JP2582863B2 - Gray mold control agent containing N-indanylcarboxylic acid amide derivative as active ingredient - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an agent for controlling gray mold on various agricultural and horticultural crops, which contains an N-indanylcarboxylic acid amide derivative as an active ingredient.

[Problems to be solved by conventional technology and invention]

Conventionally, procymidone [N-
Since (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide] and other cyclic imide fungicides showed high activity against gray mold fungi parasitic on agricultural and horticultural crops, It has been widely used in general. However, in recent years, pathogenic bacteria exhibiting resistance to these fungicides (hereinafter referred to as “drug-resistant bacteria”) have become widespread, and in many cases, they have become practically unusable.

Therefore, at present, there is no drug showing efficacy in all cases of gray mold, and there is a strong demand for the development of a drug that is equally effective against both drug-resistant bacteria and drug-sensitive bacteria.

[Means for solving the problem]

The present inventors have conducted intensive studies in view of the above problems, and as a result, among various N-indanylcarboxylic acid amide derivatives, only a specific compound having a methyl group at the 3-position of the indanyl group is gray mold. The present inventors have found that they show particularly excellent activity against diseases, and have completed the present invention.

That is, the gist of the present invention resides in a gray mold control agent containing an N-indanylcarboxylic acid amide derivative represented by the following general formula (I) as an active ingredient.

[In the above formula, A is a group Or (In the above groups, X represents a halogen atom, a methyl group or a trifluoromethyl group, Y represents a hydrogen atom, a methyl group or a halogen atom), and R ₁ and R
₂ each independently represents a hydrogen atom or a lower alkyl group. Hereinafter, the present invention will be described in detail.

In the general formula (I), A is a group Or Represents Preferably Or It is. In the group A, X represents a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; a methyl group; or a trifluoromethyl group, and is preferably a chlorine atom, a bromine atom, a methyl group, or a trifluoromethyl group. In group A,
Y represents a hydrogen atom; a methyl group; or a halogen atom such as a fluorine atom, a chlorine atom, and a bromine atom.
It is a hydrogen atom or a methyl group. R ¹ and R ² each independently represent a hydrogen atom; or a lower alkyl group such as a methyl group, an ethyl group or an n-propyl group, and is preferably a methyl group.

Specific examples of the compound of the present invention represented by the general formula (I) include compounds as described in Tables 1 and 2, but the compound of the present invention is not limited thereto. Absent.

The compound of the present invention is produced according to the following reaction formula.

(Wherein, A, R ₁ and R ₂ have the same meanings as described above.) The above reaction is carried out by reacting a carboxylic acid represented by the general formula (II) or a reactive derivative thereof with an aminoindane represented by the general formula (III) The reaction is carried out with a derivative in the presence or absence of a solvent inert to the reaction.

The carboxylic acid represented by the general formula (II) or a reactive derivative thereof used in the reaction is used in an amount of 0.5 to 1.5 equivalents, preferably 0.9 to 1.1 equivalents to the aminoindan derivative represented by the general formula (III). Is done. This reaction is -70 ° C
To the boiling point of the solvent used, preferably from -40 ° C to the boiling point of the solvent.

Examples of the carboxylic acids represented by the general formula (II) or reactive derivatives thereof include corresponding carboxylic acids, acid halides such as acid anhydrides and acid chlorides, and carboxylic esters. .

Examples of the solvent used in the reaction include benzene, aromatic hydrocarbons such as toluene, carbon tetrachloride, halogenated hydrocarbons such as chloroform, aromatic halogenated hydrocarbons such as chlorobenzene, diethyl ether, tetrahydrofuran, Examples thereof include ethers such as dioxane, esthetics such as ethyl acetate, and polar solvents such as dimethylsulfoxide, dimethylformamide, and water.

In order to allow this reaction to proceed smoothly, an appropriate reaction assistant can be used depending on the type of the carboxylic acid represented by the general formula (II) or a reactive derivative thereof.

Examples of the reaction assistant include a dehydrating agent such as ethoxyacetylene, dicyclohexylcarbodiimide, and phosphorus pentoxide when a carboxylic acid is used, and a dehydrating agent such as N-methylmorpholine and triethylamine when an acid anhydride is used. Aromatic bases such as tertiary amines, pyridine, picoline and N, N-diethylaniline; tertiary amines such as triethylamine when using an acid halide; aromatic bases such as pyridine and picoline; Sodium, alkali metal hydroxides such as potassium hydroxide, alkali metal hydrides such as sodium hydroxide, or alkali metal alcoholates such as sodium ethylate; and sodium ethoxide when carboxylic acid esters are used. Alkali metal alcoholates such as can be used

These reaction auxiliaries can be used usually in an amount of 0.01 to 5.0 equivalents, preferably 0.9 to 1.1 equivalents, based on the aminoindan derivative represented by the general formula (III).

In some cases, the compound of the present invention can be produced, for example, according to the following reaction formula.

(In the formula, A, R ₁ and R ₂ have the same meanings as described above.) In the above reaction, the acyltetrahydroquinoline derivative represented by the general formula (IV) is reacted at −40 ° C. to 200 ° C. in the presence of an acid catalyst.
The transition is preferably carried out at 0 ° C to 150 ° C.

Examples of the acid catalyst include sulfuric acid, phosphoric acid, polyphosphoric acid and Lewis acid, and the amount thereof can be used from 0.001 equivalent to a large excess with respect to the acyltetrahydroquinoline derivative.

All of the compounds thus obtained have an excellent bactericidal activity against the incomplete mycota of various agricultural and horticultural crops, particularly against the fungus of gray mold.

When using the compound of the present invention as a gray mold control agent for agricultural and horticultural use, the compound may be used as it is, but in order to effectively disperse the active ingredient in the application scene, an auxiliary agent is used according to a conventional method. And used in the form of an emulsion, a wettable powder or the like.

Examples of the solvent which is one of the auxiliary agents in the agricultural and horticultural gray mold control agent of the present invention include water, alcohols (eg, methyl alcohol, ethyl alcohol, ethylene glycol), and ketones (eg, acetone, methyl ethyl ketone, cyclohexanone). , Ethers (ethyl ether, dioxane, cellosolves, etc.), aliphatic hydrocarbons (kerosene, kerosene, fuel oil, etc.), aromatic hydrocarbons (benzene, toluene, xylene, solvent naphtha, methyl naphthalene, etc.), halogens Suitable hydrocarbons (dichloroethane, trichlorobenzene, carbon tetrachloride, etc.), acid amides (dimethylformamide, etc.), esters (ethyl acetate, butyl acetate, glycerin esters of fatty acids, etc.), nitriles (acetonitrile, etc.) And one or more of these Compound is used.

Examples of fillers include clays such as kaolin and bentonite; talcs such as talc and pyrophyllite; diatomaceous earth; mineral powders such as oxides such as white carbon; soybean powder; and CM.
Suitable are plant powders such as C, and one or a mixture of two or more thereof.

Further, a surfactant may be used as a spreading agent, a dispersant, an emulsifier, or a penetrant. Examples of the surfactant include nonionic surfactants (polyoxyethylene alkyl allyl ether, polyoxyethylene sorbitan monolaurate, etc.), cationic surfactants (alkyl dimethyl benzyl ammonium chloride, alkyl pyridinium chloride, etc.), Anionic surfactants (alkyl benzene sulfonate, lignin sulfonate, higher alcohol sulfate), amphoteric surfactants (alkyl dimethyl betaine, dodecylaminoethyl glycine, etc.) and the like can be mentioned.

These surfactants are used as one type or a mixture of two or more types depending on the application.

Upon application of the agricultural and horticultural gray mold control agent of the present invention, when used in the form of an emulsion, the compound of the present invention 10 to 50
Parts, 10 to 80 parts of a solvent and 3 to 20 parts of a surfactant are mixed at an appropriate ratio to prepare a stock solution, which is diluted to a predetermined concentration with water before use, and applied by a method such as spraying.

When used in the form of a wettable powder, the compound of the present invention 5
To 80 parts and 10 to 90 parts of a bulking agent and 1 to 20 parts of a surfactant are mixed in an appropriate ratio, and the mixture is diluted with water or the like as in the case of an emulsion.

Further, the gray mold control agent for agricultural and horticultural use of the present invention may be used in combination with other active ingredients that do not inhibit the bactericidal effect of the present active ingredient, such as fungicides, insecticides, acaricides, and the like. it can.

The method for applying the gray mold control agent for agricultural and horticultural use of the present invention can be suitably applied to foliage application. For foliage application,
Usually, the emulsion or wettable powder is diluted with water so as to contain 10 to 1000 ppm, and the dilution is applied 10 to 500 per 10 ares.

The gray mold control agent of the present invention can be particularly preferably applied to vegetables and grapes. When the present invention is applied to vegetables, as shown in the test examples described later, the activity is exhibited by spraying a chemical on foliage.

On the other hand, the application time of the present invention is applied after the flowering period of vegetables and grapes.

〔Example〕

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

 Hereinafter, “parts” indicates “parts by weight”.

Production Example 1 3-methyl-N- (1,1,3-trimethylindane-4
-Yl) -thiophene-2-carboxamide (Table 1 above)
Preparation of Compound No. 1) of No. 1 N- (3-methylthiophen-2-carbonyl) -2,
1.5 g of 2,4-trimethyl-1,2,3,4-tetrahydroquinoline
Was added in 10 ml of 85% sulfuric acid at room temperature. The reaction solution was heated to 60 ° C. and stirred at the same temperature for 3 hours. The reaction solution was poured into ice water and extracted with 50 ml of ethyl acetate. The extract was washed sequentially with water and brine, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was recrystallized from ethyl acetate and n-hexane to give 3-methyl-N-
1.3 g of (1,1,3-trimethylindan-4-yl) -thiophene-2-carboxamide (Compound No. 1) was obtained. The yield was 87%. The melting point was 95 to 96 ° C.

Compounds No. 2 to No. 20 were produced according to Production Example 1.

Production Example 2 1,3-dimethyl-N- (1,1,3-trimethylindane-
4-yl) pyrazole-4-carboxamide (compound N
Production of o.21) To a solution of 5-chloro-1,3-dimethyl-N- (1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide (1 g) in ethanol (20 ml) was added 10% Pd / C (50 mg). Catalytic reduction was performed by adding as a catalyst. After the completion of the reaction, the catalyst was separated and the liquid was concentrated. Water and ethyl acetate were added to the residue for liquid separation. The organic layer was washed sequentially with water and brine, and then dried over anhydrous sodium sulfate. The concentrate was recrystallized from toluene to obtain 0.85 g of 1,3-dimethyl-N- (1,1,3-trimethylindan-4-yl) pyrazole-4-carboxamide (Compound No. 21). The yield was 95%. The melting point was 159 to 161 ° C.

Compounds No. 22 to No. 30 were produced according to Production Example 2.

Formulation Example 1 20 parts of Compound No. 1, 75 parts of diatomaceous earth, and 5 parts of a surfactant containing alkylbenzenesulfonic acid as a main component were uniformly ground and mixed to obtain a wettable powder.

Formulation Example 2 Compound No. 3 40 parts, white carbon 10 parts, diatomaceous earth 47
Department, "Solpol" 5039 (trademark of Toho Chemical Industry Co., Ltd.
3 parts of a surfactant mainly composed of polyoxyethylene alkylaryl aryl ether sulfonate) were uniformly pulverized and mixed to obtain a wettable powder.

Formulation Example 3 30 parts of compound No. 2, 15 parts of "Solpol" 3005X (trademark of Toho Chemical Industry Co., Ltd., a mixture of a nonionic surfactant and an anionic surfactant), 25 parts of xylene, dimethyl Emulsion was obtained by mixing and dissolving 30 parts of formamide.

Next, the usefulness of the present invention as a gray mold agent will be shown by test examples.

In addition, the compound of this invention is shown by the compound number of Table-1 and Table-2, and the compound used for the comparison control is shown by the following compound symbol of Table-3 and Table-4.

Test Example 1 Drug Sensitive Cucumber Gray Mold Control Effect Test Cotyledon cucumber grown in a 6 cm diameter pot (variety:
A wettable powder prepared in the same manner as in Formulation Example 1 was diluted to a predetermined concentration with water and sprayed with foliage at a rate of 10 ml per pot. After the chemical solution was air-dried, spores of Botrytis cinerea were inoculated, and the subsequent disease state was maintained at 23 ° C. for 4 days after the inoculation. The survey method was as follows. That is, the disease degree is determined by calculating the diseased area percentage of the surveyed leaves, and according to the degree, 0, 1, 3, 5
And the number of leaves n ₀ , n ₁ , n ₃ , corresponding to each disease index
to investigate the n _5, was calculated from the following equation. (N is the total number of leaves in the survey) The control value was calculated by the following formula.

The results are shown in Table 5 below.

Test Example 2 Test of drug-resistant cucumber gray mold control effect Cucumber at the cotyledon stage (cultivar:
A wettable powder prepared in the same manner as in Formulation Example 1 was diluted to a predetermined concentration with water and sprayed with foliage at a rate of 10 ml per pot. After air-drying with chemicals, inoculate spores of Botrytis cinerea, a drug-resistant gray mold fungus,
Four days after the inoculation, the post-disease state maintained at a humidity of 23 ° C. was investigated. The survey method was as follows. That is, the degree of disease is obtained by calculating the diseased area percentage of the survey leaf, and according to the degree, 0,
Number of leaves corresponding to each disease index classified into indices 1, 3, and 5
n ₀ , n ₁ , n ₃ , and n ₅ were investigated and calculated by the following equation. (N is the total number of leaves in the survey) The control value was calculated by the following formula.

The results are shown in Table 6 below.

[Effects of the Invention] The gray mold control agent of the present invention has an excellent bactericidal activity against Botrytis cinerea of various crops. It has extremely high activity against bacteria that are sensitive to benzimidazole, thiophanate fungicides and cyclic imide fungicides, as well as those that show resistance, and is useful as an agricultural and horticultural gray mold control agent It is.

In addition, the compound of the present invention has almost no harmful effects on plants despite its permeability to plants, and also has low toxicity to humans and livestock or fish. It is extremely useful for

Claims (1)

(57) [Claims] 1. A gray mold control agent comprising an N-indanylcarboxylic acid amide derivative represented by the following general formula (I) as an active ingredient. [In the above formula, A is a group Or (In the above groups, X represents a halogen atom, a methyl group or a trifluoromethyl group, Y represents a hydrogen atom, a methyl group or a halogen atom), and R ₁ and R
₂ each independently represents a hydrogen atom or a lower alkyl group. ]