JPH06228101A - Isonicotinic acid amide derivative, its production and agricultural and horicultural disease damage controlling agent - Google Patents

Abstract

PURPOSE:To obtain a new isonicotinic acid amide derivative having excellently controlling activity as an agricultural and horticultural disease damage controlling agent. CONSTITUTION:An isonicotinic acid amide derivative of formula I (R<1> and R<2> are 1-6C alkyl and R<1> and R<2> form 3-10C cycloalkyl with adjacent C; R<3> is 1-15C alkyl, 2-12C alkenyl or phenylalkyl; X is halogen; Y is halogen or 1-6C alkyl) such as N-(2,6-dichloroisonicotinoyl)-2-methylalanine-isopropyl ester. The compound of formula I is obtained by reacting a compound of formula II with a compound of formula III. The compound of formula I, for example, shows excellently sterilizing effect on blast of rice plant and bacterial leaf blight of rice plant and has now phytotoxicity.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel isonicotinic acid amide derivative, a process for producing the same, and an agricultural and horticultural disease control agent containing the same.

[0002]

As an isonicotinic acid amide derivative,
The following compounds are known. The following formula is disclosed in JP-A-62-161761:

[0003]

[Chemical 4]

Compounds having the bactericidal activity shown by are disclosed. The following formula is disclosed in JP-A-63-284162:

[0005]

[Chemical 5]

Compounds having phytoprotective activity of the following are disclosed. The following formula is disclosed in JP-A-1-272569:

[0007]

[Chemical 6]

Compounds having a plant protective activity of the following are disclosed. The following formula is disclosed in JP-A-1-283270:

[0009]

[Chemical 7]

Compounds having plant protection activity, represented by: are disclosed. Japanese Patent Laid-Open No. 1-283271 discloses the following formula:

[0011]

[Chemical 8]

Compounds having a plant protective activity represented by are disclosed. The following formula is disclosed in JP-A-1-283284:

[0013]

[Chemical 9]

Compounds having phytoprotective activity are disclosed: However, the isonicotinic acid amide derivative of the present invention and its agricultural and horticultural disease control activity are not disclosed in the above publication.

[0015]

An object of the present invention is to provide a novel isonicotinic acid amide derivative, a process for producing the same, and an agricultural and horticultural disease control agent containing the same.

[0016]

Means for Solving the Problems As a result of research for solving the above problems, the present inventors have found that a novel isonicotinic acid amide derivative has a remarkable controlling activity as an agricultural and horticultural disease controlling agent. Heading out, the present invention has been completed. That is, the present invention is as follows. The first invention is represented by the following formula (I):

[0017]

[Chemical 10]

(Wherein R ¹ and R ² are the same or different alkyl groups each having 1 to 6 carbon atoms; or R ¹ and R ² are carbon atoms to which they are bonded. And R ³ can form a cycloalkyl group having 3 to 10 carbon atoms; R ³ is an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkyl moiety having carbon atoms Represents a phenylalkyl group of 1 to 6; X represents a halogen atom; Y represents a halogen atom or an alkyl group having 1 to 6 carbon atoms).

The second invention is the following formula (II):

[0020]

[Chemical 11]

(Wherein, X and Y have the same meanings as described above) and the following formula (III):

[0022]

[Chemical 12]

(Wherein R ¹ , R ² and R ³ have the same meanings as described above), and the isonicotine represented by the above-mentioned formula (I) is reacted. The present invention relates to a method for producing an acid amide derivative.

A third invention relates to an agricultural and horticultural disease control agent containing an isonicotinic acid amide derivative represented by the above-mentioned formula (I) as an active ingredient.

The present invention will be described in detail below. The novel isonicotinic acid amide derivative (I), which is the above-mentioned target compound, and the compounds (II) and (III), which are raw materials for producing the same
R ¹ , R ² , R ³ , X, and Y in are as follows.

R ¹ and R ² are linear or branched alkyl groups having 1 to 6 carbon atoms; preferably those having 1 to 4 carbon atoms (eg, methyl group, (Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, etc.); and more preferably a methyl group. R ¹ and R ² may form a cycloalkyl group having 3 to 10 carbon atoms together with the carbon atom to which they are bonded; preferably those having 3 to 8 carbon atoms. Well (eg, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, etc.); and more preferably those having 3 to 6 carbon atoms.

R ³ is a straight-chain or branched alkyl group having 1 to 15 carbon atoms, a straight-chain or branched alkenyl group having 2 to 12 carbon atoms, or an alkyl moiety is straight-chain. Alternatively, a branched phenylalkyl group having 1 to 6 carbon atoms and the like can be given. The alkyl group for R ³ preferably has 1 to 10 carbon atoms;
More preferably, it has 1 to 6 carbon atoms.
The alkenyl group for R ³ preferably has 1 to 8 carbon atoms; and more preferably has 1 to 5 carbon atoms. In the phenylalkyl group for R ³ , the phenyl moiety may have a halogen atom (eg, chlorine atom, bromine atom, iodine atom, fluorine atom, etc.) as a substituent; the number of carbon atoms in the alkyl moiety is preferably Is 1 to 4, more preferably 1 to 3. The most preferred phenylalkyl group includes, for example, benzyl group, phenethyl group, phenylpropyl group and the like.

X is a halogen atom (eg, chlorine atom, iodine atom, bromine atom, fluorine atom, etc.); preferably chlorine atom. Examples of Y include a halogen atom and a linear or branched alkyl group having 1 to 6 carbon atoms. The halogen atom for Y is preferably a chlorine atom. The alkyl group in Y is preferably one having 1 to 4 carbon atoms (for example, the same as those described as R ¹ and R ² ); and more preferably a methyl group.

The compound (I) of the present invention can be synthesized by reacting the compound (II) with the compound (III) in a solvent in the presence of a base, as shown below.

[0030]

[Chemical 13]

(In the formula, R ¹ , R ² , R ³ , X and Y have the same meanings as described above.) The solvent is not particularly limited as long as it does not directly participate in the reaction, and for example, Chlorinated or unchlorinated aromatics such as benzene, toluene, xylene, methylnaphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, dichloromethane, dichloroethane, trichloroethylene, cyclohexane, Aliphatic and alicyclic hydrocarbons; diethyl ether,
Ethers such as tetrahydrofuran, dioxane; ketones such as acetone, methyl ethyl ketone; amides such as N, N-dimethylformamide, N, N-dimethylacetamide; acetonitrile,
Nitriles such as propionitrile; organic bases such as triethylamine, pyridine, N, N-dimethylaniline; 1,3-dimethyl-2-imidazolidinone; dimethylsulfoxide; water; Can be mentioned.

The amount of the solvent used is the compound (I
The compound (II) can be used in a concentration range of 5 to 80% by weight, and preferably the compound (II) is used in a concentration of 10 to 70% by weight.

The base is not particularly limited and includes, for example,
Organic bases (eg triethylamine, pyridine, N,
N-dimethylaniline, DBU, etc., alkali metal alkoxides (eg, sodium methoxide, sodium ethoxide, etc.), inorganic bases (eg, sodium hydride, sodium amide, sodium hydroxide, potassium hydroxide, sodium carbonate, hydrogen carbonate) Sodium, potassium carbonate, etc.) and the like.

The amount of the base used is the compound (I
It can be used in an amount of 0.001 to 5 times by mole with respect to I); preferably 0.8 to 5 times by mole; more preferably 1.0 to 2.0 times by mole. The reaction temperature is not particularly limited; it is within the temperature range of room temperature to the boiling point of the solvent used; preferably 20 to 150.
C .; more preferably 30 to 80.degree.

The reaction time varies depending on the above-mentioned concentration and temperature, but is usually 5 minutes to 8 hours, preferably 10 minutes to 2 hours. The amount of the raw material compound used is 0.5 to 2 times mol of the compound (III) with respect to the compound (II), and preferably 0.7 to 1.5 times mol.

The compound (II) can be prepared, for example, according to J. Amer.
Chem. Soc. 80, 5481 (1958), according to the method shown in the following formula.

[0037]

[Chemical 14]

Examples of the compound (II) are shown in the table below.
Each substitution corresponding to compounds 1-21 shown in 1-3
Each compound (II) consisting of the type of group [Compound (II)₁~
(II) _{twenty one}Called. For example, this compound (II)₁And
X and Y in the formula of compound (II) are chlorine atoms.
is there. ] Can be mentioned. Compound (III) is
Manufactured by a known method
can do.

[0039]

[Chemical 15]

Examples of the compound (III) are shown in the table below.
Each substitution corresponding to compounds 1-21 shown in 1-3
Each compound (III) consisting of the type of group [Compound (III)₁~ (I
II) _{twenty one}Called. For example, this compound (III)₁Is a compound
R in the formula represented by the formula (III)¹, R²And R³The
It is a chill group. ] Can be mentioned. Compound (I)
As, for example, compounds 1 to 21 shown in Tables 1 to 3
[Compound 1 means X and X in the formula represented by Compound (I).
And Y is a chlorine atom, R¹, R ²And R³Is a methyl group
Is. ] Can be mentioned.

After completion of the reaction, the desired compound (I) produced as described above is subjected to usual post-treatments such as extraction, concentration and filtration, and if necessary, recrystallization, various chromatography and other usual treatments. It can be appropriately purified by the above method.

The compound (I) of the present invention is a plant disease (eg, viral disease, caused by phytopathogenic fungi).
Blast disease caused by filamentous fungi and bacteria,
It is effective in the prevention and treatment of sesame leaf blight, leaf blight, white leaf blight, rice blight bacterial disease, gray mold disease, etc.). Further, it also has an excellent effect against the resistant bacteria of the existing pesticides causing the above-mentioned diseases.

The agricultural / horticultural disease control agent of the present invention contains at least one compound (I) as an active ingredient. Compound (I) can be used alone,
Usually, by a conventional method, a carrier, a surfactant, a dispersant, an auxiliary agent, etc. are mixed, and powder, emulsion, fine granules, granules, wettable powder,
It is preferably formulated and used as a composition such as an oily suspension or an aerosol.

Examples of the carrier include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate or urea; hydrocarbons (kerosene, mineral oil, etc.), aromatic carbonization. Hydrogen (benzene, toluene, xylene, etc.),
Chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene glycol acetate, dibutyl maleate, etc.), alcohol Liquid carriers such as compounds (methanol, n-hexanol, ethylene glycol, etc.), polar solvents (dimethylformamide, dimethylsulfoxide, etc.), water; gas carriers such as air, nitrogen, carbon dioxide gas, Freon (in this case, mixed injection) Can be mentioned).

Examples of surfactants and dispersants which can be used to improve the performance of the present agent such as adhesion to plants, improvement of absorption, dispersion of agents, emulsification and spreading are, for example, alcohol sulfates and alkyls. Examples thereof include sulfonate, lignin sulfonate, polyoxyethylene glycol ether and the like. Then, in order to improve the properties of the preparation, for example, carboxymethyl cellulose,
Polyethylene glycol, gum arabic and the like can be used as an auxiliary agent.

In the preparation of the present agent, the above-mentioned carrier, surfactant, dispersant and auxiliary agent can be used alone or in appropriate combination according to the purpose.
The concentration of the active ingredient when the compound (I) of the present invention is formulated is usually 1 to 50% by weight in the case of emulsion and 0.3 in the case of powder.
25% by weight, usually 1 to 90% by weight for wettable powders, usually 0.5 to 5% by weight for granules, usually 0.5 to 5% by weight for oils, usually 0.1 to 5% by weight for aerosols. is there. These formulations can be diluted to an appropriate concentration and sprayed on plant foliage, soil, water surface of paddy field or directly applied to various applications depending on the purpose.

[0047]

EXAMPLES The present invention will be specifically described below with reference to examples. It should be noted that these examples do not limit the scope of the present invention. Example 1 [Synthesis of Compound (I)] (1) N- (2,6-dichloroisonicotinoyl) -2-
Synthesis of methylalanine-isopropyl ester (Compound 4) 2,6-dichloroisonicotinoyl chloride (2.1
g, 0.01 mmol), 2-methylalanine-isopropyl ester (1.3 g, 0.011 mmol) and triethylamine (2.0 g, 0.02 mmol) in dimethylformamide (30 ml), 40-45.
The mixture was stirred at ° C for 3 hours. After the reaction was completed, water was added, and then
The mixture was extracted with ethyl acetate, the ethyl acetate layer was washed with water, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained oil was purified by column chromatography (Wakogel C-200, eluted with toluene: ethyl acetate = 10: 1) to obtain 2.9 g of the desired product which was light yellowish brown crystals.

(2) Synthesis of other target compounds (I) in Tables 1 to 3 Other target compounds (I) in Tables 1 to 3 were synthesized according to the method described above. The compounds (I) synthesized as described above are shown in Tables 1 to 3.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

Example 2 [Preparation of preparation] (1) Preparation of granules 5 parts by weight of compound 2, 25 parts by weight of bentonite and 67 parts by weight of white carbon were uniformly mixed, and then 15 parts by weight of water was added. After kneading, the mixture was granulated and dried to obtain a granule.

(2) Preparation of wettable powder 10 parts by weight of compound 1 and 69.75 parts by weight of kaolin,
18 parts by weight of white carbon, 1.8 parts by weight of Neoperex powder (trade name; manufactured by Kao Corporation) and 0.45 parts by weight of Demol EP (trade name; manufactured by Kao Corporation) were uniformly mixed. It was crushed to obtain a wettable powder. In addition, when using this agent as a foliar spray,
It was diluted to 0.00 to 2000 times.

(3) Preparation of emulsion 60 parts by weight of compound 21, 23 parts of methyl ethyl ketone,
17 parts by weight of polyoxyethylene nonylphenyl ether was uniformly mixed and dissolved to obtain an emulsion. In addition, when this agent is used as a foliar spray,
Diluted 4,000 times.

(4) Preparation of Dust Formulation 2 parts by weight of compound 4 and 98 parts by weight of clay were uniformly mixed to obtain a dusting product.

Example 3 [Efficacy test] (1) Control efficacy test against rice blast (preventive effect) Ten rice (cultivar: Nihonbare) was grown in a plastic pot having a diameter of 5 cm and 2.5 leaves were obtained. 200 to 2 of each wettable powder of the compound (I) shown in Tables 1 to 3 prepared according to Example 2 in a water containing a surfactant (0.01%). It was diluted to 000 ppm and sprayed at 10 ml per pot. After spraying, it was cultivated in a glass greenhouse for 2 days, and then a conidial suspension of rice blast fungus prepared from diseased leaves was uniformly spray-inoculated onto plant leaves. After inoculation,
After growing for 5 days in a humid chamber at 28 ° C, the degree of rice blast lesions appearing on the leaves was investigated.

The bactericidal effect was evaluated in 6 levels (0: whole diseased, 1: lesion area is about 60%, 2: lesion area is about 40%, in comparison with the degree of lesions in the untreated section. 3: The lesion area is about 20%, 4: The lesion area is 10% or less, and 5: No lesion). Evaluation of drug damage is in 6 levels (0: no damage,
1: Little damage, 2: Little damage, 3: Most damage,
(4: The damage was severe, 5: The damage was very serious). In addition, as a comparative drug,

[0058]

[Chemical 16]

A commercially available compound (EDD
Prepared in the same manner as for compound (I) using P). The results are shown in Table 4.

[0060]

[Table 4]

(2) Control efficacy test against rice blast (water application) Ten rice plants (cultivar; Nihonbare) were cultivated in a plastic pot having a diameter of 5 cm, and seedlings of 1.0 leaf stage were prepared. Each wettable powder of the compound (I) shown in Tables 1 to 3 prepared according to Example 2 was diluted to 200 to 2,000 ppm with water containing a surfactant (0.01%) to give rice. 2 ml was poured per bowl on the surface of water near. After spraying, it was cultivated in a glass greenhouse for 4 days, and then a conidial suspension of rice blast fungus prepared from diseased leaves was uniformly spray-inoculated onto plant leaves. After inoculation, it was grown in a humid chamber at 28 ° C. for 5 days, and the degree of rice blast lesions appearing on the leaves was examined.

The bactericidal effect and the phytotoxicity were evaluated by the same method as described in (1) above. In addition, as a comparative drug,

[0063]

[Chemical 17]

Using a commercially available compound (probenazole) as shown in the above, it was prepared in the same manner as in the case of the compound (I). The results are shown in Table 5.

[0065]

[Table 5]

(3) Control Efficacy Test Against White Leaf Blight of Rice Ten rice plants (cultivar; Nihonbare) were grown in a plastic pot having a diameter of 5 cm, and the seedlings of Example 3 were used in 3.0 leaf stage. The granules of the compound (I) shown in Tables 1 to 3 prepared according to the above were applied to 200 g per 10 are of soil. After application, grow in a glass greenhouse for 3 days, then
A conidial suspension of rice leaf blight fungus prepared from diseased leaves was inoculated at the cutting site of plant leaves cut with scissors. After inoculation, the plants were grown for 14 days in a humid chamber at 28 ° C., and the degree of rice leaf blight disease lesions appearing on the leaves was examined.

The bactericidal effect and the phytotoxicity were evaluated by the same method as described in (1) above. As the comparative drug, probenazole described in (2) above was used and prepared in the same manner as in the case of compound (I). The results are shown in Table 6.

[0068]

[Table 6]

[0069]

INDUSTRIAL APPLICABILITY The novel isonicotinic acid amide derivative of the present invention is useful as an agricultural and horticultural disease control agent.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Koichi Morikuni 5 1978, Kozuushi, Ube City, Yamaguchi Prefecture 5 1978, Ube Research Co., Ltd. (72) Katsunori Takada 5 1978, Koubeshi, Ube, Yamaguchi Prefecture Ube Institute, Ube Institute

Claims (3)

[Claims] 1. The following formula: (In the formula, R ¹ and R ² each represent an alkyl group having 1 to 6 carbon atoms which are the same or different from each other; or R ¹ and R ² represent a carbon atom together with the carbon atom to which they are bonded. A cycloalkyl group having 3 to 10 carbon atoms can be formed; R ³ is an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or an alkyl moiety having 1 to 6 carbon atoms. Represents a phenylalkyl group; X represents a halogen atom; Y represents a halogen atom or a carbon atom number of 1 to
Represents 6 alkyl groups. ) Isonicotinic acid amide derivative represented by. 2. The following formula: (In the formula, X and Y have the same meanings as described in claim 1.) and a compound represented by the following formula: (In the formula, R ¹ , R ² and R ³ have the same meanings as described in claim 1.) The compound represented by formula (I) according to claim 1 is reacted. Method for producing nicotinic acid derivative. 3. An agricultural and horticultural disease control agent comprising the isonicotinic acid derivative represented by formula (I) according to claim 1 as an active ingredient.