JPH0665208A - New @(3754/24)azolylmethyl)cyclopentanol derivative, its production and use as agrichemical and pharmaceutical - Google Patents

Abstract

PURPOSE:To provide a new (azolylmethyl)cyclopentanol derivative useful as an active component of agrichemicals such as agricultural and horticultural fungicide or pharmaceuticals such as an anti-aromatase agent. CONSTITUTION:The (azolylmethyl)cyclopentanol derivative of formula I (X is halogen, 1-5C alkyl, haloalkyl, phenyl, cyano or nitro; (n) is integer of 0-5; A is CH or N), e.g. 2-(p-chlorobenzyl)-4,4-dimethyl-1-(1H-1,2,4-triazol-1-ylmethyl) cyclopentanol. The compound of formula I can be produced by benzylating a 2-oxocyclopentacarboxylic acid alkyl ester derivative of formula VII with a halide of formula VI (Z<1> is halogen) in the presence of a base to obtain a compound of formula V (R<1> is alkyl), hydrolyzing and decarboxylating the compound, converting the obtained compound of formula IV into an oxaspiroheptane derivative of formula III and reacting the derivative with an azole compound of formula II.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a (azolylmethyl) cyclopentanol derivative which can be used as an active ingredient of agricultural chemicals and pharmaceuticals.

[0002]

[Prior art]

As the (azolylmethyl) cyclopentanol derivative, for example, JP-A-62-149667 discloses a compound represented by the formula (A) of Chemical formula 3 which can be used as an active ingredient of a bactericide (in the formula, Y ² represents a halogen atom, an alkyl group, a haloalkyl group, a phenyl group, a cyano group or a nitro group, which may be the same or different, t is 0 to 5
, Where A is CH or N).

[Chemical 3] Further, Japanese Patent Application Laid-Open No. 1-93574 also describes a compound of formula (B) of formula 4 (in the formula, R ² and R ³ independently represent a hydrogen atom or an alkyl group of C 1 to C 5). Shows,
Y ¹ is a halogen atom, an alkyl group, a haloalkyl group,
A phenyl group, a cyano group or a nitro group, which may be the same or different, m represents an integer of 0 to 2,
A is CH or N).

[Chemical 4]

[0003]

However, the (azolylmethyl) cyclopentanol derivative of the formula (I) of Chemical formula 5 has not been known yet, and its usefulness has not been examined. The present invention has been made for the purpose of establishing a method for producing a (azolylmethyl) cyclopentanol derivative of the formula (I) and clarifying its usefulness. Therefore, an object of the present invention is to provide a novel (azolylmethyl) cyclopentanol derivative, a method for producing the same, and a use thereof. (In the formula, X represents a halogen atom, a C1 to C5 alkyl group, a haloalkyl group, a phenyl group, a cyano group or a nitro group, which may be the same or different, n represents an integer of 0 to 5, A
Indicates CH or N).

[Chemical 5]

[0004]

SUMMARY OF THE INVENTION
In the compound of formula (B) described in 93574, the alkyl group substituted on the cyclopentane ring is bonded to the carbon atom adjacent to the carbon atom bonded to the hydroxyl group and the (azolylmethyl) group (α-position) On the other hand, it becomes another (β position)
The present invention has been completed by finding that the compound bonded to the carbon atom of is useful as an active ingredient of agricultural chemicals and pharmaceuticals.

The present invention has the following structural features. The first invention relates to a (azolylmethyl) cyclopentanol derivative of formula (I) (In the formula, X represents a halogen atom, a C1 to C5 alkyl group, a haloalkyl group, a phenyl group, a cyano group or a nitro group, which may be the same or different, n represents an integer of 0 to 5, A is
CH or N).

[Chemical 6]

The second invention relates to an agricultural and horticultural fungicide containing the (azolylmethyl) cyclopentanol derivative of the formula (I) as an active ingredient. (In the formula, each of X, n and A has the same content as above.)

The present invention will be described in detail below. Expression (I)
The (azolylmethyl) cyclopentanol derivative can be produced as follows. That is, in the reaction formula of Chemical formula 7, a 2-oxocyclopentanecarboxylic acid alkyl ester derivative of the formula (VII) is benzylated with a (unsubstituted or substituted benzyl) halide of the formula (VI) in the presence of a base. , A 1- (unsubstituted or substituted benzyl) -2-oxocyclopentanecarboxylic acid alkyl ester derivative of the formula (V) is obtained. (Hereinafter, this step is referred to as a benzylation reaction.) Then, the compound (V) is hydrolyzed and decarboxylated to give a compound of the formula (I
V) of 2- (unsubstituted or substituted benzyl) cyclopentanone derivative is obtained. (Hereinafter, this step is referred to as hydrolysis / decarboxylation reaction) (In the formula, X and n each have the same meaning as above. R ¹ is C
Shows a ₁ ~ C ₄ alkyl group. Z ¹ represents a halogen atom)

[Chemical 7] Next, as shown in the reaction formula of Chemical formula 8, compound (IV) is reacted with dimethyloxosulfonium methylide or dimethylsulfonium methylide to obtain an oxaspiroheptane derivative of formula (III). (Hereinafter, this step is referred to as an epoxidation reaction.) Then, the compound (III) is reacted with an azole compound of the formula (II) to give the desired product (azolylmethyl) cyclopentanol derivative of the formula (I). Obtainable.
(Hereinafter, this step is referred to as an azole formation reaction) (In the formula, each of X, n, and A has the same content as above)

[Chemical 8]

Examples of the diluent used in the series of reactions in the process for producing the (azolylmethyl) cyclopentanol derivative of the formula (I) of the present invention include the following.
Hydrocarbons such as benzene, toluene, xylene and hexane. Halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride. Alcohols such as methanol and ethanol. Diethyl ether, diisopropyl ether,
Ethers such as tetrahydrofuran and dioxane. In addition, acetonitrile, acetone, dimethylformamide, 1-methyl-2-pyrrolidinone, dimethyl sulfoxide and the like.

In the production method of the present invention, the reaction may be carried out in the presence of a base or an acid in addition to the above-mentioned diluent. Examples of the base used here include the following. Alkali metal carbonates such as sodium carbonate and potassium carbonate. Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. Alkali metal hydrogen compounds such as sodium hydride and potassium hydride. Organometallic compounds of alkali metals such as n-butyllithium. Other organic tertiary amines such as triethylamine and pyridine. Examples of the acid include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid and sulfuric acid, and organic acids such as formic acid, acetic acid, butyric acid and p-toluenesulfonic acid.

(Benzylation reaction) In the reaction formula of Chemical formula 7, the 2-oxocyclopentanecarboxylic acid alkyl ester derivative of the formula (VII) is dissolved in the above diluent to obtain the formula (VI).
Benzylation with (unsubstituted or substituted benzyl) halides in the presence of a base to give 1- (unsubstituted or substituted benzyl) -2-oxocyclopentanecarboxylic acid alkyl ester derivatives of formula (V). The reaction temperature at this time may be any temperature from the freezing point to the boiling point of the diluent, preferably 0 to 100 ° C.

(Hydrolysis / Decarboxylation) The compound (V) thus obtained is hydrolyzed / decarboxylated to give the compound of formula (IV) 2
It can be easily converted to a-(unsubstituted or substituted benzyl) -4,4-dimethylcyclopentanone derivative with a high yield. The hydrolysis / decarboxylation reaction can be carried out under either acidic or basic conditions. When carried out under acidic conditions, it is desirable to use acetic acid as a solvent in addition to water, and an inorganic acid such as hydrochloric acid or hydrobromic acid is used as a catalyst. The reaction temperature at this time is 50 ° C to the reflux point, preferably 80 ° C to the reflux point. When carried out under basic conditions, it is desirable to use lower alcohol and aromatic hydrocarbon together with water.
An alkali metal base, preferably sodium hydroxide or potassium hydroxide, is used as a base. The reaction temperature at this time is 50 ° C to the reflux point, preferably 80 ° C to the reflux point. The reaction time under acidic or basic conditions is in the range of 2 to 24 hours, and it is more preferable to carry out the reaction with stirring.

(Epoxidation reaction) The oxaspiroheptane derivative of the formula (III) is obtained by converting the compound (IV) into, for example, organic synthesis (Org.Syn.) 49, 78 (1968). And Journal of American. It can be produced according to the method described in Chemical Society (J. Amer. Chem. Soc.) 1965, 1353. Dimethyloxosulfonium methylide, or dimethylsulfonium, prepared from a base (for example, sodium hydride) and trimethylsulfoxonium iodide or trimethylsulfonium iodide in the above diluent (in particular, dimethyl sulfoxide is preferred). It is advisable to react the methylide with the compound (IV). The amount of dimethyloxosulfonium methylide or dimethylsulfonium methylide used is preferably 1.0 to 2.0 equivalents of the compound of formula (IV). The reaction temperature at this time is preferably in the range of 25 to 100 ° C. The reaction time is preferably in the range of 1 to 40 hours. After completion of the above reaction,
After cooling the reaction mixture, it was extracted with an organic solvent such as ethyl acetate, chloroform, methylene chloride, benzene, etc. in ice water to separate the organic layer, which was then washed with water and dried, and then the solvent was removed under reduced pressure. The desired compound (II
I can get) The purification treatment can be performed by subjecting it to recrystallization, silica gel column chromatography or the like.

The oxaspiroheptane derivative of the formula (III) thus obtained has a (unsubstituted or substituted benzyl) group and an oxygen atom at the 1-position and 4-position of the 1-oxaspiro [2.4] heptane ring. In the configuration of and, it has two types of three-dimensional structure, cis type and trans type.
Separation of these stereoisomers can be performed, for example, by chromatography (thin layer, column, high performance liquid chromatography, etc.). In addition, the characteristics of these three-dimensional structures can be revealed by, for example, an NMR spectrum.

(Azolization reaction) In order to obtain the (azolylmethyl) cyclopentanol derivative of the formula (I), for example, a solution of the azole compound of the formula (II) in the above-mentioned diluent is added, if necessary, to the above-mentioned compound. In the presence of a base of formula (II
When the oxaspiroheptane derivative of I) is added in an amount of 0.5 to 1.0 equivalent, or conversely, the azole compound of the formula (II) is reacted with a solution of the compound (III) in a diluent in the presence of a base. Good. The reaction temperature at this time may be any temperature from the freezing point to the boiling point of the diluent as a solvent, but is preferably 0 to 140 ° C, more preferably 60 ° C.
Temperatures in the range of ~ 140 ° C. The reaction time is 1 to 10
It is preferable to carry out the reaction with stirring within the range of time. The (azolylmethyl) cyclopentanol derivative of the formula (I) has two types of stereoisomers, a cis type and a trans type derived from the isomer of the compound (III). Further, although there are optical isomers derived from the 1-position and 2-position of the cyclopentane ring, the present invention includes all single isomers and a mixture of each isomer in an arbitrary ratio. Since the compound (I) has an azole ring, it can be used in the form of an inorganic acid salt, an organic acid salt, a metal complex salt or the like.

When the compound of the present invention is used as an active ingredient of agricultural chemicals, it can be used as it is, but usually it is used in various forms such as powders, wettable powders, granules and emulsions together with formulation auxiliary agents. To use. At this time in the formulation,
0.1 to 95% by weight of one or more compounds of the present invention,
It is preferably formulated so as to contain 0.5 to 90% by weight, more preferably 2 to 70% by weight. Examples of carriers, diluents, and surfactants used as formulation aids include solid carriers such as talc, kaolin, bentonite, diatomaceous earth, white carbon, and clay. Liquid diluents include water, xylene, toluene, chlorobenzene, cyclohexane, cyclohexanone, dimethylsulfoxide, dimethylformamide, alcohol and the like. The surfactant should be used properly depending on its effect, and as an emulsifier, polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan monolaurate, etc. As a dispersant, lignin sulfonate, dibutyl naphthalene sulfonate, etc.,
Examples of the wetting agent include alkyl sulfonates and alkyl phenyl sulfonates.

The above-mentioned preparations include those to be used as they are and those to be used after diluting to a predetermined concentration with a diluent such as water. The concentration of the compound of the present invention when diluted and used is 0.001
The range of ~ 1.0% is desirable. The amount of the compound of the present invention used is 20 to 5000 g, and more preferably 50 to 1000 g, per ha of agricultural and horticultural land such as fields, rice fields, orchards and greenhouses. The concentrations and amounts of these substances used vary depending on the dosage form, the time of use, the method of use, the place of use, the target crop, etc., and therefore it is of course possible to increase or decrease without sticking to the above range. Furthermore, the compound of the present invention can be used in combination with other active ingredients such as fungicides, insecticides, acaricides and herbicides.

Next, the case where the compound of the present invention is used as an active ingredient of a medicine will be described. In this case as well, it can be used as it is, but usually, together with the formulation adjuvant, tablets, pills, powders, elixirs, emulsions, solutions,
It is used by formulating it in various forms such as syrup, suspension, spray, ointment, gelatin soft capsule, gelatin hard capsule, suppository, sterile injectable solution and sterile packaged powder.

Suitable carriers or diluents include, for example, lactose, dextrol, sucrose, sorbitol, mannitol, starch, calcium phosphate, calcium silicate, microcrystalline cellulose, polyvinylpyrrolidone, cellulose, polyoxyethylene sorbitan monooleate, Gelatin, syrup, methyl cellulose, methyl oxybenzoate, propyl oxybenzoate, talc,
Mention may be made of magnesium stearate and water. In addition, a lubricant, a wetting agent, an emulsifier, a suspension agent,
Preservatives, sweeteners or flavors may be added.

For oral administration, the compound can be mixed with a carrier and a diluent to give a powder or powder, compressed into tablets, or filled into gelatin capsules. Alternatively, these mixtures may be dissolved in a liquid such as glucose aqueous solution, isotonic saline solution or sterile water, and intravenously administered or injected.

When the compound of the present invention is used as an anti-aromatase agent, the compound is added in an amount of 0.01 to 500 m in the dosage form.
Since it can be used by being contained in an amount of g, more preferably 0.1 to 300 mg, it is preferable to formulate into a dosage unit form. The compound is effective over a wide dosage range. For example, the daily dose is usually 0.005 to 100
It is within the range of mg / kg. When treating an adult human, about 0.1 to 40 mg / kg may be administered in a single dose or in divided doses. However, the actual dose will depend on the age of the individual patient,
The above-mentioned dose range may be exceeded because it is determined by a doctor in light of the severity of symptoms, the route of administration, etc., but this case is also included within the scope of the present invention.

[0021]

EXAMPLES The present invention will be specifically described with reference to Production Examples, Reference Production Examples, Formulation Examples, and Test Examples. The present invention is not limited to the following production examples, formulation examples and test examples as long as the gist thereof is not exceeded. Production Example 1 2- (p-chlorobenzyl) -4,4-dimethyl-1-
(1H-1,2,4-triazol-1-ylmethyl)
To 5 ml of cyclopentanol (I-1) dimethylformamide, 0.2 g of 60% oily sodium hydride was added after washing with dry benzene. Then, with stirring under cooling with water, 0.33 g of 1,2,4-triazole
Was added little by little, and the mixture was further stirred for 1 hour. To this mixture was added 4- (p-chlorobenzyl) -6,6-dimethyl-1-oxaspiro [2.4] heptane (III-1) 1.
0 g was added, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the reaction mixture was poured into ice water, extracted with ethyl acetate, washed with water and dried,
After concentration, the residue was separated and purified by silica gel column chromatography (n-hexane: ethyl acetate = 2: 1), and recrystallized from a mixed solvent of ethyl acetate: hexane (1: 7),
Colorless powdery 2- (p-chlorobenzyl) -4,4-dimethyl-1- (1H-1,2,4-triazole-1-
Ilmethyl) cyclopentanol (I-1) was obtained. Yield 0.2 g (yield 16%) m. p. 85-86 ° C

60 MHz- ¹ H-NMR (CDCl ₃ , ppm, δ) 0.94 (s, 3H, CH ₃ ) 1.10 (s, 3H, CH ₃ ) 1.20-2.30 (m, 5
H) 2.40-2.60 (m, 2H) 3.10 (bs, 1H) 4.09 (bs, 2H) 7.
05 (d, 2H, J = 8Hz) 7.25 (d, 2H, J = 8Hz) 7.90 (s, 1H)
8.04 (s, 1H)

Production Example 2 2- (p-chlorobenzyl) -4,4-dimethyl-1-
(1H-Imidazol-1-ylmethyl) cyclopentanol (I-2) To 5 ml of dimethylformamide, 0.2 g of 60% oily sodium hydride was added after washing with dry benzene. Next, 0.33 g of imidazole was added little by little under stirring with cooling with water, and the mixture was further stirred for 1 hour. To this mixture, 4-
1.0 g of (p-chlorobenzyl) -6,6-dimethyl-1-oxaspiro [2.4] heptane (III-1) was added, and the mixture was reacted at 80 ° C. for 2 hours, allowed to cool and then poured into ice water, and ethyl acetate was added. After extraction with water, washing with water, drying, and concentration, a solid was obtained. This was recrystallized with a mixed solvent of hexane: ethyl acetate (7: 1) to give colorless powdery 2- (p-chlorobenzyl) -4,
4-Dimethyl-1- (1H-imidazol-1-ylmethyl) cyclopentanol (I-2) was obtained. Yield 0.45 g (yield 35%) m. p. 132-133 ° C

60 MHz- ¹ H-NMR (CDCl ₃ , ppm, δ) 0.95 (s, 3H, CH ₃ ) 1.10 (s, 3H, CH ₃ ) 1.30-2.40 (m, 5
H) 2.65 (d, 2H, J = 6Hz) 2.85 (bs, 1H) 3.62 (d, 1H, J =
14Hz) 4.00 (d, 1H, J = 14Hz) 6.90 (bs, 2H) 7.05 (d, 2H,
J = 8Hz) 7.25 (d, 2H, J = 8Hz) 7.42 (bs, 2H)

Reference Production Example 4- (p-chlorobenzyl) -6,6-dimethyl-1-
Production of oxaspiro [2.4] heptane (III-1) Production of 4,4-dimethylcyclohexanone 4,4-Dimethyl-2-cyclohexen-1-one 1
Dissolve 0.0 g in 60 ml of ethanol and add Pd-C (1
0%) 0.4 g was added and catalytic reduction was performed at room temperature and atmospheric pressure.
After the absorption of hydrogen was completed, the catalyst was removed by filtration and the filtrate was concentrated to obtain 4,4-dimethylcyclohexanone as colorless needles. Yield 9.8 g (yield 96%) m.p. p. 37-39 ° C

2,2-Dimethyl adipic acid 80% nitric acid 80 ml was heated to 90 ° C., 0.1 g of ammonium metavanadate as a catalyst was dissolved in this, and while stirring, 25 g of 4,4-dimethylcyclohexanone
Was first added in a small amount, and after confirming generation of brownish-colored nitric oxide (start of reaction), the mixture was cooled and maintained at 50 to 60 ° C., and the rest was gradually added over 1 hour. After the reaction was completed, it was cooled with ice to precipitate crystals. After the crystals were collected by filtration, the filtrate was concentrated under reduced pressure, and the precipitated crystals were collected by filtration. The crystals collected by filtration were combined to obtain 2,2-dimethyladipic acid. Yield 25.5 g (74% yield) m.p. p. 86-88 ° C

2,2-Dimethyl adipic acid dimethyl ester 2,2-Dimethyl adipic acid was esterified in methanol by a conventional method under a sulfuric acid catalyst to obtain 2,2-dimethyl adipic acid dimethyl ester. Yield 63%

2-Methoxycarbonyl-4,4-dimethylcyclopentanone (VII-1) 28% sodium methoxide methanol solution 31.5
g was weighed out, methanol was distilled off under reduced pressure, and the residue (sodium methoxide 8.8 g) contained 2,2-dimethyladipic acid dimethyl ester 30 g and toluene 150.
ml was added and refluxed for 4 hours. Cool the reaction mixture 10%
It was poured into hydrochloric acid, extracted with ethyl acetate, washed with water, dried and concentrated, and the residue was distilled under reduced pressure to give 2-methoxycarbonyl-
4,4-Dimethylcyclopentanone (VII-1) was obtained. Yield 53% b. p. 120-125 ° C / 3mmHg

2- (p-chlorobenzyl) -4,4-
Dimethyl-2- (methoxycarbonyl) cyclopentanone (V-1) 14 g of 2-methoxycarbonyl-4,4-dimethylcyclopentanone (VII-1) was dissolved in 150 ml of toluene, and 60% oily hydrogenation under cooling and stirring. Sodium (3.6
g) washed with dry benzene was added. further,
After adding 14.6 g of p-chlorobenzyl chloride (VI-1) dropwise, the mixture was refluxed for 2 hours. After the reaction was completed, the toluene layer was washed with 10% hydrochloric acid and water, and the toluene was distilled off,
2- (p-chlorobenzyl) -4,4-dimethyl-2-
(Methoxycarbonyl) cyclopentanone (V-1) was obtained. The compound (V-1) was used for the reaction in the unpurified state.

2- (p-chlorobenzyl) -4,4-
Dimethylcyclopentanone (IV-1) 2- (p-chlorobenzyl) -4,4-dimethyl-2-
To (methoxycarbonyl) cyclopentanone (V-1),
A mixed solution of 47% hydrobromic acid and acetic acid (50 ml each) was added, the mixture was refluxed for 2 hours, extracted with ethyl acetate, the solvent was distilled off, and the residue was separated by silica gel column chromatography (hexane: ethyl acetate = 10: 1). 2- (p-chlorobenzyl)-
4,4-Dimethylcyclopentanone (IV-1) was obtained. Yield 8.9g (47% yield)

60 MHz- ¹ H-NMR (CDCl ₃ , ppm, δ) 1.05 (s, 3H, CH ₃ ) 1.17 (s, 3H, CH ₃ ) 1.40-3.33 (m,
7H) 7.07 (d, 2H, J = 8Hz) 7.27 (d, 2H, J = 8Hz)

4- (p-chlorobenzyl) -6,6-
Dimethyl-1-oxaspiro [2.4] heptane (III-
1) Sodium hydride (0.37 g of oily sodium hydride washed with dry benzene) was added to 8 ml of dry dimethyl sulfoxide, and 2.05 g of trimethylsulfoxonium iodide was gradually added at room temperature, followed by stirring for 1 hour. did. 2- (p-chlorobenzyl)-
After adding 2 g of 4,4-dimethylcyclopentanone (IV-1) and stirring at room temperature for 2.5 hours, the reaction solution was poured into ice water,
It was extracted with n-hexane. After washing with water and drying, the solvent was distilled off, and the residue was subjected to silica gel column chromatography (hexane: ethyl acetate = 10: 1) to give 4- (p-chlorobenzyl).
-6,6-Dimethyl-1-oxaspiro [2.4] heptane (III-1) was obtained. Yield 1.15g (yield 57%)

60 MHz- ¹ H-NMR (CDCl ₃ , ppm, δ) 1.05 (s, 3H, CH ₃ ) 1.15 (s, 3H, CH ₃ ) 1.40-1.70 (m, 4
H) 2.30-2.86 (m, 5H) 7.05 (d, 2H, J = 8Hz) 7.20 (d, 2
(H, J = 8Hz)

Formulation Example 1: Dust Part by weight Compound (I-1) 3 Cla 40 talc 57 is ground and mixed and used as a powder.

Formulation Example 2: Wettable powder Part by weight Compound (I-2) 50 Lignin sulfonate 5 Alkyl sulfonate 3 Diatomaceous earth 42 is ground and mixed to obtain a wettable powder, which is diluted with water before use.

Formulation Example 3: Granules (parts by weight) Compound (I-1) 5 Bentonite 43 Cle 45 Lignin sulfonate 7 is evenly mixed, further water is added and kneaded, and the mixture is granulated and dried by an extrusion type granulator. And make granules.

Formulation Example 4: Emulsion parts by weight Compound (I-2) 20 polyoxyethylene alkylallyl ether 10 polyoxyethylene sorbitan monolaurate 3 xylene 67 is uniformly mixed and dissolved to obtain an emulsion.

Test Example 1 Cucumber gray mold control effect test Cucumber leaf (cultivar: Sagamihanjiro) at the time of the first true leaf cultivated in a biscuit pot with a diameter of 10 cm was treated with a wettable powder form as in Formulation Example 2. The product was diluted and suspended with water to a predetermined concentration and sprayed in an amount of 5 ml per pot. After air-drying the sprayed leaves, potato-black
A circular section (4 mm in diameter) of Botrytis cinerea containing agar that had been cultured for 3 days at 20 ° C in Sugar agar was directly attached to the center of the leaf and kept under high humidity conditions at 20-22 ° C. On the third day after the inoculation, the lesion area ratio of cucumber gray mold was investigated, and the control value was calculated by the formula 1. The results are shown in Table 1.

[Formula 1] Control value (%) = (1-lesion area ratio of sprayed area / lesion area ratio of non-dispersed area) × 100

[Table 1]

Test Example 2 Wheat Leaf Rust Control Test A seedling wheat (variety: Norin No. 64, 16 plants / pot) in the second leaf stage cultivated in a biscuit pot with a diameter of 10 cm was hydrated as in Formulation Example 2. The drug formulation is suspended in water by diluting it to the specified concentration, and
It was sprayed in the proportion of pots. After air-drying the sprayed leaves, a suspension of wheat rust disease summer spores collected from scab was spray-inoculated and kept under high humidity conditions at 20-23 ° C for 24 hours. Then, it was managed in a glass greenhouse, and 7 to 10 days after the inoculation, the lesion area ratio of wheat leaf rust was investigated, the control value was calculated by the formula 1, and the results are shown in Table 1.

Test Example 3 Wheat Powdery Mildew Control Effect Test A seedling wheat of the second leaf stage (cultivar: Norin 64, 16 / pot) cultivated in a clay pot with a diameter of 10 cm was prepared as in Formulation Example 2. Water-dispersible powder is diluted and suspended in water to a prescribed concentration, and 5 ml /
It was sprayed in the proportion of pots. The sprayed leaves were air-dried, spray-inoculated with a suspension of wheat powdery mildew spores collected from scab leaves, kept under high humidity at 20 to 24 ° C for 24 hours, and then stored in a greenhouse. On the 9th to 11th days after the inoculation, the lesion area ratio of wheat powdery mildew is investigated, and the control value is calculated by the formula 1,
The results are shown in Table 1.

Test Example 4 Antibacterial test against various pathogens In this example, the compound (I-1) and the compound (I-2) according to the present invention were used.
It shows the results of testing the antibacterial properties against various plant pathogenic fungi. Test method: The compounds of the present invention were each tested at a predetermined concentration (100 pp
m) was dissolved in dimethylsulfoxide, and 0.6 ml of the solution was mixed well with 60 ml of PAS medium at 60 ° C. in a 100 ml Erlenmeyer flask and poured into a petri dish to solidify.
On the other hand, the test bacteria previously cultivated on a plate medium were punched out with a cork borer having a diameter of 4 mm and inoculated on the above drug-containing plate medium. After inoculation, cultivate at a suitable temperature for growth of each bacterium for 1 to 3 days, measure the growth of the bacterium by the fungal diameter, compare it with the growth of the bacterium in the drug-free section, and use the formula 2 to determine the hyphal elongation inhibition rate. I asked.

[Equation 2] R = 100 (dc-dt) / dc (wherein R = hyphal elongation inhibition rate (%) dc = untreated plate diameter of fungal cells dt = drug-treated plate surface diameter of bacteria) Is shown in Table 2 according to the following criteria. Growth inhibition rate 5 Mycelial growth inhibition rate of 100 to 90% or more 4 Mycelial growth inhibition rate of less than 90 to 70% 3 Mycelial growth inhibition rate of less than 70 to 40% 2 Mycelial growth inhibition rate Less than 40 to 20% or more 1 Less than 20% hyphal elongation inhibition rate

[0042]

[Table 2]

The abbreviations in Table 2 indicate the following. Po; Pyricularia oryzae Rice blast fungus Cm; Cochliobolus miyabeanus Rice sesame leaf blight fungus Gf; Gibberella fujikuroi Rice stiletto fungus Hs; Sclerotinia sclerotiorum sclerotiorum fungus Fn; Fusarium oxysporum f.sp.niveum Watermelon creeper fungus Fc; Fusarium oxysporum f.sp.cucumerinum Cucumber cracker fungus Fr; Fusarium oxysporum f.sp. Anthracnose fungus Cb; Cercospora beticola sugar beet leaf spot fungus Vm; Valsa mali Apple rot leaf spot fungus Mf; Disease

[0044]

EFFECT OF THE INVENTION (Azolylmethyl) of Formula (I) of the Present Invention
The cyclopentanol derivative is a novel compound and can be used as an active ingredient of agricultural chemicals and pharmaceuticals.

Claims (2)

[Claims] 1. A (azolylmethyl) cyclopentanol derivative represented by the formula (I) (wherein X is a halogen atom,
C1-C5 alkyl group, haloalkyl group, phenyl group,
A cyano group or a nitro group, which may be the same or different, n represents an integer of 0 to 5, and A represents CH or N). [Chemical 1] 2. A fungicide containing the (azolylmethyl) cyclopentanol derivative of the formula (I) of formula 2 as an active ingredient (wherein X is a halogen atom, a C1 to C5 alkyl group, a haloalkyl group, a phenyl group, A cyano group or a nitro group, which may be the same or different, n is
A represents an integer of 0 to 5 and A represents CH or N). [Chemical 2]