JPH02134369A - Imidazole-based compound - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I [X is -CHO or -CH=NOH; Y is H, Cl or Br: Z is 2-6C straight-chain alkyl or phenyl which may be replaced with halogen; Q is H,-SO2R<1> (R<1> is alkyl, dialkylamino, phenyl, etc.) or -CH(R<2>)(R<3>) {R<2> is H, CH3 or alkoxy; R<3> is alkoxy, -OCH2CH2Si(CH3)3, phenyl, etc.}]. EXAMPLE:1-Dimethylsulfamoyl-2-(hydroxyiminomethyl)-4(5)-phenylmidazole. USE:An intermediate for producing agricultural and horticultural controller against harmful organisms, germicide for drugs, etc. PREPARATION:A compound shown by formula II [Q' is -SO2R<1> or -CH(R<2>)(R<3>); Z' is H, Cl, Br or Z] is formylated in the presence of n-C4H9Li, THF, etc., at -80 to 30 deg.C for 1-24 hours to give a corresponding compound shown by formula I.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to novel imidazole compounds, which are used in the production of agricultural and horticultural pest control agents or pharmaceutical fungicides. [Disclosure of the Invention] The present invention provides a compound having the formula (I), wherein , Z is a C!-4 linear alkyl group optionally substituted with a halogen atom, or a phenyl group optionally substituted with a halogen atom, Q is a hydrogen atom, -3O,R1(R'
is an alkyl group; a dialkylamino group: or a phenyl group optionally substituted with an alkyl group), or -CI
l(R") (It3) group (R" is a hydrogen atom, methyl group or alkoxy group, R1 is an alkoxy group, OC
llmCllgSi (C1ls) s group, or a phenyl group optionally substituted with an alkyl group or an alkoxy group), provided that X, Y, Z and Q are simultaneously each -0110 group, a hydrogen atom, a phenyl group and This invention relates to an imidazole compound represented by the following formula (excluding cases where it is a dimethylsulfamoyl group). - In the definition of formula (I), C,-, straight-chain alkyl groups include, for example, ethyl group, n-propyl group, n-butyl group,
Examples include n-pentyl group and n-hexyl group. Other alkyl moieties constituting alkyl groups, dialkylamino groups, alkoxy groups, etc. include those of CI-6, such as methyl, ethyl, propyl, butyl, pentyl, and hexyl groups; Examples of the halogen atom, which may be chain-like or have a side chain, include fluorine atom, chlorine atom, bromine atom, and iodine atom, and their C! -4 When the number of substitutions on the linear alkyl group or phenyl group is two or more, they may be the same or different. In the definition of Q in general formula (I), -sowR' group and -CI
The (R") (R') group is commonly used as a protecting group, for example, in the Journal of Organic Chemistry (J, Org, Che+s, P),
I, 1107° (I98B), representative examples of which include dimethylsulfamoyl group, methanesulfonyl group, benzenesulfonyl group, 1-(I-ethoxyethyl) group, dimethoxymethyl methoxymethyl group, methoxymethyl group, trimethylsilylethoxymethyl (SEM)m, benzyl group, and the like. For example, the imidazole compound represented by the following formula (■') can be converted into a product (I'
-1) to (B4). (In the formula, 2° is a hydrogen atom, a chlorine atom, a bromine atom, an alkyl group optionally substituted with a halogen atom, or a phenyl group optionally substituted with a halogen atom, and X, Y
and Q are as described above). - In the definition of formula (B), the halogen atom is a fluorine atom,
Examples include a chlorine atom, a bromine atom, and an iodine atom, and examples of the alkyl group include those after C1-1, which may be linear or have a side chain. In reaction formula (I), Q' is -3O, R'(R' is an alkyl group; a dialkylamino group; or a phenyl group optionally substituted with an alkyl group) or -CIl (R
") (R") group + R" is a hydrogen atom, methyl group or alkoxy group, R3 is an alkoxy group, 0C11xCI
IiSi(CII+) 3 group, or a phenyl group optionally substituted with an alkyl group or an alkoxy group), and Y and Z' are as described above. The mineral acids used in reaction formula [1] include hydrochloric acid, sulfuric acid, etc., the alcohols include methanol, ethanol, etc., and the s+ttou mineral acid salts include N11. Examples include Oll.hydrochloride and Nlll0I+.sulfate. In the oxime formation reaction, instead of pyridine, alcohols such as methanol, ethanol, and isopropanol, ethers such as monoglyme, diglyme, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, and diethylene glycol, dichloroethane, chloroform, and tetrachloroethane are used as solvents. Halogenated hydrocarbons such as 11, benzene, monochlorobenzene, nitrobenzene, aromatic hydrocarbons such as toluene, nitriles such as acetonitrile, dimethyl sulfoxide, dimethylformamide, water, etc. may be used, and furthermore, from these A mixed solvent of selected solvents may be used. When carrying out a two-phase reaction using a mixed solvent, a phase transfer catalyst such as triethylbenzylammonium chloride or trioctylmethylammonium chloride may be used. You can also do it. In addition, an inorganic base or an organic base can be used as the base. Examples of the inorganic base include carbonates of alkali metals or alkaline earth metals such as sodium carbonate, potassium carbonate, calcium carbonate, and sodium hydrogen carbonate, and hydroxides. Examples include hydroxides or hydrides of alkali metals or alkaline earth metals such as sodium, potassium hydroxide, calcium hydroxide, and lithium hydride. Examples of the organic base include diethylamine, triethylamine, and 4-dimethylaminopyridine. In reaction formula [1], the compound represented by formula (II) can be converted into a product (■-1
) to (■-3). In cases other than when A, Q' are -CIl (Rχ) (R') groups, and R: and R3 are the same or different alkoxy groups: B, Q' are -CIl (R') ) (R') group and R
When 1 and R3 are the same or different alkoxy groups:
C, Q' are -CHxOCIItCIIxSi (C1
lt) In the case of s group (method other than reaction A above) In reaction formula [2], Q'' is a -So!R' group (R' is an alkyl group, nidialkylamino group; or may be substituted with an alkyl group) phenyl group) or -CIl (R”)
(R group [R” is a hydrogen atom, methyl group, or alkoxy group, R3 is an alkoxy group, QC!IxC1ltS
i (CIls) is a z group, or a phenyl group which may be substituted with an alkyl group or an alkoxy group. However, R
3 and R3 are both alkoxy groups), R1', R3' and R4 are independently alkoxy groups, and Y and Z. is as described above. Solvents used in the above reaction A include aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene, chloroform, carbon tetrachloride, methylene chloride,
Cyclic or acyclic aliphatic hydrocarbons such as dichloroethane, trichloroethane, n-hexane, cyclohexane,
Ethers such as diethyl ether, dioxane, and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, acetonitrile,
Nitriles such as propionitrile, dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide,
Examples of acid acceptors include aprotic polar solvents such as sulfolane; examples of acid acceptors include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metals such as anhydrous potassium carbonate and anhydrous calcium carbonate; Examples include earth metal carbonates, alkali metal hydrides such as sodium hydride, inorganic bases such as alkali metals such as sodium metal, or organic bases such as triethylamine. The above reaction B is a reversible reaction, and the target product (n-2) can be obtained by heating while removing the generated R4.II. In the same reaction, as the alkoxy group for R1' and R'', a methoxy group or an ethoxy group is particularly preferable.
) The imidazole compound represented by any one of - formula (I [I)
It is derived from the compound represented by The compound represented by formula (III) is highly effective as a paleonticide for agricultural and horticultural applications, as will be described later. In reaction formula [3], 11al is a halogen atom, Y, 2
° and Q are as described above. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the solvent and acid acceptor used in the dimethylsulfamoylation reaction include those similar to those used in reaction A of reaction formula [2]. In the dehydration reaction, it is desirable to use a organic base such as pyridine as a solvent. As a dehydrating agent, instead of acetic anhydride, trichloroacetic anhydride, trichloroacetonitrile, trichloroacetyl chloride, oxalyl chloride, thionyl chloride, phosphorus oxychloride, phosphorus trichloride, phosphorus pentoxide, phosphonitriline chloride, phosgene (dimer), Cyanuric chloride, titanium tetrachloride, formic acid, etc. can also be used. In the reaction formula [3], when Y is a hydrogen atom in the compound represented by formula (V), it may be reacted with a chlorinating agent or a brominating agent at -50 to +100°C for 1 to 24 hours, if desired. can be substituted with a compound in which Y is a chlorine atom or a bromine atom, and further can be dimethylsulfamoylated to derive a compound represented by the general formula (lI[). As shown in the reaction formulas [1] and [3], the compound represented by the -a formula (II) is used in agriculture and horticulture via the formyl compound and oxime compound represented by the -a formula (l). In the process of producing a compound represented by the general formula (Ill) that is effective as a biological control agent or a medicinal bactericidal agent, the oximation reaction in reaction formula [1] and the dehydration reaction in reaction formula [3] When a common organic solvent such as pyridine is added and a mineral acid salt is used, the formyl compound and oxime compound represented by the formula (Io) are not isolated, and the formula (II
) It is possible to directly produce the compound represented by the formula (III). Among the compounds represented by each of the above formulas, - formula (+)
The compound represented by formula (I-a) means (I-b), and the compound represented by -i formula (Io) means (I'
-a) (I' -b
), and the compound represented by -a formula (It) has a tautomer represented by -, and the compound represented by formula (V) has (II-a) (■-b
), and the compound represented by formula (III) is (Ill-a) (
III-b). Note that the compound represented by the formula (IV) has a tautomer represented by the formula (IV). (X, Y, Z, Z', Q and Q' in each of the above formulas are as described above). Therefore, when producing the compound represented by the general formula (U) using the compound represented by the general formula (IV) as a raw material, the compound represented by the -C formula CII-a) and/or (II-b) is obtained. and - formula (II-a)
When producing a compound represented by general formula (Io) using a compound represented by and/or (■-b) as a raw material, the general formula (Io) and/or
A compound represented by I'-b) is obtained. However, when Q in one formula is a hydrogen atom, the compound represented by the general formula (I'-a) and the compound represented by the general formula (I'-b> become tautomers.Similarly, tautomerism When producing a compound represented by general formula (III) using a compound represented by general formula (V) in which a compound exists as a raw material, -IC formula (III-a)
A compound represented by and/or (ill-b) is obtained. As described above, due to the reaction of adding four dimethylsulfamoyl groups to a starting compound having tautomers, a mixture of two isomers or one of the isomers can be obtained. Whether a mixture or one of the isomers is obtained is determined by the raw material compound, the type of reaction for obtaining the target product from the raw material compound, each reaction condition, etc. Note that when a mixture is obtained, the mixing ratio thereof is determined in the same manner. Synthesis (I) of 1-dimethylsulfamoyl-2-(hydroxyiminomethyl)-4(5)-phenylimidazole (compound 1kl) .1, added 12.14 g of anhydrous potassium carbonate, and heated under reflux for 2 hours. After cooling, an acetone solution 45 containing 25.25 g of dimedyl sulfamoyl chloride was added dropwise.
After the dropwise addition was completed, the reaction mixture was heated under reflux for 4.5 hours to complete the reaction. After the reaction was completed, the reaction product was cooled, the solid was removed by filtration, the solvent was distilled off under reduced pressure, and the solvent was purified by silica gel column chromatography (developing solvent: methylene chloride) to obtain 1-dimethylsulfate with a melting point of 96 to 100°C. Famoil-4 (5
)-phenylimidazole (17.8 g) was obtained. [2] 17 g of 1-dimethylsulfamoyl-4(5)-phenylimidazole obtained in the above step (I) was dissolved in 290 g of tetrahydrofuran, and the solution was heated to 70 g in a nitrogen atmosphere.
After cooling to ℃, 1.6N of n-butyl lithium hexane solution 51- was added dropwise over 30 minutes.Completion of 6 dropwise addition a-7
After stirring at 0° C. for 30 minutes, a tetrahydrofuran solution 12 containing 6 g of N,N-dimethylformamide was added dropwise, and after the dropwise addition was completed, the mixture was allowed to react with stirring for 15 hours while slowly raising the temperature to room temperature. After the reaction was completed, the reaction product was poured into ice water and extracted with ethyl acetate. The extracted layer was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure, followed by silica gel column chromatography (developing solvent: ethyl acetate/hexane-1/2).
to obtain 12.8 g of 1-dimethylsulfamoyl-2-formyl-4(5)-phenylimidazole having a melting point of 86-89°C. [3] 11.16 g of l-dimethylsulfamoyl-2-formyl-4(5)-phenylimidazole obtained in the above step [2] and 5.56 g of hydroxylamine hydrochloride were dissolved in pyridine 120- and heated to room temperature. After dropping 24 drops of acetic anhydride, the temperature was gradually raised to 100°C.
The reaction was allowed to proceed for 2 hours. After the reaction was completed, the solvent in the reaction product was distilled off under reduced pressure, water 125- was added to the residue, and the precipitated solid was filtered off. This crude product was dissolved in ethyl acetate and purified by silica gel column chromatography (developing solvent = ethyl acetate) to obtain 5.55 g of 2-cyano-4(5)-phenylimidazole with a melting point of 203-205°C. . Note that the synthetic method of converting a formyl group into a cyano group, as seen in this step [3], is a well-known method in the art, and is known to proceed stepwise. J.B. Ferris et al. reported the synthesis of 4-cyanoimidazole [imidazole-4-carbonitrile] via 4-(hydroxyiminomethyl)imidazole [imidazole-4-carbaldevido oxime]. There is (J, Org, Chcv, n, 19-2
4. (I976) ). In this step [3], the target product 1-dimethylsulfamoyl-2-(hydroxyiminomethyl)-4
(5)-Femylimidazole (melting point 151-155°C
) (compound 1) was obtained, followed by 2-(acetoxyiminomethyl)-1-dimethylsulfamoyl-4(5)
It is thought that 2-cyano-4(5)-phenylimidazole is produced through -phenylimidazole (melting point 158 to 162°C) and the like. (Reference: Final product manufacturing process) (a) 2-cyano-4(5
)-Phenylimidazole 1.352 g was dissolved in chloroform 100-, N-chlorosuccinimide 1.17
5 g was added, and the mixture was reacted under heating and reflux for 4 hours. After the reaction was completed, the reaction product was poured into water and extracted with chloroform. The extracted layer was washed with water, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and purified by silica gel column chromatography (developing solvent: methylene chloride) to obtain 4(5)-chloro with a melting point of 149-151'c. -2-cyano-
1.28 g of 5(4)-phenylimidazole was obtained. (b) 4(5)-chloro-2- obtained in the above step (a)
Cyano-5(4)-phenylimidazole 0.43 g
Dissolved in acetone 6-, anhydrous potassium carbonate 0.29
g and dimethylsulfamoyl chloride 0.36 g
was added, and the mixture was reacted under heating under reflux for 30 minutes. After the reaction was completed, the reaction product was poured into water and extracted with ethyl acetate. The extracted layer was washed with water, dried with anhydrous sodium sulfate,
After distilling off the solvent under reduced pressure, it was purified by silica gel column chromatography (developing solvent: methylene chloride), and the melting point was 1.
4(5)-Chloro-2-cyano-1 at 06-109°C
0.5 g of -dimethylsulfamoyl-5(4)-phenylimidazole was obtained. As a result of analysis by NMR spectrum, the above compound was found to contain approximately equal proportions of 4-chloro-2-cyano-1-dimethylsulfamoyl-5-phenylimidazole and 5-chloro-2-cyano-1-dimethylsulfamoyl. It was an isomer mixture with -4-phenylimidazole. (1) 2.9 g of a mixture of these isomers obtained in the same manner as in step (a) above was allowed to stand at room temperature for 24 hours, and then purified by silica gel column chromatography using methylene chloride as a developing solvent to obtain a mixture with a melting point of 109. 4-chloro-2-cyano-1-dimethylsulfamoyl-5- at ~112°C
1.15 g of phenylimidazole (compound A) was obtained. Additionally, 0.7 g of 4(5)-chloro-2-cyano-5(4)-phenylimidazole was also obtained through this purification and separation. Kanazoko-1 4-chloro-2-formyl-1-dimethylsulfamoyl-5-phenylimidazole (combined magnetic compound 2-b) and 4-chloro-2-(hydroxyiminomethyl)-1-dimethylsulfa Synthesis of moyl-5-phenylimidazole (compound ?h3-b) 4(5)-phenylimidazole was dissolved in chloroform with N
- 4 (obtained by heating chlorination with chlorosuccinimide)
5)-Chloro-1-dimethylsulfamoyl-5 was prepared in the same manner as in Synthesis Example 1 (I) using 5)-chloro-5(4)-phenylimidazole (melting point 232-235°C). (4)-Phenylimidazole (M point 1
00-110°C) was obtained. After heating, this was purified and separated to obtain 4-chloro-1-dimethylsulfamoyl-5-phenylimidazole, and 4-chloro-2-4-chloro-1-dimethylsulfamoyl-5-phenylimidazole with a melting point of 102-106°C was obtained in the same manner as in Synthesis Example 1 [2]. Formyl-1
-dimethylsulfamoyl-5-phenylimidazole (compound a2-b) was obtained. Then, 4-chloro-2-(hydroxyiminomethyl)-1-dimethylsulfamoyl-5-phenylimidazole (compound Na5-b) can be obtained from this in the same manner as in Synthesis Example 1 [3]. [Reference = J! Finished product production process] Synthesis example 1 [3] via compounds 1b2-b and 3-b
4(5)-chloro-2-cyano-5(4)-phenylimidazole having a melting point of 149 to 151°C is obtained in the same manner as in Synthesis Example 1. 4-chloro-2-cyano-1-dimethylsulfamoyl-5-phenylimidazole (compound A) can be obtained in the same manner as in steps a) and (v). Jit3 4(5)-chloro-5(4)-(3-chloropropyl)
-1-dimethylsulfamoyl-2-formylimidazole (compound Hidden 4) and 4(5)-chloro-5(4)-
Synthesis of (3-chloropropyl)-1-dimethylsulfamoyl-2-(hydroxyiminomethyl)imidazole (compound Nn5) (I) Reacting 4.5-dichloroimidazole with chloromethyl methyl ether to produce 4.5- Dichloro-1-methoxymethylimidazole (nl&,
11.5090) was obtained. This slowly crystallized on standing (melting point 41-44°C). 4,5-dichloro-1 in a four-eye flask under nitrogen atmosphere.
- 20 g of methoxymethylimidazole and 200 g of dry tetrahydrofuran were charged, and 70 g of a 1.6 M n-butyllithium hexane solution was gradually added dropwise while keeping the temperature below -70° C. with dry ice-acetone. The temperature was maintained at the same temperature for several minutes, and then 13 g of trimethylchlorosilane was added dropwise at a temperature below -70°C. After the completion of the dropwise addition, the temperature was gradually returned to room temperature while stirring overnight. After distilling off the solvent under reduced pressure, 200 d of dry tetrahydrofuran was added to the residue under a nitrogen atmosphere, and 70 ml of a 1.6 M n-butyllithium hexane solution was gradually added dropwise while keeping the temperature below -70°C with dry ice-acetone. After finishing, keep at the same temperature for 30 minutes, then! - 27 g of chloro-3-iodopropane was added dropwise at a temperature below 70°C. After completion of the drop, 1 @ Stirring 1
↑ Below, the temperature was gradually returned to room temperature to complete the reaction. After the reaction was completed, the solvent was distilled off under reduced pressure, and the resulting residue was poured into water, diluted hydrochloric acid was added, and the mixture was stirred at room temperature for 30 minutes, followed by extraction with methylene chloride. This methylene chloride layer was washed with water and then dried over anhydrous sodium sulfate. After drying, methylene chloride was distilled off to obtain 23 g of 4-chloro-5-(3-chloropropyl)-1-methoxymethylimidazole as an oil. [2] 4-chloro-5(3-chloropropyl)-1-methoxymethylimidazole 23 obtained in step (I) above
was reacted with 15 ml of concentrated hydrochloric acid and 120 ml of ethanol under reflux for 5 hours. After the reaction was completed, the reaction product was poured into water and washed with methylene chloride. The aqueous layer was made alkaline with potassium carbonate, the precipitated solid was filtered, washed with water, and dried.
7.5 g of 4(5)-chloro-5(4)-(3-chloropropyl)imidazole at 0°C was obtained. [3] 4(5)-chloro-5( obtained in the above step [2])
4) Dissolve 7.5 g of -(3-chloropropyl)imidazole in 100% of anhydrous acetonitrile, add 5.7 g of anhydrous potassium carbonate, and 6.5 g of dimethylsulfamoyl chloride.
g was added thereto, and the mixture was allowed to react at room temperature for 18 hours. After the reaction was completed, the reaction product was poured into water, extracted with ethyl acetate, and the ethyl acetate layer was washed with water and then dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, it was purified by silica gel column chromatography (developing solvent: methylene chloride) to obtain 4(5)-chloro-5 with a melting point of 104-106°C.
(4) 3.8 g of -(3-chloropropyl)-1-dimethylsulfamoylimidazole was obtained. This compound is essentially 4-chloro-5-(3-chloropropyl)-
It was found by NMR to be 1-dimethylsulfamoylimidazole. In addition, the raw material 4(5)-chloro-
5(4)-(3-chloropropyl)imidazole2.
5g was also recovered. (4) 4(5)-chloro=5 obtained in step (3) above
(4) 2.86 g of -(3-chloropropyl)-1-dimethylsulfamoylimidazole was dissolved in 50% of tetrahydrofuran, cooled to -70°C under a nitrogen atmosphere, and
．． 6.7 m of 6M n-butyllithium hexane solution
was added dropwise over 3 minutes. After stirring at -70°C for 30 minutes, 0.8 of N,N-dimethylformamide was added.
A tetrahydrofuran solution 5- containing g was added dropwise, and after the dropwise addition was completed, the reaction was allowed to proceed with stirring for 3 hours while slowly raising the temperature to room temperature. After the reaction was completed, the reaction product was poured into water and extracted with methylene chloride. The extract layer was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 3.1 g of a residue. A part of this residue was purified by silica gel column chromatography (developing solvent: ethyl acetate/hexane-172) to obtain 4(5)-chloro-5(4)-(3
-chloropropyl)-1-dimethylsulfamoyl-2
-Formylimidazole (Compound Arashi 4) was obtained. This compound was found by NMR to be essentially 4-chloro-5-(3-chloropropyl)-1-dimethylsulfamoyl-2formylimidazole. As a result, the above residue is 4(5)-chloro-5(4)
-(3-chloropropyl)-1-dimethylsulfamoyl-2-formylimidazole and 4 (5)-chloro-
It was found to be a mixture containing 5(4)-(3-chloropropyl)-1-dimethylsulfamoylimidazole in a ratio of 6:4. [5] Dissolve 0.48 g of anhydrous sodium acetate and 0.41 g of hydroxylamine hydrochloride in 30 g of water, add 60 g of an ethanol solution containing 2.8 g of the residue obtained in step [4] at room temperature, and cool to room temperature. The mixture was allowed to react for 18 hours. After the reaction was completed, the reaction mixture was poured into water and extracted with ethyl acetate. The ethyl acetate layer was washed with water and then dried over anhydrous sodium sulfate. After drying, ethyl acetate was distilled off, and the residue was purified and separated using silica gel column chromatography (developing solvent: methylene chloride, then ethyl acetate) to obtain 4(5)-chloro-5(4) with a melting point of 151-154°C. −(3
-chloropropyl)-1-dimethylsulfamoyl-2
(Hydroxyiminomethyl)imidazole (compound 5
) 1.0 g was obtained. [Reference C final product manufacturing process] Compound 11h5 obtained in the above step (5) and acetic anhydride were reacted at 80°C to obtain 4(5) with a melting point of 117 to 120°C.
-Chloro-5(4)-(3-chloropropyl)-2-cyanoimidazole was obtained 0 Then continue with Synthesis Example 1 [Reference: Final product manufacturing process] Same method as steps (a) and (t) and 4(5)-chloro-5( with a melting point of 87-92°C
4) -(3-Chloropropyl)-2-cyano-1-dimethylsulfamoylimidazole was obtained, followed by 4-chloro-5-(3-chloropropyl)-2- with a melting point of 106-11 °C. Cyano-1-dimethylsulfamoylimidazole (compound B) can be obtained. Kanazoko■-Work 4 (5)-(3-chloropropyl)-1-dimethylsulfamoyl-2-formylimidazole (compound video 6
) and 4 (5) Synthesis of -(3-chloropropyl)-1-dimethylsulfamoyl-2-(hydroxyiminomethyl)imidazole (compound-7) Method similar to Synthesis Example 3 [4] and [5] from 4(5)(3-chloropropyl)-1-dimethylsulfamoylimidazole (oil) to 4(5)-(3-chloropropyl)-1-dimethylsulfamoyl-2-formylimidazole(compound- 6) and 4 (5)-(3-chloropropyl)-
1-dimethylsulfamoyl-2-(hydroxyiminomethyl)imidazole (compound animation 7) can be obtained. The raw material 4(5)-(3-chloropropyl)-1dimethylsulfamoylimidazole is a new compound described at the end of the literature, but 4(5)-(3) was prepared according to Synthesis Example 3 [3].
-chloropropyl)imidazole, and Synthesis Example 3
It can be synthesized from 1-dimethylsulfamoylimidazole via 5-(3-chloropropyl)-1-dimethylsulfamoylimidazole according to (I). [Reference: Final product manufacturing process] 4(5)-(3-chloropropyl)-2-cyano Imidazole (melting point 102-1
05°C) is obtained. This was chlorinated with N-chlorosuccinimide in methanol and 4(5)-chloro-5(4
)-(3-Chloropropyl)-2-cyanoimidazole (melting point 117-120°C) is obtained 0 Then continue with Synthesis Example 1 [Reference: FX final product manufacturing process] Same as steps (a) and (t) 4-chloro-5-(3-chloropropyl)-2-cyano-1-dimethylsulfamoylimidazole (compound B) can be obtained by the process. Combined [2-formyl-4(5)-phenylimidazole (compound animation 8) and 2-(hydroxyiminomethyl)-4(5
)-Phenylimidazole (Compound Magnetism 9) Synthesis [1] Synthesis Example 1 13.5 g of l-dimethylsulfamoyl-2-formyl-4(5) phenylimidazole obtained in the same manner as in (2), methanol 200- and 17
．． 20% of 5% hydrochloric acid was mixed and reacted at room temperature overnight with stirring. After the reaction was completed, the reaction product was neutralized with a saturated aqueous sodium carbonate solution, extracted with ethyl acetate, and dried over anhydrous sodium sulfate. Thereafter, ethyl acetate was distilled off, the obtained crystals were washed with methylene chloride, and 2-formyl-4(5)-phenylimidazole (compound +8) 6 with a melting point of 192 to 195°C was prepared.
．． 9g was obtained. [2] 2-formyl-4 (obtained in step [1])
5)-2-(hydroxyiminomethyl)-4(5)-phenylimidazole (compound-9) having a melting point of 204 to 207°C can be obtained from -phenylimidazole in the same manner as in Synthesis Example 1 [3]. [Reference: Final product manufacturing process] Synthesis example 1 In the same manner as in (3), combine magnetokinetic 9 and 2(acetoxyiminomethyl)-4(5)-phenylimidazole, etc. to obtain 2-cyano-4(5)-phenylimidazole. can be obtained by following Synthesis Example 1 [Reference;
Final product manufacturing process] 4-chloro-2-cyano-1-dimethylsulfamoyl-5-phenylimidazole (compound A) can be obtained in the same manner as in steps (a) to (t). Next, in order to supplementarily explain the method for producing an imidazole compound according to the present invention, a synthetic example using a methoxymethyl group or a jetoxymethyl group as a protecting group in the imidazole ring will be described as a reference example. Synthesis of 4,5-dichloro-2-formyl-1-methoxymethylimidazole and 4,5-dichloro-2-(hydroxyiminomethyl)-1-methoxymethylimidazole (I) 4.5-dichloroimidazole Reacted with chloromethyl methyl ether to give 4,5-dichloro-
1-methoxymethylimidazole (nl&, 11.5
090) was obtained. This slowly crystallized on standing (melting point 41-44°C). [2] 4,5-dichloro-1- obtained in the above step [1]
400 g of methoxymethylimidazole was dissolved in 4,000 g of tetrahydrofuran, cooled to -70 DEG C. under a nitrogen stream, and 1,500 ml of a 1.6 M hexane solution of butyllithium was added dropwise over 1 hour. After the dropwise addition was completed, the solution was stirred at -70°C for 30 minutes, and then N, N-
193.8 g of dimethylformamide was added dropwise, and after the dropwise addition was completed, the reaction was allowed to continue while stirring for 15 hours while slowly raising the temperature to room temperature. After the reaction was completed, the reaction product was poured into water and extracted with ethyl acetate. The extracted layer was washed with water, dried with anhydrous sodium sulfate,
The solvent was distilled off under reduced pressure to give 4,5-dichloro-2-formyl-1-methoxymethylimidazole (n"11.534
2) 461 g was obtained. [3] 4,5-dichloro-2- obtained in the above step [2]
461 g of formyl-1-methoxymethylimidazole and 306 g of hydroxylamine hydrochloride were mixed with 3.6 g of pyridine.
After dissolving in 00- and stirring at room temperature for 30 minutes, acetic anhydride 90- was added dropwise at room temperature (the internal temperature rose to 40°C).
After the completion of 0 dropwise addition, the temperature was gradually raised to carry out a reaction at 80 to 90°C. After the reaction was completed, the solvent in the reaction mixture was distilled off under reduced pressure, water was added to the residue, and the mixture was extracted with ethyl acetate. The extracted layer was washed with dilute hydrochloric acid, water, and dried over anhydrous sodium sulfate. After that, the solvent was distilled off under reduced pressure, and the melting point was 187-18.
4.5-dichloro-2-cyanoimidazole at 9°C was obtained. Note that this step proceeds in stages, and 4,5-dichloro-2-
(hydroxyiminomethyl)-1-methoxymethylimidazole, 2-(acetoxyiminomethyl)-4,5-
Dichloro-1-methoxymethylimidazole, 4.5-
It is thought that 4,5-dichloro-2-cyanoimidazole is produced through dichloro-2-cyano-1-methoxymethylimidazole (melting point 53.5-54.5°C) and the like. Reference ■-1 Synthesis of 2-formyl-1-jethoxymethylimidazole and 2-(hydroxyiminomethyl)imidazole (I) J, Org, Chem, Q, 4038~
4040. (I980), 2-formyl-1-jethoxymethylimidazole was obtained as an oil from 1-jethoxymethylimidazole. 2-( Hydroxyiminomethyl)imidazole is obtained. Note that this 2-(hydroxyiminomethyl)imidazole can be dehydrated with acetic anhydride to obtain 2-cyanoimidazole (melting point: 176°C) useful as an intermediate compound for agricultural chemicals, medicines, and the like. Representative examples of imidazole compounds according to the present invention are shown in Table 1. Ri-1-Table (I-a) (I-b) Among the compounds listed in Table 1, compounds 1th2-b and 3-th are compounds represented by the formula (I-b), and the other compounds are In order to show the utility of the final product, which is a mixture of compounds represented by general formulas (I-a) and (■b), derived from the imidazole compound according to the present invention as an intermediate compound, Reference test examples for agricultural and horticultural pest control agents are described. Kintama Fuida ■ Cucumber in a 7.5 cm diameter plastic pot (variety: Yotsuba)
was cultivated, and when it reached the two-leaf stage, it was inoculated by spraying with a suspension of downy mildew spores. After 6 hours, 125p of each test compound was added.
A chemical solution lO- adjusted to a concentration of pm was sprayed using a spray gun. After being kept in a constant temperature room at 22 to 24° C. for 6 days, the area of lesions on the first leaf was investigated, and the control index was determined according to the evaluation criteria below, and the results shown in Table 2 were obtained. The E111 control effect was determined by visual observation of the degree of disease onset of the test plants during the survey, and the control index was determined using the following five levels. (Control index) 3: 2: 1: [Incidence level] The lesion area where no lesions are observed is less than 10% of the untreated area. The lesion area is less than 40% of the untreated area. Less than 70% of the lesion area in the untreated area is 70% or more of the untreated area

Claims (1)

[Claims] General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, X is a -CHO group or -CH=NOH group, and Y
is a hydrogen atom, a chlorine atom or a bromine atom, Z is a C_2_-_6 straight chain alkyl group which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom, Q is a hydrogen atom , -SO_2R^1 group (R
^1 is an alkyl group; a dialkylamino group; or a phenyl group which may be substituted with an alkyl group), or -
CH(R^2)(R^3) group (R^2 is a hydrogen atom, methyl group or alkoxy group, R^3 is an alkoxy group,
-OCH_2CH_2Si(CH_3)_3 group, or a phenyl group which may be substituted with an alkyl group or an alkoxy group). An imidazole compound represented by the following formula, except when X, Y, Z, and Q are each a -CHO group, a hydrogen atom, a phenyl group, or a dimethylsulfamoyl group.