JPH10316676A - Pyridylimidazole compound and agricultural and horticultural microbicide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound capable of industrially and advantageously being synthesized, certain in effect, safely used, and capable of being used as an agricultural or horticultural microbicide. SOLUTION: This compound is pyridylimidazole compound of formula I (X is H, a halogen, a 1-6C alkyl, and a 1-6C haloalkyl, etc.; Y and Z are each independently H, a 1-6C alkyl, a 1-6C haloalkyl, or a halogen, etc.; R is H, a metallic atom, or a 1-6C alkylcarbonyloxymethyl, etc.; with the proviso that a compound in which X is H or Br and all of Y, Z and R are H, is omitted) or a salt thereof, for instance, 2-(5-ethyl-2-pyridyl)-4-trifluoromethylimidazole. The compound of formula I in which X and R are each H is obtained by heating 1,1-dibromo-3,3,3-trifluoroacetone with a sodium acetate solution and reacting the product with 2-formylpyridines of formula II and ammonia water at (-10)-100 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel pyridyl imidazole compound and a fungicide for agricultural and horticultural use.

[0002]

2. Description of the Related Art In the cultivation of agricultural and horticultural crops, a large number of control agents are used against crop diseases, but their use is insufficient due to insufficient control effect or the emergence of drug-resistant pathogens. Due to their limitations, their potential to cause phytotoxicity and contamination of plants, and their high toxicity to humans, fish and livestock, there are not many satisfactory control agents that are not always satisfactory. Therefore, there is a strong demand for a drug that can be safely used with few such disadvantages. As disclosures of compounds related to the compound of the present invention, USP.
No. 4,314,844 describes the physical properties of compound [A] and that compounds [A] and [B] have herbicidal activity. However, although there is a description of the bactericidal activity, the specific test results are not described. Further, although the structure and elemental analysis value are described for the compound [C], there is no description of the physical properties, and no description is given regarding the biological activity.

[0003]

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[0004] In addition, in the above-mentioned literature, 24 compounds are specifically exemplified for the compound represented by the general formula [D], but there is no description regarding the production method and the like, and the compound is not actually synthesized. .

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel pyridylimidazole compound which can be synthesized industrially advantageously, is a safe and effective fungicide for agricultural and horticultural use.

[0006]

The present invention provides a compound of the formula [I]

[0007]

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[Wherein X is a hydrogen atom, a halogen atom, C
_1-6 alkyl group, C _1-6 haloalkyl group, C _1-6 alkylthio group, hydroxy group, formyl group, hydroxyiminomethyl group, C _1-6 alkoxyiminomethyl group, nitro group, cyano group, C _1-6 Alkoxycarbonyl group, optionally substituted phenyl group, optionally substituted benzoyl group, C _1-6 alkoxy group, C _1-6 alkylcarbonyloxy group, di C _1-6 alkoxymethyl group, hydroxymethyl group, C _1-6 alkylcarbonyloxymethyl group, (C
_An amino group which may be substituted with a _1-6 alkyl group or a C _1-6 alkylcarbonyl group). Y and Z each independently represent a hydrogen atom, a C _1-6 alkyl group, a C _1-6 haloalkyl group, a C _3-6 cycloalkyl group, a halogen atom,
_1-6 alkoxy group, C _2-6 alkenyloxy group, C _1-6
Represents an alkylthio group, a C _1-6 alkylcarbonyloxy group or a benzoyloxy group which may be substituted. R
Is a hydrogen atom, a metal atom, a C _1-6 alkylcarbonyloxymethyl group, an optionally substituted benzoyloxymethyl group, a di C _1-6 alkylcarbamoyloxymethyl group,
C _1-6 alkoxycarbonyloxymethyl group or di C
Represents a _1-6 alkylcarbamoyl group. However, compounds in which X is hydrogen or bromine and Y, Z and R are all hydrogen are excluded. And a salt thereof, and a fungicide for agricultural and horticultural use comprising the compound.

In the compound of the present invention, X is a hydrogen atom,
Halogen source such as fluorine, chlorine and bromine, methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t
-Butyl, a C _1-6 alkyl group such as a hexyl group, fluoromethyl, 1-fluoroethyl, 2-fluoroethyl,
Difluoromethyl, trifluoromethyl, difluorochloromethyl, fluoro chloro, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, tribromomethyl, trifluoroethyl ethyl, C _1-6 haloalkyl groups such as pentafluoroethyl ethyl, methylthio, C _1-6 alkylthio group such as ethylthio, propylthio, isopropylthio, butylthio group, hydroxy group, formyl group, cyano group, hydroxyiminomethyl group, methoxyiminomethyl, ethoxyiminomethyl, propoxyiminomethyl, isopropoxymethyl, butoxyimino C such as methyl, t-butoxyiminomethyl group
_1-6 alkoxyiminomethyl group, nitro group, cyano group,
C _1-6 alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, t-butoxycarbonyl group, (C _1-4 alkyl group such as methyl, ethyl group, methoxy, ethoxy group, etc. C _1-4 alkoxy group, fluorine, chlorine, a halogen atom such as bromine, nitro group, acetylamino group, may be substituted with dimethyl amino group) phenyl group, (such as methyl, ethyl C _{1- 4} C such as alkyl group, methoxy, ethoxy group, etc.
_1-4 alkoxy group, halogen atom such as fluorine, chlorine, bromine, etc., nitro group, acetylamino group, dimethylamino group and the like may be substituted) benzoyl group, methoxy, ethoxy, propoxy, isopropoxy, butoxy, t - C _1-6 alkoxy group such as butoxy, acetoxy, propionyloxy, C _1-6 alkylcarbonyloxy group such as iso-butyryloxy group, dimethoxymethyl, diethoxymethyl, dipropoxymethyl, diisopropoxymethyl, di Di C _1-6 alkoxymethyl group such as butoxymethyl group, hydroxymethyl group, methylcarbonyloxymethyl, ethylcarbonyloxymethyl, propylcarbonyloxymethyl, isopropylcarbonyloxymethyl, butylcarbonyloxymethyl, t-
C _1-6 alkylcarbonyloxy methyl or butyl carbonyloxy methyl group, (methyl, ethyl, C _1-6 alkyl or acetyl, such as isopropyl, propionyl, substituted by C _1-6 alkylcarbonyl group such as isobutyryl Represents an amino group.

Y and Z each independently represent a hydrogen atom, C _1-6 such as methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, hexyl, etc.
C _1-6 haloalkyl groups such as alkyl group, fluoromethyl, difluoromethyl, trifluoromethyl, trichloromethyl, chloromethyl, dichloromethyl, bromomethyl, and pentafluoromethyl groups; C such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl groups
_3-6 cycloalkyl group, fluorine, chlorine, bromine, halogen atoms such as iodine, methoxy, ethoxy, propoxy,
C such as isopropoxy, butoxy and t-butoxy groups
_C1-6 alkoxy group, vinyloxy, C _2-6 alkenyloxy groups such as allyloxy group, methylthio, ethylthio, propylthio, C _1-6 alkylthio groups such as isopropyl thio group, acetoxy, propionyloxy, such as isobutyryl group C _1-6 alkylcarbonyloxy group, (C _1-4 alkyl group such as methyl, ethyl group, C _1-4 alkoxy group such as methoxy, ethoxy group, halogen atom such as fluorine, chlorine, bromine, nitro group, acetyl Benzoyloxy group which may be substituted with an amino group, a dimethylamino group or the like).

R is a hydrogen atom, iron, nickel,
Metal atoms such as transition metals such as cobalt, manganese, copper and zinc; C _1-6 alkylcarbonyloxymethyl groups such as acetoxymethyl, propionyloxymethyl and isobutyryloxymethyl groups; (C ₁ groups such as methyl and ethyl groups) _-4 alkyl, methoxy, ethoxy, etc. C _1-4
Which may be substituted with a halogen atom such as an alkoxy group, fluorine, chlorine and bromine, a nitro group, an acetylamino group, a dimethylamino group, etc.) C _1-6 alkylcarbamoyloxymethyl group, methoxycarbonyloxymethyl, ethoxycarbonyloxymethyl, propoxycarbonyloxymethyl, isopropoxyoxycarbonylmethyl group and other C _1-6 alkoxycarbonyloxymethyl groups, dimethylcarbamoyl, diethylcarbamoyl,
Represents a diC _1-6 alkylcarbamoyl group such as dipropylcarbamoyl and dibutylcarbamoyl.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The compound of the present invention can be produced by the following method. Production Method 1 Among compounds [I] of the present invention, a compound wherein X and R are both hydrogen atoms can be produced by the following method.

[0013]

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(Wherein Y and Z have the same meanings as described above.) 1,1-Dibromo-3,3,3-trifluoroacetone is heated with an aqueous solution of sodium acetate for a short time, and then subjected to the general formula [II] The compound represented by the formula (I-1) can be produced by reacting with 2-formylpyridines represented by formula (1) and aqueous ammonia at -10 ° C to 100 ° C.
Further, it can be produced by using an ammonium salt such as ammonium acetate instead of the ammonia water. Solvents that can be used in the reaction include water, alcohols such as methanol and ethanol, ethers such as tetrahydrofuran (THF), carboxylic acids such as acetic acid, N, N-dimethylformamide (DMF), dimethyl sulfoxide (D
MSO), acetonitrile and the like.

Production method 2 In the compound [I] of the present invention, X represents a chlorine atom, a bromine atom, a C _1-6 alkyl group, a C _1-6 haloalkyl group, a C _{1-6
Alkylthio} group, formyl group, C _1-6 alkoxyiminomethyl group, hydroxyiminomethyl group, cyano group, C
Those having a _1-6 alkoxycarbonyl group or an optionally substituted benzoyl group can be produced by the following method.

[0016]

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(Where Y and Z have the same meanings as described above,
V represents a halogen atom, R ¹ and R ² represent a C _1-6 alkyl group, and X ′ represents a C _1-6 alkyl group, a C _1-6 alkoxycarbonyl group or a benzoyl group which may be substituted. . )

In any of X, Y and Z, C
_The compound having a _1-6 alkylsulfinyl group or a C _1-6 alkylsulfonyl group can be produced by oxidizing the corresponding compound having a C _1-6 alkylthio group.

Production method 3 In compound [I] of the present invention, X represents a hydroxy group,
Those having a _1-6 alkoxy group can be produced by the following method.

[0020]

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(Where Y and Z have the same meanings as described above,
R ² represents a C _1-6 alkyl group. DAST stands for diethylaminosulfur trifluoride. ) Production method 4 In the compound [I] of the present invention, X represents a nitro group or (C
Those having an amino group (which may be substituted with a _1-6 alkyl group or a C _1-6 alkylcarbonyl group) can be produced by the following method.

[0022]

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(Wherein, Y, Z, and V have the same meanings as described above, and R ³ represents a C _1-6 alkyl group or a C _1-6 alkylcarbonyl group.)

Production Method 5 Among the compounds [I] of the present invention, those in which X may be substituted with a phenyl group or a C _1-6 alkyl group can be produced by the following method.

[0025]

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(Where Y and Z have the same meanings as described above,
R ⁴ represents a C _1-6 alkyl group or a phenyl group which may be substituted. ) The 2-formylpyridines represented by the general formula (II) and the α-diketones represented by the general formula (III) are reacted at -10 to 100 ° C in the presence of aqueous ammonia or an ammonium salt such as ammonium acetate. It can be produced by reacting. Solvents that can be used in the reaction include water, alcohols such as methanol and ethanol, ethers such as THF, organic carboxylic acids such as acetic acid, DMF, and DMF.
MSO, acetonitrile and the like.

Production Method 6 In the compound [I] of the present invention, R represents a C _1-6 alkylcarbonyloxymethyl group, an optionally substituted benzoyloxymethyl group, a diC _1-6 alkylcarbamoyloxymethyl group, Those having a _1-6 alkoxycarbonyloxymethyl group or a diC _1-6 alkylcarbamoyl group can be produced by the following method.

[0028]

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(Wherein, X, Y, Z, and V have the same meanings as described above, and R represents a C _1-6 alkylcarbonyloxymethyl group, an optionally substituted benzoyloxymethyl group,
_1-6 alkylcarbamoyl oxymethyl group, a C _1-6 alkoxycarbonyloxy methyl group or di-C _1-6 alkylcarbamoyl group. The reaction is carried out without a solvent or using an appropriate organic solvent in the presence of a base, and usually two kinds of products, a 4-CF ₃ form and a 5-CF ₃ form, can be obtained. Examples of the solvent that can be used for the reaction include water, alcohols such as methanol and ethanol, ethers such as THF, organic carboxylic acids such as acetic acid, DMF, DMSO, and acetonitrile. In addition, as the base used in this reaction,
Carbonates such as sodium carbonate and potassium carbonate, metal hydroxides such as sodium hydroxide, sodium methylate,
Examples thereof include metal alkoxides such as potassium t-butoxide, and organic bases such as triethylamine and pyridine.

Production Method 7 Among the compounds represented by the formula [I], a compound in which R is a metal atom can be prepared, for example, by adding 2 equivalents of the compound in which R is a hydrogen atom in the formula [I] to acetone, ethanol or the like. It can be produced by dissolving in an organic solvent and adding one equivalent of an aqueous solution or an ethanol solution of a metal salt such as a metal chloride.

The 2-formylpyridines represented by the formula [II] can be produced by any of the following methods.

[0032]

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(In the formula, V ′ represents a bromine atom or an iodine atom.) 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.

[0034]

The compounds of the present invention will be described in more detail with reference to Examples and Reference Examples. Example 1 Synthesis of 2- (5-ethyl-2-pyridyl) -4-trifluoromethylimidazole (Compound No. 1)

[0035]

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5.05 g (0.06 g) of anhydrous sodium acetate
2 mol) was dissolved in 15 ml of water and 1,1-dibromo-
8.53 g of 3,3,3-trifluoroacetone (0.0
32 mol) and heated briefly at 70 ° C. After cooling to room temperature, 5-ethyl-2-pyridinealdehyde4.
05 g (0.030 mol) and 80 ml of a methanol solution were added, and 30 ml of concentrated aqueous ammonia was further added dropwise. THF
5 ml was added to make a homogeneous solution, and the mixture was stirred at room temperature for 4 hours.
After the reaction solution was concentrated under reduced pressure, water and ethyl acetate were added to carry out liquid separation. The ethyl acetate layer was dehydrated with low-water magnesium sulfate and concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography to obtain 3.31 g of the desired compound.
Yield 46%. m. p 140-142 ° C.

Example 2 Synthesis of 2- (5-ethyl-2-pyridyl) -4-trifluoromethyl-5-bromoimidazole (Compound No. 2)

[0038]

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1.67 g of anhydrous potassium carbonate (0.01
2 mol), a small amount of water was added to form a paste, and then 2- (5
A solution of 2.77 g (0.011 mol) of 2-ethyl-2-pyridyl) -5-trifluoromethylimidazole in 80 ml of chloroform was added. 2.21 g of bromine
(0.014 mol) of a chloroform solution (15 ml) was added dropwise at room temperature, and the mixture was stirred for 2 hours. The reaction solution was washed sequentially with an aqueous sodium hydrogen sulfite solution and brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was washed with hexane to obtain 3.23 g of the desired compound. Yield 88% m.p. p 113-114 ° C

Example 3 2- (5-ethyl-2-pyridyl) -4-trifluoromethyl-5-methylthioimidazole (Compound No.
Synthesis of 3)

[0041]

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2- (5-ethyl-2-pyridyl) -4-
Trifluoromethyl-5-bromoimidazole 0.5
0 g (1.56 mmol) of tetrahydrofuran 10 m
1.56 N n at −70 ° C. under a nitrogen atmosphere.
-BuLi hexane solution (21 ml, 3.3 mmol) was added dropwise, and the mixture was further stirred at -70 ° C for 1 hour. Then, dimethyl disulfide (0.294 g, 3.12 mmol) was added.
2 hours at -70 ° C, 1 hour at -40 ° C, and 2 hours at room temperature.
Stirred for days. The reaction solution was added to an aqueous ammonium chloride solution, extracted with ethyl acetate, the organic layer was dried over magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel chromatography to obtain 0.20 g of the desired compound
I got Yield 35% m. p 115-120 ° C

Example 4 1-acetoxymethyl-2- (5-ethyl-2-pyridyl) -4-trifluoromethyl-5-bromoimidazole (Compound No. 4) and 1-acetoxymethyl-2
Synthesis of-(5-ethyl-2-pyridyl) -5-trifluoromethyl-4-bromoimidazole (Compound No. 5)

[0044]

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2- (5-ethyl-2-pyridyl) -4-
Trifluoromethyl-5-bromoimidazole 0.8
0 g (2.5 mmol) in 20 ml of tetrahydrofuran
0.35 g (2.5 mmol) of potassium carbonate
Was added and stirred at room temperature for 30 minutes. Then, 0.57 g (3.8 mmol) of acetoxymethyl chloride (purity 72%)
l) and heat to reflux for 6 hours.
70 g (5.0 mmol) and 0.57 g (3.8 mmol) of acetoxymethyl chloride were added, and the mixture was heated under reflux for 15 hours. After allowing to cool, water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The obtained residue was purified by silica gel chromatography to obtain the desired compound (Compound No. 4: Compound No. 4).
0.27 g of a 5 = 5: 1 mixture). Yield 28% m. p 70-74 ° C ¹ H-NMR (CDCl ₃ )

Example 5 Synthesis of 2- (5-ethyl-2-pyridyl) -4-trifluoromethyl-5- (4-methylphenyl) imidazole (Compound No. 46)

[0047]

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1- (4-methylphenyl) -3,3,3
-Trifluoro-1,2-propanedione 0.80 g
(3.7 mmol), 0.60 g (4.4 mmol) of 5-ethyl-2-pyridine aldehyde, and 1.65 g (21.4 mmol) of ammonium acetate are suspended in 25 ml of acetic acid, and the mixture is suspended at room temperature for 15 minutes and further 8 hours. Heated to reflux.
The reaction solution was added to ice water, neutralized with concentrated aqueous ammonia, and extracted with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate, concentrated under reduced pressure, and the obtained residue was purified by silica gel chromatography to obtain the target compound 0.2
3 g were obtained. Yield 19% m. p 163-165 ° C

Reference Example 1 1- (1-ethoxyethyl) -2- (5-ethyl-2-
Synthesis of (pyridyl) -4-trifluoromethyl-5-bromoimidazole

[0050]

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2- (5-ethyl-2-pyridyl) -4-
2.50 g of trifluoromethyl-5-bromoimidazole
To a solution of (7.14 mmol) in 25 ml of chloroform, 1.03 g (14.3 mmol) of ethyl vinyl ether and a catalytic amount of p-toluenesulfonic acid (PTS) were added, and the mixture was stirred at room temperature overnight. The mixture was added to ice water, extracted with chloroform, and the organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography (n-hexane: ethyl acetate = 5: 1),
2.39 g of the desired product was obtained. Yield 85.4% mp. 52-5
3 ℃

Reference Example 2 1- (1-ethoxyethyl) -2- (5-ethyl-2-
Synthesis of (pyridyl) -4-trifluoromethyl-5-chloroimidazole

[0053]

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1- (1-ethoxyethyl) -2- (5-
Ethyl-2-pyridyl) -4-trifluoromethyl-5
1.00 g (2.55 mmol) of bromoimidazole T
The HF 20 ml solution was cooled to -70 ° C under a nitrogen atmosphere, and 1.
2.4 ml of 6N n-BuLi hexane solution (3.8 mmol)
1) was added dropwise, and the mixture was stirred at -70 ° C for 1 hour. Then, 0.51 g (3.82 mmol) of N-chlorosuccinimide was added, and the mixture was stirred at -60 ° C for 60 hours. The mixture was added to water, extracted with ethyl acetate, and the organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain 0.97 g of a crude product. ¹ H-NMR (CDCl ₃ , δ ppm) 8.45 (1H, d), 8.0
4 (1H, d) 7.62 (1H, dd), 7.05 (1H, q), 3.41 (2H, m), 2.70 (2H,
q), 1.88 (3H, d), 1.27 (3H, t), 1.15 (3H, t)

Example 6 2- (5-ethyl-2-pyridyl) -4-trifluoromethyl-3-chloroimidazole (Compound No. 11)
Synthesis of

[0056]

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0.97 g of the crude product of Reference Example 2 was dissolved in 10 ml of methanol, and 5 ml of 1N hydrochloric acid was added.
Stirred for hours. Water was added, the mixture was extracted with ethyl acetate, and the organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, silica gel chromatography (n-
Hexane: ethyl acetate = 4: 1) and the obtained crystals were washed with n-hexane to obtain 0.23 g of the desired compound. Yield 33%, mp. 119-121 ° C

Reference Example 3 1- (1-ethoxyethyl) -2- (5-ethyl-2-
Synthesis of (pyridyl) -4-trifluoromethyl-5-ethylimidazole

[0059]

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1- (1-ethoxyethyl) -2- (5-
Ethyl-2-pyridyl) -4-trifluoromethyl-5
-Bromoimidazole (0.80 g, 2.0 mmol) in TH
F15ml, 1.6N at -78 ° C under nitrogen atmosphere
1.9 ml (3.0 mmol) of n-BuLi hexane solution
After stirring at -78 ° C for 1 hour, ethyl iodide 0.6 was added.
0 g (3.9 mmol) was added, the temperature was returned from -70 ° C to room temperature, and the mixture was stirred overnight. After addition to water, the mixture was extracted with chloroform, washed with saturated saline, and then the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The crude product was subjected to silica gel chromatography (n-hexane: ethyl acetate = 25:
Purification in 1) gave 0.46 g of the desired product. Yield 66%, n
_D ^24.5 1.5048

Example 7 2- (5-ethyl-2-pyridyl) -4-trifluoromethyl-5-ethylimidazole (Compound No. 56)
Synthesis of

[0062]

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1- (1-ethoxyethyl) -2- (5-
Ethyl-2-pyridyl) -4-trifluoromethyl-5
0.30 g (1.0 mmol) of -ethylimidazole was dissolved in 6 ml of methanol, 3 ml of 0.1N hydrochloric acid was added, and the mixture was stirred at room temperature for 24 hours. After concentration under reduced pressure, a saturated aqueous solution of sodium hydrogen carbonate was added, and the mixture was extracted with chloroform. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the residue was purified by silica gel chromatography (n-hexane: ethyl acetate = 5: 1) to obtain 0.25 g of the desired product. Yield 9
8%, mp. 59-61 ° C

Reference Example 4 1- (1-ethoxyethyl) -2- (5-ethyl-2-
Synthesis of (pyridyl) -4-trifluoromethyl-5-formylimidazole

[0065]

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1- (1-ethoxyethyl) -2- (5-
Ethyl-2-pyridyl) -4-trifluoromethyl-5
-Bromoimidazole 5.00 g (12.8 mmol) in T
Dissolve in 100 ml of HF and 1.6 at -70 ° C under nitrogen atmosphere.
Nn-BuLi hexane solution 12 ml (19.2 mmol
l) was added dropwise, and the mixture was stirred at -70 ° C for 1 hour.
79 g (38.2 mmol) was added, and the mixture was stirred at -65 to -55 ° C for 5 hours. The mixture was added to water and extracted with ethyl acetate. The organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by silica gel chromatography (n-hexane: ethyl acetate = 20: 1),
2.09 g of the desired product was obtained. Yield 48% ¹ H-NMR (CDCl ₃ , δ ppm) 10.34 (1 H, s), 8.
51 (1H, d), 8.10 (1H, d), 7.67 (1H, dd), 7.00 (1H, q), 3.40 (2
H, m), 2.73 (2H, q), 1.91 (3H, d), 1.30 (3H, t), 1.08 (3H, t)

Example 8 1- (1-ethoxyethyl) -2- (5-ethyl-2-
Synthesis of (pyridyl) -4-trifluoromethyl-5-methoxyiminomethylimidazole (Compound No. 74)

[0068]

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1- (1-ethoxyethyl) -2- (5-
Ethyl-2-pyridyl) -4-trifluoromethyl-5
-0.35 g (1.03 mmol) of formylimidazole are dissolved in 20 ml of methanol and methoxyamine hydrochloride is dissolved in 0.3 ml of methanol.
09 g (1.08 mmol) was added, and the mixture was heated and refluxed at room temperature for 2 hours and further for 2 hours. After cooling, the mixture was added to water, extracted with ethyl acetate, the organic layer was washed with water, and further washed with saturated saline.
It was dried over anhydrous magnesium sulfate. After concentration under reduced pressure, the residue was purified by silica gel chromatography (n-hexane: ethyl acetate = 3: 1) to obtain 0.14 g of the desired product. Yield 46%, mp. 110-112 ° C

Example 9 5-bromo-2- (5-ethyl-2-pyridyl) -4-
Synthesis of trifluoromethylimidazole copper (II) salt (Compound No. 72)

[0071]

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0.3 g of 5-bromo-2- (5-ethyl-2-pyridyl) -4-trifluoromethylimidazole
(0.0009 mol) was dissolved in 7 ml of acetone, and 0.06 g (0.0047 mol) of cupric chloride was added thereto with stirring.
Was dissolved in ethanol (3 ml) and added dropwise at room temperature. After stirring overnight, the solvent was distilled off under reduced pressure, and the residue was washed with water and ether to obtain 0.33 g of the desired compound. Yield 92
%, Mp. 250 ° C up

[0073]

[Table 1001]

[0074]

[Table 1002]

[0075]

[Table 1003]

[0076]

[Table 1004]

[0077]

[Table 1005]

[0078]

[Table 1006]

[0079]

[Table 1007]

[0080]

[Table 1008]

[0081]

[Table 1009]

[0082]

[Table 1010]

* 1: ¹ H-NMR [(Compound No.
4), (CDCl ₃ , δ ppm)]: 8.42 (d, 1
H), 8.09 (d, 1H), 7.63 (dd, 1
H), 6.70 (d, 2H), 2.70 (q, 2H),
2.06 (s, 3H), 1.28 (t, 3H) * 2: ¹ H-NMR [(Compound No. 5), (CDCl
₃ , δ ppm)]: 8.44 (d, 1H), 8.09
(D, 1H), 7.64 (dd, 1H), 6.66
(D, 2H), 2.70 (q, 2H), 2.03 (s,
3H), 1.28 (t, 3H)

The compound of the present invention has excellent bactericidal activity against a wide variety of filamentous fungi.
It can be used to control various diseases that occur when cultivating agricultural and horticultural crops including turf and grass. For example, rice blast disease (Pyricularia oryzae) Sheath Blight (Rhizoctonia solani) bakanae (Gibberella fujikuroi) Gomaha blight (Cochliobolus miyabeanus) barley brownish ear disease (Ustilago nuda) Wheat Fusarium head blight (Gibberella zeae) brown rust ( Puccinia recondita) Memonbyo (Pseudocercosporella herpotrichoides) glume blotch (Leptosphaeria nodorum) powdery mildew (Erysiphe graminis f. sp. tritici ) pink snow mold disease (Micronectriella nivalis) potato late blight (Phytophthora infestans) peanut brown spot disease (Mycosphaerella arachidis ) sugar beet brown spot disease (Cercospora beticola) cucumber powdery mildew (Sphaerotheca fuliginea) rot (Sclerotinia sclerotiorum) gray mold (Botrytis cinerea) downy mildew (Pseudoperonospora cubensis) tomato leaf blight (Cladosporium fulvum) plague (Pytophthora infestans ) Eggplant Black blight ( Corynespora melongenae ) Onion Gray rot ( Botrytis al lii) Strawberry powdery mildew ( Sohaerotheca humuli ) Apple powdery mildew ( Podosphaera leucotricha) Black scab ( Venturia inaequalis ) Moniliania disease ( Monilinia mali ) Oyster anthracnose ( Gloeosporium kaki ) Peach leaf rot ( Monilinia fructicola ) ( Uncinula necator) Downy mildew ( Plasmopara viticola ) Pear Red scab ( Gymnosporangium asiaticum) Black spot ( Alternaria kikuchiana ) Tea Ring spot ( Pestalotia theae) Anthracnose ( Colletotrichum theae-sinensis ) Citrus scab ( Elisinoe fawcetti ) It can be used to control blue mold ( Pennisillium italicum ), western grass, snow rot, and Sclerotinia borealis .

In recent years, various pathogens have developed resistance to benzimidazole agents, dicarboximide agents and acylalanine agents, resulting in insufficient efficacy of these agents. Is desired. The compound of the present invention is a drug having an excellent bactericidal effect not only on sensitive strains but also on pathogens resistant to benzimidazole agents, dicarboximide agents and acylalanine agents. Diseases more preferably applied include wheat powdery mildew, apple scab, gray mold on cucumber, downy mildew, grape downy mildew 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 contacts such as ship bottoms and fish nets. Also, by mixing the compound of the present invention into paints, fibers, and the like, it can be used as an antibacterial and fungicide for walls and bathtubs, shoes and clothes. Some of the compounds of the present invention exhibit insecticidal, acaricidal and herbicidal activities.

[0087]

[Means for Solving the Problems]

(Bactericide) When the compound of the present invention thus obtained is actually applied, it can be used in a pure form without adding other components, and a form that can be taken by a general pesticide for the purpose of using it as a pesticide, That is, they can be used in the form of wettable powders, granules, powders, emulsions, aqueous solvents, suspensions, flowables and the like. When a solid agent is intended as an additive or carrier, a soybean grain, vegetable powder such as flour, diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite, clay or other mineral fine powder, benzoic acid Organic and inorganic compounds such as soda, urea, and sodium sulfate are used. When a liquid dosage form is intended, petroleum fractions such as kerosene, xylene and solvent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil, vegetable oil, water Is used as a solvent.
In order to obtain a uniform and stable form in these preparations, a surfactant may be added, if necessary.

The wettable powders, emulsions and flowables thus obtained are used by diluting them to a predetermined concentration with water to prepare suspensions or emulsions, and powders and granules are sprayed on plants as they are. Is done. The compound of the present invention exerts a sufficient effect when used alone, but may be used in combination with one or more kinds of various fungicides, insecticides, acaricides, or synergists. Fungicides, insecticides, acaricides, nematicides, and plant growth regulators that can be used by mixing with the compound of the present invention include the following.

Disinfectant: Copper agent: basic copper chloride, basic copper sulfate, etc. Sulfur agent: thiuram, maneb, mancozeb, polycarbamate, propineb, ziram, zineb, etc. Polyhaloalkylthio agent: captan, dichlorfluanide, phor Pets, etc. Organic chlorine agents: chlorothalonil, fthalide, etc. Organic phosphorus agents: IBP, EDDP, tolclofosmethyl,
Pyrazophos, fosetyl, etc. Benzimidazole agents: thiophanate methyl, benomyl, carbendazim, thiabendazole, etc. Dicarboxyimide agents: iprodione, vinclozolin, procymidone, fluoroimide, etc.

Carboxamide agents: oxycarboxin, mepronil, flutranyl, teclophthalam, triclamide, pencyclon, etc. Acylalanine agents: metalaxyl, oxadixyl, furalaxyl, etc. SBI agents: triadimefon, triadimenol, bitertanol, microbutanyl, hexaconazole, propico Nazole, trifumizole, prochloraz, pefurazoate, fenarimol, pyrifenox, triforine, flusilazole, etaconazole, diclobutrazol, fluotrimazole, flutriafen, penconazole, diniconazole, cyproconazole, imazalil, tridemorph, fenpropimorph, butiobate, etc. Antibiotics: polyoxin, blasticidin S, kasugamycin, validamycin, Acid dihydrostreptomycin, etc. Others: propamocarb hydrochloride, quintozene, hydroxy isoxazole, methasulfocarb, Anirajin,
Isoprothiolane, probenazole, quinomethionate, dithianone, dinocab, diclomedine, mepanipyrim, ferimzone, fluazinam, pyroquilon, tricyclazole, oxolinic acid, dithianone, iminoctadine acetate, simoxanil, pyrrolnitrin, metasulfocarb, dietofencaribine, citapfencarburinabine , Dozine, dimethomorph, phenazine oxide, etc.

Insecticides and miticides: Organophosphorus and carbamate insecticides: phenthion, fenitrothion, diazinon, chlorpyrifos, ES
P, bamidothion, fentoate, dimethoate, formotion, marathon, trichlorfon, thiomethon,
Hosmet, dichlorvos, acephate, EPBP,
Methyl parathion, oxydimetone methyl, ethion,
Salithione, cyanophos, isoxathion, pyridafenthion, hosalon, methidathion, sulprophos, chlorfenvinphos, tetrachlorvinphos, dimethylvinphos, propaphos, isofenphos, ethylthiometon, profenophos, pyraclophos, monocrotophos, azinphosmethyl, aldicarb, mesomil, thiodicarb, Carbofuran, carbosulfan, benfracarb, flatiocarb, propoxur, BPMC,
MTMC, MIPC, carbaryl, pirimicarb, ethiophencarb, phenoxycarb and the like.

Pyrethroid insecticides: permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropatrin, pyrethrin, allethrin, tetramethrin, resmethrin, dimethrin, propmethrin, phenothrin, prothrin, fluvalinate, cyfluthrin, cyhalothrin, flucitrinate, ethitol Fenprox, cycloprothrin, trolametrin, silafluofen, brofenprox, acrinasuri, etc. Benzoylurea and other insecticides: diflubenzuron, chlorfluazuron, hexaflumuron, triflumuron, tetrabenzuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyfen, methoprene, cartap, thiocyclam, bensultap, benzoepin, Diafenthiuron, acetamiprid, nitenpyram, imidacloprid, fipronil, nicotine sulfate, rotenone, methaldehyde, machine oil, microbial pesticides such as BT and entomopathogenic viruses, and the like. Nematicides: fenamiphos, phosthiazate and the like. Acaricides: chlorbenzilate, phenisobromolate, dicophor, amitraz, BPPS, benzomate,
Hexitiazox, fenbutatin oxide, polynactin, quinomethionate, CPCBS, tetradiphone, avermectin, milbemectin, clofentezin, cyhexatin, pyridaben, fenpyroximate, tebufenpyrad, pyrimidifen, phenothiocarb, dienochlor and the like. Plant growth regulator: gibberellins (eg gibberellin A
_3, gibberellin A _4, gibberellin A ₇₎ IAA, NA
A.

[0093]

【Example】

[Bactericide] Next, some examples of the composition of the present invention will be described. However, the additives and the addition ratio are not limited to these examples, and can be varied in a wide range. Parts in Formulation Examples are parts by weight.

Example 10 Water-dispersible powder 40 parts of the compound of the present invention 53 parts of diatomaceous earth 4 parts of higher alcohol sulfate ester 3 parts of alkylnaphthalene sulfonate If the above are uniformly mixed and finely pulverized, the active ingredient 40
% Wettable powder.

Example 11 Emulsion 30 parts of the compound of the present invention 33 parts of xylene 30 parts of dimethylformamide 7 parts 7 parts of polyoxyethylene alkyl allyl ether By mixing and dissolving the above, an emulsion having an active ingredient of 30% is obtained.

Example 12 Suspending agent 10 parts of the compound of the present invention 4 parts of sodium ligninsulfonate 4 parts of sodium dodecylbenzenesulfonate 1 part of xanthan gum 0.2 part of water 84.8 parts If wet milled, a 10% active ingredient suspension is obtained.

[0097]

Next, Test Examples show that the compounds of the present invention are useful as effective components of various plant disease controlling agents. The control effect was determined by visually observing the growth of lesions and flora that appeared on leaves, stems and the like at the time of the survey, and calculating the control effect.

Test Example 1 Cucumber Gray Mold Control Test Cucumber cultivated in unglazed pots (variety "Sagami Hanshiro")
An emulsion of the compound of the present invention was sprayed on the seedlings at a concentration of 200 ppm of the active ingredient. After spraying, air-dry at room temperature, a spore suspension (containing glucose and yeast extract) of cucumber gray mold fungus ( Botrytis cinerea ) is inoculated dropwise onto cucumber cotyledons, and a high humidity, constant temperature room (20
C) for 4 days. The lesion diameter on the cotyledon was compared with that of untreated, and the control effect was determined.
% Or more. 1, 2, 3, 4, 6, 8, 11, 22, 26, 27, 3
0, 33, 50, 51, 52, 57, 58, 60, 68 On the other hand, the following control agent A (the compound described in US Pat. No. 4,314,844) showed no control effect.

[0099]

Embedded image

Test Example 2 Wheat Powdery Mildew Control Test Wheat seedlings (variety "Chihoku", cultivated in unglazed pots)
(0.1-1.2 leaf stage), the emulsion of the compound of the present invention was sprayed at a concentration of 200 ppm of the active ingredient. After spraying, air-dry at room temperature, and wheat powdery mildew ( Erysiphe gram)
inia f. sp. tritici ) were shaken off and inoculated and kept in a greenhouse at 22-25 ° C. for 7 days.
The appearance of lesions on the leaves was compared with that of no treatment, and the control effect was determined. As a result, the following compounds showed an excellent control effect of 75% or more. 1, 2, 3, 4, 8, 11, 21, 22, 27, 30,
32, 33, 49, 50, 51, 52, 56, 61, 6
2, 64, 68, 74 On the other hand, the control agent A had no control effect.

Test Example 3 Cucumber downy mildew control test Cucumber cultivated in an unglazed pot (variety "Sagami Hanshiro")
An emulsion of the compound of the present invention was sprayed on the seedlings at a concentration of 200 ppm of the active ingredient. After spraying, air dry naturally at room temperature to remove the cucumber downy mildew ( Pseudoperonospora cu)
a spore suspension of Bensis) was sprayed and inoculated and maintained 4 days in a thermostatic chamber of repeating light and dark and wet and dry every 12 hours (25 ° C.). The appearance of lesions on the leaves was compared with that of no treatment, and the control effect was determined. As a result, the following compounds showed an excellent control effect of 75% or more. 2, 3, 11, 26, 30, 32, 33, 50, 53,
59 On the other hand, the control agent A did not show any control effect.

Test Example 4 Test for Control of Grape Downy Mildew Leaves of leaves of openly planted grapes (variety "Kaiji", 3rd grade) were punched into a 30 mm-diameter disc, and an emulsion of the compound of the present invention, a chemical solution having a concentration of 200 ppm of the active ingredient, were prepared. Dipped. After immersion, air-dry at room temperature, grape downy mildew ( Plasmopar)
a viticola) a zoosporangia suspension is spray inoculation was held for 10 days in a constant temperature chamber under illumination (20 ° C.). The appearance of lesions on the leaves was compared with that of no treatment, and the control effect was determined. As a result, the following compounds showed an excellent control effect of 75% or more. 3, 8, 21, 22, 27, 33, 50, 51, 52,
56, 59, 68, 74 On the other hand, the control agent A did not show any control effect.

Test Example 5 Apple Scab Control Test Apple seedlings (cultivar “Kunimitsu”, 3
~ 4 leaf stage), the emulsion of the compound of the present invention
Sprayed at a concentration of pm. After spraying, air-dry at room temperature and scab of apple ( Venturia inaequali)
The conidia of s ) were inoculated and kept in a high humidity constant temperature room (20 ° C.) where light and dark were repeated every 12 hours for 2 weeks. The appearance of lesions on the leaves was compared with that of no treatment, and the control effect was determined. As a result, the following compounds showed an excellent control effect of 75% or more. 1, 2, 6, 8, 11, 26, 27, 30, 32, 3
3, 50, 56, 59, 74 On the other hand, the control agent A described above did not show any control effect.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shinsuke Sano 345 Takada, Odawara-shi, Kanagawa Japan Nippon Soda Co., Ltd.Odawara Research Institute Co., Ltd.

Claims (2)

[Claims] 1. A compound of the formula [I] Wherein X is a hydrogen atom, a halogen atom, a C _1-6 alkyl group, a C _1-6 haloalkyl group, a C _1-6 alkylthio group, a hydroxy group, a formyl group, a hydroxyiminomethyl group,
C _1-6 alkoxyiminomethyl group, nitro group, C _1-6 alkoxycarbonyl group, phenyl group which may be substituted,
A benzoyl group which may be substituted, a C _1-6 alkoxy group,
C _1-6 alkylcarbonyloxy group, di C _1-6 alkoxymethyl group, hydroxymethyl group, C _1-6 alkylcarbonyloxymethyl group, or (substituted with C _1-6 alkyl group or C _1-6 alkylcarbonyl group May be done)
Represents an amino group. Y and Z each independently represent a hydrogen atom, a C _1-6 alkyl group, a C _1-6 haloalkyl group, a C _3-6
Represents a cycloalkyl group, a halogen atom, a C _1-6 alkoxy group, a C _2-6 alkenyloxy group, a C _1-6 alkylthio group, a C _1-6 alkylcarbonyloxy group or a benzoyloxy group which may be substituted. R represents a hydrogen atom, a metal atom, a C _1-6 alkylcarbonyloxymethyl group, an optionally substituted benzoyloxymethyl group, diC
_1-6 alkylcarbamoyl oxymethyl group, a C _1-6 alkoxycarbonyloxy methyl group or di-C _1-6 alkylcarbamoyl group. However, compounds in which X is hydrogen or bromine and Y, Z and R are all hydrogen are excluded. ] The pyridyl imidazole compound represented by these, or its salt. 2. A compound of the formula [I] (Wherein X, Y, Z and R have the same meanings as described above), which comprises one or more pyridylimidazole compounds represented by the formula (1) as an active ingredient. .