Fungicidal imidazol-1-yl-carboxylic acid ester derivatives

The present invention relates to derivatives of imidazol-1-yl-carboxylic acid esters, processes for preparing the same and fungicidal compositions comprising the derivative as an active component.
Known compounds analogous to the imidazol-1-yl-carboxylic acid ester derivatives of the present invention include, for example, benzyl imidazol-1-yl-carboxylate (see Journal of the Organic Chemistry, 47(23), 4471-4477). However, this compound was no fungicidal activity.
An object of the present invention is to provide novel imidazol-1-yl-carboxylic acid ester derivatives having high fungicidal activity.
Another object of the invention is to provide a process for preparing the derivative.
Another object of the invention is to provide fungicidal compositions comprising the derivative as an active component.
Other features of the present invention will become apparent from the following description.
The imidazol-1-yl-carboxylic acid ester derivatives of the present invention are novel compounds which have not been disclosed in literature and are represented by the following formula (I) ##STR3## wherein R.sup.1 is lower alkyl, cycloalkyl or R.sup.3 (CH.sub.3).sub.2 C-- (wherein R.sup.3 is halogenomethyl, acyloxymethyl or alkoxycarbonyl), R.sup.2 is a hydrogen atom, lower alkyl or cycloalkyl, X is a hydrogen atom, halogen atom, lower alkyl, cycloalkyl, lower alkenyl, lower alkoxyl, lower alkenyloxy, lower alkynyloxy, lower alkylthio, haloalkyl, haloalkenyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, substituted or unsubstituted phenoxy, nitro, cyano, --COR.sup.4 (wherein R.sup.4 is lower alkoxyl, lower alkenyloxy, benzyloxy, lower alkylamino or anilino) or ##STR4## (wherein R.sup.5 and R.sup.6 are each lower alkyl, acyl, sulfonyl or lower alkoxycarbonyl), n is an integer of from 1 to 3, Y and Z are the same or different and are each an oxygen atom or sulfur atom, a is 0 or 1, and b is 1 or 2.
Examples of lower alkyl groups in the above formula are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl and like alkyl groups having 1 to 6 carbon atoms.
Examples of cycloalkyl groups are those having 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl and cyclohexyl.
Examples of halogenomethyl groups are chloromethyl, bromomethyl, fluoromethyl and the like.
Examples of acyloxymethyl groups are acetyloxymethyl, propionyloxymethyl, benzoyloxymethyl, benzoyloxymethyl groups having a halogen atom, C.sub.1-3 alkyl, C.sub.1-3 alkoxy or like substituent on the phenyl ring, and the like.
Examples of lower alkoxycarbonyl groups are alkoxycarbonyl groups in which the alkoxy portion has 1 to 6 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl and propyloxycarbonyl.
Examples of halogen atoms include fluorine, chlorine, bromine and iodine atoms.
Examples of lower alkenyl groups are those having 2 to 6 carbon atoms, such as vinyl, propenyl and butenyl.
Examples of lower alkoxyl groups are those having 1 to 6 carbon atoms, such as methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butoxy, isobutyloxy and sec-butyloxy.
Examples of lower alkenyloxy groups are those having 2 to 6 carbon atoms, such as vinyloxy, propenyloxy and butenyloxy.
Examples of lower alkynyloxy groups are those having 2 to 6 carbon atoms, such as ethynyloxy, propynyloxy and butynyloxy.
Examples of lower alkylamino groups are mono- and di-alkylamino groups having 1 to 6 carbon atoms, such as monomethylamino, monoethylamino, monopropylamino, dimethylamino, diethylamino and dipropylamino.
Examples of acyl groups are acetyl, propionyl, benzoyl and benzoyl groups having a halogen atom, C.sub.1-3 alkyl, C.sub.1-3 alkoxy or like substituent on the phenyl ring.
Examples of sulfonyl groups are methylsulfonyl, ethylsulfonyl, benzenesulfonyl and benzenesulfonyl groups having a halogen atom, C.sub.1-3 alkyl, C.sub.1-3 alkoxy or like substituent on the phenyl ring.
Examples of lower alkylthio groups are alkylthio groups having 1 to 6 carbon atoms, such as methylthio, ethylthio, propylthio and butylthio.
Examples of haloalkyl groups are alkyl groups having 1 to 6 carbon atoms and substituted with at least one halogen atom, such as monochloromethyl, dichloromethyl, trichloromethyl, monobromomethyl, dibromomethyl, monofluoromethyl, difluoromethyl, trifluoromethyl, 1,2-dichloroethyl, 1,2-dibromoethyl, 1,1,2-trichloroethyl and monofluoroethyl.
Examples of haloalkenyl groups are alkenyl groups having 2 to 6 carbon atoms and substituted with halogen atoms, such as 2,2-dichlorovinyl and 2,2-dibromovinyl.
Examples of substituents on the phenyl ring of phenyl, benzyl and phenoxy groups are the above-mentioned halogen atoms, lower alkyl groups, lower alkoxy groups, nitro group, cyano group, etc.
The compounds of the present invention represented by the formula (I) are useful as agricultural and horticultural fungicides as will be described below.
The compounds of the invention, which can be prepared by various processes, are prepared easily generally by the process represented by Reaction Formula-1 or Reaction Formula-2 given below. ##STR5## wherein R.sup.1, R.sup.2, X, n, Y, Z, a and b are as defined above. ##STR6## wherein R.sup.1, R.sup.2, X, n, Y, Z, a and b are as defined above.
According to Reaction Formula-1, the compound of the invention is prepared by reacting a carbinol derivative of the formula (II) with an N,N'-carbonyldiimidazole of the formula (III). This reaction is conducted in a suitable solvent or without using any solvent. Examples of useful solvents are ethers such as diethyl ether, dibutyl ether, tetrahydrofuran and dioxane, hydrocarbon halides such as methylene chloride, 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. and mixtures of such solvents. Although the proportions of the compound of the formula (II) and the compound of the formula (III) are not limited specifically, usually about 0.5 to about 2 moles, preferably about 0.7 to about 1.5 moles, of the latter is used per mole of the former. The reaction, which can be carried out either at room temperature or with heating, proceeds suitably usually at room temperature to around the boiling point of the solvent used and takes generally about 1 to about 10 hours.
According to Reaction Formula-2, the compound of the present invention is prepared by reacting a carbinol derivative of the formula (II) with a compound of the formula (IV) and subsequently reacting imidazole with the resulting compound of the formula (V).
These reactions are conducted in a suitable solvent or in the absence of solvent. Examples of useful solvents are ethers such as diethyl ether, dibutyl ether, tetrahydrofuran and dioxane, hydrocarbon halides such as methylene chloride, chloroform, dichloroethane and carbon tetrachloride, aromatic hydrocarbons such as benzene, toluene and xylene, ethyl acetate, dimethylformamide, dimethyl sulfoxide, pyridine, etc. and mixtures of such solvents.
In reacting the compound of the formula (II) with the compound of the formula (IV), the compound of the formula (IV) is used in the form of a gas or liquid, or a solution of the latter in such a solvent is added dropwise to the former. According to the present invention, a compound producing the compound of the formula (IV) is usable in place of the compound (IV). Any of known compounds, such as trichloromethyl chloroformate, is usable insofar as it is capable of producing the compound of the formula (IV) under the reaction conditions. The proportions of the compound of the formula (II) and the compound of the formula (IV) are not limited specifically, but it is preferable to use about 0.5 to about 5 moles, more preferably about 1 to about 3 moles, of the latter per mole of the former. Preferably, the reaction system contains a basic compound. Any of various known basic compounds, such as triethylamine, tributylamine, dimethylaniline, diethylaniline and pyridine, is usable insofar as the compound is capable of capturing the hydrogen chloride resulting from the reaction. Such a basic compound is used in an amount usually of about 0.5 to about 5 moles, preferably about 1 to about 3 moles, per mole of the compound of the formula (II). The reaction, which can be conducted either at room temperature or with cooling, usually proceeds favorably at about -10.degree. C. to room temperature and generally takes about 1 to about 15 hours.
The compound of the formula (V) thus produced is used, as isolated or as it is without isolation, for the subsequent reaction.
In reacting imidazole with the compound (V) resulting from the above reaction, the proportions of these two compounds are not limited specifically, but it is usually preferable to use about 0.5 to about 2 moles, more preferably about 0.7 to about 1.5 moles, of imidazole per mole of the compound (V). It is desirable that a basic compound, such as those mentioned above, be also present in the system for this reaction. The basic compound is used usually in an amount of about 0.5 to about 2 moles, preferably about 0.7 to about 1.5 moles, per mole of the compound of the formula (V). The reaction, which can be carried out either at room temperature or with heating, favorably proceeds usually at room temperature to around the boiling point of the solvent used and generally takes about 1 to about 10 hours.
With reference to Reaction Formulae-1 and -2, the compound of the formula (II) to be used as a starting material is easily prepared by a known process, for example, by the process represented by Reaction Formula-3, -4 or -5. ##STR7## wherein R.sup.1, X, n, Y and b are as defined above, and X' is a halogen atom.
With reference to Reaction Formula-3, the reaction of the compound of the formula (VI) with the compound of the formula (VII) is conducted in water or in an organic solvent. Examples of useful solvents are ethers such as diethyl ether, dibutyl ether, tetrahydrofuran and dioxane, hydrocarbon halides such as methylene chloride, chloroform and dichloroethane, aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetonitrile, dimethylformamide, dimethyl sulfoxide and the like. Although the proportions of the compound (VI) and the compound (VII) to be used are not limited specifically, usually about 0.5 to about 2 moles, preferably about 1 to about 1.5 moles, of the latter is used per mole of the former. For the reaction, a basic agent is used, or the phenolic compound represented by the formula (VI) is used in the form of a sodium salt or potassium salt. Examples of useful basic agents are alkali carbonates such as sodium carbonate and potassium carbonate, alkali hydroxides such as sodium hydroxide and potassium hydroxide, metallic sodium, sodium methylate, sodium hydride and the like. The reaction is carried out usually at a temperature of about 50.degree. to about 150.degree. C. and generally takes about 5 to 15 hours.
With the reference to Reaction Formula-3, the reaction wherein the compound of the formula (VIII) is reduced to the compound of the formula (IIa) can be carried out by various processes such as a catalytic reduction process and a process employing a reducing agent. For example, when the catalytic reduction process is resorted to, the compound (VIII) is hydrogenated in a solvent such as methanol, ethanol or like alcohol or acetonitrile, using a catalyst such as noble metal, noble metal oxide or Raney catalyst. Among such catalysts, platinum, platinum oxide and nickel are preferred. While the reaction can be conducted at a suitable temperature within a wide range, the preferred temperature is about 20.degree. to 50.degree. C. The reaction can be carried out at atmospheric pressure or increased pressure. When the process employing a reducing agent is resorted to, the reaction is conducted using a catalyst such as aluminum isopropylate or sodium borohydride and a solvent such as methanol, ethanol or like alcohol or diethyl ether, tetrahydrofuran or like ether. The catalyst is used usually in an amount of about 0.1 to about 2 moles, preferably about 0.5 to about 1.5 moles, per mole of the compound of the formula (VIII). The reaction temperature is usually in the range of 0.degree. to 100.degree. C. ##STR8## wherein R.sup.1, R.sup.2, X, Y, n, a and b are as defined above, X' is a halogen atom, and R.sup.3 is the same as R.sup.1 or lower alkoxyl.
The reaction represented by Reaction Formula-4 or -5, which is the common Grignard Reaction, is conducted in an ether solvent such as diethyl ether, dibutyl ether or tetrahydrofuran. Although the proportions of a halide of the formula (IX) or (XI) and magnesium to be reacted therewith are not limited specifically, it is usually desirable to use 0.5 to 1.5 moles, more desirably 0.8 to 1.2 moles, of the latter per mole of the former. The reaction proceeds favorably at 0.degree. C. to around the boiling point of the solvent and generally takes about 1 to about 10 hours. The resulting Grignard reagent is subsequently reacted as it is with an aldehyde, ketone or carboxylic acid ester derivative represented by the formula (X) or (XII). The compound of the formula (X) or (XII) is used usually in an amount of about 0.1 to about 3 moles, preferably about 0.5 to about 2.5 moles, per mole of the halide of the formula (IX) or (XI). This reaction proceeds favorably at about 0.degree. about 50.degree. C. and generally takes about 0.5 to about 3 hours.
The compound of the present invention obtained by the foregoing processes can be easily isolated from the reaction mixture and purified by a usual method such as solvent extraction, solvent dilution method, recrystallization or column chromatography, whereby the desired compound can be prepared with a high purity.
The compound of the invention is characterized by high fungicidal activity and a wide activity spectrum. The present compound exhibits outstanding fungicidal activity on various pathogens, for example, of powdery mildew, scab, smut, gray mold, anthracnose, blast, leaf spots (caused by helminthosporia), sheath blight, etc. Moreover, the compound of the invention exhibits no phytotoxicity at a concentration required for controlling these pathogens and is low in toxicity to warm-blooded animals. Accordingly, the present compound is effectively usable for preventing diseases of agricultural plants such as vegetables, fruit trees, rice and mulberry trees.
For use an a fungicide, the compound of the invention may be used as it is, while it is generally used as admixed with auxiliary agents which are commonly used for formulating agricultural chemical preparations. Thus, the compound is formulated into a composition which is not limited in type. Suitably, the composition is in the form of a powder, emulsifiable concentrate, granules, wettable powder or flowable concentrate. Useful auxiliary agents are a wide variety of those commonly used in the art and including, for example, extenders such as kieselguhr, kaolin, clay, bentonite, white carbon and talc, surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester, sodium alkylbenzenesulfonate, sodium lignosulfonate, sodium alkylsulfate, sodium polyoxyethylenealkylsulfate and salt of naphthalenesulfonic acid-formalin condensation product, organic solvents such as benzene, toluene, xylene, acetone, cyclohexanone, methanol, ethanol, isopropyl, alcohol, dioxane, dimethylformamide, dimethyl sulfoxide and carbon tetrachloride, etc.
Although the amount of the present compound to be incorporated into the fungicidal composition of the invention is not limited specifically, it is desirable to suitably admix auxiliary agents with the compound so that the composition contains usually about 0.1 to about 90 wt.%, preferably about 1 to about 70 wt.%, of the active component.
The present fungicidal composition may be used as it is without dilution or as diluted to about 500- to about 10,000-fold. Although the suitable dosage can not be determined specifically but varies with the type of composition, method and timing of application, kind of disease to be treated, etc., it is desirable to use about 5 to about 200 g/10a of the composition calculated as the active component.

The present invention will be described in greater detail with reference to the following reference examples, examples, formulation examples and test examples.
REFERENCE EXAMPLE 1
Preparation of 1-(p-chlorophenoxy)-3,3-dimethyl-2-butanone
A 12.8 g quantity of p-chlorophenol, 13.4 g of 1-chloro-3,3-dimethyl-2-butanone, 13.8 g of anhydrous potassium carbonate and 100 ml of acetonitrile were placed into a 200-ml egg plant type flask and refluxed for 8 hours. The resulting potassium chloride was filtered off from the reaction mixture, and the filtrate was concentrated in a vacuum to obtain crude crystals, which were recrystallized from n-hexane, giving 16.0 g of the above-identified desired compound, m.p. 62.degree.-63.degree. C.
REFERENCE EXAMPLE 2
Preparation of 1-(p-chlorophenoxy)-3,3-dimethyl-2-butanol
Into a 200-ml egg plant type flask were placed 9.0 g of 1-(p-chlorophenoxy)-3,3-dimethyl-2-butanone and 80 ml of methanol, and 0.8 g of sodium borohydride was further placed into the flask with cooling and stirring. After stirring the mixture at room temperature for 1 hour, the reaction mixture was concentrated in a vacuum, and 50 ml of water was added to the resulting residue, followed by extraction with 30 ml of ether twice. The combined ethereal extract was washed with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated in a vacuum. The residue was purified by silica gel column chromatography, giving 8.5 g of the above-identified desired compound.
REFERENCE EXAMPLE 3
Preparation of 1-(p-chlorophenyl)-3,3-dimethyl-2-butanol
A 10 ml quantity of ether solution of 4.3 g of (0.05 mole) of pivalaldehyde was added dropwise to a solution of p-chlorobenzylmagnesium chloride (0.055 mole) in 100 ml of ether with cooling and stirring. The mixture was thereafter stirred at room temperature for 1 hour and then placed into 5% aqueous solution of hydrochloride acid containing pieces of ice. After separating off the oily layer, the aqueous layer was subjected to extraction with ether. The ethereal extract and the oily layer were combined together, washed with saturated sodium chloride aqueous solution, dried over anhydrous magnesium sulfate and distilled to remove the solvent, affording 10.5 g of the above-identified desired compound in the form of a white solid.
REFERENCE EXAMPLE 4
Preparation of 1-(p-chlorophenoxy)-3,3-dimethyl-4-chloro-2-butanone
Into a 100-ml egg plant type flask were placed 2.4 g of 1-(p-chlorophenoxy)-3,3-dimethyl-4-hydroxy-2-butanone, 2.6 g of triphenylphosphine and 50 ml of carbon tetrachloride, which were then refluxed for 18 hours. The reaction mixture was cooled, the crystals separating out were filtered off, and the filtrate was concentrated in a vacuum. The residue obtained was purified by silica gel column chromatography, giving 1.8 g of the above-identified desired compound.
REFERENCE EXAMPLE 5
Preparation of 1-(p-chlorophenoxy)-3,3-dimethyl-4-chloro-2-butanol
Into a 100-ml egg plant type flask were placed 2.6 g of 1-(p-chlorophenoxy)-3,3-dimethyl-4-chloro-2-butanone and 40 ml of methanol, and 0.2 g of sodium borohydride was further placed into the flask with cooling and stirring. After stirring the mixture at room temperature for 1 hour, the reaction mixture was concentrated in a vacuum, and 50 ml of water was added to the resulting residue, followed by extraction with 30 ml of ether twice. The combined ethereal extract was washed with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated in a vacuum. The residue obtained was purified by silica gel column chromatography, giving 2.3 g of the above-identified desired compound.
REFERENCE EXAMPLE 6
Preparation of 1-(p-chlorophenylthio)-3,3-dimethyl-2-butanone
A 14.45 g quantity of p-chlorothiophenol and 13.8 g of anhydrous potassium carbonate were added to 200 ml of acetonitrile, and 13.45 of 1-chloro-3,3-dimethyl-2-butanone was added in small portions to the mixture while stirring the mixture. After stirring the mixture at 70.degree. to 75.degree. C. for 6 hours, the solid separating out was filtered off. The filtrate was concentrated to obtain a residue, which was subjected to extraction with benzene. To the extract was added 200 ml of 10% sodium hydroxide solution, followed by stirring at room temperature for 1 hour. The benzene layer was separated off, washed with water, then dried over anhydrous magnesium sulfate and distilled in a vacuum to remove the solvent, giving 20.2 g of the above-identified desired compound in the form of a pale yellow oil.
REFERENCE EXAMPLE 7
Preparation of 1-(p-chlorophenylthio)-3,3-dimethyl-2-butanol
A 0.4 g quantity of sodium borohydride was added in small portions to a solution of 2.43 g of 1-(p-chlorophenylthio)-3,3-dimethyl-2-butanone in 50 ml of methanol at a temperature of up to 10.degree. C. with stirring. After the completion of addition, the mixture was stirred at room temperature for 30 minutes and then distilled in a vacuum to remove the methanol. The residue was subjected to extraction with ether. The extract was washed with water, then dried over anhydrous magnesium sulfate and distilled to remove the solvent, affording 2.4 g of the above-identified desired compound in the form of a colorless oil.
REFERENCE EXAMPLE 8
Preparation of 1-(p-chlorophenoxy)-2-methyl-2-propanol
To 100 ml of ether solution of 24 g of methylmagnesium bromide was added dropwise 30 ml of ether solution of 10.7 g of ethyl p-chlorophenoxyacetate at a temperature of up to 10.degree. C. with stirring. The mixture was thereafter stirred at room temperature for 1 hour and then placed into 10% aqueous hydrochloric acid solution with ice cooling. The oily layer was subjected to extraction with ether, and the extract was washed with saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate and distilled to remove the solvent, giving 8.9 g of the above-identified desired compound in the form of a colorless oil.
REFERENCE EXAMPLE 9
Preparation of 1-(p-chlorophenoxy)-2,3-dimethyl-2-butanol
To 50 ml of ether solution of 12 g of methylmagnesium bromide was added dropwise in small portions 30 ml of ether solution of 10.6 g of p-chlorophenoxy methyl isopropyl ketone at a temperature of up to 10.degree. C. with stirring. The mixture was thereafter stirred at room temperature for 1 hour and then placed into 100 ml of 10% aqueous solution of hydrochloric acid with ice cooling. The ethereal layer was separated off, washed with saturated aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate and distilled to remove the solvent, affording 9.1 g of the above-identified desired compound in the form of a pale yellow oil.
EXAMPLE 1
Preparation of 1'-(m-chlorophenoxy)-3',3'-dimethyl-2'-butyl imidazol-1-yl-carboxylate
A 1.6 g quantity of 1-(m-chlorophenoxy)-3,3-dimethyl-2-butanol, 1.4 g of N,N'-carbonyldiimidazole and 40 ml of ethyl acetate were placed into a 100-ml egg plant type flask and refluxed for 3 hours. The reaction mixture was concentrated in a vacuum, and the resulting residue was purified by silica gel column chromatography, giving 1.6 g of the above-identified desired compound.
M.p.: 67.degree.-68.degree. C.
______________________________________Elementary analysis: C H N______________________________________Calcd. for C.sub.16 H.sub.19 N.sub.2 O.sub.3 Cl (%) 59.54 5.93 8.68Found (%) 59.01 5.88 8.81______________________________________
NMR spectrum (CDCl.sub.3) .delta. ppm: 1.10 (9H), 4.10 (2H), 5.15 (1H), 6.50-7.10 (5H), 7.25 (1H), 7.98 (1H).
These results indicated that the compound obtained was ##STR9##
EXAMPLE 2
Preparation of 1'-(o-chlorophenoxy)-3',3'-dimethyl-2'-butyl imidazol-1-yl-carboxylate
A 2.3 g quantity of 1-(o-chlorophenoxy)-3,3-dimethyl-2-butanol, 0.81 ml of pyridine and 50 ml of ethyl acetate was placed into a 100-ml four-necked flask, and 0.6 ml of trichloromethyl chloroformate was added dropwise to the mixture with cooling and stirring. The mixture was thereafter stirred at room temperature for 15 hours and then cooled again. To the mixture were added 0.7 g of imidazole and 0.81 ml of pyridine, and the resulting mixture was stirred at room temperature for 30 minutes and further refluxed for 3 hours. The reaction mixture was washed with water and saturated aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate and concentrated in a vacuum. The residue obtained was purified by silica gel column chromatography, giving 1.5 g of the above-identified desired compound.
M.p.: 123.degree.-124.degree. C.
______________________________________Elementary analysis: C H N______________________________________Calcd. for C.sub.16 H.sub.19 N.sub.2 O.sub.3 Cl (%) 59.54 5.93 8.68Found (%) 58.98 5.90 8.75______________________________________
NMR spectrum (CDCl.sub.3) .delta. ppm: 1.10 (9H), 4.10 (2H), 5.17 (1H), 6.60-7.20 (5H), 7.28 (1H), 8.00 (1H).
These results indicated that the compound obtained was ##STR10##
EXAMPLES 3-69
The compounds listed in Table 1 below were prepared in the same manner as in Example 1 or 2 using suitable starting materials.
TABLE 1__________________________________________________________________________Ex. No. Formula Property NMR spectrum (CDCl.sub.3) .delta. ppm__________________________________________________________________________ ##STR11## m.p. 71-72.degree. C. 1.05 (9H), 4.10 (2H), 5.17 (1H), 5.17 (1H), 6.60-7.20 (6H), 7.29 (1H), 8.00 (1H)4 ##STR12## m.p. 45-46.degree. C. 1.10 (9H), 4.10 (2H), 5.15 (1H), 6.65-6.85 (4H), 6.95 (1H), 7.28 (1H), 8.00 (1H)5 ##STR13## m.p. 52-53.degree. C. 1.07 (9H), 4.10 (2H), 5.13 (1H), 6.60 (2H), 6.90 (1H), 7.04 (2H), 7.25 (1H), 7.96 (1H)6 ##STR14## m.p. 67-68.degree. C. 1.05 (9H), 4.10 (2H), 5.15 (1H), 6.56 (2H), 6.91 (1H), 7.17 (1H), 7.27 (1H), 7.98 (1H)7 ##STR15## m.p. 116-117.degree. C. 1.05 (9H), 4.15 (2H), 5.21 (1H), 6.50-7.35 (6H), 8.00 (1H)8 ##STR16## m.p. 125-126.degree. C. 1.10 (9H), 4.25 (2H), 5.20 (1H), 6.78 (2H), 6.92 (1H), 7.30 (1H), 8.00 (3H)9 ##STR17## m.p. 110-111.degree. C. 1.10 (9H), 4.20 (2H), 5.20 (1H), 6.82 (2H), 6.95 (1H), 7.30 (1H), 7.41 (2H), 8.00 (1H)10 ##STR18## m.p. 83-84.degree. C. 1.10 (9H), 4.17 (2H), 5.18 (1H), 6.60 (1H), 6.71 (2H), 6.93 (1H), 7.30 (3H), 8.00 (1H)11 ##STR19## m.p. 72-73.degree. C. 1.05 (9H), 1.16 (6H), 2.75 (1H), 4.15 (2H), 5.15 (1H), 6.60 (2H), 6.90 (1H), 6.95 (2H), 7.23 (1H), 7.95 (1H)12 ##STR20## m.p. 80-81.degree. C. 1.05 (9H), 2.17 (3H), 4.10 (2H), 5.12 (1H), 6.58 (2H), 6.88 (3H), 7.25 (1H), 7.98 (1H)13 ##STR21## m.p. 90-91.degree. C. 1.05 (9H), (9H), 4.15 (2H), 5.15 (1H), 6.73 (2H), 6.90 (1H), 7.10-7.40 (8H), 7.98 (1H)14 ##STR22## m.p. 109-110.degree. C. 1.05 (9H), 1.23 (9H), 4.10 (2H), 5.15 (1H), 6.62 (2H), 6.90 (1H), 7.12 (2H), 7.25 (1H), 7.98 (1H)15 ##STR23## m.p. 72-73.degree. C. 1.05 (9H), 2.23 (3H), 4.13 (2H), 5.15 (1H), 6.40-6.70 (3H), 6.90 (2H), 7.25 (1H), 8.00 (1H)16 ##STR24## m.p. 70-71.degree. C. 1.05 (9H), 3.80 (2H), 4.13 (2H), 5.15 (1H), 6.60-7.30 (9H), 6.90 (1H), 7.30 (1H), 8.00 (1H)17 ##STR25## m.p. 69-70.degree. C. 1.05 (9H), 1.15 (3H), 2.50 (2H), 4.12 (2H), 5.15 (1H), 6.62 (2H), 6.92 (3H), 7.25 (1H), 7.98 (1H)18 ##STR26## m.p. 66-67.degree. C. 0.88 (3H), 1.05 (9H), 1.60 (2H), 2.50 (2H), 4.10 (2H), 5.15 (1H), 6.60 (2H), 6.90 (3H), 7.25 (1H), 7.98 (1H)19 ##STR27## m.p. 73-74.degree. C. 0.88 (3H), 1.05 (9H), 1.20-1.70 (4H), 2.50 (2H), 4.10 (2H), 5.15 (1H), 6.60 (2H), 6.90 (3H), 7.25 (1H), 7.96 (2H)20 ##STR28## m.p. 100-101.degree. C. 0.77 (3H), 1.05 (9H), 1.15 (3H), 1.50 (2H), 2.45 (1H), 4.10 (2H), 5.15 (1H), 6.62 (2H), 6.90 (3H), 7.25 (1H), 7.98 (1H)21 ##STR29## m.p. 96-97.degree. C. 1.05 (9H), 1.10-1.90 (11H), 4.10 (2H), 5.15 (1H), 6.60 (2H), 6.90 (3H), 7.25 (1H), 7.95 (1H)22 ##STR30## m.p. 77-78.degree. C. 1.05 (9H), 3.62 (3H), 4.10 (2H), 5.15 (1H), 6.63 (4H), 6.90 (1H), 7.27 (1H), 7.98 (1H)23 ##STR31## m.p. 69-70.degree. C. 1.05 (9H), 2.35 (3H), 4.10 (2H), 5.15 (1H), 6.65 (2H), 6.90 (1H), 7.07 (2H), 7.25 (1H), 6.98 (1H)24 ##STR32## m.p. 57-58.degree. C. 1.05 (9H), 3.62 (3H), 4.10 (2H), 5.13 (1H), 6.20-6.45 (3H), 6.90 (2H), 7.27 (1H), 7.98 (1H)25 ##STR33## m.p. 66-67.degree. C. 1.05 (9H), 3.52 (3H), 4.15 (2H), 5.15 (1H), 6.70 (4H), 6.90 (1H), 7.25 (1H), 7.95 (1H)26 ##STR34## m.p. 88-89.degree. C. 1.05 (9H), 1.32 (3H), 3.83 (2H), 4.10 (2H), 5.10 (1H), 6.60 (4H), 6.90 (1H), 7.23 (1H), 7.95 (1H)27 ##STR35## m.p. 62-63.degree. C. 1.07 (9H), 4.10 (2H), 5.15 (1H), 6.65 (2H), 6.70 (4H), 6.90 (1H), 7.05 (2H), 7.25 (1H), 7.98 (1H)28 ##STR36## -- 1.05 (9H), 4.12 (2H), 5.15 (1H), 6.60 (1H), 6.70 (4H), 6.90 (2H), 7.30 (1H), 8.00 (1H)29 ##STR37## -- 1.10 (9H), 4.15 (2H), 5.20 (1H), 6.67 (1H), 6.92 (2H), 7.15 (1H), 7.30 (1H), 8.00 (1H)30 ##STR38## m.p. 67-68.degree. C. 1.05 (9H), 1.97 (3H), 2.10 (3H), 4.05 (2H), 5.15 (1H), 6.48 (1H), 6.70 (2H), 6.90 (1H), 7.25 (1H), 7.98 (1H)31 ##STR39## m.p. 83-84.degree. C. 1.07 (9H), 1.95 (3H), 4.05 (2H), 5.15 (1H), 6.50 (1H), 6.90 (3H), 7.28 (1H), 8.00 (1H)32 ##STR40## m.p. 54.8.degree. C. 0.97 (3H), 1.06 (9H), 1.72 (2H), 3.35 (2H), 4.10 (2H), 5.12 (1H), 6.62 (4H), 6.97 (1H), 7.19 (1H), 7.98 (1H)33 ##STR41## m.p. 98-99.degree. C. 1.10 (9H), 4.10 (2H), 5.20 (1H), 6.81 (1H), 6.88 (1H), 7.05 (2H), 7.30 (1H), 8.00 (1H)34 ##STR42## m.p. 102-103.degree. C. 1.05 (9H), 4.15 (2H), 5.17 (1H), 6.50 (1H), 6.70 (1H), 6.90 (1H), 6.98 (1H), 7.30 (3H)35 ##STR43## m.p. 59-60.degree. C. 1.07 (9H), 3.70 (6H), 4.10 (2H), 5.12 (1H), 6.20 (1H), 6.28 (1H), 6.58 (1H), 6.90 (1H), 6.95 (1H), 7.25 (1H)36 ##STR44## m.p. 95-96.degree. C. 1.05 (9H), 4.10 (2H), 5.12 (1H), 6.60 (2H), 6.80 (1H), 6.90 (1H), 7.28 (1H), 7.98 (1H)37 ##STR45## m.p. 102-103.degree. C. 1.05 (9H), 2.10 (6H), 4.10 (2H), 5.10 (1H), 6.40 (1H), 6.50 (1H), 6.80 (1H), 6.90 (1H), 7.20 (1H), 7.93 (1H)38 ##STR46## -- 1.05 (9H), 4.10 (2H), 5.20 (1H), 6.90 (1H), 7.10 (2H), 7.30 (1H), 8.00 (1H)39 ##STR47## -- 1.05 (6H), 2.22 (1H), 4.10 (2H), 5.05 (1H), 6.6-7.2 (4H), 6.92 (1H), 7.30 (1H), 8.0 (1H),40 ##STR48## -- 0.80-1.90 (9H), 4.10 (2H), 5.10 (1H), 6.6-7.2 (4H), 6.90 (1H), 7.30 (1H), 8.0 (1H)41 ##STR49## -- 0.80-1.90 (9H), 4.10 (2H), 5.30 (1H), 6.60-7.20 (4H), 6.90 (1H), 7.30 (1H), 8.00 (1H)42 ##STR50## m.p. 37-38.degree. C. 0.9-1.1 (11H), 4.10 (2H), 5.10 (1H), 6.6-7.2 (4H), 6.90 (1H), 7.30 (1H), 8.0 (1H)43 ##STR51## -- 1.1 (6H), 1.22 (6H), 2.2 (1H), 2.8 (1H), 4.10 (2H), 5.10 (1H), 6.6-7.2 (4H), 6.90 (1H), 7.30 (1H), 8.0 (1H)44 ##STR52## -- 1.05 (6H), 1.22 (9H), 2.2 (1H), 4.10 (2H), 5.10 (1H), 6.6-7.2 (4H), 6.90 (1H), 7.30 (1H), 8.00 (1H)45 ##STR53## -- 1.05 (6H), 2.2 (1H), 3.62 (3H), 4.05 (2H), 5.05 (1H), 6.68 (4H), 6.90 (1H), 7.28 (1H), 7.98 (1H)46 ##STR54## -- 1.45 (3H), 4.40 (2H), 5.28 (1H), 6.60-7.30 (7H), 7.90 (1H)47 ##STR55## m.p. 85.8.degree. C. 1.08 (9H), 1.33 (3H), 4.15 (2H), 4.22 (2H), 5.15 (1H), 6.70 (2H), 6.90 (1H), 7.25 (1H), 7.78 (2H), 7.97 (1H)48 ##STR56## m.p. 85.0.degree. C. 0.98 (3H), 1.08 (9H), 1.65 (2H), 4.10 (2H), 4.15 (2H), 5.13 (1H), 6.68 (2H), 6.90 (1H), 7.25 (1H), 7.80 (2H), 7.98 (1H)49 ##STR57## m.p. 81.4.degree. C. 1.09 (9H), 4.15 (2H), 4.65 (2H), 5.00-5.40 (3H), 5.85 (1H), 6.70 (2H), 6.90 (1H), 7.25 (1H), 7.80 (2H), 7.98 (1H)50 ##STR58## oil 1.09 (9H), 3.72 (3H), 4.15 (2H), 5.13 (1H), 6.70-7.55 (6H), 7.93 (1H)51 ##STR59## oil 0.93 (3H), 1.08 (9H), 1.20-1.70 (4H), 4.15 (2H), 4.20 (2H), 5.15 (1H), 6.70-7.60 (6H), 7.96 (1H)52 ##STR60## oil 1.09 (9H), 4.15 (2H), 5.17 (1H), 5.25 (2H), 6.80-7.60 (11H), 8.00 (1H)53 ##STR61## m.p. 147.3.degree. C. 1.08 (9H), 2.95 (3H), 4.15 (2H), 5.12 (1H), 6.40 (1H), 6.67 (2H), 6.90 (1H), 7.27 (1H), 7.55 (2H), 7.95 (1H)54 ##STR62## m.p. 134.9.degree. C. 0.93 (3H), 1.08 (9H), 1.57 (2H), 3.26 (2H), 4.15 (2H), 5.12 (1H), 6.28 (1H), 6.68 (2H), 6.90 (1H), 7.26 (1H), 7.55 (2H), 7.95 (1H)55 ##STR63## m.p. 118.1.degree. C. 1.05 (9H), 4.15 (2H), 5.15 (1H), 6.68 (2H), 6.90 (1H), 6.90-7.55 (6H), 7.65 (1H), 7.95 (1H), 8.40 (1H)56 ##STR64## oil 1.06 (9H), 1.18 (3H), 3.35 (2H), 4.13 (2H), 5.13 (1H), 6.55 (1H), 6.70-7.30 (6H), 7.92 (1H),57 ##STR65## m.p. 54.8.degree. C. 1.07 (9H), 1.15 (6H), 4.13 (3H), 5.10 (1H), 6.48 (1H), 6.70-7.30 (6H), 7.90 (1H)58 ##STR66## oil 1.09 (9H), 2.95 (6H), 4.15 (2H), 5.15 (1H), 6.60-7.35 (6H), 8.00 (1H)59 ##STR67## m.p. 83-85.degree. C. 1.04 (9H), 3.62 (3H), 4.10 (2H), 5.16 (1H), 6.56-7.40 (7H), 7.98 (1H)60 ##STR68## yellow oil 1.06 (9H), 1.26 (6H), 4.12 (2H), 4.88 (1H), 5.12 (1H), 6.58-7.40 (7H), 7.98 (1H)61 ##STR69## yellow oil 0.70-1.90 (7H), 1.08 (9H), 4.08 (2H), 4.12 (2H), 5.16 (1H), 6.58-7.40 (7H), 7.90 (1H)62 ##STR70## yellow oil 1.08 (9H), 2.06 (3H), 4.16 (2H), 5.12 (1H), 6.58-7.40 (6H), 7.60 (1H), 8.0 (1H)63 ##STR71## yellow oil 1.08 (9H), 1.12 (3H), 2.22 (2H), 4.12 (2H), 5.12 (1H), 6.58-7.42 (6H), 8.0 (1H), 8.60 (1H)64 ##STR72## m.p. 40-42.degree. C. 1.08 (9H), 4.16 (2H), 5.16 (1H), 6.60-7.80 (11H), 7.98 (1H), 8.74 (1H),65 ##STR73## yellow oil 1.10 (9H), 2.84 (3H), 4.18 (2H), 5.18 (1H), 6.64-7.40 (6H), 8.02 (1H), 8.30 (1H),66 ##STR74## yellow oil 1.06 (9H), 2.30 (3H), 4.16 (2H), 5.12 (1H), 6.70-7.42 (10H), 7.80 (1H), 8.90 (1H)67 ##STR75## yellow oil 1.08 (9H), 1.26 (3H), 3.90-4.30 (4H), 5.16 (1H), 6.30-7.40 (7H), 8.0 (1H)68 ##STR76## yellow oil 1.04 (9H), 1.18 (3H), 2.30 (2H), 4.12 (2H), 5.12 (1H), 6.30-7.40 (6H), 7.98 (1H), 8.60 (1H)69 ##STR77## yellow oil 1.08 (9H), 2.84 (3H), 4.18 (2H), 5.16 (1H), 6.30-7.42 (6H), 7.90 (1H), 8.42__________________________________________________________________________ (1H)
EXAMPLE 70
Preparation of 1'-(p-chlorophenyl)-3',3'-dimethyl-2'-butyl imidazol-1-yl-carboxylate
A 2.14 g quantity of 1-(p-chlorophenyl)-3,3-dimethyl-2-butanol and 0.78 g of pyridine were placed into 30 ml of ethyl acetate and cooled to a temperature of up to 10.degree. C. A 0.6 ml quantity of trichloromethyl chloroformate was added dropwise in small portions to the mixture with stirring. The resulting mixture was stirred at room temperature for 1 hour. with addition of 0.68 g of imidazole and 0.78 g of pyridine, the mixture was subsequently heated to 70.degree. to 80.degree. C. for 2 hours. The reaction mixture was cooled to room temperature, washed with water, dried over anhydrous sodium sulfate and distilled to evaporate off the solvent, giving 2.9 g of the above-identified desired compound.
M.p.: 121.5.degree.-122.degree. C.
______________________________________Elementary analysis: C H N______________________________________Calcd. for C.sub.16 H.sub.19 N.sub.2 ClO.sub.2 (%) 62.72 6.26 9.15Found (%) 62.60 6.23 9.22______________________________________
NMR spectrum (CDCl.sub.3) .delta. ppm: 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).
These results indicated that the compound obtained was ##STR78##
EXAMPLE 71
Preparation of 1'-(p-chlorophenyl)-2'-cyclohexylethyl imidazol-1-yl-carboxylate
A 2.40 g quantity of 1-(p-chlorophenyl)-2-cyclohexyl ethanol and 2.0 g of N,N'-carbonyldiimidazole were placed into 30 ml of ethyl acetate, and the mixture was refluxed for 3 hours with stirring. The reaction mixture was then cooled to room temperature, washed with water twice and thereafter dried over anhydrous magnesium sulfate. The product was distilled to remove the solvent, giving 3.3 g of the above-identified desired compound.
M.p.: 80.5.degree.-81.degree. C.
______________________________________Elementary analysis: C H N______________________________________Calcd. for C.sub.18 H.sub.21 N.sub.2 ClO.sub.2 (%) 65.03 6.37 8.43Found (%) 65.21 6.32 8.50______________________________________
NMR spectrum (CDCl.sub.3) .delta. ppm: 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).
These results indicated that the compound obtained was ##STR79##
EXAMPLES 72-100
The compounds listed in Table 2 below were prepared in the same manner as in Example 70 or 71 using suitable starting materials.
TABLE 2__________________________________________________________________________Ex. No. Formula Property NMR spectrum (CDCl.sub.3) .delta. ppm__________________________________________________________________________72 ##STR80## m.p. 98.5-99.degree. C. 1.06 (s, 9H), 2.9 (m, 2H), 5.0 (m, 1H), 6.7-7.2 (m, 7H), 7.9 (m, 1H)73 ##STR81## m.p. 70-70.5.degree. C. 0.9-1.2 (m, 6H), 2.0 (m, 1H), 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)74 ##STR82## m.p. 72.5-73.degree. C. 0.7-2.0 (m, 9H), 2.9 (m, 2H), 5.1 (m, 1H), 6.9 (m, 1H), 7.0-7.1 (m, 4H), 7.2 (m, 1H), 6.9 (m, 1H)75 ##STR83## m.p. 128-128.5.degree. C. 1.06 (s, 9H), 2.9 (m, 2H), 5.0 (m, 1H), 6.9 (m, 1H), 6.7-7.1 (m, 4H), 7.2 (m, 1H) .9 (m, 1H)76 ##STR84## m.p. 109.5-110.degree. C. 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, 7H)77 ##STR85## m.p. 90- 90.5.degree. C. 1.06 (s, 9H), 2.2 (s, 3H), 2.9 (m, 2H), 5.0 (m, 1H), 6.9-7.1 (m, 4H), 7.2 (m, 1H), 6.9 (m, 1H)78 ##STR86## m.p. 82-82.5.degree. C. 1.1 (s, 9H), 1.3 (m, 3H), 2.2 (m, 2H), 2.9 (m, 2H), 5.0 (m, 1H), 6.9 (m, 1H9, 6.9-7.1 (m, 4H), 7.2 (m, 1H) .9 (m, 1H)79 ##STR87## m.p. 86.5-87.degree. C. 1.1 (s, 9H), 1.3 (d, 6H), 2.1 (m, 1H), 3.0 (m, 2H), 5.0 (m, 1H), 6.9 (m, 1H), 6.9-7.1 (m, 4H) 7.2 (m, 1H), .9 (m, 7H)80 ##STR88## m.p. 98-98.5.degree. C. 1.06 (s, 9H), 1.2 (s, 9H), 2.9 (m, 2H), 5.0 (m, 1H), 6.9 (m, 1H), 6.9-7.1 (m, 4H), 7.2 (m, 1H), 6.9 (m, 1H)81 ##STR89## m.p. 82.5-83.degree. C. 1.06 (s, 9H), 2.9 (m, 2H), 3.7 (s, 3H), 5.0 (m, 1H), 6.9 (m, 1H), 7.0-7.2 (m, 4H), 7.2 (m, 1H), 7.9 (m, 1H)82 ##STR90## m.p. 81.5-82.degree. C. 1.1 (s, 9H), 1.3 (m, 3H), 2.9 (m, 2H), 4.0 (m, 2H), 5.0 (m, 1H), 6.9 (m, 1H), 6.9-7.1 (m, 4H), 7.2 (m, 1H), 7.9 (m, 1H)83 ##STR91## m.p. 80.5-81.degree. C. 1.06 (s, 9H), 3.0 (m, 2H), 5.0 (m, 1H), 6.7-7.3 (m, 11H), 7.9 (m, 1H)84 ##STR92## m.p. 111.5-112.degree. C. 1.06 (s, 9H), 3.0 (m, 2H), 5.0 (m, 1H), 6.7-7.4 (m, 11H), 7.9 (m, 1H)85 ##STR93## m.p. 97-97.5.degree. C. 1.06 (s, 9H), 3.0 (m, 2H), 5.1 (m, 1H), 6.8-7.2 (m, 6H), 7.9 (m, 1H)86 ##STR94## m.p. 113.5-114.degree. C. 1.06 (s, 9H), 3.0 (m, 2H), 5.1 (m, 1H), 6.8-7.3 (m, 6H), 7.9 (m, 1H)87 ##STR95## m.p. 93-93.5.degree. C. 1.06 (s, 9H), 2.2 (s, 3H), 2.9 (m, 2H), 5.0 (m, 1H), 6.8-7.2 (m, 6H), 7.9 (m, 1H)88 ##STR96## m.p. 97-97.5.degree. C. 1.1 (s, 9H), 2.3 (s, 3H), 3.0 (m, 2H), 5.0 (m, 1H), 6.7-7.2 (m, 6H), 7.9 (m, 1H)89 ##STR97## m.p. 106.5-107.degree. C. 1.06 (s, 9H), 2.9 (m, 2H), 5.0 (m, 1H), 6.9 (m, 1H), 7.05-7.2 (m, 3H), 7.22 (m, 1H), 7.9 (m, 1H)90 ##STR98## m.p. 90.5-91.degree. C. 1.1 (s, 9H), 3.0 (m, 2H), 5.0 (m, 1H), 6.8-7.2 (m, 5H), 7.9 (m, 1H)91 ##STR99## m.p. 99-99.5.degree. C. 1.1 (s, 9H), 3.0 (m, 2H), 5.0 (m, 1H), 6.8-7.2 (m, 5H), 7.9 (m, 1H)92 ##STR100## m.p. 112-112.5.degree. C. 1.1 (s, 9H), 3.0 (m, 2H), 5.0 (m, 1H), 6.8 (s, 1H), 6.8-7.2 (m, 6H), 7.9 (m, 1H)93 ##STR101## m.p. 70.5-71.degree. C. 0.7-2.0 (m, 11H), 2.9 (m, 2H), 5.1 (m, 1H), 6.9 (m, 1H), 6.9-7.1 (m, 4H), 7.2 (m, 1H), 7.9 (m, 1H)94 ##STR102## yellow oil 1.1 (s, 9H), 1.3 (m, 3H), 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)95 ##STR103## m.p. 71.5-72.degree. C. 0.7-1.7 (m, 11H), 2.9 (m, 2H), 5.2 (m, 1H), 6.9 (m, 1H), 6.9-7.1 (m, 4H), 7.2 (m, 1H), 7.9 (m, 1H)96 ##STR104## yellow oil 1.2 (m, 9H), 1.3 (m, 3H), 2.0 (m, 2H), 2.9 (m, 2H), 5.0 (m, 1H), 6.9 (m, 1H), 6.9-7.1 (m, 4H), 7.2 (m, 1H) .9 (m, 1H)97 ##STR105## m.p. 71.5-72.degree. C. 0.8-2.0 (m, 9H), 2.95 (m, 2H), 5.2 (m, 1H), 6.9 (m, 1H), 7.0-7.2 (m, 4H), 7.22 (m, 1H), 7.96 (m, 1H)98 ##STR106## m.p. 68-68.5.degree. C. 0.7-2.0 (m, 9H), 2.2 (s, 3H), 3.0 (m, 2H), 5.0 (m, 1H), 6.9 (m, 1H), 6.9-7.2 (m, 4H), 7.22 (m, 1H), 7.9 (m, 1H)99 ##STR107## pale yellow oil 0.8-2.3 (m, 7H), 2.9 (m, 2H), 5.2 (m, 1H), 6.9 (m, 1H), 6.9-7.2 (m, 4H), 7.2 (m, 1H), 7.9 (m, 1H)100 ##STR108## white crystal m.p. 69.5-70.degree. 0.8-1.1 (m, 6H), 1.16 (s, 9H), 2.0 (m, 1H), 2.82 (m, 2H), 5.0 (m, 1H), 6.8 (m, 1H), 6.9-7.1 (m, 4H), 7.12 (m, 1H) 7.84 (m,__________________________________________________________________________ 1H)
EXAMPLE 101
Preparation of 1'-(p-chlorophenoxy)-3',3'-dimethyl-4'-chloro-2'-butyl imidazol-1-yl-carboxylate
A 2.6 g quantity of 1-(p-chlorophenoxy)-3,3-dimethyl-4-chloro-2-butanol, 1.8 g of N,N'-carbonyldiimidazole and 40 ml of ethyl acetate were placed into a 100-ml egg plant type flask and refluxed for 3 hours. The reaction mixture was concentrated in a vacuum, and the resulting residue was purified by silica gel column chromatography, giving 2.1 g of the above-identified desired compound.
M.p.: 65.7.degree. C.
______________________________________Elementary analysis: C H N______________________________________Calcd. for C.sub.16 H.sub.18 N.sub.2 O.sub.3 Cl.sub.2 (%) 53.80 5.08 7.84Found (%) 53.62 5.14 7.76______________________________________
NMR spectrum (CDCl.sub.3) .delta. ppm: 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).
These results indicated that the compound obtained was ##STR109##
EXAMPLE 102
Preparation of 1'-(p-ethylphenoxy)-3',3'-dimethyl-4'-bromo-2'-butyl imidazol-1-yl-carboxylate
A 3.0 g quantity of 1-(p-ethylphenoxy)-3,3-dimethyl-4-bromo-2-butanol, 0.81 ml of pyridine and 50 ml of ethyl acetate were placed into a 100-ml four-necked flask, and 0.6 ml of trichloromethyl chloroformate was added dropwise to the mixture with cooling and stirring. The mixture was thereafter stirred at room temperature for 18 hours and then cooled again. To the mixture were added 0.7 g of imidazole and 0.81 ml of pyridine, and the resulting mixture was stirred at room temperature for 30 minutes and further refluxed for 3 hours. The reaction mixture was washed with water and saturated aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate and concentrated in a vacuum. The residue obtained was purified by silica gel column chromatography, giving 3.0 g of the above-identified desired compound.
M.p.: 47.1.degree. C.
______________________________________Elementary analysis: C H N______________________________________Calcd. for C.sub.18 H.sub.23 N.sub.2 O.sub.3 Br (%) 54.69 5.86 7.09Found (%) 54.58 5.92 7.01______________________________________
NMR spectrum (CDCl.sub.3) .delta. ppm: 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).
These results indicated that the compound obtained was ##STR110##
EXAMPLES 103-111
The compounds listed in Table 3 below were prepared in the same manner as in Example 101 or 102 using suitable starting materials.
TABLE 3__________________________________________________________________________Ex. No. Formula Property NMR spectrum (CDCl.sub.3) .delta. ppm__________________________________________________________________________103 ##STR111## m.p. 67.6.degree. C. 1.02 (6H), 3.32 (2H), 4.10 (2H), 5.32 (1H), 6.58 (2H), 6.90 (1H), 7.03 (2H), 7.20 (1H), 7.93 (1H)104 ##STR112## oil 1.12 (6H), 2.00 (3H), 3.90 (2H), 4.10 (2H), 5.30 (1H), 6.62 (2H), 6.90 (1H), 7.05 (2H), 7.25 (1H) 7.95 (1H)105 ##STR113## m.p. 85.4.degree. C. 1.20 (6H), 4.20 (4H), 5.45 (1H), 6.62 (2H), 6.90 (1H), 7.05 (2H), 7.10-7.50 (6H), 7.80 (1H), 7.95 (1H)106 ##STR114## m.p. 51.3.degree. C. 1.20 (3H), 1.30 (6H), 4.05 (2H), 4.10 (2H), 5.55 (1H), 6.62 (2H), 6.90 (1H), 7.05 (2H), 7.12 (1H) 7.92 (1H)107 ##STR115## m.p. 64.5.degree. C. 1.15 (3H), 1.20 (6H), 2.55 (2H), 3.45 (2H), 4.20 (2H), 5.40 (1H), 6.68 (2H), 6.90 (1H), 6.95 (2H) 7.30 (1H), 8.00 (1H)108 ##STR116## oil 1.12 (6H), 1.15 (3H), 2.00 (3H), 2.53 (2H), 3.90 (2H), 4.15 (2H), 5.35 (1H), 6.63 (2H), 6.90 (1H), 6.95 (2H), 7.28 (1H), 7.98 (1H)109 ##STR117## oil 1.15 (3H), 1.20 (6H), 2.52 (2H), 4.20 (2H), 5.42 (1H), 6.60 (1H), 6.85 (1H), 6.90 (2H), 7.25 (4H) 7.65 (1H), 7.92 (1H)110 ##STR118## oil 1.15 (3H), 1.18 (3H), 1.30 (6H), 2.45 (2H), 4.00 (2H), 4.07 (2H), 5.50 (1H), 6.58 (2H), 6.83 (1H) 6.90 (2H), 7.20 (1H), 7.90 (1H)111 ##STR119## oil 1.20 (3H), 1.30 (6H), 4.02 (2H), 4.10 (2H), 5.52 (1H), 6.55-7.25 (7H), 7.90 (1H),__________________________________________________________________________
EXAMPLE 112
Preparation of 1'-(p-chlorophenoxy)-3,',3'-dimethyl-2'-butyl imidazol-1-yl-thiocarboxylate
A 2.3 g quantity of 1-(p-chlorophenoxy)-3,3-dimethyl-2-butanol, 0.81 ml of pyridine and 50 ml of ethyl acetate were placed into a 100-ml four-necked flask, and 0.77 ml of thiophosgene was added dropwise to the mixture with cooling in an ice bath and stirring. The mixture was thereafter stirred at room temperature for 18 hours. To the mixture were then added 0.7 g of imidazole and 0.81 ml of pyridine, and the resulting mixture was refluxed for 3 hours. The reaction mixture was washed with water and saturated aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate and concentrated in a vacuum. The residue obtained was purified by silica gel column chromatography, giving 1.5 g of the above-identified desired compound in an oily form.
______________________________________Elementary analysis: C H N______________________________________Calcd. for C.sub.16 H.sub.19 N.sub.2 O.sub.2 SCl (%) 56.71 5.65 8.27Found (%) 56.43 5.88 8.10______________________________________
NMR spectrum (CDCl.sub.3) .delta. ppm: 1.10 (9H), 4.14 (2H), 5.72 (1H), 6.60 (2H), 6.88 (1H), 7.04 (2H), 7.45 (1H), 8.18 (1H).
These results indicated that the compound obtained was ##STR120##
EXAMPLE 113
Preparation of 1'-(p-ethylphenoxy)-3',3'-dimethyl-2'-butyl imidazol-1-yl-thiocarboxylate
A 2.2 g quantity of 1-(p-ethylphenoxy)-3,3-dimethyl-2-butanol, 0.81 ml of pyridine and 50 ml of ethyl acetate were placed into a 100-ml four-necked flask, and 0.77 ml of thiophosgene was added dropwise to the mixture with cooling in an ice bath and stirring. The mixture was thereafter stirred at room temperature for 18 hours. To the mixture were added 0.7 g of imidazole and 0.81 ml of pyridine, and the resulting mixture was refluxed for 3 hours. The reaction mixture was washed with water and saturated aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate and concentrated in a vacuum. The residue obtained was purified by silica gel column chromatography, giving 1.3 g of the above-identified desired compound in the form of an oil.
______________________________________Elementary analysis: C H N______________________________________Calcd. for C.sub.18 H.sub.24 N.sub.2 O.sub.2 S (%) 65.03 7.28 8.43Found (%) 64.97 7.34 8.31______________________________________
NMR spectrum (CDCl.sub.3) .delta. ppm: 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).
These results indicated that the compound obtained was ##STR121##
EXAMPLE 114
Preparation of 1'-(p-chlorophenyl)-4',4'-dimethyl-3'-amyl imidazol-1-yl-thiocarboxylate
A 2.3 g quantity of 1-(p-chlorophenyl)-4,4-dimethyl-3-amyl alcohol, 0.81 ml of pyridine and 50 ml of ethyl acetate were placed into a 100-ml four-necked flask, and 0.77 ml of thiophosgene was added dropwise to the mixture with cooling and stirring. The mixture was thereafter stirred at room temperature for 18 hours and then cooled again. To the mixture were added 0.7 g of imidazole and 0.81 ml of pyridine, and the resulting mixture was stirred at room temperature for 30 minutes and further refluxed for 3 hours. The reaction mixture was washed with water and saturated aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate and concentrated in a vacuum. The residue obtained was purified by silica gel column chromatography, giving 1.1 g of the above-identified desired compound.
M.p.: 66.5.degree. C.
______________________________________Elementary analysis: C H N______________________________________Calcd. for C.sub.17 H.sub.21 N.sub.2 OSCl (%) 60.61 6.28 8.32Found (%) 60.42 6.35 8.28______________________________________
NMR spectrum (CDCl.sub.3) .delta. ppm: 0.98 (9H), 2.05 (2H), 2.62 (2H), 5.55 (1H), 6.92 (1H), 7.00 (4H), 7.48 (1H), 8.20 (1H).
These results indicated that the compound obtained was ##STR122##
EXAMPLE 115
Preparation of 1'-(p-chlorophenyl)-3',3'-dimethyl-2'-butyl imidazol-1-yl-thiocarboxylate
A 2.1 g quantity of 1-(p-chlorophenyl)-3,3-dimethyl-2-butanol, 0.81 ml of pyridine and 50 ml of ethyl acetate were placed into a 100-ml four-necked flask, and 0.77 ml of thiophosgene was added dropwise to the mixture with cooling and stirring. The mixture was thereafter stirred at room temperature for 18 hours and then cooled again. To the mixture were added 0.7 g of imidazole and 0.81 ml of pyridine, and the resulting mixture was stirred at room temperature for 30 minutes and further refluxed for 3 hours. The reaction mixture was washed with water and saturated aqueous solution of sodium chloride, dried over anhydrous magnesium sulfate and concentrated in a vacuum. The residue obtained was purified by silica gel column chromatography, giving 1.2 g of the above-identified desired compound.
M.p.: 86.8.degree. C.
______________________________________Elementary analysis: C H N______________________________________Calcd. for C.sub.16 H.sub.19 N.sub.2 OSCl (%) 59.52 5.93 8.68Found (%) 59.31 6.01 8.73______________________________________
NMR spectrum (CDCl.sub.3) .delta. ppm: 1.10 (9H), 2.92 (2H), 5.65 (1H), 6.88 (1H), 7.00 (4H), 7.40 (1H), 8.12 (1H).
These results indicated that the compound obtained was ##STR123##
EXAMPLES 116-132
The compounds listed in Table 4 below were prepared in the same manner as in Examples 112, 113, 114 and 115 using suitable starting materials.
TABLE 4__________________________________________________________________________Ex. No. Formula Property NMR spectrum (CDCl.sub.3) .delta. ppm__________________________________________________________________________116 ##STR124## oil 1.10 (9H), 4.12 (2H), 5.78 (1H), 6.60-7.30 (6H), 7.50 (1H), 8.20 (1H)117 ##STR125## m.p. 41.2.degree. C. 1.10 (9H), 4.20 (2H), 5.72 (1H), 6.50-7.10 (5H), 7.47 (1H), 8.19 (1H)118 ##STR126## oil 1.10 (9H), 4.17 (2H), 5.72 (1H), 6.75 (2H), 6.86 (1H), 7.18 (2H), 7.45 (1H), 8.17 (1H)119 ##STR127## oil 1.10 (9H), 2.20 (3H), 4.16 (2H), 5.75 (1H), 6.56 (2H), 6.83 (1H), 6.90 (2H), 7.45 (1H), 8.15 (1H)120 ##STR128## oil 1.10 (9H), 2.20 (3H), 4.16 (2H), 5.73 (1H), 6.40-6.70 (3H), 6.88 (1H), 6.90 (1H), 7.45 (1H), 8.15 (1H)121 ##STR129## oil 0.88 (3H), 1.10 (9H), 1.52 (2H), 2.45 (2H), 4.15 (2H), 5.72 (1H), 6.57 (2H), 6.83 (1H), 6.90 (2H), 7.46 (1H), 8.15 (1H)122 ##STR130## oil 1.10 (9H), 2.75 (1H), 4.18 (2H), 5.75 (1H), 6.65 (2H), 6.85 (1H), 6.93 (2H), 7.45 (1H), 8.15 (1H)123 ##STR131## oil 1.10 (9H), 1.26 (9H), 4.16 (2H), 5.75 (1H), 6.60 (2H), 6.85 (1H), 7.10 (1H), 7.42 (1H), 8.13 (1H)124 ##STR132## oil 1.10 (9H), 4.20 (2H), 5.75 (1H), 6.73 (2H), 6.85 (1H), 7.05-7.45 (8H), 8.20 (2H)125 ##STR133## oil 1.10 (9H), 3.65 (3H), 4.15 (2H), 5.70 (1H), 6.60 (4H), 6.86 (1H), 7.45 (1H), 8.15 (1H)126 ##STR134## m.p. 94.1.degree. C. 1.10 (9H), 4.15 (2H), 5.70 (1H), 6.60 (1H), 6.85 (1H), 6.92 (1H), 7.15 (1H), 7.45 (1H), 8.15 (1H)127 ##STR135## m.p. 59.0.degree. C. 1.10 (9H), 2.12 (6H), 4.15 (2H), 5.70 (1H), 6.40 (2H), 6.75 (1H), 6.82 (1H), 7.40 (1H), 8.10 (1H)128 ##STR136## oil 1.00 (9H), 2.08 (2H), 2.60 (2H), 5.55 (1H), 6.90 (4H), 7.05 (5H), 7.45 (1H), 8.15 (1H)129 ##STR137## oil 0.98 (9H), 1.05 (6H), 2.00 (2H), 2.60 (2H), 5.55 (1H), 6.88 (1H), 6.92 (4H), 7.45 (1H), 8.15 (1H)130 ##STR138## oil 0.98 (9H), 2.00 (2H), 2.60 (2H), 3.62 (3H), 5.53 (1H), 6.60 (2H), 6.88 (1H), 6.92 (2H), 7.45 (1H), 8.15 (1H)131 ##STR139## m.p. 101.3.degree. C. 0.98 (9H), 2.05 (2H), 2.60 (2H), 5.55 (1H), 6.80 (1H), 6.90 (1H), 7.10 (2H), 7.45 (1H), 8.15 (1H)132 ##STR140## oil 1.08 (9H), 2.96 (2H), 5.65 (1H), 6.82 (1H), 7.00 (5H), 7.40 (1H), 8.10 (1H)__________________________________________________________________________
EXAMPLE 133
Preparation of 1'-(p-chlorophenylthio)-3',3'-dimethyl-2'-butyl imidazol-1-yl-carboxylate
A 2.4 g quantity of 1-(p-chlorophenylthio)-3,3-dimethyl-2-butanol and 2.0 g of N,N'-carbonyldiimidazole were placed into 30 ml of ethyl acetate, and the mixture was refluxed for 3 hours with stirring. The reaction mixture was then cooled to room temperature, washed with water twice, dried over anhydrous magnesium sulfate and distilled to remove the solvent. The residue was purified by silica gel column chromatography, giving 2.9 g of the above-identified desired compound in the form of a pale yellow oil.
______________________________________Elementary analysis: C H N______________________________________Calcd. for C.sub.16 H.sub.19 N.sub.2 SO.sub.2 Cl (%) 56.71 5.65 8.27Found (%) 56.89 5.64 8.30______________________________________
NMR spectrum (CDCl.sub.3) .delta. ppm: 0.92 (9H), 3.62 (2H), 4.92 (1H), 6.62-7.30 (6H), 7.90 (1H).
These results indicated that the compound obtained was ##STR141##
EXAMPLE 134
Preparation of 1'-(o-chlorophenylthio)-3',3'-dimethyl-2'-butyl imidazol-1-yl-carboxylate
A 2.4 g quantity of 1-(o-chlorophenylthio)-3,3-dimethyl-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 in small portions to the solution while the solution was being cooled at a temperature of up to 10.degree. C. With addition of 0.8 g of pyridine and 0.7 g of imidazole, the mixture was then refluxed for 3 hours with stirring. The mixture resulting from the reaction was washed with water, dried and concentrated. The residue was purified by silica gel column chromatography, giving 2.8 g of the above-identified desired compound in the form of a pale yellow oil.
______________________________________Elementary analysis: C H N______________________________________Calcd. for C.sub.16 H.sub.19 N.sub.2 SO.sub.2 Cl (%) 56.71 5.65 8.27Found (%) 56.82 5.63 8.29______________________________________
NMR spectrum (CDCl.sub.3) .delta. ppm: 0.91 (9H), 3.65 (2H), 5.01 (1H), 6.5-7.3 (6H), 7.90 (1H).
These results indicated that the compound obtained was ##STR142##
EXAMPLE 135-149
The compounds listed in Table 5 below were prepared in the same manner as in Example 133 or 134 using suitable staring materials.
TABLE 5__________________________________________________________________________Ex. No. Formula Property NMR spectrum (CDCl.sub.3) .delta. ppm__________________________________________________________________________135 ##STR143## yellow oil 0.92 (9H), 3.04 (2H), 4.90 (1H), 6.8 (1H), 7.0-7.40 (6H), 7.90 (1H)136 ##STR144## yellow oil 0.92 (9H), 3.02 (2H), 4.92 (1H), 6.68-7.32 (6H), 7.88 (1H)137 ##STR145## yellow oil 0.92 (9H), 2.30 (3H), 3.02 (2H), 4.90(1H), 6.68-7.32 (6H), 7.90 (1H)138 ##STR146## yellow oil 0.94 (9H), 1.02 (9H), 3.02 (2H), 4.92 (1H), 6.60-7.32 (6H), 7.90 (1H)139 ##STR147## yellow oil 0.92 (9H), 1.30 (3H), 2.40 (2H), 3.02 (2H), 4.92 (1H), 6.72-7.30 (6H), 7.88 (1H)140 ##STR148## yellow oil 0.92 (9H), 1.02-1.30 (6H), 2.42 (1H), 3.02 (2H), 4.90 (1H), 6.68-7.32 (6H), 7.90 (1H)141 ##STR149## yellow oil 0.94 (9H), 3.02 (2H), 3.70 (3H), 4.92 (1H), 6.60-7.36 (3H), 7.92 (1H)142 ##STR150## yellow oil 0.92 (9H), 1.32 (3H), 3.0 (2H), 3.88 (2H), 4.88 (1H), 6.54-7.30 (6H), 7.88 (1H)143 ##STR151## yellow oil 0.92 (9H), 3.02 (2H), 4.92 (1H), 6.62-7.30 (5H), 7.90 (1H)144 ##STR152## yellow oil 0.92 (9H), 2.50 (1H), 3.04 (2H), 4.52 (2H), 6.62-7.32 (6H), 7.88 (1H)145 ##STR153## yellow oil 0.92 (9H), 1.80 (3H), 3.02 (2H), 4.30 (1H), 4.92 (2H), 6.60-7.36 (6H), 7.90 (1H)146 ##STR154## yellow oil 0.92 (9H), 2.32 (3H), 3.08 (2H), 4.92 (1H), 6.70-7.32 (5H), 7.88 (1H)147 ##STR155## yellow oil 0.92 (9H), 2.30 (3H), 3.02 (2H), 4.90 (1H) 6.70-7.32 (6H), 7.90 (1H)148 ##STR156## yellow oil 0.92 (9H), 2.32 (3H), 3.04 (2H), 4.90 (1H), 6.68-7.32 (6H), 7.90 (1H)149 ##STR157## yellow oil 0.92 (9H), 3.02 (2H), 4.92 (1H), 6.8-7.32 (4H), 7.90__________________________________________________________________________ (1H)
EXAMPLE 150
Preparation of 1'-(p-chlorophenoxy)-2'-methyl-2'-propyl imidazol-1-yl-carboxylate
A 2.0 g quantity of 1-(p-chlorophenoxy)-2-methyl-2-propanol and 2.0 g of N,N'-carbonyldiimidazole were placed into 30 ml of ethyl acetate, and the mixture was refluxed for 3 hours with stirring. The reaction mixture was then cooled to room temperature, washed with water twice, dried over anhydrous magnesium sulfate and distilled to remove the solvent. The residue was purified by silica gel column chromatography, giving 2.4 g of the above-identified desired compound in the form of a pale yellow oil.
______________________________________Elementary analysis: C H N______________________________________Calcd. for C.sub.14 H.sub.15 N.sub.2 O.sub.3 Cl (%) 59.056 5.310 9.838Found (%) 59.224 5.278 9.921______________________________________
NMR spectrum (CDCl.sub.3) .delta. ppm: 1.62 (6H), 4.10 (2H), 6.60-7.22 (6H), 7.88 (1H).
These results indicated that the compound obtained was ##STR158##
EXAMPLE 151
Preparation of 1'-(p-chlorophenoxy)-2',3'-dimethyl-2'-butyl imidazol-1-yl-carboxylate
A 2.9 g quantity of 1-(p-chlorophenoxy)-2,3-dimethyl-2-butanol and 0.8 g of pyridine were placed into 30 ml of ethyl acetate, and the mixture was stirred at a temperature of up to 10.degree. C. A 0.6 ml quantity of trichloromethyl chloroformate was added dropwise in small portions to the mixture. The resulting mixture was thereafter stirred at room temperature for 2 hours. Subsequently, 0.8 g of pyridine and 0.7 g of imidazole were added to the mixture, and the mixture was refluxed with stirring for 3 hours, thereafter cooled to room temperature, washed with water, dried over anhydrous magnesium sulfate and distilled to remove the solvent. The residue was purified by silica gel column chromatography, giving 2.8 g of the above-identified desired compound in the form of a pale yellow oil.
______________________________________Elementary analysis: C H N______________________________________Calcd. for C.sub.16 H.sub.19 N.sub.2 O.sub.3 Cl (%) 59.536 5.933 8.678Found (%) 59.712 5.892 8.704______________________________________
NMR spectrum (CDCl.sub.3) .delta. ppm: 1.20 (6H), 1.62 (3H), 2.40 (1H), 4.18 (2H), 6.6-7.30 (6H), 7.90 (1H).
These results indicated that the compound obtained was ##STR159##
EXAMPLES 152-178
The compounds listed in Table 6 below were prepared in the same manner as in Example 150 or 151 using suitable starting materials.
TABLE 6__________________________________________________________________________Ex. No. Formula Property NMR spectrum (CDCl.sub.3) .delta.__________________________________________________________________________ ppm152 ##STR160## yellow oil 1.68 (6H), 4.10 (2H), 6.7-7.3 (7H), 7.90 (1H)153 ##STR161## yellow oil 0.88-2.34 (8H), 1.60 (3H), 4.12 (2H), 6.62-7.20 (6H), 7.88 (1H)154 ##STR162## yellow oil 0.9-2.40 (11H), 1.60 (3H), 4.10 (2H), 6.62-7.24 (6H), 7.88 (1H)155 ##STR163## yellow oil 0.9-2.72 (12H), 4.18 (1H), 6.60-7.22 (7H), 7.90 (1H)156 ##STR164## yellow oil 0.8-2.3 (14H), 4.12 (2H), 6.60-7.22 (6H), 7.88 (1H)157 ##STR165## yellow oil 0.9-2.42 (22H), 4.18 (2H), 6.6-7.30 (6H), 7.88 (1H)158 ##STR166## yellow oil 1.68 (6H), 4.10 (2H), 6.6-7.4 (7H), 7.88 (1H)159 ##STR167## yellow oil 1.2 (6H), 1.62 (3H), 2.40 (1H), 4.18 (2H), 6.6-7.30 (7H), 7.90 (1H)160 ##STR168## yellow oil 0.9-2.42 (22H), 4.12 (2H), 6.6-7.30 (7H), 7.90 (1H)161 ##STR169## yellow oil 1.2 (3H), 1.68 (6H), 2.50 (2H), 4.08 (2H), 6.6-7.2 (6H), 7.88 (1H)162 ##STR170## yellow oil 0.9-1.8 (9H), 1.55 (3H), 2.3-2.8 (3H), 4.22 (2H), 6.60-7.20 (6H), 7.88 (1H)163 ##STR171## yellow oil 1.1 (3H), 0.9-2.0 (11H), 1.6 (3H), 2.40 (2H), 4.20 (2H), 6.6-7.2 (6H), 7.88 (1H)164 ##STR172## yellow oil 0.82-2.60 (19H), 4.14 (2H), 6.60-7.22 (6H), 7.88 (1H)165 ##STR173## yellow oil 0.9-1.34 (12H), 1.60 (3H), 2.4-3.0 (2H), 4.30 (2H), 6.60- 7.22 (6H), 7.90 (1H)166 ##STR174## yellow oil 1.60 (6H), 4.10 (2H), 6.70-7.26 (5H), 7.90 (1H)167 ##STR175## yellow oil 0.90-2.42 (22H), 4.12 (2H), 0.62-7.30 (5H), 7.88 (1H)168 ##STR176## yellow oil 0.82-2.40 (14H), 4.10 (2H), 0.62-7.30 (5H), 7.88 (1H)169 ##STR177## yellow oil 1.2 (6H), 0.9-2.3 (11H), 1.60 (3H), 4.24 (2H), 6.6-7.2 (6H), 7.90 (1H)170 ##STR178## yellow oil 1.36 (3H), 1.70 (6H), 3.88 (2H), 4.08 (2H), 6.70 (4H), 6.88 (1H), 7.18 (1H), 7.90 (1H)171 ##STR179## yellow oil 0.9-1.8 (9H), 1.60 (3H), 2.40 (1H), 3.88 (2H), 4.18 (2H), 6.70 (4H), 6.88 (1H), 7.18 (1H), 7.90 (1H)172 ##STR180## yellow oil 0.8-2.3 (17H), 3.88 (2H), 4.18 (2H), 6.68 (4H), 6.90 (1H), 7.20 (1H), 7.90 (1H)173 ##STR181## yellow oil 1.3 (3H), 0.9-2.4 (11H), 1.60 (3H), 3.82 (2H), 4.22 (2H), 6.68 (4H), 6.90 (1H), 7.20 (1H), 6.90 (1H)174 ##STR182## yellow oil 1.30 (9H), 1.70 (3H), 4.10 (2H), 6.68-7.30 (6H), 7.90 (1H)175 ##STR183## yellow oil 1.68 (6H), 3.70 (3H), 4.10 (2H), 6.70 (4H), 6.88 (1H), 7.18 (1H), 7.90 (1H)176 ##STR184## yellow oil 1.22 (3H), 1.70 (6H), 2.8 (1H), 4.1 (2H), 6.65-7.22 (6H), 7.90 (1H)177 ##STR185## yellow oil 1.62 (6H), 4.12 (2H), 6.60-7.22 (6H), 7.88 (1H)178 ##STR186## yellow oil 1.60 (6H), 4.10 (2H), 6.62-7.22 (6H), 7.88 (1H)__________________________________________________________________________
FORMULATION EXAMPLE 1
(25% wettable powder)
______________________________________Ingredient Parts by wt.______________________________________Compound of invention 25White carbon 45Kieselguhr 16Sodium salt of higher alcohol sulfate 2Sodium salt of .beta.-naphthalenesulfonic 2acid-formalin condensation productAlkyl phenyl phenol sulfate 10 100______________________________________
The above ingredients were thoroughly mixed together by a mixer and finely divided by a pulverizer to obtain a 25% wettable powder.
FORMULATION EXAMPLE 2
(20% emulsificable concentrate)
______________________________________Ingredient Parts by wt.______________________________________Compound of invention 20Polyoxyethylene styryl phenyl ether 8Sodium dodecylbenzenesulfonate 4Xylene 68 100______________________________________
The above ingredients were mixed together to obtain a 20% emulsificable concentrate.
TEST EXAMPLE 1
Control effect on cucumber powdery mildew
The wettable powder prepared in Formulation Example 1 was sprayed, as diluted to a specified concentration, onto cucumber seedlings (in two- to three-leaf stage) planted in 200-ml pots (7.5 cm in diameter). After the composition dried in air, a suspension of spores of Sphaerotheca fuliginea causing the above disease was sprayed onto the seedlings for inoculation. Two weeks thereafter, the lesion area percentage was determined, and the control effect was calculated from the following equation. ##EQU1##
The seedlings were also checked for phytotoxicity.
Table 7 shows the results.
TABLE 7______________________________________Compound Concentration Control effectNo. (ppm) (%) Phytotoxicity______________________________________ 1 12.5 92 none 2 12.5 90 none 3 12.5 95 none 4 12.5 100 none 5 12.5 100 none 6 12.5 95 none 10 12.5 100 none 11 12.5 100 none 12 12.5 93 none 13 12.5 100 none 14 12.5 100 none 17 12.5 95 none 18 12.5 92 none 19 12.5 90 none 22 12.5 97 none 26 12.5 95 none 32 12.5 100 none 39 12.5 95 none 43 12.5 92 none 44 12.5 90 none 45 12.5 90 none 47 12.5 95 none 48 12.5 90 none 49 12.5 92 none 50 12.5 66 none 51 12.5 70 none 52 12.5 60 none 53 12.5 80 none 54 12.5 85 none 55 12.5 60 none 56 12.5 65 none 58 12.5 60 none 59 12.5 80 none 60 12.5 85 none 61 12.5 85 none 63 12.5 90 none 64 12.5 75 none 65 12.5 80 none 66 12.5 60 none 67 12.5 60 none 68 12.5 65 none 69 12.5 60 none 70 12.5 100 none 71 12.5 90 none 72 12.5 96 none 73 12.5 92 none 75 12.5 100 none 76 12.5 100 none 77 12.5 98 none 78 12.5 95 none 79 12.5 100 none 80 12.5 95 none 81 12.5 95 none 85 12.5 92 none 86 12.5 90 none 87 12.5 90 none 88 12.5 92 none 89 12.5 90 none 92 12.5 98 none 96 12.5 85 none 97 12.5 90 none 99 12.5 95 none101 12.5 100 none102 12.5 98 none103 12.5 100 none104 12.5 74 none105 12.5 66 none106 12.5 60 none107 12.5 100 none108 12.5 82 none109 12.5 75 none110 12.5 68 none111 12.5 57 none112 12.5 100 none113 12.5 95 none114 12.5 85 none115 12.5 100 none116 12.5 90 none117 12.5 87 none118 12.5 100 none119 12.5 90 none120 12.5 85 none121 12.5 97 none122 12.5 100 none123 12.5 95 none124 12.5 100 none125 12.5 92 none126 12.5 88 none127 12.5 85 none128 12.5 65 none129 12.5 80 none130 12.5 95 none131 12.5 73 none132 12.5 93 none133 12.5 95 none134 12.5 80 none135 12.5 83 none136 12.5 98 none137 12.5 90 none138 12.5 90 none139 12.5 85 none140 12.5 80 none141 12.5 90 none142 12.5 86 none143 12.5 75 none144 12.5 75 none145 12.5 80 none146 12.5 85 none147 12.5 75 none148 12.5 75 none149 12.5 70 none150 12.5 95 none151 12.5 90 none152 12.5 80 none153 12.5 90 none154 12.5 60 none155 12.5 75 none156 12.5 68 none157 12.5 63 none158 12.5 90 none159 12.5 86 none161 12.5 92 none162 12.5 90 none163 12.5 72 none164 12.5 69 none166 12.5 83 none168 12.5 72 none170 12.5 90 none171 12.5 86 none174 12.5 89 none176 12.5 90 none177 12.5 93 none______________________________________
TEST EXAMPLE 2
Control effect on cucumber gray mold
The wettable powder prepared in Formulation Example 1 was sprayed, as diluted to a specified concentration, onto cucumber seedlings (in two- to three-leaf stage) planted in 200-ml pots (7.5 cm in diameter). After the composition dried in air, a suspension of spores of Botrytis cinerea causing the above disease was sprayed onto the seedlings for inoculation. Seven days thereafter, the lesion area percentage was determined, and the control effect was calculated in the same manner as in Test Example 1. The seedlings were also checked for phytotoxicity.
Table 8 shows the results.
TABLE 8______________________________________Compound Concentration Control effectNo. (ppm) (%) Phytotoxicity______________________________________ 1 200 60 none 2 200 52 none 3 200 75 none 4 200 100 none 5 200 100 none 6 200 100 none 10 200 100 none 11 200 100 none 12 200 75 none 13 200 93 none 14 200 97 none 15 200 64 none 16 200 50 none 17 200 73 none 18 200 65 none 19 200 50 none 20 200 55 none 21 200 48 none 22 200 83 none 26 200 85 none 30 200 90 none 32 200 100 none 35 200 85 none 37 200 85 none 47 200 100 none 48 200 95 none 49 200 100 none 51 200 84 none 53 200 66 none 54 200 70 none 55 200 60 none 56 200 75 none 57 200 75 none 58 200 60 none 59 200 90 none 60 200 90 none 61 200 95 none 62 200 80 none 63 200 85 none 64 200 68 none 65 200 82 none 66 200 80 none 67 200 65 none 68 200 70 none 69 200 65 none 70 200 90 none 72 200 85 none 73 200 70 none 74 200 65 none 75 200 100 none 76 200 100 none 77 200 90 none 78 200 95 none 79 200 90 none 80 200 85 none 81 200 90 none 84 200 80 none 86 200 65 none 87 200 70 none 88 200 60 none 92 200 60 none 94 200 75 none 95 200 70 none 96 200 60 none 97 200 55 none101 200 100 none102 200 100 none103 200 96 none104 200 74 none105 200 68 none106 200 55 none107 200 100 none108 200 82 none109 200 78 none110 200 62 none111 200 50 none112 200 75 none113 200 100 none114 200 88 none115 200 100 none116 200 65 none117 200 60 none118 200 100 none119 200 55 none120 200 45 none121 200 80 none122 200 70 none123 200 65 none124 200 74 none125 200 100 none126 200 55 none127 200 43 none128 200 66 none129 200 75 none130 200 92 none131 200 45 none132 200 83 none133 200 85 none134 200 64 none135 200 70 none136 200 95 none137 200 100 none138 200 85 none139 200 95 none140 200 95 none141 200 90 none142 200 85 none143 200 64 none144 200 72 none145 200 65 none146 200 60 none147 200 66 none148 200 70 none149 200 75 none150 200 83 none151 200 78 none152 200 70 none153 200 70 none154 200 65 none155 200 76 none156 200 66 none157 200 60 none158 200 90 none161 200 88 none162 200 75 none163 200 62 none165 200 80 none167 200 60 none169 200 65 none172 200 70 none174 200 85 none175 200 90 none176 200 88 none177 200 90 none178 200 90 none______________________________________
TEST EXAMPLE 3
Curing effect on rice blast
A suspension of spores of Pyricularia oryzae causing the above disease was sprayed onto rice seedlings (in four-leaf stage) planted in 200-ml pots (7.5 cm in diameter). Twenty-four hours thereafter, the emulsifiable concentrate prepared in Formulation Example 2 was sprayed as diluted to a specified concentration onto the rice seedlings. Seven days thereafter, the lesion area percentage was determined, and the control effect was calculated in the same manner as in Test Example 1. The seedlings were also checked for phytotoxicity.
Table 9 shows the results.
TABLE 9______________________________________Compound Concentration Control effectNo. (ppm) (%) Phytotoxicity______________________________________1 500 90 none2 500 65 none3 500 95 none4 500 93 none5 500 100 none6 500 77 none10 500 100 none11 500 85 none12 500 88 none13 500 70 none14 500 75 none17 500 83 none18 500 64 none22 500 95 none26 500 98 none29 500 100 none30 500 98 none31 500 96 none32 500 100 none34 500 98 none43 500 72 none47 500 80 none48 500 85 none49 500 90 none50 500 62 none51 500 60 none52 500 55 none53 500 77 none54 500 80 none55 500 64 none56 500 60 none57 500 62 none58 500 60 none59 500 82 none60 500 85 none63 500 60 none64 500 60 none65 500 65 none66 500 60 none67 500 66 none68 500 68 none69 500 70 none70 500 100 none71 500 60 none72 500 90 none73 500 75 none74 500 60 none75 500 100 none76 500 100 none77 500 95 none78 500 90 none79 500 95 none80 500 85 none81 500 90 none89 500 75 none90 500 65 none91 500 60 none92 500 90 none97 500 75 none98 500 80 none99 500 85 none100 500 60 none101 500 100 none102 500 96 none103 500 100 none104 500 82 none105 500 71 none106 500 46 none107 500 100 none108 500 76 none109 500 58 none110 500 53 none111 500 44 none112 500 100 none113 500 80 none114 500 95 none115 500 100 none116 500 64 none117 500 55 none118 500 100 none119 500 75 none120 500 68 none121 500 78 none122 500 90 none123 500 88 none124 500 85 none125 500 100 none126 500 95 none127 500 80 none128 500 88 none129 500 95 none130 500 73 none131 500 100 none132 500 81 none133 500 100 none134 500 80 none135 500 85 none136 500 100 none137 500 92 none138 500 75 none139 500 90 none140 500 95 none141 500 90 none142 500 85 none143 500 68 none144 500 74 none145 500 83 none146 500 66 none147 500 85 none148 500 70 none149 500 83 none150 500 100 none151 500 95 none152 500 78 none153 500 80 none154 500 70 none157 500 70 none158 500 96 none159 500 90 none164 500 90 none165 500 85 none166 500 73 none167 500 65 none168 500 70 none170 500 90 none171 500 85 none172 500 80 none173 500 72 none174 500 90 none176 500 94 none177 500 96 none178 500 90 none______________________________________
TEST EXAMPLE 4
Control effect on helminthosporium leaf spots on rice
The emulsifiable concentrate prepared in Formulation Example 2 was sprayed, as diluted to a specified concentration, onto rice seedlings (in five-leaf stage) planted in 200-ml pots (7.5 cm in diameter). After the emulsion dried in air, a suspension of spores of Cochliobolus miyabeanus causing the above disease was sprayed onto the seedlings for inoculation. Seven days thereafter, the lesion area percentage was determined, and the control effect was calculated in the same manner as in Test Example 1. The seedlings were also checked for phytotoxicity.
Table 10 shows the results.
TABLE 10______________________________________Compound Concentration Control effectNo. (ppm) (%) Phytotoxicity______________________________________1 100 93 none2 100 78 none3 100 95 none4 100 100 none5 100 100 none6 100 95 none10 100 100 none11 100 100 none12 100 88 none13 100 98 none14 100 98 none16 100 73 none17 100 92 none18 100 85 none19 100 86 none20 100 90 none21 100 84 none22 100 100 none26 100 100 none32 100 100 none43 100 71 none47 100 100 none48 100 95 none49 100 100 none50 100 63 none51 100 65 none52 100 60 none53 100 85 none54 100 90 none55 100 73 none56 100 68 none57 100 66 none58 100 70 none59 100 84 none60 100 90 none61 100 82 none62 100 80 none63 100 77 none64 100 60 none65 100 80 none66 100 85 none67 100 60 none70 100 95 none72 100 90 none73 100 60 none75 100 100 none76 100 98 none77 100 90 none78 100 90 none79 100 96 none80 100 80 none81 100 85 none83 100 90 none84 100 85 none92 100 90 none93 100 60 none94 100 60 none95 100 75 none96 100 60 none97 100 80 none98 100 75 none99 100 90 none101 100 100 none102 100 98 none103 100 96 none104 100 78 none105 100 63 none106 100 59 none107 100 100 none108 100 82 none109 100 73 none110 100 53 none111 100 56 none112 100 100 none113 100 80 none114 100 93 none115 100 100 none116 100 74 none117 100 85 none118 100 100 none119 100 95 none120 100 83 none121 100 78 none122 100 93 none123 100 88 none124 100 90 none125 100 95 none126 100 100 none127 100 82 none128 100 75 none129 100 86 none130 100 96 none131 100 100 none132 100 68 none133 100 100 none134 100 80 none135 100 93 none136 100 100 none137 100 98 none138 100 75 none139 100 90 none140 100 92 none141 100 90 none142 100 88 none143 100 80 none144 100 74 none145 100 75 none146 100 70 none147 100 86 none148 100 80 none149 100 83 none150 100 100 none151 100 89 none152 100 80 none157 100 70 none158 100 90 none159 100 90 none161 100 95 none162 100 90 none163 100 74 none164 100 70 none168 100 70 none169 100 75 none170 100 90 none171 100 86 none172 100 80 none173 100 72 none174 100 88 none175 100 92 none176 100 90 none177 100 100 none178 100 92 none______________________________________

Number	Date	Country
61-7731	Jan 1986	JPX
61-31400	Feb 1986	JPX
61-297186	Dec 1986	JPX

Fungicidal imidazol-1-yl-carboxylic acid ester derivatives

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