JPS62142164A - 4,5-dichloroimidazole based compound and pest controlling agent containing said compound - Google Patents

Abstract

NEW MATERIAL:A 4,5-dichloroimidazole based compound expressed by formula I [R1 and R2 are H or alkyl, alkenyl or alkynyl which may be respectively substituted; R1 and R2 together with N may form heterocyclic ring; R3 is cyano or formula II, III or IV (Z is O or S; R4 is H, phenyl or pyridyl)]. EXAMPLE:1-Dimethylsulfamoyl-2-cyano-4,5-dichloroimidazole. USE:Useful as a pest controlling agent, capable of exhibiting improved controlling effect particularly on late blight of potato and tomato, downy mildew of cucumber and grape and blast of rice plant and further improved controlling effect on agricuturally and horticulturally noxious insects, mites, nematodes, etc. PREPARATION:As shown in the reaction formula, the reaction is carried out in the presence of a solvent and acid acceptor to afford the aimed compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to novel 4,5-cycloloimigusol compounds or pest control agents containing them as active ingredients.

(Disclosure of the Invention) The present invention is an optionally substituted alkenyl group, or an optionally substituted pyridyl group.

The present invention relates to 4,5-dichloroimidazole compounds represented by the following formulas, pest control agents containing them, and methods for producing them.

In the general formula <I), the alkyl group, alkenyl group and alkynyl group represented by R1 and R2 may be substituted with one or more halogen atoms, and the furkyl group includes a methyl group, an ethyl group, an n- Examples of alkenyl groups include propyl group, 1so-propyl group, n-butyl group, 5ee-butyl group, 1so-butyl group, ter L-butyl group, etc., and examples of alkenyl groups include ethylene group, propenyl group, butenyl group, etc. Examples of the alkynyl group include ethyne group, propyne group, butyne group, and examples of the halogen atom include chlorine atom, bromine atom, fluorine atom, and iodine atom.

In addition, R and R2 together with the nitrogen atom form a heterocycle such as a piperidine ring, a piperazine ring, a 7-olin ring, a pyrrolidine ring, etc. The pyridyl group is a nitro group, a cyano group, a methyl group, a trifluoromethyl group, May be substituted with methoxy group, acetyl group, chlorine atom, bromine atom, etc.
Among these, trifluoromethyl group is preferred.

The compound of the present invention can be produced, for example, by the following method.

(Former (III) [In the formula, R,, R2 and R1 are as described above, and Y is a halogen atom.] The above reaction is carried out in the presence of a solvent and an acid acceptor, if necessary.

Solvent: Aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene 8: Cyclic or non-cyclic aliphatic hydrocarbons such as chloroform, carbon tetrachloride, methylene chloride, dichloroethane, trichloroethane, n-hexane, cyclohexane, etc. Ethers such as ethyl ether, nooxane, and tetrahydrofuran,
Ketones such as methyl ethyl ketone and methyl isobutyl ketone Nitriles such as acetonitrile, propionitrile, acrylonitrile M: Nomethylform 7mide, N
-Aprotic polar solvents such as methylpyrrolidone, dimethyl sulfoxide, and sulfolane.

Examples of acid acceptors include Kuroiso bases such as sodium hydroxide, potassium hydroxide, alkali gold R or alkaline earth metal carbonates, and organic bases such as triethylamine.

The above reaction can also be carried out in the presence of a suitable catalyst.

Examples of this catalyst include phase transfer catalysts such as quaternary ammonium salt derivatives.

In the above reaction formula, the compound represented by
4,5 by the method described in Publication No. 11573
It can be easily obtained by treating -dichloro-2-trichloromethylimidazole with ethanol saturated with ammonia.

Next, synthesis examples related to the compounds of the present invention will be described.

Example 1 Synthesis of 1-dimethylsulfamoyl-2-cyano-4,5-cycloimig sheets C.

4. Dissolve 5.0 g of 5-dichloro-2-cyanoimigusol in 75+nl of acetonitrile, and dissolve 4.0 g of potassium carbonate.
．． 7 g was added and refluxed for 1 hour.

Then, 4.9 g of trimethylsulf 7 moyl chloride was added and the mixture was refluxed for 30 minutes. After cooling, the reaction mixture was filtered, and the filtrate was concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (Wacodel C-200) to obtain 1-dimethylsulfamoyl-1-dimethylsulfamoyl having a melting point of 100-103°C.
4.5 g of 2-cyano-4,5-dichloroimidazole was obtained.

Example 2゜〜Synthesis of -morpholinosulfonyl-2-cya/-4,5-cyclooimidazole 2-cyano-4,5-dichloroimidazole5. og
, acetonitrile 100 mθ and anhydrous potassium carbonate4.
69 g were mixed and heated under reflux for 1 hour.

After cooling to 30° C., 6.9 g of molpoly/sulfonyl chloride was added, and the mixture was heated under reflux for 30 minutes.

Subsequently, the mixture was allowed to cool to room temperature, and inorganic substances were filtered off, extracted with ethyl acetate, washed with water, and dried over sodium sulfate. After drying,
The solvent was distilled off and separated by silica gel chromatography (Wacodel C-200), and the obtained crystals were recrystallized from a mixed solvent of 1-hexane/ethanol, melted, and q t 1
0.98 g of 1-morpholinosulfonyl-2-cyano-4,5-cycloimiguzole having a temperature of 4 to 115°C was obtained.

Examples of representative compounds of the present invention are listed below.

Compound No. 1 1-Thumethylsulfamoyl-2-cyano-4,5-cycloloimiguzole Melting point 10
0 to 103°C Compound No. 2 1-Noazurusulfamoyl-2-cyano-4,5-nochloroimidazole Compound No. 3 1-pyrrolidinosulfonyl-2-cyano-4,5-cycloimiguzole Melting point 1
37-140°C Compound No. 4 1-morpholinosulfonyl-2-cyano-4,5-cycloimiguzole
Melting point 114-115℃ Compound No. 5 1-Dimethylsulfur 7moyl-2-(2-oxazoline-2-
yl)-4,5-ene chloroimixol compound No.
6 1-dimethylsul7amoy-2-(2-thiazolin-2-yl)-4,5-cycloimiguzole compound No. 7 1-dimethylsul7amoy-4,5-dichloro-imidazole-2-carboxylic acid amide compound No. ,8 1-dimethylsul7amoyru4,5
-Dichlorose miguzol-2-carboxylic acid thioamide Compound No. 9 N (4) Lifluoromethylphenyl)-1-dimethylsul7amoy-4,5-dichloro-imidazole-2-carboxylic acid amide Melting point 258-260'C Compound No, 10 N (3-chloro-5-trifluoromethyl-2-pyridinyl)-1-tmethylsul7
Amoyru 4゜5-Fuchloroimidazole-2-carboxylic acid The compound of the present invention is useful as an active ingredient of a biological control agent, especially for potatoes and tomatoes, cucumbers and grapes, as shown in the test examples below. It exhibits excellent control effects against downy mildew of tobacco, blue mold of tobacco, various soil diseases caused by Pythium, and diseases caused by algae and fungi, as well as blast of rice. The compound of the present invention has not only a preventive effect but also a therapeutic effect, and furthermore, it has excellent systemic transferability, so that by applying it to soil, it can also control diseases on the foliage. In addition, the compounds of the present invention include insects, mites, and nematodes that are harmful to agriculture and horticulture, such as diamondback moths, leafhoppers, and red bean weevils; mites such as two-spotted spider mites and false red spider mites; Shows excellent control effect against.

7,'',,,,,,'7,・',7' □ When used, as in the case of conventional agrochemical formulations, various forms such as emulsions, powders, wettable powders, liquids, etc. are used together with adjuvants. When actually using these preparations, they can be used as is or diluted to a predetermined concentration with a diluent such as water.The auxiliary agents mentioned here include carriers. , emulsifiers, suspending agents, dispersing agents, spreading agents, penetrants, wetting agents, thickeners, stabilizers, etc.
Carriers that can be added as appropriate are divided into solid carriers and liquid carriers. Solid carriers include starch, activated carbon, soybean flour, wheat flour, wood flour, fish meal, animal and vegetable powders such as milk powder, talc, and kaolin. Examples of liquid carriers include water, alcohols such as methyl alcohol and ethylene glycol, acetone, methyl ethyl ketone, etc. ketones, ethers such as dioxane and tetrahydrofuran, aliphatic hydrocarbons such as kerosene and kerosene, aromatic hydrocarbons such as xylene, trimethylbenzene, tetramethylbenzene, cyclohexane and solvent naphtha, and halogens such as chloroform and chlorobenzene. Examples include carbonized hydrocarbons, acid amides such as dimethylformamide, esters such as ethyl acetate and glycerol esters of fatty acids, nitrites such as acetonitrile, and sulfide-containing metals such as dimethyl sulfoxide.

The application concentration of the compound of the present invention varies depending on the target crop, application method, formulation form, application amount, etc. - Although it cannot be generally specified, it is usually 1 to 10,000 p per active ingredient.
pm, preferably 20 to 2.000 ppra.

In addition, if necessary, it may be mixed or used in combination with other agricultural chemicals such as insecticides, acaricides, nematicides, fungicides, antiviral agents, attractants, herbicides, plant growth regulators, etc. I can,
In this case, even better effects may be obtained.

For example, as an insecticide, acaricide, or nematicide,
0- (4-7' lomo-2-chlorophenyl) 0-ethyl S-propyl phosphorothioate, 2.2-dichlorovinyl dimethyl phosphate, ethyl 3-methyl-4-(methylthio)phenyl isopropyl phosphoroamidate, 0.0- Dumethyl 0-4-nitro-
m-Tolyl phosphorothioate, 0-ethyl 0-4-
Nitrophenyl phenylphosphonothioate, 0.0
-Diethyl 0-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate, 0.0-dimethyl O-(3,5゜6-dolychloro-2-pyridyl) phosphorothioate, o,S-dimethyl acetyl phosphoroamidothioate , 0- (2,4-dichlorophenyl) 0-ethyl S-propyl phosphorodithioate; 2-(methylthio)propionaldehyde 0-methylcarbamoyloxime, 2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate, dimethyl N,
N'-(thiobis[(methylimino)carbonyloxy]]bisethanimidothioate, S-methyl
N-(methylcarbamoyloxy)thioacetimidate, N, N-dimethyl-2-methylcarbamoyloxyimino-2-(methylthio)acetamide, 2-(
Ethylthiomethyl)phenyl methyl carbamate, 2
-dimethylamino-5,6-dimethylpyrimidine-4-
Carbamate compounds such as yl dimethylcarbamate, S,S'-2-dimethylaminotrimethylenebis(thiocarbamate) i2. 2. 2-) dichloro-1,1-bis(4-clophenyl)ethanol, 4
-chlorophenyl 2,4゜5-trichlorophenyl
Organochlorine compounds such as sulfone; organometallic compounds such as tricyclohexyltine hydroxide;
(RS)-α-cyano-3-phenoxybendi (R
S)-2-(4-chlorophenyl)-3-methylplate, 3-phenoxybenzyl (IR5)-cis, trans-3-(2,2-dichlorovinyl)-2゜2-dimercyclopropanecarpoxylate , (R5)-α-
Cyano-3-phenoxybenzyl (IR5)-cistrans-3-(2,2-dichlorovinyl″L/)-2,
2-dimethylcyclopropanecarboxylate, (S)
-α-cyano-3-phenoxybenzyl (IR)-cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate, (RS)-α-cyano-3-phenoxybenzyl (IRS 1-(4-
chlorophenyl)-3-(2,6-difluorobenzoyl)urea, 1-(3,5-cyclo-4-(3-chloro-5-toIJfluoromethyl-2-pyridyloxy)
Benzoyl urea compounds such as phenyl)-3-(2,6-difluorobenzoyl)urea, 1-(3,5-dichloro-2°4-difluorophenyl)-3-(2,6-difluorobenzoyl)urea ;2-ter
t-Butylimino-3-isopropyl-5-phenyl-
3,4,5,6-tetrahydro-2H-1,3,5-thiadiazin-4-one, trans-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2-oxothiazolidinone-3 -carboxamide, N-methylbis(
Compounds like 2,4-xylyliminomethyl)amine@
I is isopropyl (2E, 4E)-11-methoxy-3
,7,11-)dimethyl-2,4-dodecadienoate; other compounds include dinitro compounds, organic sulfur compounds, urea compounds, triazine compounds, etc. It will be done. Furthermore, B
It can also be mixed or used in combination with biological pesticides such as T agents and insect pathogen virus agents.

For example, as a fieldicide, S-benzyl 0.0-diisopropyl phosphorothioate, 0-ethyl S, S
-diphenyl phosphorodithioate, aluminum
Organophosphorus compounds such as ethylhydrogen phosphone-1; 4, 5. 6. Organochlorine compounds such as 7-titrachlorophthalide and tetrachloroisophthalonitrile; Manganese ethylene bis(dithiocarbamate) polymer, zinc ethylene bis(dithiocarbamate) polymer, complex compound of zinc and maneb, Dithiocarbamate compounds such as polymers of disinc bis(dimethyldithiocarbamate) ethylene bis(dithiocarbamate) and zinc propylene bis(dithiocarbamate); 3a, 4.7,7a-tetrahydro N-()cyclomethanesulfenyl) Phthalimide, 3a, 4.7,7a-tetrahydro-N-(1,
N-halogenothioalkyl compounds such as 1,2,2-tetrachloroethanesulfenyl)phthalimide and N-(trichloromethylsulfenyl)phthalimide; 3
- (3,5-'; dichlorophenyl-N-isopropyl-2゜4-dioxoimidazolidine-1-carboxamide, (RS)-3-(3,5-dichlorophenyl)
-5-methyl-5-vinyl-1,3-oxazolidine-
2,4-dione, N-(3,5-dichlorophenyl)-
Dicarboximide compounds such as 1,2-dimethylcyclopropane-1,2-dicarboximide; methyl 1
Benzimidazole compounds such as -(butylcarbamoyl)benzimidazol-2-yl carbamate, dimethyl 4.4° -(0-phenylene)bis(3-thioallophanate): 1-(4-chlorophenoxy)-3, 3-dimethyl-1-(LH-1゜2.4-triazol-1-yl)butanone, ■-(biphenyyl-4-yloxy)-3,3-dimethyl-1-(IH-
1,2,4-1-riazol-1-yl)butane-2-
ol, 1- (N-(4-chloro-2-trifluoromethylphenyl)-2-propoxyacetimidoylcoimidazole, 1- (2-(2,4-dichlorophenyl)-4-ethyl-1,3- dioxolan-2-ylmethyl]-IH-1,2,4-) riazole, 1- [2
-(2,4-dichlorophenyl)-4-propyl-1,
3-dioxolan-2-ylmethyl)-LH-1,2,
Azole compounds such as 4-triazole, 1-(2-(2,4-dichlorophenyl)pentyl]-IH-1,2,4-1-riazole; 2.4°-dichloro-α
-(pyrimidin-5-yl)benzhydryl alcohol, (±)-2,4'-difluoro-α-(LH-1
, 2,4-1-riazol-1-ylmethyl)benzhydryl alcohol; 3°
Benzanilide-based compounds such as -isopropoxy-0-toluanilide, α,α,α-trifluoro3°-isopropoxy-0-)ylanilide; methyl N-(2
-methoxyacetyl)-N-(2,6-xylyl)-D
Acylalanine compounds such as L-alaninate; 3
-chloro-N-(3-chloro-2,6-sinitro-4-
α, α, α-trifluorotolyl) -5-) viridinamine series such as trifluoromethyl-2-pyridinamine;
Other compounds include piperazine compounds, morpholine compounds, anthraquinone compounds, quinoxaline compounds, crotonic acid compounds, sulfenic acid compounds, urea compounds, antibiotics, and the like.

Test examples and formulation examples of the bactericidal/insecticide according to the present invention are described below.

Test example 1 Cucumber and prevention effect test diameter 1.5cm
Cultivate cucumbers (variety: Arthu) in plastic pots, and when they reach the two-leaf stage, apply chemical solution 1 containing each test compound to a specified concentration.
0+j! was sprayed using a spray gun. 24℃〜2
After being kept in a greenhouse at 5°C for one day and night, a spore suspension of downy mildew was inoculated by spraying. 6 days after inoculation, the lesion area rate on the first leaf (χ
), and the control value was determined using the following formula, and the results shown in Table 1 were obtained.

Table 1 Test Example 2 Cucumber and Disease Treatment Effect Test Diameter 7.5cm
Cucumbers (variety 2-ga-shu) were grown in plastic pots, and when they reached the two-leaf stage, they were spray-inoculated with a spore suspension of downy mildew. 6
After hours, 10 m of chemical solution containing each test compound adjusted to a predetermined concentration.
! ! was sprayed using a spray gun. 24--25℃
After being kept in the greenhouse for 6 days, the lesion area ratio (X) on the first leaf
The control value was determined in the same manner as in Test Example 1, and the results shown in Table 2 were obtained.

Table 2 Test 3 Rice Potato Fruit Test Rice (variety: Chukyo Asahi) was cultivated in a polyethylene pot with a diameter of 7.5 cm, and when it reached the 4-leaf stage, a chemical solution of each test compound was adjusted to a specified concentration (10n+j). ! was sprayed using a spray gun. After being kept in a greenhouse at 24 to 25° C. for one day and night, a spore suspension of rice blast fungus was spray inoculated. Five days after inoculation, the number of lesions on the third leaf was investigated, and the control value was calculated using the following formula.
The results shown in Table 3 were obtained.

Table 4 Test 4 Image quality test (plant pathogenic bacteria) On a potato glucose agar medium (PSA medium) containing 100 pp+m of streptomycin and each test compound adjusted to a predetermined concentration, cucumber striped horse bacterium (H Kojuku 1 side shot I transplanted bacterial flora disks (agar punchings) from Yamagakimoto Frogyo. After culturing at 20°C for 24 hours, the bacterial flora diameter was investigated.
The mycelial growth inhibition rate was determined using the following formula, and the results shown in Table 4 were obtained.

Table 4 Test Example 5 Kidney bean/Red spider mite mite killing test Diameter 7
．． Green beans (variety: Taisho Kintoki) in a plastic pot at 5 am
was cultivated, and when it reached the primary leaf stage, one primary leaf was left and the other leaves were cut off. Two-spotted spider mite larva (Dicofol)
After inoculating about 30 seedlings (and resistant to breeding chemicals), the seedlings were immersed for about 10 seconds in 20 m7+ of a chemical solution adjusted to a predetermined concentration of each test compound.

After air-drying, it was left in a constant temperature chamber with lighting at 25° C., and at the second stage of release, it was determined whether it was alive or dead, and the mortality rate was determined using the following formula, and the results shown in Table 5 were obtained.

Table 5 Formulation Example 1゜(A) Compound No. 1 50 parts by weight (B) Zeekrite 40 #
(c) Sodium ligninsulfonate 7〃(
D) Dialkyl sulfosuccinates 39 or more were uniformly mixed to prepare an aqueous phase agent.

Formulation example 2゜(a) Compound No. 3 20 parts by weight (b) Si-crite 72〃
(c) Sodium ligninsulfonate 89 or more were uniformly mixed to form an aqueous phase agent.

Formulation example 3゜(a) Compound No. 4 5 parts by weight (b) Talc 959
The above ingredients were mixed uniformly to form an aqueous phase agent.

Formulation example 4゜(a) Compound No. 2' 2
0 parts by weight (b) Xylene 60
#(c) Polyoxyethylene alkyl allyl ether 20 The above components were mixed and dissolved to form an emulsion.

Formulation example 5゜(a) 78 parts by weight of gicrite (
b) β-Naphthalenesulfonic acid soda formalin condensation proboscis 2 (c) Polyoxyethylene alkylallyl sulfate 5
#(d) White carbon 15 #
The mixture of the above components and Compound No. 1 were mixed at a weight ratio of 4:1 to form an aqueous phase agent.

Claims (1)

[Claims] 1. General formula: ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R_1 and R_2 are a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or a substituted R_1 and R_2 may form a heterocycle with the nitrogen atom, R_3 is a cyano group, ▲ has a mathematical formula, chemical formula, table, etc. ▼ group, ▲ has a mathematical formula, a chemical formula, a table, etc. There are ▼ groups or ▲ mathematical formulas, chemical formulas,
There are tables, etc. ▼ group (wherein Z is an oxygen atom or a sulfur atom, and R_4 is a hydrogen atom, an optionally substituted phenyl group, or an optionally substituted pyridyl group). ]
A 4,5-dichloroimidazole compound represented by: 2. General formulas: ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 and R_2 are hydrogen atoms, optionally substituted alkyl groups, optionally substituted alkenyl groups, or optionally substituted alkynyl groups Yes, R_1 and R_2 may form a heterocycle with the nitrogen atom, and R_3 is a cyano group, ▲ has a mathematical formula, chemical formula, table, etc. ▼ group, ▲ has a mathematical formula, chemical formula, table, etc. ▼ group or ▲ mathematical formula , chemical formulas, tables, etc. are ▼ groups (in the formula, Z is an oxygen atom or a sulfur atom, and R_4 is a hydrogen atom, an optionally substituted phenyl group, or an optionally substituted pyridyl group). ] A pest control agent characterized by containing a 4,5-dichloroimidazole compound represented by the following as an active ingredient. 3. General formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_3 is a cyano group, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ groups, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ groups or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ group (in the formula, Z is an oxygen atom or a sulfur atom, and R_4 is a hydrogen atom, an optionally substituted phenyl group, or an optionally substituted pyridyl group). ] Compounds and general formulas represented by: ▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 and R_2 are hydrogen atoms, optionally substituted alkyl groups, optionally substituted alkenyl groups, or A good alkynyl group, R_1 and R_2 may form a heterocycle with a nitrogen atom, and Y is a halogen atom] is reacted with a compound represented by the general formula: ▲Mathematical formula, chemical formula, table, etc. ▼ A method for producing a 4,5-dichloroimidazole compound, which comprises producing a 4,5-dichloroimidazole compound represented by the formula [wherein R_1, R_2, and R_3 are as described above].