromatography (eluent; hexane: ethyl acetate = 7: 3-1: 4 (V / V)) to obtain 0.28 g of the desired product (mp 1 110—1 12 ° C).

 2.64 (s, 3H), 3.78 (s, 3Η), 5.31 (s, 2H), 7.00 (s, 1Η), 7.03 (d, lH, J = 7.5Hz), 7.19 (d, 2H, J = 8.5Hz) ), 7.31 (d, 2H, J = 8.5Hz), 7.59 (t, 1H, J = 7.5Hz), 7.77 (d, 1H, J = 7.5Hz)

Example 8

5-Methoxy-1 3- (3-Methoxybenzyl) 1-1- (6-Methyl-2-pyri Jill) pyrazole (Compound No. I-47)

Dissolve 4.0 g of 5-hydroxy-1- (3-methoxybenzyl) -111 (6-methyl-2-pyridyl) pyrazole in 3 Oml of tetrahydrofuran, and obtain 3.04 g of methyl iodide, followed by silver oxide 2. 36 g was added and the mixture was stirred at room temperature for 3 hours. After filtering the insolubles and washing with tetrahydrofuran, the filtrate and the washings were combined and decompressed and concentrated. The resulting oily residue was subjected to silica gel gel chromatography (eluate; hexane: ethyl acetate). = 1: 1 (vXV)) to give the desired product 3. 28 g (n _D ²³ - was obtained ^ff l 5944)..

Example 9

5-Methoxy 1- (6-methyl-2-pyridyl) 1-3- (4-nitrobenzoyl) pyrazole (Compound No. II-7) JP9 03

 twenty five

5-Methoxy-11- (6-methyl-2-pyridyl) -13- (412-trobenzyl) pyrazole 4.6 g was suspended in 70 ml of water, and 6.8 g of potassium permanganate was added. The mixture was heated and stirred at 70 to 80 ° C for 20 hours.

 The insoluble material was filtered, washed with water, and washed with black-mouthed form. The filtrate and washings were combined and separated. The port-form layer was washed with a saturated saline solution and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the obtained crystalline residue was washed with ethyl acetate to obtain 4.2 g of the desired product (mp 173-174 ° C).

Example 10

3- [1-Hydroxy-11- (412-trophenyl) methyl] -1-5-Methoxy-1- (6-methylpyridyl) pyrazole (Compound No. II-8)

5-Methoxy-1- (6-methyl-2-pyridyl) -13- (412-trobenzoyl) Dissolve 3.2 g of pyrazole in 4 ml of methanol and heat to 5-10 ° C. Then, 0.20 g of sodium borohydride was added, and the mixture was further stirred at room temperature for 2 hours. The reaction solution was concentrated under reduced pressure to about one-third, then saline was added, and the mixture was extracted with chloroform. The chloroform layer was washed with water and dried over anhydrous magnesium sulfate. The mixture was concentrated under reduced pressure, and the obtained crude product was washed with n-hexane to obtain 2.8 g of the desired product (m128-129 ° C).

Example 1 1

3- (1-benzimidazolylmethyl) -1-5-methoxy-1- (6-methyl-2-pyridyl) virazol (Compound No.IV-1)

Dissolve 0.25 g of benzimidazole in 2 Oml of N, N-dimethylformamide, add 0.29 g of lithium carbonate, and add 3-chloromethyl-5-methoxy-1- (6-methyl-1- —Pyridyl) pyrazole 0.5 g was added, and the mixture was heated and stirred at 70 ° C. for 5 hours. After cooling, the reaction solution was poured into ice water, and extracted with ethyl acetate. After washing with saturated saline, the extract was dried over anhydrous magnesium sulfate. It was concentrated in vacuo, and the resulting crude product silica force Gerukuroma Togurafi one (eluent; chloroform: ethanol = 1 9: 1 (vZv) ) to give the desired product _{4 1 g (n D '1} . 600) was obtained.

Example 1 2

3-(4-Brozen benzyl) 1-11 (6-Methyl-1 2-pyridyl) 1,4,5,6,7-Tetrahydrol 1 H-indazole (Compound No. I-1 229)

1.5 g of 2- (4-chlorophenylacetyl) cyclohexanone and 0.9 g of (6-methyl-2-pyridyl) hydrazine were dissolved in 15 inl of ethanol, and the mixture was dissolved at room temperature.

Stir for 3 hours. After the reaction solution was concentrated under reduced pressure, ethyl acetate and water were added to separate the solution. The ethyl acetate layer was washed with saturated saline and dried over anhydrous magnesium sulfate. The crude product obtained was concentrated under reduced pressure, and the resulting crude product was separated and purified by silica gel column chromatography (eluent; hexane: acetone = 9: 1 (v / v)) to give 3- (4-cyclobenzyl) One 2—

(6—Methyl-2-pyridyl) 1, 4, 5, 6, 7—Tetrahi Draw 2 H—Inda

 22. 0 22. 1

To obtain a tetrazole 0. 6 g (n _D 1.6142) and the desired product _{0. 2 7 g (n D 1.5880} ).

Example 13

3-benzyl-1-5-ethyl-11- (6-methyl-1-pyridyl) pyrazole (Compound No. 1-230)

Dissolve 5 Omg of nickel chloride diphenyl phosphinoethane in a Grignard solution of ethyl magnesium bromide prepared from 1.2 g of bromide chill, 0.24 g of metal magnesium, and 1 Oml of ether. A solution of 0.9 g of benzyl-5-chloro-11- (6-methyl-2-pyridyl) pyrazol in ether (5 ml) was slowly added dropwise. The mixture was stirred at room temperature for 2 hours, and further heated under reflux for 2 hours. After allowing the reaction mixture to cool, ice water was added thereto, and the mixture was separated. The ether layer was washed with saturated saline and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the obtained crude product was purified by silica gel column chromatography (eluent; hexane: ethyl acetate = 9: 1) to obtain 0.45 g (n _D '1.5913) of the desired product. .

Including the above Examples, representative examples of the compounds of the present invention are shown in Tables 11 and 12, Tables 12 and 2, Tables 2 and 3, Tables 4 and 5-1, Tables 5 and 2, It is shown in Table 6.

 Halla

08

 8 € 0 / £ 6OM

£ 0 £ I0 / r6df / JOd (1st continuation)

铖

CCHCH— []

Mathematical Table 11 (continued)

Table 1 (continued)

COo o ^{m 1}

 Physical constant

No. R ⁴ R ⁵ R ¹ R ² R ³ Y

 [] mp. C

I -78 4-OAc H OCH3 CH ₃ HH CH

I-1 79 4 -OSOzCHs H OCH3 CH ₃ HH CH

I -80 4 -COCHa H OCH3 CH ₃ HH CH

I -81 4 -CSCH ₃ H OCH3 CH ₃ HH CH

I -82 4-NH ₂ H 0CH ₃ CH ₃ HH CH [104-105]

I -83 4-NHAc H OCH3 CHa H H CH [141-142 ° C]

I -84 4-HCO HCHa H 0CH ₃ CH ₃ HH CH

 25. S

T _QCT XJ

 ¾ ΗΠ UU H2 uU3 UuU3 n u IX CH X Γ— oPRu L tli n ur 1u13. • L r

 dioxy

I -87 2-Cl, 4- N0 ₂ H 0CH ₃ CH ₃ HH CH

I-88 2-CHa, 4-N0 ₂ H OCH3 CH ₃ HH CH

 I -89 2-OCH3, -NO2 H OCH3 CHa H H CH

I-90 3-Cl, 4-N0 ₂ H OCH3 CH ₃ HH CH [85-86]

 24.2

I-91 3-CH ₃ , -NO2 H 0CH ₃ CH ₃ HH CH n _D 1.5938

 26.2

3-OCH3, 4-NO2 H 0C¾ CH ₃ HH CH n _D 1.6131

I -93 3-F, 4-N0 ₂ H 0CH ₃ CH ₃ HH CH [107-108]

I -94 3-Br, 4- N0 ₂ H OCHa CH ₃ HH CH [91-92]

I—95 3-NO2, 4-CI H OCH3 CH ₃ HH CH [72-73]

I -96 3-NO2, 4-FH OCH3 CH ₃ HH CH

1-97 3-N0 ₂ , 4-Br H OCH3 CH ₃ HH CH

3-NO2, 4-CH3 H 0CH ₃ ) Hs HH CH (C)

1 1 1 (continued)

 Physical constant

Ν m ⁴ R ^{5 1} R ² R ³ Y

 [] mp ° C

1-112 4-N0 ₂ CH ₃ OCH3 CH ₃ HH CH [75-76]

I -113 4 1 N0 ₂ CH2 CH3 0CH ₃ CH ₃ HH CH

1-114 4-N0 ₂ CH (CH ₃ ) ₂ OCHs CH ₃ HH CH

1-115 4-NO2 OCH3 OCH3 CH ₃ HH CH

1-116 4-NO2 OCH2CH3 0CH ₃ CH ₃ HH CH

4-NO2 0CH (CH ₃ ) ₂ OCH3 CH ₃ HH CH

1-118 4-C 1 CH ₃ OCHs CH ₃ HH CH [51-52]

1-119 4-C 1 CH2CH3 OCH3 CH ₃ HH CH

-120 4-C 1 CH (CH ₃ ) 2 OCHs CH ₃ HH CH

 -121 UUX13 ΠΗ u u l νΠ

-122 4-C 1 0CH ₂ CH ₃ OCHs CH ₃ HH CH

-123 4-C 1 OC 麵₃ ) ₂ OCHs CH ₃ HH CH

-124 H CH ₃ OCHs CH ₃ HH CH

-125 4-CN CH ₃ OCH3 CH ₃ HH CH

-126 4 -SCH ₃ CH ₃ OCH3 CH ₃ HH CH -127 TT TT

4— SOCH3 CH ₃ OCH3 Cll3.1 CH -128 4 1 S0 ₂ CH ₃ CH ₃ OCH3 CH ₃ HH CH

-129 4 -COOCHs CH ₃ 0CH ₃ CH ₃ HH CH [71-72]

 Z6

-130 4-CH ₃ CH ₃ 0CH ₃ CH ₃ HH CH n _D 1.5838-131 4-NO2 B r OCH3 CH ₃ HH CH

1 (continued)

3 8

 () ΐ ichi

0 t

eo £ io / r6df / iDd 8 £ Ι.0 / £ 6 ΟΛΑ. € 10 / £ Z6df / X: 80 / £ 1 to £ 6 OM

Daughter

1 1 1 (continued)

Table 11 (continued)

** 1 NMR data _{(CDC 1 3), δ (} ppm)

 2.62 (s, 3Η), 3.04 (s, 3Η), 3.89 (s, 3H) 4.09 (s, 2H), 5.40 (s, 1H), 7.09 (d, 1 H, J = 7.5 Hz), 7.28 (s, 1 H), 7.42 (d, 1 H, J = 7.5 Hz), 7.5 1 (d, 2 H, J = 8.5 Hz), 7.68 (t, 1 H, J = 7.5 Hz), 7.88 (d, 2 H, J = 8.5 Hz)

** 2 NMR data _{(CDC 1 3), δ (} ppm)

 2.33 (s, 3H), 2.52 (s, 3H), 3.87 (s, 3H) 5.33 (s, 1H), 6.9 to 7.3 (m, 5H),

7.7 to 7.8 (m, 2H), 1.31 (br s. 1 H) 38

 44 Table 1-2

CD

 CO

 s box 1

P

CO oo

Cv3 C a: 3 = j! 3 O H5H03 H HH— ""

 Two. HO H H50 H H «"-^ 13o H Ho H H 1 ""-^-1 3V0 H Hgo H H 391 "" --1 ^ 3H3 H Ho H H "" -9A 3 HH30 H H "

 NO NO O HgoHo H HH-"" "∞N HOO H HHoo H H—" ""-

X Table 2 (continued)

Table 3

Thing constant

 [] P m ..

 (). C

Z ¾ 2 2

E ffi ffi ffi

-ffi E E ffi ffi E E E

X 3 1 E 1

S = o Table 4

Table 4 (continued)

Table 4 (continued)

Table 4 (continued)

Table 4 (continued)

CO

S O

 o 1 1 O

as

>-

X

 X

35 sc

EC as O

X X

 Pi

CQ EC

< Table 5 — 1 Table

Table 5-1 (continued)

 Table 52

No. Physical constant No. Physical constant

V-17 2 2 V-18

 n 1. 5884

ο

Table 6 (continued) Physical constants

No. BR ⁴ R ⁵ R ¹ R ² R ³ Y [] ra. P.

 (.C)

VI- 9 H CH ₂ OCH3 CH ₃ CH ₃ HH CH

 twenty five

_{VI- 10 H CH 2 0CH 2 CH} 3 H CH 3 HH CH n D 1.5876

VI— 11 4 1 C1 CH ₂ HH CH ₃ HH CH [110-114]

VI- 12 4 1 C1 CH ₂ 0 HH CH ₃ HH CH

VI-13 4 -C1 CH ₂ OCH3 H CH ₃ HH CH [108-110]

VI- 14 4 -C1 CH ₂ H CH ₃ CH ₃ HH CH n D 1.5956

VI-15 4 -C1 CH ₂ H CH 2 CH3 CH ₃ HH CH

VI-16 4 1 C1 CH ₂ H CH (CH ₃ ) ₂ CH ₃ HH CH

VI-1 17 4 -C1 CH ₂ H 0CH ₃ CH ₃ HH CH [110-112]

VI-18 4 -C1 CH ₂ 0CH ₃ 0CH ₃ CH ₃ HH CH

 24.2

VI-194 -C1 CH ₂ OCH, CH ₃ CH ₃ HH CH n _D 1.5932

VI-20 4 -N0 ₂ CH ₂ HH CH ₃ HH CH

VI- 21 4 -N02 CH ₂ 0 HH CH ₃ HH CH

OO

Table 6

No. (B) „R Physical constant

R ¹ R ² R ³ γ J til *

 CO

VI-22 4 -N0 ₂ CH ₂ 0CH ₃ H CHs HH CH

VI-23 4 -N0 ₂ CH ₂ H CH ₃ CHs HH CH C 79-83] VI-- 24 4 -N0 ₂ CH ₂ H CH ₂ CH ₃ CH ₃ HH Cll

VI -25 4 -N0 ₂ CH ₂ H CH (CH ₃ ) ₂ CH ₃ HH CH

VI-26 4 N0 ₂ CI "H OCHa CH ₃ HH CH [154-155] VI-274-N0 ₂ CH ₂ 0CH ₃ 0CH ₃ CH ₃ HH CH

_{VI - 28 4 -Ν0 2 · CH} 2 OCH 3 CH 3 CH 3 HH CH

VI-294-CN CH ₂ H CH ₃ CH ₃ HH CH [134- 135] VI-304 -CI CH ₂₀ CH ₃ 24, 8

CH2 CH3 CH ₃ HH CH n D 1.5889 VI-31 4 -CI CH ₂ 22, 2

0CH ₂ CH ₃ CH ₃ CHs HH CH n D 1.5845 V 32 4 -CI CH ₂ -CH ₂ CH ₂ 25.5

CH ₂ CH ₂ -CH ₃ HH CH n D 1.6106

Since the compound of the present invention has an excellent bactericidal activity against a wide variety of filamentous fungi, it can be used for controlling various diseases which occur in the cultivation of agricultural and horticultural crops including flowers, turf and pasture. For example, brown spot of sugar beet (Cercosporabeticola), brown spot of laccasei (My G osphaefe 1 1 aara ch idis) Black spot (My co s_p ha e_j e 1 l_a berkeleyi), powdery mildew of cucumber (S phaerothec ¾_ fu 1 iginea), vine wilt (My coshaerella me 1 on_i s), sclerotium disease (S c 1 erot i_n iasclerotior um), gray force, rot (Botrytiscinerea), black spot (CI adospori um) cuc ume ri num)> Gray strength of tomato, mildew (Botrytiscinerea), leaf mold (Cladospori um fu 1 vum) ^ Eggplant gray mold (Botrytiscinerea), black blight (Coryn espora me l) ong enae), powdery mildew (Erysi ph ecic ho racear um), strawberry gray mold (Botrytiscinerea), powdery mildew (Sph aerotheca humu li), gray rot of onion (Botry) tisallii), gray force, rot (Botrytiscinerea), sclerotium wilt (S—c 1 erotiniasc 1 erotior um), gray force, rot (Botrytiscinerea), apple powdery mildew (Po dosphaeraleucotricha), Black star (Venturiainae qu alis) Monilia disease (Moni 1 inia ma

1 i), oyster powdery mildew (Phy llactiniakakicola), anthracnose (G loeospori um kaki, horn spots. Cercosporakaki), peach rot (Mo niliniafructico 1a), grapes Gray mold (Botrytiscinerea), powdery mildew (Un ci nu lanecator), rot (G 1 omere 1)

1 acingu 1 ata), pear scab (Ven—tur i_a nasho 1 a), scab (Gymn osporangi um asiatic um) Black spot (A 1 ternariaki ku ci ana), ring spot of chiya (P estalotiatheae), anthracnose (Co 1 1 etotri chum theae— sinensis), citrus power, disease (Elsi no efawcetti), blue mold Disease (P enici 1 1 ium _i ta 1 i—c um), green power, rust Pen ϊ ci 1 1 i urn digitat urn), gray mold (Botrytisci ne rea) Rysiphegraminisf. S. Ho rdei), naked black bean J? (U sti 1 agonuda). Wheat red mold (G ibbere 1 1 azeae), red rust (ucc nia niarec ond ita) spot disease (C och 1 iobolussavus) ), -Eye spot disease (P seu do cercosore 1 1 aher

P o cho ides), blight (Le ptos pha erianodoum), powdery mildew (Ery si ph egraminisf · s. Trtici), red snow rot (Microne ctrie 1 1 aniva 1 is), rice Blast (Py riculariaor yz ae), sheath blight (hizoct on i a. Sol an i), idiot disease (G ibbere 1 1 afujikuroi), sesame leaf blight (Co ch liobolusmiy abe anu s), tano Bacterial scleroderma of ヾ CS CS clerotiniasclerotior um), powdery mildew (Ery siheci cho racear um), gray mold of turile (B0 tryti s_ ci ne rea), snow rot of bentograss S clerotiniaborea 1 is), powdery mildew of ochria douglas (Ery si ph egr ami nis), purpura of soybean (Cercosporakikucii), plague of potato 'tomato (Phytophhorainfest an s), downy mildew of cucumber ( It can be used for controlling Pseudoperonospora. Cubensis) and downy mildew of pigweed (Piasumoparaviitica1a).

Botrytiscine, a fungus resistant to benzimidazole fungicides (eg, thiophanate methyl, benomyl, carbendazim). rea) The compound of the present invention is also effective against sugar beet brown spot fungus (Cercosporabeticola), apple scab (Venturisinaequa 1 is), and pear scab (e η turianashico 1a) as well as susceptible bacteria.

 Furthermore, the compound of the present invention is also effective against gray mold fungi (Botryticincinea) which is resistant to dicarboximide fungicides (for example, vinclozolin, procymidone, iprodione) as well as susceptible bacteria.

 Diseases that are more preferably applied include sugar beet brown spot, wheat powdery mildew, rice blast, apple scab, gray mold of cucumber, brown spot of laccasei, and the like.

 The compound of the present invention can also be used as an antifouling agent for preventing aquatic organisms from adhering to underwater contact substances such as ship bottoms and fish nets.

When the thus-obtained compound of the present invention is actually applied, it can be used in a pure form without adding other components, and can be used in the form of a general pesticide for use as a pesticide, namely, hydration. Preparations, granules, powders, emulsions, aqueous solvents, suspensions and the like. When solid additives are used as additives and carriers, vegetable powders such as soybean grains and wheat flour, diatomaceous earth, limestone, gypsum, talc, pyrophyllite, clay, mineral oil, and mineral oils such as vegetable oils A fine powder is used. For liquid dosage form, kerosene, mineral oil, petroleum, solvent naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, mineral oil, vegetable oil, water, etc. Is used as a solvent. Surfactants can be added, if necessary, to obtain a uniform and stable form in these preparations. The wettable powder and emulsion thus obtained are diluted to a predetermined concentration with water and used as a suspension or an emulsion, and the powder and granules are used as they are by spraying them on plants. Next, some examples of the composition of the present invention will be described. However, the additives and the addition ratios are not limited to these examples, and can be changed in a wide range. Parts in Formulation Examples are parts by weight. Example 14 wettable powder

 Compound of the present invention 40 parts

 Diatomaceous earth 5 3 parts

 Higher alcohol sulfate 4 parts

 Alkyl naphthalene sulfonate 3 parts

 If the above are uniformly mixed and finely pulverized, a wettable powder with an active ingredient of 40% is obtained. Example 15 Emulsion

 Compound of the present invention 30 parts

 Xylene 3 3 parts

 Dimethylformamide 30 parts

 Polyoxyethylene alkylaryl ether 7 parts

 By mixing and dissolving the above, an emulsion containing 30% of the active ingredient is obtained.

 Example 16 Dust

 Honshiki compound 10 parts

 Talc 8 9 parts

 1 part of polyoxyethylene alkylaryl ether

 If the above are uniformly mixed and finely pulverized, a powder containing 10% of the active ingredient is obtained. Example 1 7 granules

 5 parts of the compound of the present invention

 Clay 7 3 parts

 Bentonite 20 parts

 Dioctyl sulfosuccinate sodium salt 1 part

 1 part sodium phosphate

 After the above ingredients are well ground and mixed, water is added and kneaded well.

Obtain 5% granules.

Example 18 Suspension

Compound of the present invention 10 parts Sodium ligninsulfonate 4 parts Sodium dodecylbenzenesulfonate 1 part

 Xanthan gum 0.2 parts

 Water 84.8 parts

 The above ingredients are mixed and wet-pulverized until the particle size becomes 1 micron or less, to obtain a 10% active ingredient suspending agent.

 Needless to say, the compound of the present invention is sufficiently effective alone, but it is one or two of various fungicides and insecticides and acaricides against inadequate or weak diseases or harmful insects and mites. It can be used in combination with the above.

 Representative examples of fungicides, insecticides, acaricides, and plant growth regulators that can be used by mixing with the compound of the present invention are shown below.

 〔Fungicide〕

Captan, Format, Thiuram, Zineb, Maneb, Mancozeb, Provineb, Polycarbamate, Chlorothalonil, Quintzenzen, Captahor, Hyperprodion, Procymidone, Vinclozolin, Fluoromid, Thymoxanil, Mepronil, Flutronil , Pencyclon, oxycarboxine, josetyl aluminum, propamocarb, triadimefon, triazimenol, propiconazol, diclobutrazol, bitertanol, hexaconazole, microbutanyl, flusilazole, etaconazol, fluotolimazole, flutria Fen, penconazole, dicononazole, cyproconazole, finalimol, triflumizole, prochloraz, imazalil, perfura Etridemosulf, fenpropimorph, trifolin, ptiobate, pyrifenox, azirazine, polyoxin, metalaxyl, oxadixyl, furalaxyl, isoprothiolane, probenazole, pyrrolnitrin, blastostidine S, kasugamycin, validamycin Dihydros trebutomacin sulfate, benomyl, rubendazim, thiophanate methyl, himexazole, basic copper chloride, basic copper sulphate, pentine acetate, triflatinyl hydroxide, jetfencalp, Metasulfocarp, quinomethionate, pinapacryl, lecithin, baking soda, dithianon, dinocap, phenaminosulf, diclomedine, guazatine, dozine, IBP, edifenphos, mepanipyrim, pheliamzon, triclamide, methasulfocarp, fluquinam, zequimolone, fluquinam Tech mouth phtalam, husaride.

 (Insecticides and acaricides)

 Chlorbenzylate, chlorpropylate, proclonol, phenisobromolate, dichophor, dinobutone, chlorphenamide, amitraz, BPPS, PPPS, benzomate, hexthiazox, fenbutatin oxide, polynactin, thioquinox, CPCBS, tetraxionthion, tetraquinone , Polysulfone lime, clofuentezin, fluvensmin, flufenoxuron, BCPE, sihexatin, pyridaben, fenpyroximate, fenthion, funitrothion, diazinon, chlorpyrifos, ESP, bamidothion, phenateate, Dimethoate, formotion, malathion, dipterex, thiometone, phosmet, menazone, dichlorvos, asphalt, EPBP, Rehole, methyl parathion, oxydimethone-methyl, ethion, pyraclofos, monochloride tophos, mesomeryl monochloride tophos, aldicarb, proboxur, BPMC, MTM C, Nack, Cartap, Carbosurphan, Benfracalp, Pyrimikab, Thiofencalp, phenoxycarp, permethrin, cypermethrin, decamesulin, fenvalerate, fenpropasulin, pyrethrin, allesulin, tetramethrin, resmethrin, dimethrin, propasulin, bifenthrin, prothrin, fullparinulin , Cyfluthulin, cyhalothrin, fricillinate, etofenprox, cycloprotrin, tiger mouth methrin, silaneophan, difluvenzuron, chlorfluaz Down, Torifurumuro down, Tefuru base Nzuron, buprofezin, machine oil.

 (Plant growth regulator)

Jibe Rerin acids (Tatoebajibe Rerin A _3, Jibe Lelie down eight _4, Jibe Lelie down A ₇₎ I AA, NAA.

Industrial applicability:

 Next, Test Examples show that the compound of the present invention is useful as an active ingredient of various plant disease controlling agents. The control effect was determined by visually observing the diseased state of the test plant at the time of the survey, that is, the degree of the growth of the bacterial spots on the leaves, stems and the like. ”,“ 4 ”if about 10% is recognized,“ 3 ”if about 25%,“ 2 ”if about 50%,“ 1 ”if about 75% If there is no difference from the onset of the disease, it is evaluated as “0” on a scale from 0 to 5 and indicated by 0, 1, 2, 3, 4, and 5.

Test example 1 sugar beet brown spot control test

A predetermined concentration of a wettable powder of the compound of the present invention was sprayed on sugar beet seedlings (variety "burlestree", 5 to 6-leaf stage) cultivated in a 9 cm unglazed pot, and the leaves were air-dried. Spray and inoculate a conidia spore suspension of brown spot fungus (Cercosporabetico 1a) and keep it at 24 to 28 ° C and high humidity for 1 day, then put it in a greenhouse at 23 to 30 ° C. The disease was maintained for a period of days and the control effect was determined. Table 7 shows the results.

138

 68

Table 7

 * 1 mancoz eb 7 5% wettable powder

 * 2 c l o r o t a l o n i 1 75% wettable powder

* 3 fentinhydroxide 1 7% wettable powder 93

 69

Test example 2 Sugar beet brown spot control test (Treatment test)

A conidia suspension of sugar beet brown spot fungus (Cercosporab_etico 1a) is sprayed and inoculated onto sugar beet seedlings (variety Burles linei, 5-6 leaf stage) cultivated in a 9 cm unglazed pot. Maintain at 24 to 28 ° C and high humidity for 1 day, and further maintain in a greenhouse at 23 to 30 ° C for 2 days, then spray a chemical solution of the wettable powder of the present compound at a predetermined concentration, and leave After air-drying, the plants were kept in a greenhouse for 10 days, and the disease development was investigated to determine the control effect. Table 8 shows the results.

Table 8

* 4 fen tin hyd roxide 17% wettable powder * 5 thi op ana t e-me thyl 70% wettable powder * 6 ka s ugamy ci n-HC 1 2.3% liquid Test example 3 Wheat powdery mildew control test (prevention test)

Wheat seedlings (cultivar “Norin 61”, 1.2-1.2 leaf stage) cultivated and cultivated in unglazed pots are sprayed with a solution of a wettable powder of the compound of the present invention at a predetermined concentration, and the leaves are air-dried. After that, conidiospores of wheat powdery mildew (Erysiphegr am inisf-sp. Tritici) were shaken off and inoculated, and grown in a greenhouse at 22 to 25 ° C for 7 days to investigate the control effect. Table 9 shows the results.

138

 72

Table 9 Active ingredients

Compound number Concentration Control effect

 (ppm)

 1-1 0 2 0 0 5

 1-1 1 2 0 0 5

 1-1 2 2 0 0 5

 1-1 3 2 0 0 5

 1-1 2 0 0 5

 1-1 5 2 0 0 5

 1-1 6 2 0 0 5

 1-1 8 2 0 0 5

 1-1 9 2 0 0 5

 1-2 2 2 0 0 5

 1-3 5 2 0 0 5

 1-5 2 0 0 5

 1 -4 7 2 0 0 5

 1-8 2 0 0 5

 1-7 0 2 0 0 4

 1-7 1 2 0 0 5

 1-9 0 2 0 0 4

 1-9 1 2 0 0 5

 1-9 2 2 0 0 4

 1-9 3 2 0 0 4

 1-9 2 0 0 4

 1-1 0 0 2 0 0 4

 1-1 3 6 2 0 0 5

 1-1 3 7 2 0 0 5

 1-1 4 0 2 0 0 4

 1-1 5 9 2 0 0 4

 1-1 6 3 2 0 0 4

 1-1 7 8 2 0 0 5 * 7 sulfur, 75% wettable powder

1-1 9 6 2 0 0 4

 1-2 0 0 2 0 0 5

 1-2 0 7 2 0 0 4

 1-2 1 0 2 0 0 5

 1-2 1 9 2 0 0 4

 1-2 2 0 2 0 0 5

 1-2 1 2 0 0 4

 1-2 2 2 2 0 0 5

 1-2 2 2 0 0 4

 1-2 2 8 2 0 0 4

1-2 3 0 2 0 0 4 Three

 73

Test example 4 Rice blast control test (prevention test)

A rice solution (variety “Nipponbare”, 3.0 leaf stage) grown in a plastic pot was sprayed with a chemical solution of a wettable powder of the compound of the present invention at a predetermined concentration, air-dried at room temperature, and cultured. A suspension of conidia of the blast fungus (Pyriculariaoryzae) was spray-inoculated and kept at 25 ° C in the dark for 48 hours under high humidity. Thereafter, the plants were grown in a thermostatic chamber at 25 to 27 ° C and a humidity of 70% or more. Seven days after the inoculation, the disease status was investigated, and the control effect was determined. The results are shown in Table 10.

/ 07138

 74

Table 10

* 8 is oprothiol ane 40% wettable powder * 9 fta 1 ide 50% wettable powder Test Example 5 Lingo scab control test (prevention test)

After spraying a predetermined concentration of a wettable powder of the compound of the present invention on a Lingo seedling (cultivar “Kunimitsu”, 3-4 leaf stage) cultivated in an unbaked pot and air-drying, the Lingo scab fungus nt u_ri a_ J_na a_e qua 1 is) was inoculated and kept in a room at 20 ° C and high humidity under lighting (bright and dark repeatedly) for 2 weeks, and the control effect was investigated. Table 11 shows the results.

07138

 76 Table 11

Test Example 6 Test for Control of Cucumber Gray Mold

A medicinal solution of a predetermined concentration of a wettable powder of the compound of the present invention was sprayed on young seedlings of cucumber (variety “Sagami Hanshiro”, 1.0 leaf stage) grown in unglazed pots. After spraying, the plants are air-dried at room temperature, and the fungi obtained by cultivation are sensitized to B 0 trytiscinerea benzimidazole and dicarboximid, and are hereinafter referred to as drug-sensitive bacteria. A suspension of spores (containing glucose and yeast extract) of a resistant bacterium (hereinafter referred to as a drug-resistant bacterium) was inoculated dropwise onto the true leaves of cucumber, and kept at 20 ° C, in the dark, and at a high humidity. Four days after the inoculation, the disease incidence was investigated and the control effect was determined. The results are shown in Table 12.

Table 12 Effective ingredient concentration Rk

 Compound number

 (ppm) Drug impression 囷 Drug-resistant bacteria 1 0 4 λ

 I 4 4

 2 4 ¾

 3 4 4

 4 4 4

 6 4 4 A

 Λ

 8 4

 9 4 ¾ 1 22 4 A 1 47 4 4 1 8 4 4 A 1 68 5 D

 -70 4

 One 7 1 5 0 One 91 4

 1 92 20 4

 One 94 20 4 t

 One 1 0 20 5 0 One 16 20 4

 -17 20 4 ¾ 1 22 20 4 A 1 22 20 4

 -22 4

 One 22 five

 One 22 5 * J

 -23 4 * A ±

 -25 4 A

 I- 3 5 5

 I- 5 4 4

 V- 6 4 4

 V- 1 4 4

 V- 20 4 4

 V- 22 4 4

V- 2 4 4

 V- 4 4 4

 V— 5 4 4

 VI- 4 4 4

VI-1 0 4 4

VI- 14 4 4

VI-17 4 4

VI- 1 9 4 4

VI-23 4 4

VI- 26 4 4

 VI—29 4 4

 1 I

Control agent 5 0 Control agent J " ² 3 3 Control agent ¹³ 5 0

* 1 1 thi opiiana e- met hy 1 70% wettable powder * 12 p 0 1 y0 X inec omp lex 10% wettable powder * 13v nc nc 1 ozo 1 n 50% wettable powder Test Example 7 Test for controlling laccase brown spot

A medicinal solution of a predetermined concentration of a wettable powder of the compound of the present invention was sprayed on young seedlings of laccase (cultivar “Nacateyutaka”, 4.0 bileaf stage) grown in unglazed pots. After spraying, air-dry the plants at room temperature, spray inoculate a suspension of spores of Mycosphaerel 'la _a rachidis obtained by culturing, and keep them at 24-28 ° C and high humidity for 1 day. After that, the plants were grown in a greenhouse at 23 to 30 ° C for 12 days, the disease occurrence was investigated, and the control effect was determined. The results are shown in Table 13.

07138

 80 Table 13

Claims

The scope of the claims

 1. General formula [I]

A—B—Q, No'N

R ²

(Where Q is R,

Represents

Y represents CR ⁶ or N,

R ¹ , R ² , R ³ , R ⁴ , and R ⁶ are the same or different and are each a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, Represents an alkenyloxy group, an optionally substituted alkynyloxy group, or a hydroxy group, and R ¹ and R ² may be taken together to form a ring, and R ⁵ is a hydrogen atom, halogen Atom, alkyl group which may be substituted, alkoxy group which may be substituted, alkenyloxy group which may be substituted, alkynyloxy group which may be substituted, hydroxy group, which may be substituted Represents a good alkylthio group, and R ⁴ and R ⁵ may be taken together to form a ring,

A represents an optionally substituted aryl group, an optionally substituted heterocyclic group, and B represents One C one one C one C one or

r ² r " ⁶

(In the formula, rrrrr ⁶ is the same or different, and represents a hydrogen atom, a halogen atom, a hydroxy group, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted acyloxy group, the ri and r ^2, r ³ and r ^4, or r ⁵ and r ⁶ represents an Okiso group together, further, even when the r ¹ ~r ^c and R ⁴ are taken together to form a ring cr I-good. However, if Q

In the formula, R ¹ , R ² , R ³ and R ⁶ are not all hydrogen atoms. ] The virazole derivative represented by these, or its salt.

 2. —General formula [II]

(II)

[Wherein, R represents an alkyl group, A, B, R ⁴ are as defined above. And a compound represented by the general formula [III]

(III)

[Wherein, R ¹ , R ² , R ³ and Y represent the same meaning as described above. Wherein the compound represented by the general formula [I′-1 1]

R ⁴ 0H

CI '1 1]

R ³

[In the formula, A, B, R ¹ , R ² , R ³ , R ⁴ , and Y represent the same meaning as described above. ] The manufacturing method of the compound represented by these.

 3. General formula [IV]

 A-B -NHNH2 (IV)

 [Wherein, A, B, and S represent the same meaning as described above. And a compound represented by the general formula (V):

[V]

[Wherein, R, R ¹ , R ² , R ³ and Y represent the same meaning as described above. [1'-1 2] characterized by reacting a compound represented by the formula

HO R ⁵

[I'-1 2]

A-

[In the formula, A, B, R ¹ , R ² , R ³ , R ⁵ , and Y represent the same meaning as described above. ] The manufacturing method of the compound represented by these.

 4. —General formula [I'-1]

CI ^Λ一 1]

[In the formula, A, B, R ¹ , R ² , R ³ , R ⁴ , and Y represent the same meaning as described above. And a compound represented by the general formula r-X wherein r represents an optionally substituted alkyl group, an optionally substituted alkenyl group or an optionally substituted alkynyl group; Represents a leaving group. Wherein the compound represented by the general formula [1′-1 7]

(I'-1 7)

[In the formula, A, B, R ¹ , R ² , R ³ , R ⁴ , r, and Y represent the same meaning as described above. ] The manufacturing method of the compound represented by these.

5. General formula [I '1 2] HO I 'I 2)

[In the formula, A, B, R ¹ , R ² , R ³ , R ⁵ , and Y represent the same meaning as described above. And a compound represented by the general formula r-X wherein r and X have the same meanings as described above. A compound represented by the general formula [1′-1 8] rOR ⁵

CI '1 8]

R ³

[Wherein A, B, R ¹ , R ² , R ³ , R ⁵ , r, and Y represent the same meaning as described above. ] The manufacturing method of the compound represented by these.

 6. —General formula [I]

A—— B—— Q

[I]

[In the formula, Q, Y, R ^{1 to} R ³ , A and B represent the same meaning as described above. ] A fungicide for agricultural and horticultural use, characterized by containing one or more of a azole derivative or a salt thereof as an active ingredient.