JPH06211766A - Alkoxycarboxylic acid amide derivative and agricultural fungicide containing the derivative - Google Patents

Abstract

PURPOSE:To obtain a new compound exhibiting excellent controlling effect on rice blast, etc., absolutely free from phytotoxicity to rice plant and useful as an agricultural fungicide. CONSTITUTION:The compound of formula I[X is (substituted) lower alkyl, (substituted) lower alkenyl, (substituted) cycloalkyl, etc.; Y is cyano or COOR<4> (R<4> is H, lower alkyl, etc.); R<1> is H or lower alkyl; R<2> and R<3> are H, lower alkyl or cycloalkyl; R<2> and R<3> may form 5 to 7-membered carbon ring mayjorm... together with C to which R<2> and R3 are bound], e.g. N-(1-cyano-1- ethylpropyl)-2-(2-propenyloxy)propionamide. This compound of formula I can be synthesized by reacting a compound of formula II with a compound of formula III and converting the reaction product through a compound of formula IV, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel alkoxycarboxylic acid amide derivative which has not been described in the literature and an agricultural fungicide containing the derivative as an active ingredient.

[0002]

2. Description of the Related Art Japanese Patent Application Laid-Open No. 63-132867 discloses
As a novel aryloxycarboxylic acid derivative having antibacterial activity, the following general formula (A):

[0003]

[Chemical 3]

[Wherein aryl is unsubstituted or C
_1-5 alkyl, C _1-5 alkoxy, C _1-5-alkyl -S
O _{n (n} = 0,1 or 2), halogen, NO _2, C
F ₃ , CN, CH ₃ OCH ₂ , (CH ₃ ) ₂ NCH ₂ ,
Phenyl group mono- or tri-substituted by COO alkyl, CONH ₂ or phenyl, 1- or 2-naphthyl group, optionally chlorine-substituted 2-3
- or represents a 4-pyridyl group or quinolyl group, Q is ^{- (R 5) C (R} 6) - (CH 2) m (m =
0, 1 or 2), R ¹ represents H, C _1-6 alkyl or allyl, R ² and R ³ represent H, C _1-6 alkyl (which may also contain O or S atoms in the chain) Good), C _3-7 cycloalkyl, CH ₂ —COO— (C
_1-5 alkyl), phenyl, or R ₂ and R ₃ together are — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ — or —
_{(CH 3) CH- (CH 2} ) 4 - represents, R ⁴ is CN,
Represents CONH _2, R ⁵ represents H, a _{CH 3, C 2 H 5,} R 6 denotes H, a CH _3, X represents O or S]
Although a compound represented by is disclosed, no reference is made to the compound in which aryl is an optionally substituted alkyl group or the like.

[0005]

Many compounds have been used as agricultural fungicides so far, but by continuously using the same drug for many years, it is possible to obtain fungicidal effects due to the emergence of bacteria that have acquired resistance to the drug. The decline is a problem. Therefore, regarding agricultural and horticultural fungicides, it is expected to create compounds having a new structure having a strong bactericidal effect. The present invention is intended to provide a novel agricultural and horticultural fungicide that satisfies these needs.

As a result of earnest studies to solve the above problems, the present inventors have found that an optionally substituted alkoxycarboxylic acid amide derivative has an excellent bactericidal action, and the present invention has been made. It came to completion. That is, the following general formula (1) of the present invention

[0007]

[Chemical 4]

[In the formula, X represents an optionally substituted lower alkyl group, an optionally substituted lower alkenyl group, an optionally substituted lower alkynyl group or an optionally substituted cycloalkyl group. In the formula, Y represents a cyano group or a —COOR ⁴ group (wherein R ⁴ represents a hydrogen atom, a lower alkyl group, a lower alkenyl group or a cycloalkyl group), R ¹ represents a hydrogen atom or a lower alkyl group, R ² and R ³ each independently represent a hydrogen atom, a lower alkyl group, a lower alkenyl group or a cycloalkyl group, or R ² and R ³ together with the carbon atom to which they are bonded are 5 to 7 membered. Forming a ring carbocycle, which may be substituted with a lower alkyl group] and an alkoxycarboxylic acid amide derivative represented by There is provided a disinfectant containing.

[0009]

The compound of the present invention has the following general formula (1):

[0010]

[Chemical 5]

[Wherein, X is an optionally substituted lower alkyl group, an optionally substituted lower alkenyl group, an optionally substituted lower alkynyl group or an optionally substituted cycloalkyl group. In the formula, Y represents a cyano group or a —COOR ⁴ group (wherein R ⁴ represents a hydrogen atom, a lower alkyl group, a lower alkenyl group or a cycloalkyl group), R ¹ represents a hydrogen atom or a lower alkyl group, R ² and R ³ each independently represent a hydrogen atom, a lower alkyl group, a lower alkenyl group or a cycloalkyl group, or R ² and R ³ together with the carbon atom to which they are bonded are 5 to 7 membered. Forming a ring carbocycle, which may be substituted with a lower alkyl group] and an alkoxycarboxylic acid amide derivative represented by There is provided a disinfectant containing.

In the above general formula (1), X, R ¹ ,
In the definitions of R ² , R ³ , R ⁴ and Y, specific examples of each group are shown below. Optionally substituted lower alkyl group; preferably having 1 to 6 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, n-pentyl, isopentyl, optionally substituted lower alkenyl group such as n-hexyl, trichloromethyl, methoxymethyl, cyanomethyl group; carbon number 3 to 6
And lower alkynyl groups which may be substituted , such as propenyl, butenyl, pentenyl, hexenyl, chloropropenyl, methoxypropenyl, cyanopropenyl groups;
Preferred are, for example, propynyl, butynyl, pentynyl, hexynyl, chloropropynyl, methoxypropynyl, cyanopropynyl groups and the like, which may be substituted cycloalkyl groups;
Preferred are lower alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, chlorocyclopropyl, methoxycyclopropyl, cyanocyclopropyl groups; those having 1 to 6 carbon atoms are preferred, such as methyl, ethyl, n-propyl, isopropyl, n
-Butyl, s-butyl, t-butyl, n-pentyl, isopentyl, n-hexyl group, etc., lower alkenyl group; preferably those having 3 to 6 carbon atoms, for example, propenyl, butenyl, pentenyl, hexenyl group, cyclo Alkyl group; preferably one having 3 to 6 carbon atoms, for example, a cyclopropyl, cyclopentyl, cyclohexyl group or the like, which has 5 to 7 membered carbon atoms which may be substituted with lower alkyl.
Ring; cyclohexane, 2-methylcyclohexane and the like.

The groups not specifically shown in the above groups are selected from the above atoms and groups in any combination or in accordance with the generally known common sense.

A particularly preferred compound in the above general formula (1) of the present invention is that X is an isopropyl group, a t-butyl group,
An optionally substituted propenyl group, an optionally substituted butynyl group, an optionally substituted propynyl group or an optionally substituted cyclohexyl group, and Y
Is a cyano group or —COOR ⁴ , R ¹ is a methyl group, R ² and R ³ are a methyl group, an ethyl group, an isopropyl group or an isobutyl group, and R ⁴ is a methyl group.

Of course, the stereoisomers of the compound represented by the general formula (1) are also within the scope of the present invention. The compounds of the present invention represented by the general formula (1) are shown in Table 1.

[0016]

[Table 1]

[0017]

[Table 2]

[0018]

[Table 3]

[0019]

[Table 4]

[0020]

[Table 5]

[0021]

[Table 6] The compound of the present invention can be produced, for example, by the following method (method A, method B). Method A

[0022]

[Chemical 6]

[Wherein R ¹ , R ² , R ³ , X and Y have the same meanings as described in the above general formula (1), A represents a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group, M is an alkali metal atom, for example,
R ⁵ represents a lower alkyl group, and Ac represents an acetyl group. ]

In the above reaction formula, the carboxylic acid amide derivative represented by the formula (3) is the acid halide derivative represented by the formula (2) and the amino compound represented by the formula (6), preferably the presence of a deoxidizing agent. It can be easily produced by reacting under a suitable solvent. Examples of the deoxidizing agent used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium bicarbonate; organic bases such as pyridine and triethylamine.

Examples of the solvent used in this reaction include diethyl ether, tetrahydrofuran,
Ethers such as dioxane; aromatic hydrocarbons such as benzene, toluene, xylene; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; Acetonitrile, dimethyl sulfoxide, dimethylformamide and the like, and mixed solvents thereof and the like can be mentioned.

There are no particular restrictions on the reaction temperature, but examples include room temperature to the reflux temperature of the solvent. Although the reaction time varies depending on the reaction reagent, reaction temperature, etc., the reaction time may be, for example, about 1 to several hours. After completion of the reaction, the carboxylic acid amide derivative (3) can be isolated from the reaction mixture by a conventional method such as column chromatography and recrystallization. The carboxylic acid amide derivative represented by the formula (3) is obtained by combining the acid halide derivative represented by the formula (2) and the amino compound represented by the formula (6) with phosphorus pentoxide, phosphorus oxychloride,
It can also be obtained by reacting in the presence of a dehydrating agent such as dicyclohexylcarbodiimide (DCC).

The amino compound represented by the formula (6) used in the above reaction is described, for example, in [Journal of Medicinal Chemistry, Vol. 9, page 911 (1966) and Tetrahedron Letters, page 1455 (1977).
Year)]. The acetoxycarboxylic acid amide derivative represented by the formula (4) is obtained by converting the carboxylic acid amide derivative represented by the formula (3) into sodium acetate.
It can be produced by reacting in a suitable solvent.

Examples of the solvent used in this reaction include ethers such as diethyl ether, tetrahydrofuran and dioxane; benzene, toluene,
Aromatic hydrocarbons such as xylene; halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; acetonitrile, dimethylsulfoxide, dimethylformamide, etc. The mixed solvent of can be mentioned.

There are no particular restrictions on the reaction temperature, but examples include room temperature to the reflux temperature of the solvent. Although the reaction time varies depending on the reaction reagent, reaction temperature, etc., the reaction time may be, for example, about 1 to several hours. After completion of the reaction, the acetoxycarboxylic acid amide derivative represented by the formula (4) can be isolated from the reaction mixture by a conventional method such as column chromatography and recrystallization.

The hydroxycarboxylic acid amide derivative represented by the formula (5) is prepared by appropriately converting the acetoxycarboxylic acid amide derivative represented by the formula (4) in the presence of a catalytic amount of the alkoxy alkali metal salt represented by the formula (7). It can be easily produced by reacting in a solvent.

Examples of the solvent used in this reaction include alcohols such as methanol, ethanol and propanol. There are no particular restrictions on the reaction temperature, but examples include room temperature to the reflux temperature of the solvent. Although the reaction time varies depending on the reaction reagent, reaction temperature, etc., the reaction time may be, for example, about 1 to several hours.

After completion of the reaction, the hydroxycarboxylic acid amide derivative represented by the formula (5) can be isolated from the reaction mixture by a conventional method such as column chromatography, recrystallization, etc. A crude product is sufficient for use in the process.

The hydroxycarboxylic acid amide derivative (5) thus obtained and the halide represented by the formula (8) are reacted in a suitable solvent, preferably in the presence of a deoxidizing agent, to facilitate sterilization of the present invention. The active compound alkoxycarboxylic acid amide derivative (1) can be prepared.

Examples of the deoxidizing agent used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydride and potassium hydride; pyridine,
Organic bases such as triethylamine may be mentioned.

Examples of the solvent used in this reaction include diethyl ether, tetrahydrofuran,
Ethers such as dioxane; aromatic hydrocarbons such as benzene, toluene, xylene; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; Acetonitrile, dimethyl sulfoxide, dimethylformamide and the like, and mixed solvents thereof can be mentioned.

There are no particular restrictions on the reaction temperature, but examples include room temperature to the reflux temperature of the solvent. Although the reaction time varies depending on the reaction reagent, reaction temperature, etc., the reaction time may be, for example, about 1 to several hours. After completion of the reaction, the target compound (1) was subjected to column chromatography,
It can be isolated from the reaction mixture according to a conventional method such as recrystallization. Method B

[0037]

[Chemical 7]

[Wherein R ¹ , R ² , R ³ , X and Y have the same meanings as described in the above general formula (1), M represents an alkali metal atom, for example, sodium or potassium, and A
Represents a halogen atom, an alkylsulfonyloxy group, or an arylsulfonyloxy group. ]

In the above reaction formula, the halogenated ester derivative represented by the formula (9) is obtained by combining the acid halide derivative represented by the formula (2) and the alcohol represented by the formula (13), preferably in the presence of a deoxidizing agent. It can be easily produced by reacting in a suitable solvent.

Examples of the deoxidizing agent used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium bicarbonate, and organic bases such as triethylamine and pyridine.

Examples of the solvent used in this reaction include ethers such as diethyl ether, tetrahydrofuran and dioxane; benzene, toluene,
Aromatic hydrocarbons such as xylene; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; acetonitrile, dimethylsulfoxide, dimethylformamide and the like, and These mixed solvents can be illustrated.

There are no particular restrictions on the reaction temperature, but examples include room temperature to the reflux temperature of the solvent. Although the reaction time varies depending on the reaction reagent, reaction temperature, etc., the reaction time may be, for example, about 1 to several hours. After completion of the reaction, the halogenated ester derivative (9) can be isolated from the reaction mixture by a conventional method such as column chromatography and recrystallization.

The alkoxy ester derivative represented by the formula (10) is the same as the halogenated ester derivative (9) and the formula (1).
It can be produced by reacting with an alkali metal salt represented by 4) in a suitable solvent.

Examples of the solvent used in this reaction include alcohols such as methanol, ethanol and i-propanol; ethers such as tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone; acetonitrile, dimethyl sulfoxide and dimethylformamide. And the like, and mixed solvents thereof, and alcohols and ethers are particularly preferable.

There are no particular restrictions on the reaction temperature, but examples include room temperature to the reflux temperature of the solvent. Although the reaction time varies depending on the reaction reagent, reaction temperature, etc., the reaction time can be exemplified as about 1 to several hours. After the reaction,
The alkoxy ester derivative (10) can be isolated from the reaction mixture by a conventional method such as column chromatography and recrystallization.

The alkoxycarboxylic acid derivative represented by the formula (11) can be easily produced by hydrolyzing the alkoxyester derivative (10) in the presence of an acid or an alkali in a suitable solvent.

The acid used in this reaction includes
Examples thereof include mineral acids such as hydrochloric acid and sulfuric acid. Examples of the alkali used in this reaction include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Solvents used in this reaction include alcohols such as methanol, ethanol and i-propanol; lower fatty acids such as acetic acid and propionic acid;
Etc.

There is no particular restriction on the temperature of the hydrolysis reaction, but examples include room temperature to the reflux temperature of the solvent. The reaction time varies depending on the reaction temperature, the type of acid and alkali used, and the like, but for example, a reaction time of about 1 to about 10 hours can be exemplified. After completion of the reaction, the alkoxycarboxylic acid derivative (11) can be isolated according to a conventional method such as column chromatography, recrystallization, etc., if desired, but it is not particularly required to be purified and isolated and used in the next step. A crude product is sufficient for this.

The alkoxycarboxylic acid halide derivative represented by the formula (12) is obtained by treating the alkoxycarboxylic acid derivative represented by the formula (11) with a halogenating agent such as thionyl chloride, phosphorus pentachloride and phosphorus tribromide. It can be easily manufactured by processing.

The present invention can be easily carried out by reacting an alkoxycarboxylic acid halide derivative represented by the formula (13) with an amino compound represented by the formula (7) in a suitable solvent, preferably in the presence of a deoxidizing agent. The compound alkoxycarboxylic acid amide derivative (1) can be produced.

Examples of the deoxidizing agent used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium bicarbonate; organic bases such as pyridine and triethylamine. . Examples of the solvent used in this reaction include ethers such as diethyl ether, tetrahydrofuran and dioxane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as dichloromethane, chloroform and carbon tetrachloride. Ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate; acetonitrile, dimethylsulfoxide, dimethylformamide and the like, and mixed solvents thereof.

There are no particular restrictions on the reaction temperature, but examples include room temperature to the reflux temperature of the solvent. Although the reaction time varies depending on the reaction reagent, reaction temperature, etc., the reaction time may be, for example, about 1 to several hours. After completion of the reaction, the target compound (1) was subjected to column chromatography,
It can be isolated from the reaction mixture according to a conventional method such as recrystallization.
The alkoxycarboxylic acid amide derivative (1) is obtained by reacting the alkoxycarboxylic acid derivative (12) and the amino compound (7) in the presence of a dehydrating agent such as phosphorus pentoxide, phosphorus oxychloride, dicyclohexylcarbodiimide (DCC). It is also possible to obtain

[0053]

EXAMPLES The present invention will be specifically described below with reference to examples. Production Example 1 (Synthesis Method A) N- (1-cyano-1-ethylpropyl) -2- (2-
Propenyloxy) propionamide (Compound No. 7
Synthesis of ( 0) (a) 10.0 g (79 mmol) of 2-chloropropionyl chloride dissolved in 20 ml of tetrahydrofuran
8.8 g of 2-amino-2-ethylbutyronitrile
(79 mmol), 15.9 g of triethylamine (15
8 mmol) and 30 ml of tetrahydrofuran were added dropwise under ice cooling, and the mixture was stirred at room temperature for 1 hour. Ice water was added to the reaction solution, extraction was performed with ethyl acetate, and the organic layer was washed with saturated brine. After drying over anhydrous sodium sulfate, the solvent was evaporated under reduced pressure and the obtained residue was purified by silica gel column chromatography to give N- (1-cyano-1-ethylpropyl) -2-chloropropionamide 13. 1
g was obtained (yield 82%). (B) 13.1 g of N- (1-cyano-1-ethylpropyl) -2-chloropropionamide obtained in (a)
(65 mmol) of N, N-dimethylformamide 80
It was dissolved in 8 ml of sodium acetate and dissolved in this solution.
(8 mmol) and then stirred at 80 ° C. for 10 hours. Ice water was added to the reaction solution, extraction was performed with ethyl acetate, and the organic layer was washed with saturated brine. After drying over anhydrous sodium sulfate, the residue obtained by distilling off the solvent under reduced pressure,
Purified by silica gel column chromatography, N-
11.0 g of (1-cyano-1-ethylpropyl) -2-acetoxypropionamide was obtained (yield 75%). (C) N- (1-cyano-1-ethylpropyl) -2-acetoxypropionamide 11.0 obtained in (b)
g (49 mmol) is dissolved in 100 ml of methanol,
After adding 1.0 g (5 mmol) of sodium methoxide (28% in methanol) to this solution, the mixture was stirred at room temperature for 10 hours. Water was added to the reaction solution, and methanol was distilled off under reduced pressure. It was extracted with ethyl acetate and the organic layer was washed with saturated saline. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain N- (1-cyano-1-ethylpropyl) -2-hydroxypropionamide (8.6 g, yield 96%). (D) 800 m of N- (1-cyano-1-ethylpropyl) -2-hydroxypropionamide obtained in (c)
g (4 mmol) of N, N-dimethylformamide 8 m
It was dissolved in 1 and 190 mg (5 mmol) of sodium hydride (60% in 0i1) was added to this solution under ice cooling, and the mixture was stirred at room temperature for 30 minutes. At the same temperature, 790 mg (6 mmol) of 2-propenyl bromide dissolved in 5 ml of N, N-dimethylformamide was added dropwise to this reaction solution, followed by stirring for 1 hour. Ice water was added to the reaction solution, extraction was performed with ethyl acetate, and the organic layer was washed with saturated brine. After drying over anhydrous sodium sulfate, the solvent was evaporated under reduced pressure and the obtained residue was purified by silica gel column chromatography to give N- (1-cyano-1-ethylpropyl) -2.
-(2-Propenyloxy) propionamide 760 m
g was obtained (yield 78%).

Production Example 2 (Synthesis Method B) Methyl 2- (1-cyclohexylethylcarbonylamido )
No) -2-methyl-3-methylbutyrate (Compound number
Synthesis of 91) (a) 5.6 g (56 mmol) of cyclohexanol and 9.4 g (93 mmol) of triethylamine were dissolved in 50 ml of tetrahydrofuran, and 10 g (46 mmol) of 2-bromopropionyl bromide dissolved in 30 ml of tetrahydrofuran was dissolved in this solution. , 0 ° C., and stirred at room temperature for 1 hour. Ice water was added to the reaction solution, extraction was performed with ethyl acetate, and the organic layer was washed with saturated brine. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure and the obtained residue was purified by silica gel column chromatography to obtain 8.9 g of cyclohexyl 2-bromopropionate (yield 82%). (B) 3.7 g (37 mmol) of cyclohexanol was dissolved in 30 ml of N, N-dimethylformamide, and sodium hydride (60% in 0i1) was added to this solution at room temperature.
1.5 g (38 mmol) was added and stirred for 30 minutes.
7.2 g (31 mmol) of cyclohexyl 2-bromopropionate obtained in (a) dissolved in 20 ml of N, N-dimethylformamide was added dropwise thereto at room temperature.
Stir for hours. Ice water was added to this reaction solution, extraction was performed with ethyl acetate, and the organic layer was washed with saturated brine. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure and the obtained residue was purified by silica gel column chromatography to obtain 6.2 g of cyclohexyl 2-cyclohexyl propionate (yield 80%). (C) 6.2 g (24 mmol) of cyclohexyl 2-cyclohexylpropionate obtained in (b) was dissolved in 30 ml of methanol, and 40 ml (36 mmol) of aqueous sodium hydroxide solution was added to this solution under ice cooling to give 1 at room temperature.
Stir for hours. The reaction solution was acidified with diluted hydrochloric acid, and methanol was distilled off under reduced pressure. It was extracted with ethyl acetate and the organic layer was washed with saturated saline. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain 3.9 g of 2-cyclohexylpropionic acid (yield 94%). (D) 1.0 g (6 mmol) of 2-cyclohexylpropionic acid obtained in (c) was mixed with 4 ml of thionyl chloride (55
mmol) was added and the mixture was heated under reflux for 2 hours. Excessive thionyl chloride was distilled off from the reaction mixture under reduced pressure to obtain 1.1 g of crude 2-cyclohexylpropionyl chloride. This coarse 2
1.1 g of cyclohexylpropionyl chloride was dissolved in 5 ml of diethyl ether, and methyl-2-amino-
2,3-dimethylbutyrate 1.0 g (7 mmol),
5% sodium hydroxide aqueous solution 10 ml (13 mmol)
And 10 ml of diethyl ether were added dropwise at 0 ° C. with stirring for 15 minutes. Then, the mixture was stirred at room temperature for 1 hour.
The reaction solution was extracted with ethyl acetate, and the organic layer was washed with diluted hydrochloric acid and saturated saline. After drying over anhydrous sodium sulfate, the residue obtained by evaporating the solvent under reduced pressure was purified by silica gel column chromatography to obtain methyl 2- (1
1.6 g of -cyclohexylethylcarbonylamino) -2-methyl-3-methylbutyrate was obtained (yield 92
%).

Table 2 shows the ¹ H NMR peak values of the compounds produced by the same method as in the above Production Example.

[0056]

[Table 7]

[0057]

[Table 8]

The fungicide of the present invention contains the novel alkoxycarboxylic acid amide derivative represented by the general formula (1) as an active ingredient. When the compound of the present invention is used as a bactericidal agent, it is mixed with a carrier or diluent, an additive, an auxiliary agent and the like by a known method, and a formulation form usually used as an agricultural chemical, for example, powder, granules, water. Japanese medicine, emulsion,
Used as a wettable powder, a flowable agent, etc. Also other pesticides, such as fungicides, insecticides, acaricides, herbicides,
It can be used as a mixture or in combination with plant growth regulators, fertilizers, soil conditioners and the like.

In particular, when used in combination with other fungicides, not only the pesticides used are reduced and labor is saved, but also a broader bactericidal spectrum due to the synergistic action of both drugs and a higher effect due to a synergistic action are expected. it can. Examples of the carrier or diluent used in the preparation include solid or liquid carriers generally used.

Examples of the solid carrier include clays represented by kaolinite group, montmorillonite group, illite group, polygloskite group and the like, more specifically, pyroflight, attapulgite, sepiolite, kaolinite, bentonite, vermiculite, mica and the like. Talc, etc .; gypsum, calcium carbonate, dolomite, diatomaceous earth,
Other inorganic substances such as magnesium lime, phosphorus lime, zeolite, silicic acid anhydride, and synthetic calcium silicate; plant organic substances such as soybean flour, tobacco flour, walnut flour, wheat flour, wood flour, starch, crystalline cellulose; coumarone resin, Examples thereof include synthetic or natural polymer compounds such as petroleum resins, alkyd resins, polyvinyl chloride, polyalkylene glycols, ketone resins, estil gum, cobal gum, and dumbrum gum; and waxes such as carnauba wax and beeswax and urea.

Suitable liquid carriers include, for example, paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil, and white oil; aromatic hydrocarbons such as xylene, ethylbenzene, cumene, methylnaphthalene; trichloroethylene, monochrome. Chlorinated hydrocarbons such as benzene and orthochlorotoluene; ethers such as dioxane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone, isophorone; ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate , Esters such as dibutyl maleate and diethyl succinate; methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol, Alcohols such as benzyl alcohol, ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether, ether alcohols such as diethylene glycol butyl ether; dimethylformamide, polar solvents or water such as dimethyl sulfoxide.

Others Emulsification, dispersion, wetting, spreading, spreading, binding, control of disintegration, stabilization of active ingredient of the compound of the present invention,
Surfactants and other auxiliary agents can be used for the purpose of improving fluidity, preventing rust, and preventing freezing. As examples of the surfactant used, nonionic, anionic, cationic and zwitterionic compounds may be used, but usually nonionic and / or anionic compounds are used. A compound is used.

Suitable nonionic surfactants include, for example, compounds obtained by polymerizing addition of ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol and oleyl alcohol; isooctylphenol,
Compounds obtained by polymerizing addition of ethylene oxide to alkylphenols such as nonylphenol; Compounds obtained by polymerizing addition of ethylene oxide to alkylnaphthols such as butylnaphthol and octylnaphthol; Polymerization addition of ethylene oxide to higher fatty acids such as palmitic acid, stearic acid and oleic acid Compounds: higher fatty acid esters of polyhydric alcohols such as sorevitan, compounds obtained by polymerizing addition of ethylene oxide, compounds obtained by block-polymerizing addition of ethylene oxide and propylene oxide, and the like.

Suitable anionic surfactants include, for example, alkyl sulphate salts such as sodium lauryl sulphate and oleyl alcohol sulphate amine salts; alkyls such as sodium sulfosuccinate dioctyl ester and sodium 2-ethylhexene sulphonate. Sulfonates; aryl sulfonates such as sodium isopropylnaphthalenesulfonate, sodium methylenebisnaphthalenesulfonate, sodium ligninsulfonate, sodium dodecylbenzenesulfonate, and the like.

Further, the fungicide of the present invention contains casein, gelatin, and / or gelatin for the purpose of improving the properties of the preparation and enhancing the bactericidal effect.
High molecular compounds such as albumin, glue, sodium alginate, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, polyvinyl alcohol and the like and other auxiliary agents can be used together. The above-mentioned carrier and various auxiliary agents are appropriately used alone or in combination depending on the purpose in consideration of the dosage form of the preparation, the application scene and the like.

The content of the active ingredient of the compound of the present invention in the various dosage forms thus obtained varies depending on the dosage form, but is usually 0.1 to 99% by weight, preferably 1 to 99% by weight. 60% by weight is most suitable. In the case of a wettable powder, for example, the active ingredient compound is usually 10 to 90%.
The rest is a solid carrier and a dispersion wetting agent, and a protective colloid agent, a defoaming agent and the like are added if necessary.

In the case of granules, for example, the active ingredient compound is usually contained in an amount of 1 to 35% by weight, and the balance is a solid carrier, a surfactant and the like. The active ingredient compound is uniformly mixed with the solid carrier, or is uniformly fixed or adsorbed on the surface of the solid carrier, and the particle diameter is about 0.2 to 1.5 mm. In the case of an emulsion, for example, the active ingredient compound is usually added to
Contains 30% by weight of which approximately 5 to 20% by weight
Of the emulsifier and the rest is a liquid carrier, and a spreading agent, a rust preventive agent, etc. are added if necessary.

In the case of a flowable agent, for example, the active ingredient compound is usually contained in an amount of 5 to 50% by weight, the dispersion wetting agent is contained in an amount of 3 to 10% by weight, and the balance is water. Agents, preservatives, defoamers and the like are added. The alkoxycarboxylic acid amide derivative of the present invention is
The compound of the general formula (1) can be used as it is, or can be used as an agent in any of the above-mentioned preparation forms.

The use concentration of the compound of the present invention varies depending on the target crop, the method of use, the form of formulation, the amount applied, etc.
In the case of foliage treatment, 0.1 to 10,000 ppm, preferably 1 to 5 per active ingredient is not specified.
It is 00 ppm. 10 to 10 for soil treatment
10,000 g / ha, preferably 200 to 20,000
It is 0 g / ha.

Next, several embodiments of formulation examples using the compound of the present invention will be shown. The "parts" in the following preparations are based on weight.

Formulation Example 1 (Emulsion) Compound No. 90 10 parts Xylene 45 parts Calcium dodecylbenzene sulfonate 7 parts Polyoxyethylene styryl phenyl ether 13 parts Dimethylformamide 25 parts The above components are uniformly mixed and dissolved to obtain 100 parts of emulsion. It was

Formulation Example 2 (wettable powder) Compound number: 90 20 parts Diatomaceous earth 70 parts Calcium lignin sulfonate 5 parts Naphthalene sulfonate formalin condensate 5 parts The above components were mixed and ground to obtain 100 parts wettable powder.

Formulation Example 3 (Granule) Compound No. 90 5 parts Bentonite 50 parts Talc 42 parts Sodium lignin sulfonate 2 parts Polyoxyethylene alkylaryl ether 1 part After thoroughly mixing the above, add an appropriate amount of water. The mixture was kneaded and granulated using an extrusion granulator to obtain 100 parts of granules.

Formulation Example 4 (flowable agent) Compound No .: 90 30 parts Di-2-ethylhexyl sulfosuccinate sodium salt 2 parts Polyoxyethylene nonylphenyl ether 3 parts Defoamer 1 part Propylene glycol 5 parts Water 59 parts The wet ball mill uniformly pulverized and mixed to obtain 100 parts of a flowable agent.

The fungicides containing the compound of the present invention can be prepared according to the above-mentioned preparation examples. Next, according to the test example,
The effect of controlling various plant diseases by the fungicide of the present invention will be specifically described.

Test Example (Control Test against Rice Blast) Paddy rice (variety: Koshihikari) was sown in 7-piece plastic cups each having a diameter of 7 cm and grown in a greenhouse for 3 weeks. The reagent agent emulsified according to Formulation Example 1 was diluted with water so as to have a predetermined concentration, and sprayed so as to sufficiently adhere to the leaf surface of rice. One day after spraying, inoculate with a spore suspension of rice blast fungus, and then incubate in a humid chamber at 25 ° C.
After keeping it for a day, it was sick in a greenhouse. Seven days after the inoculation, the average number of lesions per leaf was investigated and the control value was calculated by the following formula.

Control value (%) = (average number of lesions in untreated plot-
Average number of lesions in treated area) / (average lesion in untreated area) x 10
0 The results are shown in Table 3.

[0078]

[Table 9] Table 3 Compound No. Reagent concentration (ppm) Control value (%) 34 500 100 35 35 500 100 100 39 500 100 70 70 500 100 100 86 500 100 90 90 500 100 91 91 500 100 92 500 500 100 95 500 100

[0079]

The alkoxycarboxylic acid amide derivative represented by the above general formula (1) of the present invention is a novel compound which has not been described in any literature. The alkoxycarboxylic acid amide derivative represented by the above general formula (1) of the present invention is characterized in that it has an alkoxy group which may be substituted in the carboxylic acid amide skeleton. It is considered that the excellent properties of the bactericide containing the acid amide derivative are exhibited. The compound and fungicide of the present invention show an excellent controlling effect against blast disease occurring in paddy rice cultivation in foliage treatment and water surface application, and show no phytotoxicity to rice. Further, the compound of the present invention and the fungicide have an excellent controlling effect against cucumber and diseases.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shinmitsu Sawai 8-3-1 Chuo, Ami-cho, Inashiki-gun, Ibaraki Mitsubishi Petrochemical Co., Ltd. Tsukuba Research Institute

Claims (2)

[Claims] 1. A compound represented by the general formula (1): [Wherein, X represents an optionally substituted lower alkyl group, an optionally substituted lower alkenyl group, an optionally substituted lower alkynyl group or an optionally substituted cycloalkyl group, and Y Is a cyano group or -C
Represents an OOR ⁴ group (wherein R ⁴ represents a hydrogen atom, a lower alkyl group, a lower alkenyl group or a cycloalkyl group), R ¹ represents a hydrogen atom or a lower alkyl group,
R ² and R ³ each independently represent a hydrogen atom, a lower alkyl group, a lower alkenyl group or a cycloalkyl group, or R ² and R ³ together with the carbon atom to which they are bonded are 5 to 7 membered. Forms a carbocycle of the ring, which ring may be substituted with lower alkyl groups]
An alkoxycarboxylic acid amide derivative represented by. 2. A compound represented by the general formula (1): [Wherein, X represents an optionally substituted lower alkyl group, an optionally substituted lower alkenyl group, an optionally substituted lower alkynyl group or an optionally substituted cycloalkyl group, and Y Is a cyano group or -C
Represents an OOR ⁴ group (wherein R ⁴ represents a hydrogen atom, a lower alkyl group, a lower alkenyl group or a cycloalkyl group), R ¹ represents a hydrogen atom or a lower alkyl group,
R ² and R ³ each independently represent a hydrogen atom, a lower alkyl group, a lower alkenyl group or a cycloalkyl group, or R ² and R ³ together with the carbon atom to which they are bonded are 5 to 7 membered. Forms a carbocycle of the ring, which ring may be substituted with lower alkyl groups]
An agricultural fungicide containing an alkoxycarboxylic acid amide derivative represented by as an active ingredient.