JPH0466473B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to novel carboxamides, their preparation and use as agricultural fungicides. More specifically, the present invention relates to carboxamides represented by the following formula (). In the formula, X represents a halogen atom, n represents 1 or 2, R ¹ represents a lower alkyl group, and R ² and R ³ each represent a hydrogen atom or a lower alkyl group, provided that where R ¹ is a methyl group and R ²
and R ³ each represent a hydrogen atom or a methyl group, X represents a bromine atom or a fluoro atom. The compound of the above formula () can be produced by the following method, and the present invention also applies to this production method. , related. Manufacturing method (a): - In the formula, X and n are the same as above, and a compound represented by the formula: In the formula, R ¹ , R ² and R ³ are the same as above, and M represents a hydroxyl group or a halogen atom, provided that in the above, R ¹ is a methyl group, and R ² and R ³ are each a hydrogen atom or A method for producing carboxamides of the above formula (), which comprises reacting with a compound represented by the following, which represents an X bromine atom or a fluoro atom when a methyl group is represented. The present invention also relates to an agricultural fungicide containing carboxamides of the formula () as an active ingredient. In the specification of JP-A-55-66555, which was known before the filing date of the present application, the general formula: (In the formula, R ₁ represents a hydrogen atom or a lower alkyl group, R ₂ represents an alkyl group or a cycloalkyl group, and R ₁ and R ₂ may form a ring.) It is stated that acetamide derivatives have herbicidal activity. and,
The specification includes, for example, the formula A compound represented by is described. However, the above-mentioned general formula (A) does not include the compound of the above-mentioned general formula () specified in the present invention, and furthermore, there is no mention of its use as a fungicide. Furthermore, in the specification of Japanese Patent Application Laid-open No. 58-26847, which was known before the filing date of the present application, the general formula: (In the formula, R ₁ is an α-branched alkyl group, R ₂ is a hydrogen atom, a lower alkyl group or a lower alkenyl group, or R ₁ and R ₂ are an alkylene group, and X is a halogen atom or a lower alkyl group. , a lower alkoxyl group, a cyano group, or a nitro group, and n represents an integer of 1 to 3) It is described that the N-benzyl-acetamide derivative represented by the following formula has fungicidal activity for agricultural and horticultural purposes. And, in the specification, for example, the formula A compound represented by is described. However, the above general formula (B) does not include the compound of the above formula () specified in the present invention. The present inventors have carried out synthesis and biological activity screening in order to create novel compounds with biological activity. As a result, we succeeded in synthesizing novel carboxamides of the formula (), and discovered that the compound of formula () has, for example, excellent fungicidal activity for agricultural purposes. According to the research conducted by the present inventors, the carboxamides of the formula () of the present invention are novel compounds that have not been described in any known publications prior to the filing date of the present application. It has also been found that the compound of the present invention exhibits excellent control efficacy that is particularly suitable for the purpose of controlling plant diseases, and in particular, exhibits optimal and outstanding efficacy for controlling rice blast disease. Such control efficacy is due to compounds with similar chemical structures, e.g.
(A-1) and formula (B-1) described in the above-mentioned known literature
It has a much superior effect compared to the efficacy of the compound. The plant disease control activity of the compound of the present invention also exhibits a more significant effect in terms of its residual efficacy. For example, especially when controlling rice blast disease,
In relation to the fact that rice blast is the most important disease for control in rice cultivation, the residual effectiveness of the control agent is the most important factor due to the relationship between the appropriate treatment time of the agent and the time of outbreak of rice blast. The practical value of a compound is determined by its effectiveness. The compound of the present invention is an excellent biologically active compound that satisfies this point as well. Therefore, an object of the present invention is to provide carboxamides of the formula (), a method for producing the same, and use thereof as an agricultural fungicide. The above objects and many other objects and advantages of the present invention will become more apparent from the following description. In the compound of formula () of the present invention, preferably,
X represents fluoro, chloro or bromine at the p-position, n represents 1, ^R1 represents an alkyl group having 2 to 4 carbon atoms, and ^R2 and ^R3 each represent a hydrogen atom, methyl or represents ethyl, or X represents bromine at the p-position, n represents 1, R ¹ represents methyl, and R ² and R ³ each represent a hydrogen atom or methyl. In addition to the above preferred definitions ^{, it is} further particularly preferred that represent a hydrogen atom or methyl, respectively. And, as a specific example of the compound of formula (),
In particular, the following can be exemplified. That is, N-(4-chloro-α-methylbenzyl)2,
2-dichloro-1-ethyl-3,3-dimethylcyclopropanecarboxamide, N-(4-chloro-α-methylbenzyl)2,
2-dichloro-1-ethyl-3-methylcyclopropanecarboxamide, N-(4-bromo-α-methylbenzyl)2,
2-dichloro-1,3-dimethylcyclopropanecarboxamide, N-(4-bromo-α-methylbenzyl)2,
3-dichloro-1,3,3-trimethylcyclopropanecarboxamide, N-(4-chloro-α-methylbenzyl)2,
2-dichloro-1-isopropylcyclopropanecarboxamide, N-(4-bromo-α-methylbenzyl)2,
2-dichloro-1-isopropylcyclopropanecarboxamide. The carboxamides of formula () of the present invention can be easily produced, for example, by the following method. ( ^{In the} formula ^, -ethyl-3,3-dimethylcyclopropanecarboxylic acid, the reaction formula can be expressed as shown below. In the above production method (a), the compound of formula () as a raw material means a compound based on the definitions of X and n described above, and preferably X and n have the same meanings as the preferred definitions above. The compound of formula () is disclosed in, for example, JP-A-58-26847.
Specific examples thereof include 4-chloro-α-methylbenzylamine and 4-bromo-α-methylbenzylamine. Similarly, the compound of formula () which is a raw material means a compound based on the above definitions of R ¹ , R ² , R ³ and M, preferably R ¹ , R ² and R ³ have the same meanings as the above preferred definitions. shows. M preferably represents a hydroxyl group, a chloro atom or a bromine atom. The compound of formula () is partially a new compound,
Specific examples include 2,2-dichloro-1-ethyl-3-methylcyclopropanecarboxylic acid, 2,2-dichloro-1,3-dimethylcyclopropanecarboxylic acid, 2,2-dichloro-1- Ethyl-3,3-dimethylcyclopropanecarboxylic acid, 2,2-dichloro-1,3,3-trimethylcyclopropanecarboxylic acid, 2,2-dichloro-1-isopropyl-3-methylcyclopropanecarboxylic acid, 2, 2-dichloro-1-isopropyl-3,3
Examples include -dimethylcyclopropanecarboxylic acid, and acid chlorides and bromides thereof. In formula (), when M is a hydroxyl group, the compound has, for example, the formula: In the formula, R ¹ , R ² and R ³ are the same as above, and the compound represented by is oxidized with, for example, potassium permanganate, or the formula: In the formula, R ¹ , R ² and R ³ are the same as above, R represents an alkyl group, and the compound represented by the following is hydrolyzed with sodium hydroxide etc., or the formula: In the formula, R ¹ , R ² and R ³ are the same as above, and it can be obtained by oxidizing the compound represented by with potassium permanganate or the like. In formula (), when M is a halogen atom, the compound can be easily obtained by reacting a compound of formula () where M is a hydroxyl group with a halogenating agent such as thionyl chloride. . The compound of the above formula () is, for example, the formula: In the formula, R ¹ , R ² and R ³ are the same as above, and the compound represented by is hydrolyzed with sodium hydroxide etc., or the formula: In the formula, R ¹ , R ² and R ³ are the same as above, and the compound represented by and chloroform are mixed at 50%
It can be obtained by reaction in an aqueous sodium hydroxide solution under a phase transfer catalyst. The compound of the above formula () is, for example, the formula: In the formula, R ¹ R ² and R ³ are the same as above, and can be easily obtained by reacting a compound represented by the following with anhydrous sodium acetate. The compound of the above formula () is, for example, the formula: In the formula, R ¹ R ² and R ³ are the same as above, and it can be obtained by reacting a compound represented by the following with chloroform in a 50% aqueous sodium hydroxide solution under a phase transfer catalyst. The compound of the above formula () is described in the known publication Helv.
Chim.Acta (Helbertica. Himika. Acta), 23
It can be easily produced by the method described in Vol., 1940, p. 959. The compound of the formula () is, for example, the formula: In the formula, R ¹ , R ² , R ³ and R are the same as above, and it can be easily obtained by reducing a compound represented by the following with lithium aluminum hydride or the like. The compound of formula (XI) above includes some known compounds [J.Org.Chem. (Journal of Organic Chemistry) Vol. 47, 1982, 1812-
See page 1816] Generally, it can be produced by the well-known Wittig reaction. The compound of formula () can be easily obtained by reacting the compound of formula (XI) with sodium trichloroacetate. The compound of the formula () is, for example, the formula: In the formula, R ¹ , R ² and R ³ are the same as above, and it is obtained by hydrolyzing a compound represented by the following by reaction with an acid. The compound of the above formula (XII) is, for example, the formula: In the formula, R ¹ , R ² and R ³ are the same as above, and the compound represented by and chloroform are mixed at 50%
It is obtained by reacting in an aqueous sodium hydroxide solution under a phase transfer catalyst. The compound of the above formula () is, for example, the formula: In the formula, R ¹ , R ² and R ³ are the same as above, and by reacting the compound represented by and anhydrous alcohol in the presence of ethyl orthoformate,
can get. The compound of the above formula () includes known compounds, and is generally obtained from various aldehydes by an aldol condensation reaction. When carrying out the above process (a), all inert organic solvents may be mentioned as suitable diluents. Examples of such diluents include water; aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated) such as hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene. , xylene, methylene chloride,
Chloroform, carbon tetrachloride, ethylene chloride and trichloroethylene, chlorobenzene; other ethers such as diethyl ether, methyl ethyl ether, di-iso-propyl ether, dibutyl ether, propion oxide,
Dioxane, tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl-iso
-propyl ketone, methyl-iso-butyl ketone; nitriles such as acetonitrile, propionitrile, acrylonitrile; alcohols such as methanol, ethanol, iso-propanol, butanol, ethylene glycol; esters such as ethyl acetate, amyl acetate; acids Amides such as dimethylformamide, dimethylacetamide; sulfones, sulfoxides such as dimethylsulfoxide, sulfolane; and bases such as pyridine. In the above method (a), a dehydration condensation agent can be used, such as N,N'-dicyclohexylcarbodiimide. Further, in the above method (a), when an acid halide is used as a raw material of general formula (), the reaction of the present invention can also be carried out in the presence of an acid binder. Such acid binders include commonly used alkali metal hydroxides, carbonates, bicarbonates, alcoholates, etc., and tertiary amines such as triethylamine, diethylaniline, pyridine, etc. . Process (a) of the invention can be carried out within a wide temperature range. For example, it can be carried out between about -20°C and the boiling point of the mixture, preferably between about 0 and about 100°C.
Can be carried out between ℃. Further, although it is preferable to carry out the reaction under normal pressure, it is also possible to operate under increased pressure or reduced pressure. The active compounds according to the invention exhibit a strong fungicidal action and can be used in practice for controlling unwanted plant pathogens. The active compounds of the invention are generally used as fungicide (mold) agents such as Plasmodiophoromycetes, Oomycetes, chytridiomycetes, Zygomycetes, Ascomycetes, It can be used against various plant diseases caused by Basiomycetes and Deuteromycetes, and as a fungicide (bacterial) agent.
It can be used against various plant diseases caused by Rhizobiumaceae, Enterobacteriaceae, Corynebacteriaceae, and Streptomycetaceae. In particular, the compounds of the present invention exhibit extremely excellent control efficacy against rice blast disease (Pyricularia oryzae). The active compounds of the present invention exhibit good compatibility with plants at the concentration of active compound necessary for controlling plant pathogens, and therefore, when used,
It enables chemical treatment of the above-ground parts of plants, chemical treatment of rootstocks and seeds, and soil treatment. Furthermore, the compounds of the present invention have low toxicity even in warm-blooded animals and can be used safely. The active compounds according to the invention can be put into customary pharmaceutical forms. Such forms include solutions, emulsions, suspensions, powders, foams, pastes,
Granules, aerosols, active compound infiltration - natural and synthetic products, microcapsules, seed coatings, preparations with combustion devices (e.g. combustion devices such as fumigation and fume cartridges, cans and coils),
And ULV (cold mist, warm mist) can be mentioned. These drugs can be manufactured by known methods. Such a process can be carried out, for example, by combining the active compound with a vehicle, i.e. a liquid diluent; a liquefied gas diluent; a solid diluent; or a carrier, optionally a surfactant, i.e. an emulsifying agent and/or a dispersing agent; This can be done by mixing and/or using a foam-forming agent. When using water as a developing agent, for example, organic solvents can also be used as co-solvents. Liquid diluents or carriers generally include aromatic hydrocarbons (e.g. xylene, toluene, alkylnaphthalenes, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (e.g. chlorobenzenes, ethylene chlorides, chlorinated methylene, etc.), aliphatic hydrocarbons [e.g., cyclohexane, etc., paraffins (e.g., mineral oil fractions, etc.)], alcohols (e.g., butanol, glycol, and their ethers, esters, etc.), ketones (e.g., acetone, (such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone), strongly polar solvents (such as dimethyl formamide, dimethyl sulfoxide, etc.) and water. Liquefied gas diluents or carriers are gases at normal temperature and pressure, and include, for example, butane, propane, nitrogen gas, carbon dioxide, and aerosol propellants such as halogenated hydrocarbons. Solid diluents include natural minerals such as
kaolin, clay, talc, chiyolk, quartz, attapulgite, montmorillonite, diatomaceous earth, etc.),
Examples include clay synthetic minerals (eg, highly dispersed silicic acid, alumina, silicates, etc.). Solid carriers for granules include crushed and fractionated rocks (for example, calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic granules of inorganic and organic powders,
Mention may also be made of fine particles of organic matter, such as sawdust, coconut shells, corncobs and tobacco stalks. Emulsifiers and/or foaming agents include nonionic and anionic emulsifiers [e.g., polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (e.g., alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfones); salts, etc.)] and albumin hydrolysis products. Dispersants include, for example, lignin sulfite waste liquor and methylcellulose. Adhesives can also be used in the formulations (powders, granules, emulsions), such adhesion agents include carboxymethyl cellulose and natural and synthetic polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate. I can do it. Coloring agents may also be used, including inorganic pigments such as iron oxide, titanium oxide and Prussian blue, and alizarin dyes,
Organic dyes such as azo dyes or metal phthalocyanine dyes, and also iron, manganese, boron,
Mention may be made of trace elements such as copper, cobalt, molybdenum, their salts of zinc. The formulation may contain, for example, about 0.1 to about
It can contain 95% by weight, preferably about 0.5 to about 90% by weight. The active compounds according to the invention can be used in the above-mentioned formulations or in the various use forms in combination with other known compounds, such as fungicides (fungicides, bactericides), insecticides,
Acaricides, nematocides, herbicides, bird repellents, growth regulators, fertilizers and/or soil conditioners may also be present. When using the active compounds of the invention, they can be used directly as such, or in the form of formulations such as spray preparations, emulsions, suspensions, powders, pastes and granules, or prepared in further dilutions. It can be used in the following manner. The active compound can then be applied in the usual manner, e.g. by watering,
soaking, spraying, atomizing, misting,
It can be used in fumigation, irrigation, suspension formation, spreading, dusting, scattering, powder coating, wet coating, wet coating, pasty coating or feather coating. When treating the various parts of the plant, the concentration of active compound in the actual use form can be varied within a substantial range. and generally, for example, from about 0.0001 to about 1% by weight, preferably from about 0.001 to about 1% by weight.
A concentration such as about 0.5% by weight may be exemplified. For seed treatment, the amount of active compound per kg of seed is, for example, about 0.001 to about 50 g, preferably about 0.01 g.
It can be used in amounts such as ~10g. When using a clay pot, for example, approximately
0.00001 to about 0.1% by weight, especially about 0.0001 to about 0.02
Active compound concentrations of % by weight can be used. Next, the content of the present invention will be specifically explained with reference to Examples, but the present invention should not be limited thereto. Manufacturing example: Example 1 2,2-dichloro-1-ethyl-3-methylcyclopropanecarboxylic acid chloride (21.4 g) was dissolved in methylene chloride (50 ml), and this solution was
-Chloro-α-methylbenzylamine (15.5g)
and triethylamine (12.3 g) in methylene chloride (70 ml) dropwise. After finishing dropping,
Return to room temperature and continue stirring for an additional 3 hours. Pour the reaction mixture into ice water, separate the methylene chloride layer,
The aqueous layer is extracted twice with methylene chloride. The organic layers are combined and washed in the following order: 1% aqueous hydrochloric acid solution, water, 1% aqueous sodium hydroxide solution, and water. The organic layer is dried with sodium sulfate. When methylene chloride is distilled off under reduced pressure, the desired 2,2-dichloro-1-ethyl-
3,3-dimethylcyclopropanecarboxamide (32.4 g) is obtained. mp.168−170℃ Example 2 2,2-dichloro-3-ethyl-1-methylcyclopropanecarboxylic acid (1.86 g) and 4-chloro-α-methylbenzylamine (1.55 g) were dissolved in tetrahydrofuran (20 ml), and dicyclohexylcarbodiimide (2.0 g) was dissolved in tetrahydrofuran (20 ml). Add g).
Then 4-dimethylaminopyridine (0.1g)
and stir at room temperature for 12 hours. The insoluble portion is removed, and tetrahydrofuran is distilled off from the liquid under reduced pressure. Extract the remaining oil with chloroform,
The chloroform layer is washed successively with a 1% aqueous hydrochloric acid solution, a 1% aqueous sodium carbonate solution, and water, and dried over sodium sulfate. After distilling off the chloroform, the residue was purified by liquid chromatography (silica gel).
chloroform), oily N-(4-chloro-α-methylbenzyl)2,2-dichloro-3
-Ethyl-1-methylcyclopropanecarboxamide (1.58 g) is obtained. NMR (60MHz) δCDCl ₃ TMS 0.96-1.90 (m: 11H) 2.15 (t: 1H) 4.85-5.25 (m: 1H) 5.83-5.13 (m: 1H) 7.25 (s: 4H) IR (nujol) ν (cm ^-1 ) 1550, 1640, 3300 Compounds of formula () obtained by the same method as in the above example are shown in Table 1 below.

[Table] Example 3 - Reference example of raw material synthesis - Dissolve 1-bromo-2,3-dimethyl-2-butane (815 g) and triethylbenzylammonium chloride (25 g) in chloroform (2), and add 50% aqueous sodium hydroxide solution (600 g) while stirring vigorously under ice cooling. drip over 3 hours. After the dropwise addition, stirring was continued for an additional 5 hours. Pour the reaction system into ice water 2, separate the chloroform layer, and dry. When chloroform is removed under reduced pressure and the remaining oil is distilled, 1-bromomethyl-2,2-
Dichloro-1,3,3-trimethylcyclopropane (920 g) is obtained. bp.109℃/20mmHg Example 4 - Reference example of raw material synthesis - 1-Bromomethyl- obtained in Example 3 above
2,2-dichloro-1,3,3-trimethylcyclopropane (900g), anhydrous sodium acetate (350g)
g), suspend triethylbenzylammonium chloride (20 g) in toluene (2) and heat under reflux for 12 hours. After cooling, filter and remove toluene from the liquid under reduced pressure. Distilling the remaining oil,
2,2-dichloro-1,3,3-trimethylcyclopropane methyl acetate (803 g) is obtained. bp.128-130℃/60mmHg Example 5 - Reference example of raw material synthesis - 2,2-dichloro- obtained in Example 4 above
1,3,3-trimethylcyclopropane methyl acetate (800 g) was dissolved in sodium hydroxide (145
Dissolve g) in the ethanol solution (1.5) and heat under reflux for 2 hours. Concentrate the reaction solution and add water (1)
and neutralize with 10% aqueous hydrochloric acid solution. 2,2-
Dichloro-1,3,3-trimethylcyclopropane methanol (1 g) was added, left to stand at room temperature for 24 hours, and the precipitated crystals were removed to yield 2,2-dichloro-1,3,3-trimethylcyclopropane methanol (573 g). ) is obtained. mp.78-79℃ Example 6 - Reference example of raw material synthesis - Dissolve 2-ethyl-3-methyl-2-butenol (2.6 g) and tetrabutylammonium bromide (0.5 g) in chloroform (30 ml),
While stirring vigorously, 50% aqueous sodium hydroxide solution (5.4 g) is added dropwise. After the dropwise addition, stirring was continued for further 5 hours at 50°C. Pour the reaction system into 30ml of ice water,
Pressure-sensitive distillation of the chloroform layer yields 2,2-dichloro-1-ethyl-3,3-dimethylcyclopropane methanol (1.9 g). IR (nujol)
ν (cm ^-1 ) 3100−3600NMR (60MHz) δ ^CDCl3 _TMS 0.93~
1.93 (m: 1H) 3.83 (s: 2H) Example 7 - Reference example of raw material synthesis - Alpha-ethyl crotonaldehyde (49 g) in ethyl orthoformate (74 g) is added dropwise to ammonium nitrate (2.5 g) and absolute ethanol (23 g) with stirring. The mixture is stirred at room temperature for 12 hours and then distilled under vacuum to give α-ethyl crotonaldehyde diethyl acetal (46 g). bp.75-78℃/22mmHg Example 8 - Reference example of raw material synthesis - Sodium hydroxide (200g) was dissolved in water (200g) and dissolved in α-ethylcrotonaldehyde diethyl acetal (45g), triethylbenzylammonium chloride (4g), sodium bromide (0.5g) and chloroform (75ml). , dropwise while stirring. After dropping, heat the mixture to 50-60℃
Stir for another 1 hour, cool after stirring, and add water (100 ml).
and extract three times with chloroform. The organic layers are combined and dried over sodium sulfate, the solvent is removed under vacuum, and the residue is then distilled under high vacuum to give diethyl 2,2-dichloro-1-ethyl-3-methylcyclopropane-1-aldehyde. Acetal (24.3 g) is obtained. bp.85℃/2mmHg Example 9 - Reference example of raw material synthesis - 2,2-Dichloro-1-ethyl-3-methylcyclopropane-1-aldehyde diethyl acetal (22.4 g), perchloric acid (0.5 ml), dioxane (40 ml) and water (7 ml) were stirred at 50°C for 2 hours. do.
After cooling the mixture, water is added and extracted with methylene chloride. The organic layers were combined, dried over sodium sulfate, concentrated under vacuum, and the residue was distilled.
2,2-dichloro-1-ethyl-3-methylcyclopropane-1-aldehyde (17.2 g) is obtained. bp.98℃/20mmHg Example 10 - Reference example of raw material synthesis Dissolve potassium permanganese (7.5 g) and sodium carbonate (1.2 g) in water (140 ml). In this solution,
2,2-dichloro-1-ethyl-3-methylcyclopropane-1-aldehyde (8.8 g) is added dropwise. The reaction mixture is then stirred at room temperature for 7 hours. The reaction solution was made slightly acidic with sulfuric acid, and sulfur dioxide gas was blown into it for 5 minutes. Extract well with ether and dry the ether layer over sodium sulfate. When the solvent was distilled off under reduced pressure, 2,2-dichloro-1-ethyl-3-methylcyclopropane-1-carboxylic acid (6.8 g)
is obtained. mp.74℃ Example 11 - Reference example of raw material synthesis - Ethyl 2-isopropylacrylate (15.4g)
Add sodium trichloroacetate (55g) to 100~
Add over 5 hours at 120°C. After addition, 2 more
Continue stirring at the same temperature for an hour. After cooling, the reaction mixture was extracted with ether, the ether layer was washed with water,
Dry over anhydrous sodium sulfate. After distilling off the ether under reduced pressure, the residue was distilled under reduced pressure to obtain ethyl 2,2-dichloro-1-isopropylcyclopropanecarboxylate (16.8 g). bp.109-120°C/20mmHg For example, the following compound is obtained according to the method of Example 11 above. bp.94℃／20mmHg bp.115℃/20mmHg bp.109−120℃/20mmHg bp.95~100℃/25mmHg bp.100~110℃/25mmHg bp.115-125℃/20mmHg bp.125℃/20mmHg bp.150~160℃/20mmHg Example 12 - Reference example of raw material synthesis - Ethyl 2,2-dichloro-1-isopropylcyclopropanecarboxylate (22.4 g) is added to a solution of sodium hydroxide (5 g) in ethanol (100 ml). This mixture is heated to reflux for 6 hours. The ethanol is distilled off under reduced pressure and the residue is dissolved in as little water as possible. Adjust the pH to 3 with 6N hydrochloric acid and leave at 0°C overnight. The precipitated crystals are collected, washed with a small amount of cold water, and dried to give 2,2-dichloro-1-
Isopropylcyclopropanecarboxylic acid (17.6
g) is obtained. mp.67-68°C According to the method of Example 12 above, for example, the following compound is obtained. mp.100~102℃ bp.156～175℃/20mmHg mp.64~68℃ mp.150~151℃ mp.101~103℃ IR: ν(cm ^-1 ) 1700, 2850~2950 IR: ν (cm ^-1 ) 1710, 2850 ~ 2950 NMR: 60 MHz, δ ^CDCl3 _TMS 0.93 (d: 6H) 1.26 ~ 1.96 (m, 3H) 2.36 (t: 2H) 9.96 (5: 1H) Example 13 - Reference example of raw material synthesis Potassium permanganate (340g) in water (3)
The solution dissolved in 2,2-dichloro-1,
Add 3,3-trimethylcyclopropane to a solution of methanol (182 g) and sodium hydroxide (30 g) in water (250 ml) and stir for 12 hours. The mixture is then made slightly acidic with sulfuric acid. Sulfur dioxide gas is passed through this mixed solution until the manganese disulfide is completely dissolved. The reaction solution was extracted with chloroform, dried over sodium sulfate, and the chloroform was distilled off under reduced pressure to obtain 2,2-dichloro-1,3,3-trimethylcyclopropanecarboxylic acid (146 g). mp.150−151
C. According to the method of Example 13 above, the following compound is obtained. mp.103～118℃ Example 14 Reference example of raw material synthesis − 2,2-dichloro-1-ethyl-3-methylcyclopropanecarboxylic acid (18.2 g) was dissolved in chloroform (50 ml), and thionyl chloride (10 ml) was added dropwise under ice cooling. After dropping, remove the water bath and gently heat under reflux for 1 hour at room temperature and then for 1 hour. Chloroform was distilled off under reduced pressure and the remaining liquid was distilled under high vacuum to obtain 2,2-dichloro-1-ethyl-3-methylcyclopropanecarboxylic acid chloride (17.6 g). bp.105-107°C/20mmHg According to the method of Example 14 above, for example, the following compound is obtained. bp.91.5℃／25mmHg bp.98℃／20mmHg bp.96℃/22mmHg Biological test: - [Compound described in JP-A-55-66555] [Compound described in JP-A No. 56-26847] Example 15 Preparation of test compound for foliar spray efficacy test against rice blast disease Active compound: 50 parts by weight Carrier: Mixture of diatomaceous earth and kaolin (1:
5): 45 parts by weight Emulsifier; polyoxyethylene alkyl phenyl ether: 5 parts by weight The above-mentioned amounts of the active compound, carrier and emulsifier are pulverized and mixed to form a wettable powder, which is prepared by diluting the prescribed amount with water. do. Test method Paddy rice (variety: Asahi) was cultivated in clay pots with a diameter of 12 cm, and in the third to fourth seasons, 50 ml of a diluted solution of the test compound prepared as described above at a predetermined concentration was sprayed per three pots. The next day, a suspension of artificially cultured rice blast fungus spores was sprayed and ingested (twice) at 25℃ and relative humidity.
They were kept in a 100% humid room to allow infection. 7 days after vaccination,
The degree of disease per pot was graded and evaluated according to the following criteria, and the control value (%) was determined. Morbidity Spot area ratio 0 0 0.5 2 or less 1 3 to 5 2 6 to 10 3 11 to 20 4 21 to 40 5 41 or more Control value (%) = (Mobility in untreated area - Morbidity in treated area / Morbidity in untreated plot) x 100 This test is the result of 3 pots in 1 plot. The results are shown in Table 2.

[Table] Example 16 Test method for residual effect test against rice blast A diluted solution of a test compound at a predetermined concentration was sprayed in 50 ml per three pots. Five days after spraying, a suspension of artificially cultured rice blast fungus spores was spray inoculated (twice), and 25
The animals were kept in a humid room at 100% relative humidity and infected.
Seven days after inoculation, the degree of morbidity per invention was determined according to Example 8.
In the same manner as above, the classification was evaluated and the control value (%) was determined. The results are shown in Table 3 along with representative examples.

【table】

[Table] The sterilizing uses shown in Examples 15 and 16 above are representative examples, and the compounds of the present invention exemplified here are also representative examples, and the present invention should not be limited only to these.

Claims (1)

[Claims] 1 Formula: In the formula, X represents a halogen atom, n represents 1 or 2, R ¹ represents a lower alkyl group, and R ² and R ³ each represent a hydrogen atom or a lower alkyl group, provided that where R ¹ is a methyl group and R ²
and R ³ each represent a hydrogen atom or a methyl group, and X represents a bromine atom or a fluoro atom. 2 X is fluoro, chloro or bromine at p-position, n is 1, R ¹ is an alkyl group having 2 to 4 carbon atoms, and R ² and R ³ are each a hydrogen atom, methyl or ethyl A compound according to claim 1. 3 X is chloro or bromine at p-position, n is 1
The compound according to claim 1, wherein R ¹ is an alkyl group having 2 to 3 carbon atoms, and R ² and R ³ are each a hydrogen atom or methyl. 4. The compound according to claim 1, wherein X is p-bromine, n is 1, ^R1 is methyl, and ^R2 and ^R3 are each a hydrogen atom or methyl. 5 Formula: N-(4-chloro-α-methylbenzyl)2,2-dichloro-1-ethyl-3,3- according to claim 1, 2, or 3 represented by
Dimethylcyclopropanecarboxamide. 6 formula: N-(4-chloro-α-methylbenzyl)2,2-dichloro-1-ethyl-3-methylcyclopropanecarboxamide according to claim 1, 2 or 3, represented by: 7 Formula: N-(4-bromo-α-methylbenzyl)2 according to claim 1 or 4, represented by
2-Dichloro-1,3-dimethylcyclopropanecarboxamide. 8 Formula: N-(4-bromo-α-methylbenzyl)2 according to claim 1 or 4, represented by
2-Dichloro-1,3,3-trimethylcyclopropanecarboxamide. 9 Formula: N-(4-chloro-α-methylbenzyl)2,2-dichloro-1-isopropylcyclopropanecarboxamide according to claim 1, 2 or 3, represented by: 10 Formula: N-(4-bromo-α-methylbenzyl)2,2-dichloro-1-isopropylcyclopropanecarboxamide according to claim 1, 2 or 3, represented by: 11 formula In the formula, X represents a halogen atom, and n represents 1 or 2, and a compound represented by the formula: In the formula, R ¹ represents a lower alkyl group, R ² and R ³ each represent a hydrogen atom or a lower alkyl group, and M represents a hydroxyl group or a halogen atom. However, in the above, R ¹ is Methyl group and R ²
and R ³ each represent a hydrogen atom or a methyl group, X represents a bromine atom or a fluoro atom, characterized by reacting with a compound represented by the formula: A method for producing carboxamides represented by the following formula, wherein X, n, R ¹ , R ² and R ³ are the same as above. 12 Formula: In the formula, X represents a halogen atom, n represents 1 or 2, ^R1 represents a lower alkyl group, and ^R2 and ^R3 each represent a hydrogen atom or a lower alkyl group, provided that where R ¹ is a methyl group and R ²
and R ³ each represent a hydrogen atom or a methyl group, and X represents a bromine atom or a fluoro atom.