JPH07126254A - Imidazole compound and its production - Google Patents

Abstract

PURPOSE:To obtain the new compound useful as an intermediate for agrochemicals and pharmaceuticals by reacting a specific phenacyl derivative with a lower-alkyl dialkoxyacetoimidate compound. CONSTITUTION:This is a new imidazole compound expressed by formula I (Z is a phenyl which may be substituted with a lower alkyl; R is a lower alkyl), e.g. 2-(dimethoxy)-4(5)-phenylimidazole and useful as an intermediate for agrochemicals and pharmaceuticals, especially as the intermediate capable of producing an agricultural and horticultural bactericidal agent. This compound is obtained by reacting a compound [e.g. 2-(dimethoxymethyl)-4(5)- phenylimidazole] expressed by formula II with a compound (e.g. methyl diethoxyacetoimidate) expressed by formula III (A is a lower alkyl) in the presence of a base, e.g. sodium methylate under heating.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel imidazole compound and a method for producing the same, and these compounds are useful as intermediate compounds for agricultural chemicals or pharmaceuticals.

[0002]

2. Description of the Related Art Org. Chem. 47 2196
(1982) describes 2-diethoxymethyl-imidazole and a method for obtaining the same. However, the compounds and reaction conditions described therein also differ from those of the present invention. Particularly, it differs from the production method of the present invention in that the reaction is carried out in multiple steps, that it is carried out under acidic conditions, and that p-TsOH is used as a condensing agent in the reaction.

Aust. J. Chem. 24 2389
(1971) describes a method for obtaining 4-phenylimidazole-2-carbaldehyde.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an imidazole compound useful as an intermediate compound for agricultural chemicals or pharmaceuticals and a method for producing the same.

[0005]

That is, the present invention provides a compound of formula (I)

[Chemical 5] (In the formula, Z is a phenyl group which may be substituted with lower alkyl, and R is a lower alkyl group).

The phenyl group which may be substituted with lower alkyl defined by Z is, for example, an unsubstituted phenyl group,
2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl,
A phenyl group substituted with an alkyl group having 1 to 4 carbon atoms such as 4-ethylphenyl is included.

The lower alkyl group defined by R is
Included are alkyl groups having 1 to 4 carbon atoms, such as methyl and ethyl.

The compound of formula (I) can be prepared by the following method.

[Chemical 6] (In the formula, Z and R are as described above, and A is a lower alkyl group.) The mineral acid salt of the formula (II) includes hydrochloride and sulfate.

The stoichiometric ratio of the compound of formula (II) to the compound of formula (III) is 1: 1. For example, the compound of formula (III) synthesized by a known method is isolated. In the case where the compound of the formula (III) is used in the above reaction without being carried out, one or more equivalents of the compound of the formula (II) may be used.

The above reaction is carried out in the presence of a solvent and an acid acceptor. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene, cyclic or non-cyclic aliphatic hydrocarbons such as chloroform, carbon tetrachloride, methylene chloride, dichloroethane, trichloroethane, n-hexane and cyclohexane, diethyl. ether,
Dioxane, ethers such as tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, aprotic polar solvents such as dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane, etc., Examples thereof include alcohols such as methanol and ethanol, and examples of the acid acceptor include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, organic carboxylates of alkali metals such as sodium acetate, and sodium methyl ester. Alkali metal alcoholates such as sodium carbonate, anhydrous potassium carbonate, alkali metal or alkaline earth metal carbonates such as anhydrous calcium carbonate, alkali metal hydrides such as sodium hydride, sodium sodium Inorganic bases such as alkali metals, such as, or organic bases such as triethylamine. Of these, organic carboxylates of alkali metals or alkali metal alcoholates are preferable. The amount of the acid acceptor used may be 1 equivalent or more with respect to the compound of the formula (II).

The reaction temperature of this reaction is usually 20 to 150.
C., preferably 50 to 120.degree. C., and the reaction time is usually 1 to 24 hours.

The compound of formula (I) can be converted into the compound of formula (IV) by a hydrolysis reaction.

[Chemical 7] (In the formula, Z is as described above)

Mineral acids such as hydrochloric acid and sulfuric acid having a concentration of about 10% are used for the hydrolysis reaction. Reaction temperature is usually 10
The reaction time is 1 to 24 hours.

Among the compounds of the formula (IV), compounds in which Z is an unsubstituted phenyl group are known and disclosed in JP-A-2-13436.
No. 9 publication.

The compound of formula (IV) can be obtained, for example, from Japanese Patent Application Laid-Open No. 2-1.
According to the method described in JP-A-34369 or in accordance therewith, it can be induced to the agricultural and horticultural fungicide described in JP-A-1-131163.

Further, the compound of formula (I) can be converted into the compound of formula (V) by chlorination or bromination.

[Chemical 8] (In the formula, Z and R are as described above, and Y is a chlorine atom or a bromine atom.)

For the chlorination reaction or bromination reaction, chlorine, N
Chlorinating or brominating agents such as chlorosuccinimide, sodium hypochlorite, bromine, N-bromosuccinimide are used. The reaction temperature is usually 0 to 100 ° C., and the reaction time is 1 to 24 hours.

[0018]

EXAMPLES Example 1 2- (diethoxymethyl) -4 (5)-(4
Synthesis of -Methylphenyl) imidazole (Compound No. 3) To 12 ml of methanol was added 0.77 g of a 28% sodium methylate methanol solution, and 2.58 g (0.02 mol) of diethoxyacetonitrile was added dropwise at room temperature. After completion of the dropwise addition, the mixture was reacted at room temperature for 1 hour to obtain a methanol solution of methyldiethoxyacetimidate.
Methylphenacylamine hydrochloride 1.85 g (0.01 mol) was added in small portions. Next, 1.93 g of 28% sodium methylate methanol solution was added dropwise, and further 18 ml of methanol was added. The reaction mixture was reacted at room temperature for 1 hour and then heated under reflux for 2 hours.

After completion of the reaction, the reaction mixture was cooled and the solvent was distilled off under reduced pressure. The residue was extracted with methylene chloride, washed with water, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, the residue was washed with hexane, the solid was collected by filtration, and the melting point was 10
1.65 g of the target product (Compound No. 3) at 3 to 105 ° C
(Yield 64%) was obtained.

Example 2 2- (dimethoxymethyl) -4
Synthesis of (5)-(4-methylphenyl) imidazole (Compound No. 2) 2.02 g (0.02 mol) of dimethoxyacetonitrile instead of 2.58 g of diethoxyacetonitrile as a raw material
Except that the target compound (compound No. 1) having a melting point of 127 to 129 ° C. was reacted and post-treated in the same manner as in Example 1 except that
2) 1.42 g (yield 61%) was obtained.

Reference Example 4 Synthesis of (5)-(4-methylphenyl) imidazole-2-carbaldehyde 2- (diethoxymethyl) -4 obtained in Example 1
(5)-(4-methylphenyl) imidazole 1.30
A mixture of g and 9 ml of 10% hydrochloric acid was reacted at 80 to 90 ° C for 1 hour. After the reaction was completed, the reaction mixture was cooled, and 5% Na was added.
The pH was adjusted to 9 with an aqueous OH solution, and the precipitated solid was collected by filtration to obtain 0.78 g of the desired product having a melting point of 199 to 202 ° C.

Examples of the imidazole compound according to the present invention include the following. Compound No. 1: 2- (dimethoxymethyl) -4 (5)
-Phenylimidazole Compound No. 2: 2- (dimethoxymethyl) -4 (5)
-(4-methylphenyl) imidazole (melting point 127-
129 ° C.) Compound No. 3: 2- (diethoxymethyl) -4 (5)
-(4-methylphenyl) imidazole (melting point 103-
105 ° C.) Compound No. 4: 2- (dimethoxymethyl) -4 (5)
-(4-Ethylphenyl) imidazole Compound No. 5: 2- (diethoxymethyl) -4 (5)
-(4-Ethylphenyl) imidazole

Claims (2)

[Claims] 1. Formula (I): (In the formula, Z is a phenyl group which may be substituted with lower alkyl, and R is a lower alkyl group). 2. Formula (I): (Wherein Z is a phenyl group which may be substituted with lower alkyl, and R is a lower alkyl group), which is a process for producing an imidazole compound represented by the formula (II): (Wherein Z is as described above) and a compound of formula (III) (Wherein R is as described above and A is a lower alkyl group).