JPH04368373A - 4,6-dichloro-5-tetrafluoroethoxy-benzimidazole derivative, its production and agricultural and horticultural germicide containing the same as active ingredient - Google Patents

Abstract

PURPOSE:To obtain the subject new compound, having excellent controlling effects on plant disease injuries such as downy mildew or late blight caused by phycomycetes and useful as an agricultural and horticultural germicide. CONSTITUTION:A 4,6-dichloro-5-tetrafluoroethoxy-benzimidazole derivative expressed by formula I. The compound expressed by formula I is obtained by reacting a 2-cyanobenzimidazole compound expressed by formula II with dimethylsulfamoyl chloride normally in the presence of a base such as pyridine or triethylamine in the coexistence of a solvent such as hexane or benzene at ambient temperature to the refluxing temperature of the solvent.

Description

[Detailed description of the invention]

0001

[Industrial Field of Application] The present invention relates to 4,6-dichloro-5
The present invention relates to a -tetrafluoroethoxy-benzimidazole derivative, a method for producing the same, and an agricultural and horticultural fungicide containing the same as an active ingredient.

0002

[Prior Art and Problems to be Solved by the Invention] Captan, captafor, and dithiocarbamate drugs are currently widely used as agricultural and horticultural fungicides, especially as disease control agents against late blight and downy mildew. ing. However, these agents cannot be said to be satisfactory as agricultural and horticultural fungicides.

0003

[Means for Solving the Problems] In view of the above circumstances, the present inventors have conducted various studies to develop a compound that has excellent efficacy against plant diseases and has little phytotoxicity.
The inventors have discovered that the benzimidazole derivative of the present invention has excellent preventive and therapeutic efficacy against plant diseases, has excellent systemic transfer properties, and does not cause problematic phytotoxicity to crops, leading to the present invention. That is, the present invention is based on the formula
3

0004

[Chemical formula 3]

4,6-dichloro-5-tetrafluoroethoxy-benzimidazole derivative (hereinafter referred to as
It is called the compound of the present invention. ), its production method, 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]

It can be obtained by reacting the 2-cyanobenzimidazole compound shown below with dimethylsulfamoyl chloride. In this reaction, the reaction temperature range is usually room temperature to solvent reflux temperature, and the reaction time range is usually instantaneous to about 24 hours. The reaction is usually carried out in the presence of a base, and the base used is
pyridine, triethylamine, N,N-dimethylaniline, tributylamine, N-methylmorpholine, etc.
Examples include inorganic bases such as grade amines, sodium hydroxide, potassium hydroxide, and potassium carbonate. The amount of the reagents used in the reaction is usually 1 to 2 mol of dimethylsulfamoyl chloride and usually 1 to 7 mol of the base per 1 mol of the 2-cyanobenzimidazole 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. In the above production method, the 2-cyanobenzimidazole compound represented by the formula 4 has the formula 5

There is tautomerism shown by the following formula. Therefore, when the compound of the present invention is produced using these, the formula 6

[C6] Or the formula 7

One of the compounds represented by the following formula or a mixture thereof will be obtained. Therefore, Formula 3 represents a compound represented by Formula 6, a compound represented by Formula 7, or a mixture thereof. The 2-cyanobenzimidazole compound represented by Formula 4, which is a raw material compound for producing the compound of the present invention, is represented by Formula 8.

[0008]

[Chemical formula 8]

It can be obtained by reacting the 2-(trichloromethyl)benzimidazole compound shown below with ammonia. The reaction temperature range is usually -30℃
˜solvent reflux temperature, and the reaction time usually ranges from 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 8. 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 hexane,
Aliphatic hydrocarbons such as petroleum ether, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as chloroform and dichloroethane, ethers such as diethyl ether, dioxane and tetrahydrofuran, and ketones such as acetone and methyl ethyl ketone. , esters such as ethyl acetate and diethyl carbonate, nitriles such as acetonitrile and isobutylnitrile, amides such as formamide and N,N-dimethylformamide, sulfur compounds such as dimethyl sulfoxide, methanol, ethanol, 2-propanol, etc. Examples include alcohols, water, etc., or 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. 2-(trichloromethyl) represented by the formula 8
The bayzimidazole compound has the formula 9

0010

[Chemical formula 9]

The o-phenylenediamine compound represented by the following formula and the general formula 10

0012

[Chemical formula 10]

[In the formula, R represents a lower alkyl group. ]
It can be obtained by reacting with a trichloroacetimidate compound shown in The reaction temperature range is usually -30°C to the solvent reflux temperature, and the reaction time range is usually instantaneous to about 24 hours. The amount of the reagent used in the reaction is usually 1 to 1 mole of the o-phenylenediamine compound represented by the formula 9, and the trichloroacetimidate compound represented by the general formula 10.
It is 2 moles. 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, nitriles such as acetonitrile and isobutylnitrile, amides such as formamide and N,N-dimethylformamide, sulfur compounds such as dimethyl sulfoxide, methanol, ethanol, 2- Examples include alcohols such as propanol, organic acids such as formic acid, acetic acid, and propionic acid, water, and mixtures thereof. After the reaction is complete, the reaction solution is poured into ice water, for example, and the resulting crystals are filtered or extracted with an organic solvent, and then subjected to post-treatments such as washing with water and concentration, followed by chromatography, recrystallization, etc., if necessary. The desired compound can be obtained by purification by the following operations.

The 2-(trichloromethyl)benzimidazole compound represented by the formula 8 is also represented by the formula 9.
It can also be obtained by cyclizing a 2-aminotrichloroacetanilide compound obtained by reacting the o-phenylenediamine compound represented by the formula with trichloroacetyl chloride. In the cyclization reaction, the reaction temperature range is usually 40°C to the solvent reflux temperature, and the reaction time range is usually instantaneous to about 24 hours. In the cyclization 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 hexane,
Aliphatic hydrocarbons such as petroleum ether, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as chloroform and dichloroethane, ethers such as diethyl ether, dioxane and tetrahydrofuran, and ketones such as acetone and methyl ethyl ketone. , esters such as ethyl acetate and diethyl carbonate, nitriles such as acetonitrile and isobutylnitrile, amides such as formamide and N,N-dimethylformamide, sulfur compounds such as dimethyl sulfoxide, methanol, ethanol, 2-propanol, etc. Examples include alcohols, water, etc., or mixtures thereof. The reaction between the o-phenylenediamine compound represented by Formula 9 and trichloroacetyl chloride is carried out in the same manner as the reaction between the 2-cyanobenzimidazole compound represented by Formula 4 and dimethylsulfamoyl chloride. Can be done. The o-phenylenediamine compound represented by the formula 9 is represented by the formula 11

[0015]

[Chemical formula 11]

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 is usually carried out within 12 hours at a temperature ranging from 50° C. to solvent reflux temperature. Further, the reduction reaction can be carried out by using iron powder, zinc powder, or tin powder 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 reaction is usually 30
It is usually carried out within 12 hours at a temperature of 100°C to 100°C. 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 within the range of 0°C to 60°C, can also be used. . The o-nitroaniline compound represented by the formula 11 has the general formula 12

001
7]

[Chemical formula 12]

[In the formula, R' represents a lower alkyl group. ] It can be obtained by hydrolyzing the o-nitroanilide compound shown below. The reaction temperature range is usually room temperature to
Solvent reflux temperature and reaction time range is usually instantaneous to
Approximately 24 hours. 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 the reagent used in the reaction is from a catalytic amount to a large excess of the above base or acid per mole of the o-nitroanilide compound represented by Formula 12. The reaction is carried out without a solvent or in a solvent depending on the base or acid used. Usable solvents include aliphatic hydrocarbons such as hexane and petroleum ether, aromatic hydrocarbons such as benzene and toluene, halogenated hydrocarbons such as chloroform and dichloroethane, and 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, 2-propanol, etc. organic acids such as formic acid, acetic acid, propionic acid, etc.
Examples include water and mixtures thereof. Formula 12
The o-nitroanilide compound represented by the general formula
3

[0019]

[Chemical formula 13]

[In the formula, R' represents the same meaning as above. ] It can be obtained by nitration of the anilide compound shown below. The reaction temperature range is usually -40℃ to 2
0°C, and the reaction time range is usually instantaneous to about 24 hours. As the nitrating agent, fuming nitric acid, nitric acid, sodium nitrate, 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 amount of the reagent used in the reaction is from 1 mol to a large excess of the nitrating agent per 1 mol of the compound represented by the general formula (13). general formula
The anilide compound represented by formula 13 is represented by formula 14

0
021]

[Chemical formula 14]

It can be obtained by acylating the aniline compound shown below. The reaction temperature range is usually room temperature to solvent reflux temperature, and the reaction time range is usually instantaneous to about 24 hours. 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 from a catalytic amount to a large excess per mole of the aniline compound represented by Formula 14. 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 14. The reaction is carried out without a solvent or in a solvent depending on the base or acid used. Examples of solvents that can be used 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 ethyl acetate, acetonitrile and isobutylnitrile, formamide, N,N-dimethylformamide Examples include amides such as, sulfur compounds such as dimethyl sulfoxide, organic acids such as formic acid, acetic acid, propionic acid, and mixtures thereof. Formula 14
The compound represented by can be produced from 4-amino-2,6-dichlorophenol, for example, according to 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 present invention are usually mixed with solid carriers, liquid carriers, gaseous carriers, surfactants, and other formulation auxiliaries to form emulsions, wettable powders, suspensions, powders, granules, and dry powders. It is used in formulations such as flowable agents. In this case, the content of the active ingredient, the compound of the present invention, in the preparation is 0.01 to 99%, preferably 0.1 to 80%. Examples of the solid carriers mentioned above include clays (e.g., kaolin clay, diatomaceous earth, synthetic hydrated silicon oxide, fubasamiclay, bentonite, acid clay), talcs, and 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 corn cob flour,
Examples include fine powder or granules such as walnut shell powder, 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. dimethyl Formamide, dimethylacetamide), halogenated hydrocarbons (for example, dichloroethane, trichloroethylene, carbon tetrachloride), vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, etc.;
Examples include fluorocarbon gas (registered trademark), butane gas, and carbon dioxide gas. 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 anionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, polyhydric alcohol esters,
Examples include nonionic surfactants such as sugar alcohol derivatives. Examples of fixing agents and dispersing agents include casein,
Gelatin, polysaccharides (e.g., starch powder, gum arabic, cellulose derivatives such as CMC (carboxymethylcellulose), lignin derivatives such as lignin sulfonate, alginic acid), bentonite, synthetic water-soluble polymers (e.g., polyvinyl alcohol, polyvinylpyrrolidone) , polyacrylic acids), etc., and as stabilizers, for example, PAP (isopropyl acid phosphate), BHT (
2,6-di-tert-butyl-4-methylphenol), BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil, interface Examples include activators, fatty acids or esters thereof. 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 should be determined based on the target crop, target disease, degree of disease occurrence, formulation form,
Although it varies depending on the application method, application time, weather conditions, etc., it is usually 0.01 to 50 g per are, preferably 0.0
5 to 10 g, and when applying an emulsion, wettable powder, suspension, dry flowable agent, etc. diluted with water, the application concentration is 0.0001 to 0.5%, preferably 0.0005%.
~0.2%, and powders, granules, etc. are applied as they are 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 (Per
onospora brassicae), spinach downy mildew (Peronospora spinacia)
e) Tobacco downy mildew (Peronospora ta
bacina), cucumber downy mildew (Pseudop)
eronospora cubensis), downy mildew of grapes (Plasmopara viticola)
), late blight of apples, strawberries, and ginseng (Ph
ytophthora cactorum), tomato,
Gray blight of cucumbers (Phytophthora c.
apsici), pineapple blight (Phyto
Phytophthora cinnamomi), late blight of potatoes, tomatoes, and eggplants (Phytophthora cinnamomi)
infestans), late blight of tobacco, broad beans, and alliums (Phytophthora nicotiana)
e var. nicotianae), spinach damping-off (Phyhium sp.), cucumber seedling damping-off (Pythium aphanidermatu)
m), wheat brown snow rot (Pythium sp.
), tobacco seedling damping-off (Pythium debary
anum), soybean Pythium rot (
Pythium aphanidermatum, P.
debarynum, P. irregular,
p. myiotylum, P. ultimate)
. The compound of the present invention can be used as an agricultural and horticultural fungicide for fields, paddy fields, orchards, tea plantations, pastures, lawns, etc.
It 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.

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 described. Production example 4,6-dichloro-5-tetrafluoroethoxy-2-
After dissolving 2.97 g of cyanobenzimidazole in 30 ml of acetonitrile, 2.6 g of potassium carbonate was added and the mixture was heated under reflux for 20 minutes. Next, 2.1 g of dimethylsulfamoyl chloride was added and the mixture was heated under reflux for 1 hour and 30 minutes. The reaction solution was added to 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 recrystallized from hexane-ethyl acetate to obtain 1.6 g of the compound of the present invention represented by Formula 3. mp. 148 - 150 °C 1H-NMR (CDCl3) δ (ppm): 8.0 (
1H, s), 6.1 (1H, tt, J=52,3Hz)
3.1 (6H, s) Next, a production example of a 2-cyanobenzimidazole compound represented by Formula 4 will be described as a reference example. Reference Example 1 4,6-dichloro-5-(1',
1',2',2'-tetrafluoroethoxy)-2-(
Dissolve 3.4 g of benzimidazole (trichloromethyl) in 40 ml of ethanol, and add 3.4 g of 25% ammonia water at 5°C.
ml was added dropwise. After stirring at 8°C for 4 hours, 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 and dried over anhydrous sodium sulfate. The solvent is distilled off to form an oily 2-cyano-4 represented by formula 4,
3.0 g of 6-dichloro-5-(1',1',2',2'-tetrafluoroethoxy)benzimidazole was obtained. 1 H-NMR (DMSO-d6) δ (ppm): 8.
05 (1H, s), 7.00 (1H, tt, J=52,
3Hz) Next, a production example of a 2-trichloromethylbenzimidazole compound represented by Formula 8 will be described as a reference example. Reference Example 2 3,5-dichloro-4-(1',
1',2',2'-tetrafluoroethoxy)-1,2
-Dissolve 4.3 g of benzenediamine in 50 ml of acetic acid,
2.85 g of methyl trichloroacetimidate at room temperature
was added and stirred for 4 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 4,6-dichloro-5-(1
',1',2',2'-tetrafluoroethoxy)-2
-(Trichloromethyl)benzimidazole 5.28g
I got it. 1 H-NMR (CDCl3) δ (ppm): 7.90
(1H, s), 7.00 (1H, tt, J=50,3H
z) Next, a production example of an o-phenylenediamine compound represented by Formula 9 will be described as a reference example. Reference example 3 3,5-dichloro-2-nitro-4-(1',1',2
',2'-tetrafluoroethoxy)aniline 5.3g
was dissolved in a mixed solvent of 17 ml of ethyl acetate and 17 ml of acetic acid. This was added dropwise to a suspension of 4.8 g of iron powder in 3 ml of acetic acid and 30 ml of water at 50°C. After stirring at 50°C to 70°C for 15 minutes, 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 water in that order, and dried over anhydrous sodium sulfate. The solvent was distilled off to give 3,5-dichloro-4-(
1',1',2',2'-tetrafluoroethoxy)-
4.74 g of 1,2-benzenediamine was obtained. 1 H-NMR (CDCl3) δ (ppm): 6.70
(1H, s)
6.05 (1H, tt, J=53,3Hz), 2
．． 60 (4H, broad) Next, a production example of an O-nitroaniline compound represented by Formula 11 will be described as a reference example. Reference example 4 3,5-dichloro-2-nitro-4-(1',1',2
',2'-tetrafluoroethoxy)acetanilide 9
．． A mixture of 0 g, 50 ml of concentrated hydrochloric acid, and 300 ml of methanol was heated under reflux for 1.5 hours. Concentrate the reaction solution,
It was 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 3,5-dichloro-2-nitro-4-(1',1'
,2',2'-tetrafluoroethoxy)aniline6.
67g was obtained. 1H-NMR (CDCl3) δ (ppm): 6.90
(1H, s)
6.05 (1H, tt, J=53,3Hz), 5
．． 00(2H, broad) Next, general formula 12
A manufacturing example of the o-nitroanilide compound shown in will be described as a reference example. Reference Example 5 1.0 g of 3,5-dichloro-4-(1',1',2',2'-tetrafluoroethoxy)acetanilide was added to 25 ml of concentrated sulfuric acid, and 1 ml of fuming nitric acid was added thereto at -20°C.
A mixture of 2 ml of concentrated sulfuric acid and 2 ml of concentrated sulfuric acid was added dropwise. After dropping, -20℃
Stirred at ~-10°C for 1 hour. Pour the reaction solution into ice water,
The precipitated crystals were filtered off. Dissolve the crystals in ethyl acetate,
After washing with water, it was dried over anhydrous sodium sulfate. The residue obtained by distilling off the solvent was subjected to silica gel column chromatography using chloroform to obtain 3,5-dichloro-2-
0.9 g of nitro-4-(1',1',2',2'-tetrafluoroethoxy)acetanilide was obtained. 1 H-NMR (CDCl3) δ (ppm): 10.5
(1H, broad), 8.45 (1H, s),
6.05
, (1H, tt, J=52,3Hz), 2.20(3H
, s) Next, a production example of an anilide compound represented by the general formula 13 will be described as a reference example. Reference Example 6 8.48 g of 3,5-dichloro-4-(1',1',2',2'-tetrafluoroethoxy)aniline was dissolved in 50 g of acetic acid.
0 ml and acetic anhydride (5 ml), and the mixture was stirred at 80° C. for 5 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, and recrystallized from hexane-ethyl acetate.
6.94 g of -dichloro-4-(1',1',2',2'-tetrafluoroethoxy)acetanilide was obtained. 1 H-NMR (CDCl3) δ (ppm): 10.3
(1H, broad), 7.60 (1H, s),
6.00(
1H, tt, J = 52, 3Hz), 2.15 (3H, s
) Next, a production example of the compound represented by Formula 14 will be described as a reference example. Reference example 7 4-amino-2,6-dichlorophenol 10.0g
was dissolved in 100 ml of N,N-dimethylformamide,
1.3 g of potassium hydroxide was added. Tetrafluoroethylene was blown into the mixture at 60°C, and the mixture was stirred for 5 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 3,5-dichloro-4-(
8.48 of 1',1',2',2'-tetrafluoroethoxy)aniline was obtained. 1 H-NMR (CDCl3) δ (ppm): 6.65
(1H, s) 6.05, (1H, tt, J=52,3H
z),
3.90 (2H, broad) Next, a formulation example is shown. Note that parts represent parts by weight. Formulation Example 1 50 parts of the compound of the present invention, 3 parts of potassium 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 comparative compounds, the following compound (hereinafter referred to as [A]) shown by Formula 15 described in JP-A-58-148864 and mancozeb (hydrating powder), which is generally used as an algae control agent, were used. there was.

[Image Omitted] Furthermore, the control 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 extent of lesions, and the control index was determined on the following six 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.

[Table 1] Test Example 2 Tomato late blight control test (therapeutic effect) Plastic pots were filled with sandy loam, tomatoes (Ponterosa) were sown, and grown in a greenhouse for 20 days. A spore suspension of Phytophthora tomato was sprayed and inoculated on young tomato seedlings in which the second to third 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 2.

[Table 2] Test Example 3 Grape downy mildew control test (preventive effect) A plastic pot was filled with sandy loam, grapes were sown, and grown in a greenhouse for 50 days. The test drug prepared as a hydrating powder according to Formulation Example 1 is diluted with water to a specified concentration, and sprayed on the foliage of grape seedlings with the 3rd to 4th true leaves developed so 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 3.

[Table 3] Test Example 4 Grape downy mildew control test (therapeutic effect) A plastic pot was filled with sandy loam, grapes were sown, and 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 4.

[Table 4]

Effects of the Invention The compounds of the present invention have excellent control effects against various plant diseases, especially those caused by algae and fungi such as downy mildew and late blight, and furthermore, they have an excellent control effect on plant diseases caused by algae and fungi such as downy mildew and late blight. Since it does not exhibit any

Claims (3)

[Claims] Claims: 1. A 4,6-dichloro-5-tetrafluoroethoxy-benzimidazole derivative represented by the formula: 2. The 4,6-dichloro-5-tetra according to claim 1, characterized in that the 2-cyanobenzimidazole compound represented by the formula 2 and dimethylsulfamoyl chloride are reacted. A method for producing a fluoroethoxy-benzimidazole derivative. 3. A fungicide for agricultural and horticultural use, which contains the 4,6-dichloro-5-tetrafluoroethoxy-benzimidazole derivative according to claim 1 as an active ingredient.