JPH05387B2 - - Google Patents

Description

[Detailed description of the invention]

INDUSTRIAL APPLICATION FIELD The present invention relates to an imidazole carboxylic acid ester derivative, a method for producing the same, and a fungicide containing the derivative as an active ingredient. Prior Art As a compound similar to the imidazole carboxylic acid ester derivative of the present invention, for example, 1-imidazole carboxylic acid benzyl ester is known [see Journal of the Organic Chemistry, 47 (23), 4471-4477]. However, this compound has not been found to have any bactericidal activity. Disclosure of the Invention The imidazole carboxylic acid ester derivative of the present invention is a new compound that has not been described in any literature, and is represented by the following general formula (). [In the formula, R ¹ represents a lower alkyl group, a cycloalkyl group, or an R ³ (CH ₃ ) ₂ C- group (R ³ : halogenomethyl group, acyloxymethyl group, or alkoxycarbonyl group). R ² represents a hydrogen atom, a lower alkyl group or a cycloalkyl group. X is a halogen atom, a lower alkyl group, a cycloalkyl group, a lower alkenyl group, a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group, a lower alkylthio group, a haloalkyl group, a haloalkenyl group,
A phenyl group that may have a substituent, a benzyl group that may have a substituent, a phenoxy group that may have a substituent, a nitro group, a cyano group, -
COR ⁴ groups (R ⁴ : lower alkoxy group, lower alkenyloxy group, benzyloxy group, lower alkylamino group, anilino group) or

[Formula] Group (R ⁵ , R ⁶ : lower alkyl group, acyl group, sulfonyl group,
lower alkoxycarbonyl group). n represents 0 or an integer of 1 to 3. Y and Z are the same or different and represent an oxygen atom or a sulfur atom. a is 0 or 1
shows. b represents 1 or 2. ] In this specification, the lower alkyl group is
For example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl,
tert-butyl, n-pentyl, isopentyl,
Examples include alkyl groups having 1 to 6 carbon atoms such as sec-pentyl, n-hexyl, and isohexyl groups. Examples of the cycloalkyl group include cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, and cyclohexyl groups. Examples of the halogenomethyl group include chloromethyl, bromomethyl, and fluoromethyl groups. Examples of the acyloxymethyl group include acetyloxymethyl, propionyloxymethyl, benzoyloxymethyl, a halogen atom on the phenyl ring, an alkyl group having 1 to 3 carbon atoms, and 1 to 3 carbon atoms.
A benzoyloxymethyl group having a substituent such as an alkoxy group can be mentioned. Examples of lower alkoxycarbonyl groups include alkoxycarbonyl groups in which the alkoxy moiety has 1 to 6 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, and propyloxycarbonyl groups. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, and iodine atom. Examples of the lower alkenyl group include alkenyl groups having 2 to 6 carbon atoms such as vinyl, propenyl, and butenyl groups. Examples of lower alkoxy groups include methoxy,
Ethoxy, n-propyloxy, isopropyloxy, n-butoxy, isobutyloxy, sec-
Examples include alkoxy groups having 1 to 6 carbon atoms such as butyloxy group. Examples of lower alkenyloxy groups include alkenyloxy groups having 2 to 6 carbon atoms, such as vinyloxy, propenyloxy, and butenyloxy groups. Examples of lower alkynyloxy groups include alkynyloxy groups having 2 to 6 carbon atoms such as ethynyloxy, propionyloxy, and butynyloxy groups. As a lower alkylamino group. Examples include mono- and dialkylamino groups having 1 to 6 carbon atoms, such as monomethylamino, monoethylamino, monopropylamino, dimethylamino, diethylamino, and dipropylamino groups. Examples of the acyl group include acetyl, propionyl, benzoyl, and a benzoyl group having a substituent on the phenyl ring such as a halogen atom, an alkyl group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms. . Examples of the sulfonyl group include methylsulfonyl, ethylsulfonyl, benzenesulfonyl, and a benzenesulfonyl group having a substituent on the phenyl ring such as a halogen atom, an alkyl group having 1 to 3 carbon atoms, and an alkoxy group having 1 to 3 carbon atoms. be able to. Examples of lower alkylthio groups include alkylthio groups having 1 to 6 carbon atoms such as methylthio, ethylthio, propylthio, and butylthio groups. Examples of the haloalkyl group include monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl,
1 carbon number substituted with a halogen atom such as 1,2-dichloroethyl, 1,2-dibromoethyl, 1,1,2-trichloroethyl, monofluoroethyl group, etc.
-6 alkyl groups, etc. can be mentioned. Examples of the haloalkenyl group include alkenyl groups having 2 to 6 carbon atoms substituted with halogen atoms, such as 2,2-dichlorovinyl and 2,2-dibromovinyl groups. Examples of the substituent on the phenyl ring of the phenyl group, benzyl group, and phenoxy group include the above-mentioned halogen atom, lower alkyl group, lower alkoxy group, nitro group, and cyano group. The compound of the present invention represented by the above general formula () is a compound useful as a fungicide for agriculture and horticulture, as shown below. The compound of the present invention can be produced by various methods, but is generally easily produced according to the methods shown in Reaction Formula-1 and Reaction Formula-2 below. [In the formula, R ¹ , R ² , X, n, Y, Z, a and b
is the same as above. ] [In the formula, R ¹ , R ² , X, n, Y, Z, a and b
is the same as above. According to Reaction Formula-1, the compound of the present invention is produced by reacting a carbinol derivative represented by the general formula () with an N,N'-carbonyldiimidazole represented by the formula (). .
The reaction is carried out without a solvent or in a suitable solvent. Solvents used here include ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, and dioxane, methylene chloride,
Halogenated hydrocarbons such as chloroform and dichloroethane, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone, and cyclohexanone, aromatic hydrocarbons such as benzene, toluene, and xylene, ethyl acetate, acetonitrile, dimethylformamide, dimethyl sulfoxide, etc. Mixed solvents of these can be mentioned. The ratio of the compound of general formula () and the compound of general formula () to be used is not particularly limited, but the latter is usually about 0.5 to 2 times the molar amount of the former, preferably 0.7 to 1.5 times. It is preferable to use a molar amount. Although the reaction can be carried out either at room temperature or under heating, it usually proceeds suitably between room temperature and around the boiling point of the solvent used, and the reaction time is generally about 1 to 10 hours. According to Reaction Formula-2, the compound of the present invention can be obtained by reacting a carbinol derivative represented by the general formula () with a compound represented by the general formula (), and then reacting the resulting compound represented by the general formula () with the compound represented by the general formula (). Manufactured by reacting imidazole. This series of reactions is carried out without a solvent or in an appropriate solvent. Solvents used here include ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, and dioxane, halogenated hydrocarbons such as methylene chloride, chloroform, dichloroethane, and carbon tetrachloride, and aromatic carbons such as benzene, toluene, and xylene. Examples include hydrogens, ethyl acetate, dimethylformamide, dimethylsulfoxide, pyridine, and mixed solvents thereof. In the reaction between the compound of general formula () and the compound of general formula (), the compound of general formula () is introduced in gaseous or liquid form, or the compound of general formula () dissolved in the above solvent is added dropwise. Good. In the present invention, a compound that generates the general formula () may be used instead of the compound represented by the general formula (). As such a compound, any conventionally known compound can be used as long as it can generate a compound of general formula () under the reaction conditions, such as trichloromethyl chloroformate. The ratio of the compound of general formula () to the compound of general formula () is not particularly limited, but
Usually about 0.5 to 5 times the molar amount of the latter to the former.
Preferably, the amount is about 1 to 3 times the molar amount.
It is preferable that a basic compound be present in the reaction system. As the basic compound, a wide range of conventionally known compounds can be used as long as it can capture the hydrogen chloride produced by the reaction, and examples thereof include triethylamine, tributylamine, dimethylaniline, diethylaniline, and pyridines. The amount of the basic compound to be used is usually about 0.5 to 5 times the molar amount, preferably about 1 to 3 times the molar amount of the compound of general formula (). Although the reaction can be carried out either at room temperature or under cooling, it usually proceeds suitably at -10°C to around room temperature, and the reaction time is generally about 1 to 15 hours. The compound of the general formula () thus produced is subjected to the next reaction with or without isolation. In the reaction between the compound of general formula () produced in the above reaction and imidazole, the ratio of both to be used is not particularly limited, but it is usually about 0.5 to 2 times the molar amount of the latter to the former, preferably. is preferably about 0.7 to 1.5 times the molar amount. It is preferable that a basic compound similar to the above be present in the reaction system of the reaction. The amount of basic compound used is usually based on the compound of general formula ().
The amount is preferably about 0.5 to 2 times the molar amount, preferably about 0.7 to 1.5 times the molar amount. Although the reaction can be carried out either at room temperature or under heating, it usually proceeds suitably between room temperature and around the boiling point of the solvent used, and the reaction time is generally about 1 to 10 hours. In Reaction Schemes-1 and 2 above, the compound of general formula () used as a starting material can be easily produced according to a known method, for example, the method shown in Reaction Scheme-3, 4 or 5 below. [In the formula, R ¹ , X, n, Y and b are the same as above.
X′ represents a halogen atom. ] In Reaction Formula-3, the reaction between the compound of general formula () and the compound of general formula () is carried out in water or an organic solvent. Examples of the solvent used here include ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, and dioxane, halogenated hydrocarbons such as methylene chloride, chloroform, and dichloroethane, and aromatic hydrocarbons such as benzene, toluene, and xylene. , acetone, methyl ethyl ketone, ketones such as cyclohexanone, acetonitrile, dimethylformamide, dimethyl sulfoxide, and the like. The ratio of the compound of general formula () and the compound of general formula () to be used is not particularly limited, but is usually about 0.5 to 2 times the molar amount of the latter to the former.
Preferably, the amount is about equimolar to 1.5 times the molar amount. In this reaction, a base agent is used, or a phenol represented by the general formula () is used in advance as a sodium salt, potassium salt, or the like. Examples of the base agent used include alkali carbonates such as sodium carbonate and potassium carbonate, alkali hydroxides such as sodium hydroxide and potassium hydroxide, sodium metal, sodium methylate, and sodium hydride. The reaction temperature for this reaction is usually about 50 to 150°C, and the reaction is generally completed in about 5 to 15 hours. In Reaction Formula-3, various methods such as a catalytic reduction method and a method using a reducing agent can be applied to the reaction of reducing the compound of general formula () to obtain the compound of general formula (a). For example, when applying a catalytic reduction method, hydrogenation may be carried out using a noble metal, a noble metal oxide, or a Raney type catalyst in an alcohol such as methanol or ethanol, or a solvent such as acetonitrile. Among these catalysts, platinum, platinum oxide, and nickel are particularly preferred. The reaction temperature for this reaction can be appropriately selected within a wide range, but
The temperature is preferably about 50 DEG C., and the reaction can be carried out either under normal pressure or under increased pressure. Furthermore, when applying a method using a reducing agent, aluminum isopropylate, sodium borohydride, etc. are used as the catalyst, and alcohols such as methanol and ethanol, and ethers such as diethyl ether and tetrahydrofuran are used as the solvent. used. The amount of the above catalyst to be used is usually about 0.1 to 2 times the molar amount of the compound of general formula (),
Preferably, the amount is about 0.5 to 1.5 times the molar amount. The reaction temperature of this reaction is usually within the range of 0 to 1100°C. [In the formula, R ¹ , R ² , X, Y, n, a and b are the same as above. X′ is a halogen atom, and R ³ is the same as R ¹ or represents a lower alkoxy group. ] The reactions shown in Reaction Formulas 4 and 5 are general Grignard reactions, and are carried out, for example, in an ether solvent such as diethyl ether, dibutyl ether, or tetrahydrofuran. In the reaction between the halides represented by the general formulas () and () and magnesium, the ratio of the two used is not particularly limited, but the ratio of the latter to the former is usually 0.5 to 1.5.
The amount is preferably about twice the molar amount, preferably about 0.8 to 1.2 times the molar amount. This reaction proceeds suitably at 0°C to around the boiling point of the solvent, and the reaction time is generally about 1 to 10 hours. The Grignard reagent thus produced is subsequently converted to the general formula (), () without isolation.
) is reacted with aldehyde, ketone, or carboxylic acid ester derivatives. General formula (),
The usage amount of the compound represented by () is as follows:
Usually about 0.1 to 3 times the molar amount of the halide represented by the general formula () or (), preferably
The amount is preferably about 0.5 to 2.5 times the molar amount. This reaction proceeds suitably at around 0 to 50°C, and the reaction time is generally about 0.5 to 3 hours. The compound of the present invention obtained by the above method can be easily isolated and purified from the reaction mixture by conventional separation methods such as solvent extraction, solvent dilution, recrystallization, column chromatography, etc. Compounds of the invention can be produced in high purity. The compounds of the present invention are characterized by having strong fungicidal activity and a wide spectrum of activity, such as powdery mildew, scab, smut, botrytis, anthracnose, rice blast, sesame leaf blight, Demonstrates excellent bactericidal activity against various pathogens such as blight. Furthermore, the compounds of the present invention do not cause any harm to crops at concentrations necessary to control the above-mentioned pathogens, and also have low toxicity to warm-blooded animals. Therefore, the compound of the present invention can be effectively used for controlling diseases of agricultural crops such as various vegetables, fruit trees, rice, and mulberry. When applying the compound of the present invention as a fungicide, the compound of the present invention may be used as it is, but it is generally used in combination with an adjuvant commonly used in the formulation of agricultural chemicals. The dosage form is not particularly limited, but powder, emulsion, wettable powder, flowable and granule forms are suitable. As the auxiliary agent, a wide range of those commonly used in this field can be used, including fillers such as diatomaceous earth, kaolin, clay, bentonite, white carbon, and talc, polyoxyethylene alkyl ether, and polyoxyethylene alkyl phenyl ether. , surfactants such as polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, sodium alkylbenzene sulfonate, sodium lignin sulfonate, sodium alkyl sulfate, sodium polyoxyethylene alkyl sulfate, salt of naphthalene sulfonic acid formalin condensate,
Examples include organic solvents such as benzene, toluene, xylene, acetone, cyclohexanone, methanol, ethanol, isopropyl alcohol, dioxane, dimethylformamide, dimethyl sulfoxide, and carbon tetrachloride. The amount of the compound of the present invention to be incorporated into the fungicide of the present invention is not particularly limited, but the active ingredient is usually about 0.1 to 90% by weight, preferably 1 to 70% by weight.
It is preferable to add the above-mentioned auxiliary agents appropriately so as to achieve the desired level. When using the fungicide of the present invention, the fungicide of the present invention may be sprayed as is without being diluted, or may be diluted approximately 500 to 10,000 times and sprayed. The appropriate amount for application varies depending on the drug formulation, method of application, timing of application, type of target disease, etc., but it cannot be stated unconditionally, but the amount of active ingredient is usually 5 to 200 g/10
It is best to spray it so that the amount is about 100 g. Examples Reference examples, examples, formulation examples, and test examples are listed below to further clarify the present invention. Reference Example 1 Production of 1-(p-chlorophenoxy)-3,3-dimethyl-2-butanone In a 200 ml eggplant flask, 12.8 g of p-chlorophenol and 1-chloro-3,3-dimethyl-2-
13.4 g of butanone, 13.8 g of anhydrous potassium carbonate, and 100 ml of acetonitrile were charged, and the mixture was refluxed for 8 hours.
After removing potassium chloride from the reaction mixture by filtration, the liquid was concentrated under reduced pressure to obtain crude crystals. The crude crystals were recrystallized from n-hexane to obtain 16.0 g of the above target compound. Melting point 62-63℃ Reference Example 2 Production of 1-(p-chlorophenoxy)-3,3-dimethyl-2-butanol In a 200 ml eggplant flask, add 1-(p-chlorophenoxy-3,3-dimethyl- 2-butanone 9.0g
and 80 ml of methanol were charged, and 0.8 g of sodium borohydride was added while stirring while cooling. After stirring at room temperature for 1 hour, the reaction mixture was concentrated under reduced pressure, and the resulting residue was added with 50 ml of water and extracted twice with 30 ml of ether. The combined ether extracts were washed with saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain 8.5 g of the desired above compound. Ta. Reference Example 3 Production of 1-(p-chlorophenyl)-3,3-dimethyl-2-butanol 4.3 g (0.05 mol) of pivalaldehyde was added to a solution of p-chlorobenzylmagnesium chloride (0.055 mol) in 100 ml of ether under cooling and stirring. 10 ml of an ether solution of ) was added dropwise. After the addition, the reaction solution was stirred at room temperature for 1 hour, and then poured into a 5% aqueous hydrochloric acid solution containing ice chips. After separating the oil layer, the aqueous layer was extracted with ether and combined with the oil layer, washed with saturated brine, and dried over anhydrous magnesium sulfate. The above compound 10.5 becomes a white solid after distilling off the solvent.
I got g. Reference Example 4 Production of 1-(p-chlorophenoxy)-3,3-dimethyl-4-chloro-2-butanone In a 100 ml eggplant flask, add 1-(p-chlorophenoxy-3,3-dimethyl-4). -Hydroxy-2
-Butanone 2.4g, triphenylphosphine 2.6
g and 50 ml of carbon tetrachloride were added, and the mixture was refluxed for 18 hours. After cooling the reaction mixture and removing the precipitated crystals by filtration, the liquid was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain 1.8 g of the above-mentioned target compound.
I got it. Reference Example 5 Production of 1-(p-chlorophenoxy)-3,3-dimethyl-4-chloro-2-butanol 1-(p-chlorophenoxy-3,3-dimethyl-4 2.6 g of -chloro-2-butanone and 40 ml of methanol were charged, and 0.2 g of sodium borohydride was added while stirring while cooling.
After stirring at room temperature for 1 hour, the reaction mixture was concentrated under reduced pressure, and the resulting residue was added with 50 ml of water and extracted twice with 30 ml of ether. The combined ether extracts were washed with saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 2.3 g of the above-mentioned target compound. Reference Example 6 Production of 1-(p-chlorophenylthio)-3,3-dimethyl-2-butanone Put 14.45 g of p-chlorothiophenol and 13.8 g of anhydrous potassium carbonate into 200 ml of acetonitrile,
While stirring, add 1-chloro-3,3-dimethyl-
13.45 g of 2-butanone was added in small portions. The reaction mixture was stirred at 70-75°C for 6 hours, and then the precipitate was separated. Concentrate the liquid, extract the residue with benzene, and add 10% sodium hydroxide solution.
Add 200ml and stir at room temperature for 1 hour. The benzene layer was separated, washed with water, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to obtain 20.2 g of the target compound as a pale yellow oil. Reference Example 7 Production of 1-(p-chlorophenylthio)-3,3-dimethyl-2-butanol Dissolve 2.43 g of 1-(p-chlorophenylthio)-3,3-dimethyl-2-butanol in 50 ml of methanol. did. While stirring, 0.4 g of sodium borohydride was added little by little at a temperature below 10°C.
After adding the entire amount and stirring at room temperature for 30 minutes, methanol was removed under reduced pressure. The residue was extracted with ether, washed with water, and then dried over anhydrous magnesium sulfate. The above target compound is obtained as a yellowish oil by distilling off the solvent.
2.4g was obtained. Reference example 8 1-(p-chlorophenoxy)-2-methyl-2
-Production of propanol Ethyl p-chlorophenoxyacetate in 100 ml of an ether solution of 24 g of methylmagnesium bromide
A solution of 10.7 g in ether (30 ml) was added dropwise while stirring at a temperature below 10°C. After the dropwise addition, the reaction solution was stirred at room temperature for 1 hour, and then poured into a 10% aqueous hydrochloric acid solution under ice cooling. The oil layer was extracted with ether, washed with saturated brine, and dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 8.9 g of the target compound as a colorless oil. Reference Example 9 Production of 1-(p-chlorophenoxy)-2,3-dimethyl-2-butanol 10.6 g of p-chlorophenoxy isopropyl ketone in ether was added to 50 ml of an ether solution of 12 g of methylmagnesium bromide while stirring at 10°C or below. 30 ml of the solution was added dropwise little by little. After dropping, the reaction solution was stirred at room temperature for 1 hour, and then added to a 10% aqueous hydrochloric acid solution under ice cooling.
Pour into 100ml. The ether layer was separated, washed with saturated brine, and then dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 9.1 g of the target compound as a pale yellow oil. Example 1 Production of imidazole-1-carboxylic acid 1'-(m-chlorophenoxy)-3',3'-dimethyl-2'-butyl ester In a 100 ml eggplant flask, 1-(m-chlorophenoxy) )-3,3-dimethyl-2-butanol
1.6 g of carbonylimidazole, 1.4 g of carbonylimidazole, and 40 ml of ethyl acetate were charged, and the mixture was refluxed for 3 hours. The reaction mixture was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain 1.6 g of the desired above-mentioned compound. Melting point 67-68℃ Elemental analysis value (as C ₁₆ H ₁₉ N ₂ O ₃ Cl) C H N Calculated value (%) 59.54 5.93 8.68 Actual value (%) 59.01 5.88 8.81 NMR spectrum (CDCl ₃ ) δppm: 1.10 (9H ), 4.10 (2H), 5.15 (1H), 6.50~7.10
(5H), 7.25 (1H), 7.98 (1H) The compounds obtained from the above results are: It was confirmed that Example 2 Production of imidazole-1-carboxylic acid 1'-(o-chlorophenoxy)-3',3'-dimethyl-2'-butyl ester In a 100 ml four-necked flask, 1-(o-chlorophenoxy) 2.3 g of (enoxy)-3,3-dimethyl-2-butanol, 0.81 ml of pyridine, and 50 ml of ethyl acetate were charged, and 0.6 ml of trichloromethyl chloroformate was added dropwise while stirring while cooling. After the addition was completed, at room temperature.
Stirred for 15 hours. Cool again and imidazole 0.7
g and 0.81 ml of pyridine were added thereto, and the mixture was refluxed at room temperature for 30 minutes and then for a further 3 hours. The reaction mixture was washed with water and saturated brine, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain 1.5 g of the desired above compound. . Melting point 123-124℃ Elemental analysis value (as C ₁₆ H ₁₉ N ₂ O ₃ Cl) C H N Calculated value (%) 59.54 5.93 8.68 Actual value (%) 58.98 5.90 8.75 NMR spectrum (CDCl ₃ ) δppm: 1.10 (9H ), 4.10 (2H), 5.17 (1H), 6.60~7.20
(5H), 7.28 (1H), 8.00 (1H) The compounds obtained from the above results are: It was confirmed that Examples 3 to 69 The compounds shown in Table 1 below were obtained in the same manner as in Example 1 or 2 using appropriate starting materials.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

[Table] Example 70 Production of imidazole-1-carboxylic acid 1'-(p-chlorophenyl)-3',3'-dimethyl-2'-butyl ester 1-(p-chlorophenyl)-3,3-dimethyl- 2.14 g of 2-butanol and 0.78 g of pyridine were placed in 30 ml of ethyl acetate and cooled to below 10°C. Into this trichloromethyl chloroformate 0.6
ml was added dropwise little by little under stirring. After stirring this mixture at room temperature for 1 hour, 0.68 g of imidazole and 0.78 g of pyridine were added thereto, and the mixture was heated at 70 to 80° C. for 2 hours. The mixture was then cooled to room temperature, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 2.9 g of the above target compound. Melting point 121.5-122℃ Elemental analysis value (as C ₁₆ H ₁₉ N ₂ ClO ₂ ) C H N Calculated value (%) 62.72 6.26 9.15 Actual value (%) 62.60 6.23 9.22 NMR spectrum (CDCl ₃ ) δppm: 1.06 (s, 9H), 2.9 (m, 2H), 5.0 (m, 1H),
6.9 (m, 1H), 6.9-7.1 (m, 4H), 7.2 (m,
1H), 7.9 (m, 1H) The compound obtained from the above results is It was confirmed that Example 71 Production of imidazole-1-carboxylic acid 1'-(p-chlorophenyl)-2'-cyclohexylethyl ester 2.40 g of 1-(p-chlorophenyl)-2-cyclohexylethanol and 2.0 g of N,N-carbonyldiimidazole was added to 30 ml of ethyl acetate and refluxed for 3 hours while stirring. The reaction solution was then cooled to room temperature, washed twice with water, and then dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 3.3 g of the above-mentioned target compound. Melting point 80.5-81℃ Elemental analysis value (as C ₁₈ H ₂₁ N ₂ ClO ₂ ) C H N Calculated value (%) 65.03 6.37 8.43 Actual value (%) 65.21 6.32 8.50 NMR spectrum (CDCl ₃ ) δppm: 0.7-2.0 ( m, 11H), 2.9 (m, 2H), 5.0 (m,
1H), 6.9 (m, 1H), 6.7-7.2 (m, 4H), 7.2
(m, 1H), 7.9 (m, 1H) The compound obtained from the above results is It was confirmed that Examples 72-101 The compounds shown in Table 2 below were obtained in the same manner as in Example 70 or 71 using appropriate starting materials.

【table】

【table】

【table】

[Table] Example 101 Production of imidazole-1-carboxylic acid 1'-(p-chlorophenoxy)-3',3'-dimethyl-4'-chloro-2'-butyl ester In a 100 ml eggplant flask, 1-(p-chlorophenoxy)-3,3-dimethyl-4-chloro-2
-Butanol 2.6g, carbonyldiimidazole
1.8 g and 40 ml of ethyl acetate were charged, and the mixture was refluxed for 3 hours. The reaction mixture was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain 2.1 g of the desired above-mentioned compound. Melting point 65.7℃ Elemental analysis value (as C ₁₆ H ₁₈ N ₂ O ₃ Cl ₂ ) C H N Calculated value (%) 53.80 5.08 7.84 Actual value (%) 53.62 5.14 7.76 NMR spectrum (CDCl ₃ ) δppm: 1.20 (6H) , 3.45 (2H), 4.15 (2H), 5.40 (1H),
6.65 (2H), 6.90 (1H), 7.05 (2H), 7.30 (1H),
8.00 (1H) The compound obtained from the above results is It was confirmed that Example 102 Production of imidazole-1-carboxylic acid 1'-(p-ethylphenoxy)-3',3'-dimethyl-4'-bromo-2'-butyl ester In a 100 ml four-necked flask, add 1-( p-ethylphenoxy)-3,3-dimethyl-4-bromo-
3.0 g of 2-butanol, 0.81 g of pyridine and 50 ml of ethyl acetate were charged, and 0.6 ml of trichloromethyl chloroformate was added dropwise while stirring while cooling. After the dropwise addition was completed, the mixture was stirred at room temperature for 18 hours. After cooling again, 0.7 g of imidazole and 0.81 ml of pyridine were added, and after stirring at room temperature for 30 minutes, the mixture was further refluxed for 3 hours. The reaction mixture was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 3.0 g of the above-mentioned target compound. Melting point 47.1℃ Elemental analysis value (as C ₁₈ H ₂₃ N ₂ O ₃ Br) C H N Calculated value (%) 54.69 5.86 7.09 Actual value (%) 54.58 5.92 7.01 NMR spectrum (CDCl ₃ ) δppm: 1.15 (3H), 1.20 (6H), 2.53 (2H), 3.35 (2H),
4.12 (2H), 5.40 (1H), 6.65 (2H), 6.90 (3H),
7.30 (1H), 8.00 (1H) The compounds obtained from the above results are It was confirmed that Examples 103 to 111 The compounds shown in Table 3 below were obtained in the same manner as in Example 101 or 102 using appropriate starting materials.

【table】

【table】

[Table] Example 112 Imidazole-1-thiocarboxylic acid 1'-(p-
Production of chlorophenoxy)-3',3'-dimethyl-2'-butyl ester In a 100 ml four-headed flask, add 2.3 g of 1-(p-chlorophenoxy)-3,3-dimethyl-2-butanol.
g, 0.81 ml of pyridine and 50 ml of ethyl acetate were charged, and 0.77 ml of thiophosgene was added dropwise while stirring in an ice bath. After stirring at room temperature for 18 hours, imidazole
0.7 g and 0.81 ml of pyridine were added, and the mixture was refluxed for 3 hours.
The reaction mixture was washed with water and saturated brine, dried over magnesium sulfate, concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain 1.5 g of the desired compound. Properties: Oil elemental analysis value (as C ₁₆ H ₁₉ N ₂ O ₂ SCl) C H N Calculated value (%) 56.71 5.65 8.27 Actual value (%) 56.43 5.88 8.10 NMR spectrum (CDCl ₃ ) δppm: 1.10 (9H) , 4.14 (2H), 5.72 (1H), 6.60 (2H),
6.88 (1H), 7.04 (2H), 7.45 (1H), 8.18 (1H) The compounds obtained from the above results are It was confirmed that Example 113 Imidazole-1-thiocarboxylic acid 1'-(p
-ethylphenoxy)-3',3'-dimethyl-2'-
Production of butyl ester In a 100 ml four-headed flask, add 2.2 liters of 1-(p-ethylphenoxy)-3,3-dimethyl-2-butanol.
g, 0.81 ml of pyridine and 50 ml of ethyl acetate were charged, and 0.77 ml of thiophosgene was added dropwise while stirring in an ice bath. After stirring at room temperature for 18 hours, imidazole
0.7 g and 0.81 ml of pyridine were added, and the mixture was refluxed for 3 hours.
The reaction mixture was washed with water and saturated brine, dried over magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to obtain 1.3 g of the desired above-mentioned compound. Properties: Oil elemental analysis value (as C ₁₈ H ₂₄ N ₂ O ₂ S) C H N Calculated value (%) 65.03 7.28 8.43 Actual value (%) 64.97 7.34 8.31 NMR spectrum (CDCl ₃ ) δppm: 1.10 (9H) , 1.16 (3H), 2.52 (2H), 4.18 (2H),
5.72 (1H), 6.60 (2H), 6.85 (1H), 6.92 (1H),
7.45 (1H), 8.15 (1H) The compounds obtained from the above results are It was confirmed that Example 114 Imidazole-1-thiocarboxylic acid 1'-(p
-Chlorophenyl)-4',4'-dimethyl-3'-amyl ester In a 100 ml four-necked flask, 2.3 g of 1-(p-chlorophenyl)-4,4-dimethyl-3-amyl alcohol, 0.81 g of pyridine ml and ethyl acetate 50ml
was charged, and 0.77 ml of thiophosgene was added dropwise while stirring while cooling. After the dropwise addition was completed, the mixture was stirred at room temperature for 18 hours. After cooling again, 0.7 g of imidazole and 0.81 ml of pyridine were added, and the mixture was refluxed at room temperature for 30 minutes and then for a further 3 hours. The reaction mixture was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to obtain 1.1 g of the target compound. Melting point: 66.5℃ Elemental analysis value (as C ₁₇ H ₂₁ N ₂ OSCl) C H N Calculated value (%) 60.61 6.28 8.32 Actual value (%) 60.42 6.35 8.28 NMR spectrum (CDCl ₃ ) δppm: 0.98 (9H), 2.05 (2H), 2.62 (2H), 5.55 (1H),
6.92 (1H), 7.00 (4H), 7.48 (1H), 8.20 (1H) The compounds obtained from the above results are It was confirmed that Example 115 Imidazole-1-thiocarboxylic acid 1'-(p
-Chlorophenyl)-3',3'-dimethyl-2'-butyl ester In a 100 ml four-necked flask, 2.1 g of 1-(p-chlorophenyl)-3,3-dimethyl-2-butyl alcohol, 0.81 g of pyridine ml and ethyl acetate 50ml
was charged, and 0.77 ml of thiophosgene was added dropwise while stirring while cooling. After the dropwise addition was completed, the mixture was stirred at room temperature for 18 hours. After cooling again, 0.7 g of imidazole and 0.81 ml of pyridine were added, and the mixture was refluxed at room temperature for 30 minutes and then for a further 3 hours. The reaction mixture was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography to obtain 1.2 g of the target compound. Melting point: 86.8℃ Elemental analysis value (as C ₁₆ H ₁₉ N ₂ OSCl) C H N Calculated value (%) 59.52 5.93 8.68 Actual value (%) 59.31 6.01 8.73 NMR spectrum (CDCl ₃ ) δppm: 1.10 (9H), 2.92 (2H), 5.65 (1H), 6.88 (1H),
7.00 (4H), 7.40 (1H), 8.12 (1H) The compounds obtained from the above results are It was confirmed that Examples 116-132 The compounds shown in Table 4 below were obtained in the same manner as Examples 112-115 using appropriate starting materials.

【table】

【table】

[Table] Example 133 Production of imidazole-1-carboxylic acid 1'-(p-chlorophenylthio)-3',3'-dimethyl-2'-butyl ester 1-(p-chlorophenylthio)-3 , 2.4 g of 3-dimethyl-2-butanol and 2.0 g of N,N-carbonyldiimidazole were added to 30 ml of ethyl acetate and stirred under reflux for 3 hours. After cooling to room temperature, it was washed twice with water and dried over anhydrous magnesium sulfate. After evaporating the solvent, the residue was purified by silica gel column chromatography (developing solvent: benzene:ethyl acetate = 5:1) to obtain 2.9 g of the desired compound as a pale yellow oil. Elemental analysis value (as C ₁₆ H ₁₉ N ₂ SO ₂ Cl) C H N Actual value (%) 56.89 5.64 8.30 Calculated value (%) 56.71 5.65 8.27 NMR spectrum (CDCl ₃ ) δppm: 0.92 (9H), 3.62 (2H) ), 4.92 (1H), 6.62~7.30
(6H), 7.90 (1H) The compound obtained from the above results is It was confirmed that Example 134 Preparation of imidazole-1-carboxylic acid 1'-(o-chlorophenylthio)-3',3'-dimethyl-2'-butyl ester 1-(o-chlorophenylthio)-3,3-dimethyl 2.4 g of -2-butanol and 0.8 g of pyridine were dissolved in 30 ml of ethyl acetate, and 0.6 ml of trichloromethyl chloroformate was added dropwise little by little while cooling to below 10°C. After the addition, the mixture was stirred at room temperature for 2 hours. Next, 0.8 g of pyridine and 0.7 g of imidazole were added, and the mixture was further stirred under reflux for 3 hours. After the reaction was completed, the reaction solution was washed with water, dried, and concentrated. The residue was purified by silica gel column chromatography (developing solvent: benzene:ethyl acetate=5:1) to obtain 2.8 g of the desired compound as a pale yellow oil. Elemental analysis value (as C ₁₆ H ₁₉ N ₂ SO ₂ Cl) C H N Actual value (%) 56.82 5.63 8.29 Calculated value (%) 56.71 5.65 8.27 NMR spectrum (CDCl ₃ ) δppm: 0.91 (9H), 3.65 (2H) ), 5.01 (1H), 6.5~7.3
(6H), 7.90 (1H) The compound obtained from the above results is It was confirmed that Examples 135-149 The compounds shown in Table 5 below were obtained in the same manner as in Example 133 or 134 using appropriate starting materials.

【table】

【table】

[Table] Example 150 Production of imidazole-1-carboxylic acid 1'-(p-chlorophenoxy)-2'-methyl-2'-propyl ester 1-(p-chlorophenoxy)-2-methyl-2
2.0 g of -propanol and 2.0 g of N,N-carbonyldiimidazole were added to 30 ml of ethyl acetate and stirred under reflux for 3 hours. After cooling to room temperature,
It was washed twice with water and finally dried over anhydrous magnesium sulfate. After evaporating the solvent, the residue was purified by silica gel column chromatography (developing solvent: benzene:ethyl acetate = 5:1) to obtain 2.4 g of the desired compound as a pale yellow oil. Elemental analysis value (as C ₁₄ H ₁₅ N ₂ O ₃ Cl) C H N Actual value (%) 59.224 5.278 9.921 Calculated value (%) 59.056 5.310 9.838 NMR spectrum (CDCl ₃ ) δppm: 1.62 (6H), 4.10 (2H) ), 6.60~7.22 (6H), 7.88
(1H) The compound obtained from the above results is It was confirmed that Example 151 Production of imidazole-1-carboxylic acid 1'-(p-chlorophenoxy)-2',3'-dimethyl-2'-butyl ester 1-(p-chlorophenoxy)-2,3-dimethyl-2-butanol 2.9 g and 0.8 g of pyridine were placed in 30 ml of ethyl acetate and stirred at below 10°C. 0.6 ml of trichloromethylformate was dropped little by little into this, and after the dropwise addition, the reaction mixture was stirred at room temperature for 2 hours. Next, 0.8 g of pyridine and 0.7 g of imidazole were added, and the mixture was refluxed with stirring for an additional 3 hours, cooled to room temperature, washed with water, and dried over anhydrous magnesium sulfate. After distilling off the solvent, the residue was subjected to silica gel column chromatography (developing solvent;
The product was purified with benzene:ethyl acetate=5:1) to obtain 2.8 g of the desired compound as a pale yellow oil. Elemental analysis value (as C ₁₆ H ₁₉ N ₂ O ₃ Cl) C H N Actual value (%) 59.712 5.892 8.704 Calculated value (%) 59.536 5.933 8.678 NMR spectrum (CDCl ₃ ) δppm: 1.20 (6H), 1.62 (3H) ), 2.40 (1H), 4.18 (2H),
6.60-7.30 (6H), 7.90 (1H) The compounds obtained from the above results are It was confirmed that Examples 152 to 178 The compounds shown in Table 6 below were obtained in the same manner as in Example 150 or 151 using appropriate starting materials.

【table】

【table】

【table】

[Table] Formulation example 1 (25% hydrating agent) Formulation Parts by weight Compound of the present invention 25 White carbon 45 Diatomaceous earth 16 Higher alcohol sodium sulfate 2 β-Naphthalene sulfonic acid formalin Sodium salt of condensate 2 Alkylphenylphenol sulfate 10 100 The above various components were thoroughly mixed using a mixer and then finely ground using a pulverizer to obtain a 25% wettable powder. Formulation Example 2 (20% emulsion) Formulation Parts by weight Compound of the present invention 20 Polyoxyethylene styryl phenyl ether 8 Sodium dodecylbenzenesulfonate 4 Xylene 68 100 The above various components were mixed and stirred to obtain a 20% emulsion. Test example 1 Control effect on powdery mildew of cucumber (Powdery mildew) Example 1 of compounding on young cucumber seedlings (variety: Natsuaki Setsei No. 2, 2nd to 3rd leaf stage) planted in pots (7.5cm, 200ml volume)
A diluted solution of the wettable powder prepared in step 1 was sprayed at a predetermined concentration.
After air-drying, the cucumber powdery mildew fungus (Sphaerotheca
fuliginea) was inoculated by spraying. Two weeks later, the lesion area ratio was measured, and the control value was calculated from the following formula. The presence or absence of drug damage was also investigated. The results are shown in Table 7.

【table】

【table】

【table】

[Table] Test example 2 Control effect on gray mold of cucumbers Mixing example 1 with young cucumber seedlings (variety: Natsuaki Setsei No. 2, 2nd to 3rd leaf stage) planted in pots (7.5cm, 200ml capacity)
A diluted solution of the wettable powder prepared in step 1 was sprayed at a predetermined concentration.
After air-drying, Botrytis
cinerea) was inoculated by spraying. 7 days later,
The lesion area ratio was measured, and the control value was calculated in the same manner as in Test Example 1. The presence or absence of drug damage was also investigated. The results are shown in Table 8.

【table】

【table】

【table】

【table】

[Table] Test Example 3 Therapeutic effect on rice blast (Rice blast) A spore suspension of rice blast fungus (Pyricularia oryzae) was applied to rice seedlings (variety: Nipponbare, 4-leaf stage) planted in pots (7.5 cm, 200 ml). Spray inoculated. After 24 hours, the diluted emulsion prepared in Formulation Example 2 was sprayed at a predetermined concentration. After 7 days, the lesion area ratio was measured, and the control value was calculated in the same manner as in Test Example 1. The presence or absence of drug damage was also investigated. The results are shown in Table 9.

【table】

【table】

【table】

[Table] Test example 4 Rice sesame leaf blight (Helminthospotium
Control effect on rice seedlings (variety: Nipponbare, 5-leaf stage) planted in pots (7.5 cm, 200 ml) with a diluted solution of the emulsion prepared in Formulation Example 2 at a predetermined concentration. After air-drying, a spore suspension of Cochliobolus miyabeanus was spray inoculated. After 7 days, the lesion area ratio was measured, and the control value was calculated in the same manner as in Test Example 1.
The presence or absence of drug damage was also investigated. The results are shown in Table 10.

【table】

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1. General formula [In the formula, R ¹ represents a lower alkyl group, a cycloalkyl group, or an R ³ (CH ₃ ) ₂ C- group (R ³ : halogenomethyl group, acyloxymethyl group, or alkoxycarbonyl group). R ² represents a hydrogen atom, a lower alkyl group or a cycloalkyl group. X is a halogen atom, a lower alkyl group, a cycloalkyl group, a lower alkenyl group, a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group, a lower alkylthio group, a haloalkyl group, a haloalkenyl group,
A phenyl group that may have a substituent, a benzyl group that may have a substituent, a phenoxy group that may have a substituent, a nitro group, a cyano group, -
COR ⁴ groups (R ⁴ : lower alkoxy group, lower alkenyloxy group, benzyloxy group, lower alkylamino group, anilino group) or [Formula] group (R ⁵ , R ⁶ : lower alkyl group, acyl group, sulfonyl group,
lower alkoxycarbonyl group). n represents 0 or an integer of 1 to 3. Y and Z are the same or different and represent an oxygen atom or a sulfur atom. a is 0 or 1
shows. b represents 1 or 2. ] An imidazole carboxylic acid ester derivative represented by 2 General formula [In the formula, R ¹ represents a lower alkyl group, a cycloalkyl group, or an R ³ (CH ₃ ) ₂ C- group (R ³ : halogenomethyl group, acyloxymethyl group, or alkoxycarbonyl group). R ² represents a hydrogen atom, a lower alkyl group or a cycloalkyl group. X is a halogen atom, a lower alkyl group, a cycloalkyl group, a lower alkenyl group, a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group, a lower alkylthio group, a haloalkyl group, a haloalkenyl group,
A phenyl group that may have a substituent, a benzyl group that may have a substituent, a phenoxy group that may have a substituent, a nitro group, a cyano group, -
COR ⁴ groups (R ⁴ : lower alkoxy group, lower alkenyloxy group, benzyloxy group, lower alkylamino group, anilino group) or [Formula] group (R ⁵ , R ⁶ : lower alkyl group, acyl group, sulfonyl group,
lower alkoxycarbonyl group). n represents 0 or an integer of 1 to 3. Y represents an oxygen atom or a sulfur atom. a represents 0 or 1. b represents 1 or 2. ] Carbinol derivative and formula represented by [In the formula, Z represents an oxygen atom or a sulfur atom. ] by reacting with N,N'-carbonyldiimidazole represented by the general formula [In the formula, R ¹ , R ² , X, n, Y, Z, a and b
is the same as above. ] A method for producing an imidazole carboxylic acid ester derivative, which comprises obtaining an imidazole carboxylic acid ester derivative represented by: 3 General formula [In the formula, R ¹ represents a lower alkyl group, a cycloalkyl group, or an R ³ (CH ₃ ) ₂ C- group (R ³ : halogenomethyl group, acyloxymethyl group, or alkoxycarbonyl group). R ² represents a hydrogen atom, a lower alkyl group or a cycloalkyl group. X is a halogen atom, a lower alkyl group, a cycloalkyl group, a lower alkenyl group, a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group, a lower alkylthio group, a haloalkyl group, a haloalkenyl group,
A phenyl group that may have a substituent, a benzyl group that may have a substituent, a phenoxy group that may have a substituent, a nitro group, a cyano group, -
COR ⁴ groups (R ⁴ : lower alkoxy group, lower alkenyloxy group, benzyloxy group, lower alkylamino group, anilino group) or [Formula] group (R ⁵ , R ⁶ : lower alkyl group, acyl group, sulfonyl group,
lower alkoxycarbonyl group). n represents 0 or an integer of 1 to 3. Y represents an oxygen atom or a sulfur atom. a represents 0 or 1. b represents 1 or 2. ] Carbinol derivatives and general formula represented by [In the formula, Z represents an oxygen atom or a sulfur atom. ] The general formula which is then produced by reacting with the compound represented by [In the formula, R ¹ , R ² , X, n, Y, Z, a and b
is the same as above. ] The compound represented by the formula and imidazole are reacted to form the general formula [In the formula, R ¹ , R ² , X, n, Y, Z, a and b
is the same as above. ] A method for producing an imidazole carboxylic acid ester derivative, which comprises obtaining an imidazole carboxylic acid ester derivative represented by: 4 General formula [In the formula, R ¹ represents a lower alkyl group, a cycloalkyl group, or an R ³ (CH ₃ ) ₂ C- group (R ³ : halogenomethyl group, acyloxymethyl group, or alkoxycarbonyl group). R ² represents a hydrogen atom, a lower alkyl group or a cycloalkyl group. X is a halogen atom, a lower alkyl group, a cycloalkyl group, a lower alkenyl group, a lower alkoxy group, a lower alkenyloxy group, a lower alkynyloxy group, a lower alkylthio group, a haloalkyl group, a haloalkenyl group,
A phenyl group that may have a substituent, a benzyl group that may have a substituent, a phenoxy group that may have a substituent, a nitro group, a cyano group, -
COR ⁴ groups (R ⁴ : lower alkoxy group, lower alkenyloxy group, benzyloxy group, lower alkylamino group, anilino group) or [Formula] group (R ⁵ , R ⁶ : lower alkyl group, acyl group, sulfonyl group,
lower alkoxycarbonyl group). n represents 0 or an integer of 1 to 3. Y and Z are the same or different and represent an oxygen atom or a sulfur atom. a is 0 or 1
shows. b represents 1 or 2. ] A disinfectant containing an imidazole carboxylic acid ester derivative represented by the following as an active ingredient.