JPH04308580A - Benzimidazole dericative, its production and agricultural and horticultural antimicrobial agent containing the same as active ingredient - Google Patents

Abstract

PURPOSE:To provide the subject novel compound useful as an antimicrobial agent for horticulture. CONSTITUTION:2-Cyano-1-dimethylsulfamoyl-5,6-bis(1',1',2',2')-tetraflu oroethoxy) benzimidazole of formula I. The compound of formula I is obtained by reacting a benzimidazole compound of formula II with dimethylsulfamoyl chloride usually in the presence of a base such as pyridine or triethylamine in a solvent such as hexane.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a benzimidazole derivative, a method for producing the same, and a fungicide for agricultural and horticultural use containing the same as an active ingredient.

0002

BACKGROUND OF THE INVENTION As agricultural and horticultural fungicides, captan, captafor, and dithiocarbamate drugs are currently widely used, particularly in the fields of late blight and downy mildew. However, all of these drugs have only a preventive effect and do not show any therapeutic effect, and are not suitable for disease control by drug treatment after the onset of the disease. In other words, in terms of the practical application situation for plant disease control, in some cases spraying may be done after the onset of the disease.In particular, for control agents for algae and fungi where disease symptoms develop rapidly, it is necessary to have high preventive efficacy and excellent penetration transfer. There is a great need for sexual and therapeutic efficacy. Under these circumstances, metalaxyl [N-(2,6-dimethylphenyl)-N-(methoxyacetyl)alanine methyl ester], which has excellent permeability and therapeutic activity, was developed; However, its excellent therapeutic activity has not been fully demonstrated. Currently, particularly in the field of grape disease control, there is a desire for the emergence of therapeutic agents that have new effects and excellent systemic transferability. Conventionally, it has been described in JP-A-58-148864, JP-A-62-205063, etc. that certain benzimidazole derivatives are used as active ingredients of fungicides. However, these compounds are insufficient in terms of efficacy and systemic transferability for controlling plant diseases, especially those of algae and fungi such as downy mildew and late blight. It is difficult to say that it is necessarily satisfactory for reasons such as causing phytotoxicity to plants.

0003

[Means for Solving the Problems] In view of the above circumstances, the present inventors have developed a method that has excellent efficacy against plant diseases.
As a result of various studies in order to develop a compound with less phytotoxicity, we found that the benzimidazole derivative of the present invention has excellent preventive and therapeutic efficacy against plant diseases, has excellent systemic transferability, and has no problem with the plants to be controlled. The present invention was based on the discovery that no chemical damage occurs. That is, the present invention is represented by the formula 3

0004

[Chemical formula 3]

The present invention provides a benzimidazole derivative represented by the following formula (hereinafter referred to as the compound of the present invention), a method for producing the same, and an agricultural and horticultural fungicide containing the same as an active ingredient. Hereinafter, the method for producing the compound of the present invention will be explained in detail. The compound of the present invention has the following formula:

[0006]

[C4]

A benzimidazole compound represented by:
Obtained by reacting with dimethylsulfamoyl chloride. In the above production method, the reaction temperature and reaction time can usually achieve their objectives within the range of room temperature to solvent reflux temperature and instantaneous to about 24 hours, respectively. The reaction is usually carried out in the presence of a base, and the bases used include pyridine, triethylamine, N
, N-dimethylaniline, tributylamine, tertiary amines such as N-methylmorpholine, sodium hydroxide,
Examples include inorganic bases such as potassium hydroxide and potassium carbonate. The amount of the reagents used in the reaction is usually 1 to 2 mols of dimethylsulfamoyl chloride and usually 1 to 7 mols of the base per 1 mol of the benzimidazole compound represented by Formula 4. In the above reaction, although a solvent is not necessarily required, it is usually carried out in the presence of a solvent. Solvents that can be used in this reaction include aliphatic hydrocarbons such as hexane and petroleum ether, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as chloroform and dichloroethane, diethyl ether, dioxane, and tetrahydrofuran. ethers such as acetone, ketones such as methyl ethyl ketone, esters such as ethyl acetate and diethyl carbonate, nitriles such as acetonitrile and isobutyl nitrile, amides such as formamide and N,N-dimethylformamide, sulfur such as dimethyl sulfoxide. Examples include compounds and mixtures thereof. After the reaction is completed, the reaction solution is subjected to conventional post-treatments such as organic solvent extraction, water washing, and vacuum concentration of the organic layer, and if necessary, purification by chromatography, recrystallization, etc. The compound of the present invention can be obtained. The benzimidazole compound represented by Formula 4, which is a raw material compound for producing the compound of the present invention, is represented by Formula 5.

0
008]

[C5]

It can be obtained by reacting the 2-(trichloromethyl)benzimidazole compound shown below with ammonia. The purpose of the reaction can be achieved by setting the reaction temperature and reaction time in the range of usually -30°C to the solvent reflux temperature, and in the range of instantaneous to about 24 hours. The amount of the reagent used in the above reaction is usually 6 mol to a large excess of ammonia per 1 mol of the 2-(trichloromethyl)benzimidazole compound represented by Formula 5. In the above reaction, although a solvent is not necessarily required, it is usually carried out in the presence of a solvent. Solvents that can be used in this reaction include aliphatic hydrocarbons such as hexane and petroleum ether, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as chloroform and dichloroethane, diethyl ether, dioxane, and tetrahydrofuran. ethers such as acetone, ketones such as methyl ethyl ketone, esters such as ethyl acetate and diethyl carbonate, nitriles such as acetonitrile and isobutyl nitrile, amides such as formamide and N,N-dimethylformamide, sulfur such as dimethyl sulfoxide. compounds, alcohols such as methanol, ethanol, 2-propanol,
Examples include water and mixtures thereof. After the reaction is completed, the reaction solution is neutralized with an inorganic acid such as hydrochloric acid, and then subjected to post-treatments such as extraction with an organic solvent, washing with water, and concentrating the organic layer to obtain the desired compound. The 2-(trichloromethyl)benzimidazole compound represented by the formula 5 is represented by the formula 6

0010

[C6]

The o-phenylenediamine compound represented by the following and the general formula 7

0012

[C7]

[In the formula, R represents a lower alkyl group. ]
It can be obtained by reacting with a trichloroacetimidate compound shown in The reaction temperature and reaction time of the above-mentioned reaction can usually achieve the objective within a range of -30° C. to solvent reflux temperature, and in a range of instantaneous to about 24 hours. The amount of reagents used in the reaction is
O-phenylenediamine compound 1 represented by formula 6
The amount of the trichloroacetimidate compound represented by the general formula 7 is usually 1 to 2 mol based on the mol. In the above reaction, although a solvent is not necessarily required, it is usually carried out in the presence of a solvent. Solvents that can be used in this reaction include aliphatic hydrocarbons such as hexane and petroleum ether;
Aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as chloroform and dichloroethane, ethers such as diethyl ether, dioxane and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone,
Nitriles such as acetonitrile and isobutylnitrile,
Amides such as formamide and N,N-dimethylformamide, sulfur compounds such as dimethyl sulfoxide, alcohols such as methanol, ethanol, and 2-propanol, organic acids such as formic acid, acetic acid, and propionic acid, water, etc., or mixtures thereof. can be given. After the reaction is complete, the reaction solution is
For example, by pouring into ice water, filtering the obtained crystals or extracting with an organic solvent, performing post-treatments such as washing with water and concentration, and if necessary, purifying by operations such as chromatography and recrystallization. The desired compound can be obtained.

The 2-trichloromethylbenzimidazole compound represented by the formula 5 is a 2-aminotrichloroacetanilide compound obtained by reacting the o-phenylenediamine compound represented by the formula 6 with trichloroacetyl chloride. It can also be obtained by cyclization. The cyclization reaction can usually achieve its purpose at a temperature ranging from 40° C. to the solvent reflux temperature and within a time period ranging from instantaneous to 24 hours. In the above reaction, although a solvent is not necessarily required, it is usually carried out in the presence of a solvent. Solvents that can be used in this reaction include aliphatic hydrocarbons such as hexane and petroleum ether, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as chloroform and dichloroethane, diethyl ether, dioxane, and tetrahydrofuran. ethers such as acetone, ketones such as methyl ethyl ketone, esters such as ethyl acetate and diethyl carbonate, nitriles such as acetonitrile and isobutyl nitrile, amides such as formamide and N,N-dimethylformamide, sulfur such as dimethyl sulfoxide. Examples include compounds, alcohols such as methanol, ethanol, and 2-propanol, water, and mixtures thereof. formula
The reaction between the o-phenylenediamine compound represented by Formula 6 and trichloroacetyl chloride can be carried out in the same manner as the reaction between the compound represented by Formula 4 and dimethylsulfamoyl chloride. The o-phenylenediamine derivative represented by the formula 6 is represented by the formula 8

[
0015

[Chemical formula 8]

It can be obtained by reducing the o-nitroaniline compound shown below. For example, as a reduction method,
A method of reduction using sodium sulfide or sodium hydrosulfide in a mixture of water and a lower alcohol such as methanol or ethanol can be used. The reaction can usually be carried out at a temperature ranging from 50° C. to the solvent reflux temperature, and can usually achieve its purpose within 12 hours. In addition, in a mixture of water and an organic acid such as acetic acid or an inorganic acid such as hydrochloric acid or sulfuric acid,
The reduction reaction can be carried out using a method using zinc powder or tin powder. The reaction is usually carried out at a temperature ranging from 30°C to 100°C, and the reaction can usually reach its purpose within 12 hours. Furthermore, a method of hydrogenation using a catalyst such as platinum dioxide or palladium-carbon in an organic solvent such as ethanol or ethyl acetate under normal pressure or pressure, usually at a temperature in the range of 0°C to 60°C can be used. . Formula 8
The o-nitroanphosphorus compound represented by the general formula:

[0017]

[Chemical formula 9]

[In the formula, R' represents a lower alkyl group. ] It can be obtained by hydrolyzing the o-nitroanilide compound shown below. The reaction temperature and reaction time are usually in the range of room temperature to solvent reflux temperature, and instantaneous to about 24
You can reach your goal within a certain amount of time. The reaction is usually carried out in the presence of a base or acid, and examples of the base used include inorganic bases such as sodium hydroxide and potassium hydroxide, and examples of the acid include inorganic acids such as hydrochloric acid and sulfuric acid. can give. The amount of reagents used in the reaction is determined by the formula
The above base or acid is used in a catalytic amount to a large excess relative to 1 mol of the o-nitroanilide compound represented by Chemical Formula 9. As a solvent, depending on the base or acid used, solvent-free or
Aliphatic hydrocarbons such as hexane and petroleum ether, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as chloroform and dichloroethane, ethers such as diethyl ether, dioxane and tetrahydrofuran, acetone and methyl ethyl ketone. Ketones, nitriles such as acetonitrile and isobutylnitrile, amides such as formamide and N,N-dimethylformamide,
Sulfur compounds such as dimethyl sulfoxide, methanol,
Examples include alcohols such as ethanol and 2-propanol, organic acids such as formic acid, acetic acid, and propionic acid, water, and mixtures thereof. The o-nitroanilide compound represented by the formula 9 has the general formula 10

[0019]

[Chemical formula 10]

[In the formula, R' represents the same meaning as above. ] It can be obtained by nitration of the anilide compound shown below. The reaction can achieve its purpose in an instant to about 24 hours at a reaction temperature in the range of -40°C to 20°C. As the nitrating agent, fuming nitric acid, nitric acid, sodium nitrate, and potassium nitrate can be used, and as the solvent, acetic acid, acetic anhydride, sulfuric acid, fuming sulfuric acid, water, or a mixture thereof can be used. The anilide compound represented by general formula 10 is represented by formula 11

[0021]

[Chemical formula 11]

It can be obtained by acylating the aniline compound shown below. The reaction temperature and reaction time can usually achieve their objectives within the range of room temperature to solvent reflux temperature and instantaneous to about 24 hours, respectively. The reaction is usually carried out in the presence of a base or an acid, and the bases used include tertiary amines such as pyridine, triethylamine, N,N-dimethylaniline, tributylamine, and N-methylmorpholine, sodium hydroxide, etc. Examples of the acid include organic acids such as formic acid, acetic acid, and propionic acid, and inorganic acids such as sulfuric acid. The amount of the above-mentioned base or acid used in the reaction is determined by the amount of the aniline compound 1 represented by formula 11.
Catalytic amount to large excess relative to mole. In the above reaction, examples of the acylating agent include corresponding acid anhydrides, acid halides, ester compounds, carboxylic acids, and the like. The amount of the above-mentioned acylating agent used in the reaction is from 1 mol to a large excess per 1 mol of the aniline compound represented by Formula 11. Depending on the base or acid used, the solvent may be no solvent, aliphatic hydrocarbons such as hexane or petroleum ether, aromatic hydrocarbons such as benzene or toluene, halogenated hydrocarbons such as chloroform or dichloroethane, or diethyl. Ethers such as ether, dioxane, and tetrahydrofuran; ketones such as acetone and methyl ethyl ketone; nitriles such as ethyl acetate, acetonitrile, and isobutyl nitrile; amides such as formamide and N,N-dimethylformamide; and sulfur compounds such as dimethyl sulfoxide. , organic acids such as formic acid, acetic acid, propionic acid, or mixtures thereof. The aniline compound represented by the formula 11 is represented by the formula 12

[0023]

[Chemical formula 12]

It can be obtained by reducing the nitro compound shown below. The reduction reaction can be carried out in the same manner as the reduction reaction of the o-nitroaniline compound represented by Formula 8 above. The nitro compound represented by the formula 12 is represented by the formula 13

[0025]

[Chemical formula 13]

It can be obtained by nitration of the compound shown below. The reaction is carried out at a reaction temperature in the range of -30°C to 50°C,
The goal can be achieved in an instant to about 24 hours. As the nitrating agent, nitric acid, sodium nitrate, or potassium nitrate can be used, and as the solvent, acetic acid, acetic anhydride, sulfuric acid, fuming sulfuric acid, water, or a mixture thereof can be used. The compound represented by Formula 13 can be produced from pyrocatechol, for example, by the method described in JP-A-2-138247.

The compound of the present invention can be used as an active ingredient in agricultural and horticultural fungicides without adding any other ingredients. However, the compounds of the invention are usually carried on a solid carrier,
Mixed with liquid carriers, gaseous carriers, surfactants, and other formulation auxiliaries to form emulsions, wettable powders, suspensions, powders, granules,
It is used in formulations such as dry flowables. In this case, the active ingredient content of the compound of the present invention as an active ingredient in the preparation is 0.01 to 99%, preferably 0.1 to 80%.
It is. Examples of the above-mentioned solid carrier include clays (
(e.g., kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide, fubasamiclay, bentonite, acid clay), talcs, other inorganic minerals (e.g., sericite, calcite powder, quartz powder, activated carbon, calcium carbonate, hydrated silica), chemical Fertilizers (e.g., ammonium sulfate, ammonium phosphorus, ammonium nitrate, urea, ammonium chloride) or fine powders or granules such as corn cob flour and walnut shell flour can be mentioned, and liquid carriers include water, alcohols (e.g., methanol, ethanol, ethylene glycol, cellosolve), ketones (e.g.
acetone, methyl ethyl ketone, isophorone), aromatic hydrocarbons (e.g. benzene, toluene, xylene, ethylbenzene, methylnaphthalene), aliphatic hydrocarbons (e.g. n-hexane, cyclohexanone, kerosene, kerosene), esters (e.g. ,Ethyl acetate,
butyl acetate), nitriles (e.g. acetonitrile, isobutyronitrile), ethers (e.g. dioxane, diisopropyl ether), acid amides (e.g. dimethylformamide, dimethylacetamide,
) halogenated hydrocarbons (e.g. dichloroethane,
Examples of the gaseous carrier, ie, propellant, include fluorocarbon gas, butane gas, carbon dioxide gas, and the like. Examples of surfactants include alkyl sulfates, alkylaryl esters, alkyl sulfonates, alkylaryl sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkylaryl ether phosphate ester salts, naphthalene sulfonic acid formalin condensation Examples include anionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, polyhydric alcohol esters, and nonionic surfactants such as sugar alcohol derivatives. Examples of fixing agents and dispersants include casein, gelatin, polysaccharides (for example, starch powder, gum arabic, cellulose derivatives such as CMC (carboxymethyl cellulose), lignin derivatives such as lignin sulfonate, alginic acid), bentonite, synthetic water-soluble Examples of stabilizers include PAP (isopropyl acid phosphate), BHT (2,6-di-tert-
butyl-4-methylphenol), BHA (2-ter
t-Butyl-4-methoxyphenol and 3-tert-
(mixtures with butyl-4-methoxyphenol), vegetable oils, mineral oils, surfactants, fatty acids or esters thereof, and the like.

Methods for applying the compound of the present invention include foliar spraying, soil treatment, seed disinfection, etc., but any application method commonly used by those skilled in the art can be used. When the compound of the present invention is used as an active ingredient in an agricultural and horticultural fungicide, the amount of the active ingredient applied will vary depending on the target crop, target disease, degree of disease occurrence, formulation form, application method, application timing, weather conditions, etc. , usually 0.0 per are
The amount is 1 to 50 g, preferably 0.05 to 10 g. When applying an emulsion, wettable powder, suspension, dry flowable agent, etc. diluted with water, the applied concentration is 0.0001 to 0.00 g.
5%, preferably 0.0005-0.2%,
Powders, granules, etc. should be applied as is without any dilution.

Examples of plant diseases that can be controlled with the compounds of the present invention include the following diseases. Downy mildew of vegetables and radish (Peronospo)
ra brassicae), spinach downy mildew (
Peronospora spinaciae), Tobacco downy mildew (Peronospora tabaci)
na), downy mildew of cucumber (Pseudoperono
spora cubensis), downy mildew of grapes (P
Phytophtho lasmoparaviticola), apple, strawberry, and ginseng blight (Phytophtho
ra cactorum), gray late blight of tomatoes and cucumbers (Phytophthora capsici),
Pineapple blight (Phytophthora ci)
nnamomi), late blight of potatoes, tomatoes, and eggplants (
Phytophthora infestans), late blight of tobacco, broad beans, and alliums (Phytophthora infestans);
a nicotianae var. nicotia
nae), spinach damping-off (Phyhium s
p. ), cucumber seedling damping-off (Pythium apha
nidermatum), wheat brown snow rot (Pyth
ium sp. ), tobacco seedling damping-off (Pythium
debaryanum), soybean Pythium
rot(Pythium aphanidermatu
m, P. debarynum, P. irregu
lare, P. myiotylum, P. ultimate
imam). The compound of the present invention can be used in fields, paddy fields, orchards,
It can be used as an agricultural and horticultural fungicide for tea gardens, pastures, lawns, etc., and can also be used in combination with other agricultural and horticultural fungicides. Furthermore, it can also be used in combination with insecticides, acaricides, nematicides, herbicides, plant growth regulators, and fertilizers.

[0030]

EXAMPLES The present invention will be explained in more detail below with reference to production examples, formulation examples, and test examples, but the present invention is not limited to these examples. First, a production example of the compound of the present invention will be shown. Production Example 2 - Cyano-5,6-bis(1',1',2',2'-
Tetrafluoroethoxy)benzimidazole 4.79
g was dissolved in 50 ml of acetonitrile, 3.8 g of potassium carbonate was added, and the mixture was heated under reflux for 15 minutes. Next, 2.8 g of dimethylsulfamoyl chloride was added, and 1
The mixture was heated to reflux for 5 minutes. The reaction solution was added to ice water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous sodium sulfate, and concentrated. The obtained residue was subjected to column chromatography using toluene, and then recrystallized from hexane-ethyl acetate to give 2-cyano-1-dimethylsulfamoyl-5,6-bis(1',1', 2'
, 2'-tetrafluoroethoxy)benzimidazole was obtained. mp 128.4°C 1H-NMR (CDCI3) δ (ppm): 8.00
(1H, s), 7.90 (1H, s), 6.00 (2H
, tt, J=54.3Hz), 3.10 (6H, s)

[
Next, an example of the production of the benzimidazole compound represented by the formula 4 will be described. Reference Example 1 5.9 g of 5,6-bis(1',1',2',2'-tetrafluoroethoxy)-2-(trichloromethyl)benzimidazole was dissolved in 50 ml of ethanol and heated at 5°C.
The mixture was added dropwise to 10 ml of 25% ammonia water. After stirring for 2 hours at an internal temperature of 5°C, the reaction solution was poured into a mixture of ice and concentrated hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous sodium sulfate, and concentrated. oily 2-cyano-5
, 4.8 g of 6-bis(1',1',2',2'-tetrafluoroethoxy)benzimidazole was obtained. 1H-NMR (DMSO-d6) δ (ppm): 7.
95 (2H, s), 6.85 (2H, tt, J=52,
3Hz)

Next, 2- shown in formula 5
An example of producing a trichloromethylbenzimidazole compound will be described. Reference Example 2 4.74 g of 4,5-bis(1',1',2',2'-tetrafluoroethoxy)-1,2-benzenediamine was dissolved in 40 ml of acetic acid, and methyl trichloroacetimidate 2 was dissolved at room temperature. .85g was added and stirred for 2 hours. The reaction solution was poured into ice water, and the precipitated crystals were filtered off. The crystals were dissolved in ethyl acetate, washed with water, and then dried over anhydrous sodium sulfate. The solvent was distilled off to give 5,6-bis(1',
1',2',2'-tetrafluoroethoxy)-2-(
5.93 g of trichloromethyl)benzimidazole was obtained. 1H-NMR (DMSO-d6) δ (ppm): 7.
90 (2H, s), 6.90 (2H, tt, J=52,
3Hz)

Next, o- shown in formula 6
An example of producing a phenylenediamine compound will be described. Reference example 3 2-nitro-4,5-bis(1',1',2',2'-
5.8 g of (tetrafluoroethoxy)aniline was dissolved in a mixed solvent of 15 ml of ethyl acetate and 15 ml of acetic acid. This was added dropwise to a suspension of 4.3 g of iron powder in 4 ml of acetic acid and 40 ml of water at an internal temperature of 50°C. 30 at 50℃~60℃
After stirring for a minute, the reaction solution was filtered through Celite, and the filtrate was extracted with ethyl acetate. The organic layer was washed with an aqueous sodium bicarbonate solution and then with water, dried over anhydrous sodium sulfate, and concentrated.
4.74 g of 4,5-bis(1',1',2',2'-tetrafluoroethoxy)-1,2-benzenediamine was obtained. 1H-NMR (CDCl3) δ (ppm): 6
．． 65 (2H, s), 5.85 (2H, tt, J=52
, 2Hz), 3.30 (4H, broad)

Next, an example of the production of the o-nitroaniline compound represented by the formula (8) will be described. Reference example 4 2-nitro-4,5-bis(1',1',2',2'-
7.49 g of tetrafluoroethoxy)acetanilide,
1. A mixture of 15 ml of concentrated hydrochloric acid and 110 ml of methanol.
The mixture was heated under reflux for 5 hours. The reaction solution was concentrated, poured into ice water, and made alkaline with potassium carbonate. After extraction with ethyl acetate, the organic layer was washed with water and dried over anhydrous sodium sulfate. The solvent was distilled off and 2-nitro-4,5-bis(1'
, 1', 2', 2'-tetrafluoroethoxy)aniline (5.88 g) was obtained. 1H-NMR (CDCl3) δ
(ppm): 8.20 (1H, s), 6.90 (1H,
s), 6.35 (2H, broad), 5.95 (2H
, tt, J=52,3Hz)

Next, an example of the production of an o-nitroanilide compound represented by the general formula 9 will be described. Reference Example 5 6.7 g of 3,4-bis(1',1',2',2'-tetrafluoroethoxy)acetanilide was dissolved in 60 ml of concentrated sulfuric acid.
A mixture of 5 ml of fuming nitric acid and 10 ml of concentrated sulfuric acid was added dropwise thereto at -20°C. After dropping, -20℃~-1
The mixture was stirred at 0°C for 1 hour. The reaction solution was poured into ice water, and the precipitated crystals were filtered off. The crystals were dissolved in ethyl acetate, washed with water, and then dried over anhydrous sodium sulfate. The residue obtained by distilling off the solvent was subjected to silica gel column chromatography using chloroform to obtain 2-nitro-4,5-bis(1
7.49 g of ',1',2',2'-tetrafluoroethoxy)acetanilide was obtained. 1H-NMR (CDCl
3) δ (ppm): 10.45 (1H, broad)
, 9.05 (1H, s), 8.25 (1H, s), 5
．． 95 (2H, tt, J = 53, 2Hz), 2.30 (
3H,s)

Next, an example of the production of an anilide compound represented by the general formula (10) will be described. Reference example 63,4-bis(1'
, 1', 2', 2'-tetrafluoroethoxy)aniline was dissolved in 70 ml of acetic acid and 4 ml of acetic anhydride, and the mixture was stirred at an internal temperature of 80°C for 20 minutes. The reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. The residue obtained by distilling off the solvent was subjected to silica gel column chromatography using chloroform and ethyl acetate to obtain 3,4-bis(1',1',
6.78 g of 2',2'-tetrafluoroethoxy)acetanilide was obtained. 1H-NMR (CDCl3) δ(
ppm): 8.0 (1H, broad), 7.65 (
1H, broad), 7.20-7.40 (2H), 5
．． 90 (2H, tt, J=53,3Hz), 2.15 (
3H,s)

Next, an example of the production of the aniline compound represented by Formula 11 will be described. Reference Example 7 10.0 g of 3,4-bis(1',1',2',2'-tetrafluoroethoxy)nitrobenzene was dissolved in ethyl acetate 3
It was dissolved in a mixed solvent of 0 ml of acetic acid and 30 ml of acetic acid. This is 4
It was gradually added dropwise to a suspension of 7.0 g of iron powder in 7 ml of acetic acid and 70 ml of water at 0°C. After stirring at 50°C to 70°C for 1.5 hours, the reaction solution was filtered through Celite, and the filtrate was extracted with ethyl acetate. The organic layer was washed successively with an aqueous sodium bicarbonate solution and water, dried over anhydrous sodium sulfate, and concentrated. The obtained residue was subjected to column chromatography using chloroform to obtain 3,4-bis(1',1',
2',2'-tetrafluoroethoxy)aniline 8.2
6g was obtained. 1H-NMR (CDCl3) δ (ppm): 7.10
(1H, d, J=8Hz), 6.35-6.70 (2H
),
5.85 (2H, tt, J=53,3Hz), 2.70
(2H,s)

Next, a production example of the compound represented by Formula 12 will be described. Reference Example 8 1,2-bis(1',1',2
10 g of ',2'-tetrafluoroethoxy)benzene was added dropwise, and the mixture was stirred at an internal temperature of 10°C for 2.5 hours. The reaction solution was added to ice water and extracted with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and concentrated. The residue was subjected to silica gel column chromatography using methylene chloride, and 3
, 10.5 g of 4-bis(1',1',2',2'-tetrafluoroethoxy)nitrobenzene was obtained. 1H-NMR (CDCl3) δ (ppm): 8.15
-8.35 (2H), 7.65 (1H, d, J=10
Hz),
6.05 (2H, tt, J=53,3Hz)

00
[39] Next, a production example of the compound represented by Formula 13 will be described. Reference Example 9 11.7 g of pyrocatechol was dissolved in 110 ml of N,N-dimethylformamide, and 3.1 g of potassium hydroxide was added. Tetrafluoroethylene was blown into the mixture at an internal temperature of 80°C, and the mixture was stirred for 6 hours. After cooling to room temperature, the reaction solution was added to water and extracted with diethyl ether. The organic layer was dried over anhydrous sodium sulfate and concentrated, and the resulting residue was subjected to silica gel column chromatography using methylene chloride to obtain 1,2-bis(1',1',2'
,2'-tetrafluoroethoxy)benzene 32.5g
I got it. 1H-NMR (CDCl3) δ (ppm): 7.35
(4H, broad), 5.95 (2H, tt, J=5
3,2Hz)

[0040] Next, formulation examples will be shown. Note that parts represent parts by weight. Formulation Example 1 50 parts of the compound of the present invention, 3 parts of calcium ligninsulfonate
1 part, 2 parts of sodium lauric sulfate, and 45 parts of synthetic hydrated silicon oxide are thoroughly ground and mixed to obtain a wettable powder of the compound of the present invention. Formulation Example 2 25 parts of the compound of the present invention, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC, and 69 parts of water were mixed and wet-pulverized until the particle size of the active ingredient became 5 microns or less. Obtain a clouding agent. Formulation Example 3 2 parts of the compound of the present invention, 88 parts of kaolin clay and 10 parts of talc are thoroughly ground and mixed to obtain a powder of the compound of the present invention. Formulation Example 4 An emulsion of the compound of the present invention is obtained by thoroughly mixing 20 parts of the compound of the present invention, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, and 60 parts of xylene. Formulation Example 5 2 parts of the compound of the present invention, 1 part of synthetic hydrogenated silicon, 2 parts of calcium lignosulfonate, 30 parts of bentonite and 65 parts of kaolin clay were thoroughly ground and mixed, water was added and the mixture was thoroughly kneaded, followed by granulation and drying. By doing so, granules of the compound of the present invention are obtained. Next, test examples will show that the compounds of the present invention are useful as agricultural and horticultural fungicides. As a comparative compound, the formula described in JP-A No. 62-205063 was used.
The following compound represented by Chemical Formula 14 (hereinafter referred to as [A]) was used.

[0041]

[Chemical formula 14]

[0042] The pesticidal efficacy was determined by visual observation of the diseased state of the test plants at the time of investigation, that is, the bacterial flora on leaves, stems, etc., and the degree of lesions, and the pesticidal index was determined in the following 6 levels. 5: No lesions observed at all. 4: Lesion area is less than 10% of the untreated area 3:
〃 30 〃2:
〃 50 〃1
:〃 75
〃0: 〃
75% or more Test Example 1 Tomato late blight control test (preventive effect) A plastic pot was filled with sandy loam, tomatoes (Ponterosa) were sown, and grown in a greenhouse for 20 days. 2nd~
A test chemical prepared as a hydrating powder according to Formulation Example 1 was diluted with water to a predetermined concentration and sprayed on the foliage of tomato seedlings with three true leaves developed so as to sufficiently adhere to the leaf surface. After spraying, a spore suspension of Phytophthora tomato was sprayed and inoculated. After vaccination, 2
After being left at 0° C. for one day under humid conditions, the plants were further grown for 7 days under lighting, and the pesticidal efficacy was investigated. The results are shown in Table 1.

[0043]

[Table 1]

Test Example 2 Grape downy mildew control test (preventive effect) A plastic pot was filled with sandy loam, grapes were sown,
It was grown in a greenhouse for 50 days. The test drug, which has been made into a hydrating powder according to Formulation Example 1, is diluted with water to the specified concentration, and sprayed on the foliage of grape seedlings with the third to fourth true leaves developed, making sure that it adheres sufficiently to the leaf surface. did. After spraying, a spore suspension of grape downy mildew was sprayed and inoculated. After inoculation, the seeds were left at 20° C. for 1 day under high humidity, and then grown under lighting for 7 days, and the pesticidal efficacy was investigated. The results are shown in Table 2.

[0045]

[Table 2]

Test Example 3 Grape mildew control test (therapeutic effect) Plastic pots were filled with sandy loam, grapes were sown,
It was grown in a greenhouse for 50 days. A spore suspension of grape downy mildew was sprayed and inoculated onto young grape seedlings in which the 3rd to 4th true leaves had developed. After inoculation, leave it for one day at 20°C under high humidity, then dilute the test drug made into a wettable powder according to Formulation Example 1 with water to a specified concentration, and spread it on the stems and leaves so that it fully adheres to the leaf surface. Spread. After spraying, the plants were allowed to grow for 7 days under illumination, and the pesticidal efficacy was investigated. The results are shown in Table 3.

[0047]

[Table 3]

Test Example 4 Cucumber Downy Mildew Control Test (Preventive Effect) A plastic pot was filled with sandy loam, and cucumbers (Sagami Hanshiro) were sown and grown in a greenhouse for 14 days. Thereafter, the test drug prepared as a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration, and the solution was sprayed on the leaves so as to sufficiently adhere to the leaf surface. After spraying, spray a spore suspension of cucumber downy mildew.
Inoculated. After inoculation, the seeds were left at 20° C. for 1 day under high humidity, and then grown under lighting for 7 days, and the pesticidal efficacy was investigated. The results are shown in Table 4.

[0049]

[Table 4]

Test Example 5 Cucumber downy mildew control test (therapeutic effect) A plastic pot was filled with sandy loam, and cucumbers (Sagami Hanshiro) were sown and grown in a greenhouse for 14 days. Cucumbers at the cotyledon stage were sprayed and inoculated with a spore suspension of cucumber downy mildew. After inoculation, after leaving it for one day at 20°C under high humidity, Formulation Example 1
A test chemical prepared as a hydrating powder according to the method was diluted with water to a predetermined concentration, and the solution was sprayed on the foliage so that it would sufficiently adhere to the leaf surface. After spraying, the plants were allowed to grow for 7 days under illumination, and the pesticidal efficacy was investigated. The results are shown in Table 5.

[0051]

[Table 5]

[0052]

Effects of the Invention The compounds of the present invention have excellent control effects against various plant diseases, particularly those caused by algae and fungi such as downy mildew and late blight, and furthermore, they do not cause problematic phytotoxicity to cover plants. Because it is free from oxidation, it can be used for various purposes as an active ingredient in agricultural and horticultural fungicides.

Claims (3)

[Claims] [Claim 1] Formula 1 [Chemical formula 1] A benzimidazole derivative represented by 2. The method for producing a benzimidazole derivative according to claim 1, which comprises reacting a benzimidazole compound represented by the formula 2 with dimethylsulfamoyl chloride. 3. A fungicide for agriculture and horticulture, which contains the benzimidazole derivative according to claim (1) as an active ingredient.