JPH03246283A - Isoxazole derivative and insecticide containing the derivative as active component - Google Patents

Abstract

NEW MATERIAL:The compound of formula I (A is 1-4C alkyl; E is H or 1-4C alkyl; X is H or 1-6C alkyl; Y is 1-6C alkyl). EXAMPLE:N-(3-methylisoxazol-4-yl)methyl-N',N'-dimethyl-2-nitro-1,1-eth enediamine. USE:An insecticide. PREPARATION:The objective compound can be produced by reacting a nitroethylene derivative of formula II (L is eliminable group such as alkylthio, alkylsulfinyl or Cl) with an isoxazole derivative of formula III usually in a solvent such as methylene chloride at 0-150 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel isoxazole derivative and an insecticide containing the same as an active ingredient.

[Prior Art] JP-A No. 59-65047 describes the following general formula; represents a straight-chain, branched or cyclic alkyl or alkenyl group, or an optionally substituted aryl or heteroaryl group, and X represents an optionally alkyl-substituted methylene or a chemical bond, provided that R2 represents a single bond; It has been disclosed that the compounds represented by (in some cases non-aryl) are agents that affect the circulatory system and are particularly useful as hypotensive agents. However, specifically, only 2-pyridyl, 3-pyridyl, and 4-pyridyl groups are disclosed as the heteroaryl group for R1, and the isoxazole group is not described at all.

On the other hand, among the heterocyclic derivatives having insecticidal activity, 1-nitro-2,2-diaminoethylene derivatives are described in JP-A-64-70468 as 1-nitro-2-pyridinyl as pyridine derivatives. Methylaminoethylene derivatives are disclosed.

Furthermore, in JP-A-2-171, the following general formula [wherein,
One of xl and X2 is an electron-withdrawing group, the other is a hydrogen atom or an electron-withdrawing group, R1 is a group via a nitrogen atom, R2 is a hydrogen atom or a group via a carbon, nitrogen or oxygen atom, n represents 0.1 or 2, and A represents a heterocyclic group or a cyclic hydrocarbon group.

However, R1 represents a group represented by B-N-pyrrolidinoethylamino. ] α-unsaturated amines are insecticidal,
Disclosed as an acaricide. However, specific examples of the heterocyclic group of A include only a pyridyl group, a quinolyl group, a pyrazinyl group, and a thiazolyl group, and the inoxazole group is not disclosed at all.

JP-A-61+183271 discloses 1(isoxacylylmethyl)-2-totromethylene)imidazolidines, 1-(isoxacylylmethyl)-2 to tromethylene)tetrahydropyrimidines, etc. , these are all 1,3-diaza cyclic alkanes.

Other inoxazole derivatives include (1) the organophosphorus insecticide Zolaprofos [e.g.
Described in Publication No. 2-59156, etc.] (2) Agrochemical fungicide H
ymexazol [e.g. Chem, Pharm,
Bull, 14.1277 (1966), etc.] (3) Herbicide l5ouron [For example, Jpn, P
e5tic, Inf.

No, 37. P47 (1980) etc.] are known. The respective structural formulas are shown below.

V [Problem to be solved by the invention] In recent years, due to the long-term use of insecticides, insect pests have developed resistance.
Control using conventional insecticides has become difficult. For example, a wide range of insect pests are resistant to typical insecticides such as organic phosphorus agents and carbamate agents, making it difficult to control them. Furthermore, the development of resistance to synthetic pyrethroid insecticides, which have attracted attention in recent years, has been reported. On the other hand, some organic phosphorus agents or carbamate agents are highly toxic, and others disturb the ecosystem due to their persistence, creating an extremely worrying situation. Therefore, it shows excellent effects even against pests that are resistant to conventional insecticides at low doses.
Moreover, the development of new insecticides with low toxicity and low persistence is expected.

[Means for Solving the Problems] As a result of intensive research to address this situation, the present inventors discovered a novel isoxazole derivative having excellent insecticidal activity and completed the present invention. .

That is, the gist of the present invention resides in an inoxazole derivative represented by the following general formula (I) and an insecticide containing this as an active ingredient.

(In the above formula, A represents an alkyl group of 00 to C4, and E
represents a hydrogen atom or a C0 to C4 alkyl group,
represents a hydrogen atom or an alkyl group of 01 to C6, and Y
represents a hydrogen atom or an alkyl group of 00 to C6. ) Hereinafter, the present invention will be explained in detail.

In the above general formula (I), 0 represented by A or E
As the 1-C4 alkyl group, methyl group, ethyl group,
n-propyl group, isopropyl group, n-butyl group, t-
Straight-chain or branched-chain alkyl groups such as butyl groups may be mentioned, and examples of the 00-C6 alkyl group represented by X or Y include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Straight chain or branched chain alkyl groups such as t-butyl group, n-pentyl group, and n-hexyl group are mentioned.

In the present invention, from the viewpoint of insecticidal activity, the general formula (I
), A represents a 01-C3 alkyl group, E represents a hydrogen atom or a C□-C3 alkyl group, X represents a hydrogen atom or a C□-C4 alkyl group, and Y represents a hydrogen atom or a C0-C4 alkyl group. Compounds representing a C4 alkyl group are preferred.

Specific examples of the compounds of the present invention represented by the general formula (I) include those shown in Table 1, but the compounds of the present invention are not limited to these.

Table-1 next, The method for producing the compound of the present invention will be explained.

The isoxazole derivative represented by general formula (I) is For example, it can be synthesized according to the following reaction formula.

(III) (In the above formula, 1 1 1 Y is as defined in the above general formula (I), and L represents a leaving group such as an alkylthio group, an alkylsulfinyl group or a chlorine atom) Solvents preferably used in the reaction include methylene chloride, chloroform, halogenated hydrocarbons such as 1.1.2.2-tetrachloroethane, ethers, ethers such as tetrahydrofuran and dioxane, benzene,
Examples include aromatic hydrocarbons such as toluene and xylene, aprotic polar solvents such as acetonitrile, dimethylformamide and dimethyl sulfoxide, alcohols such as methanol, ethanol, isopropyl alcohol and butanol, and water.

The reaction is usually carried out at a temperature range of 0 to 150°C.

The nitroethylene derivative represented by the above general formula (II) can be easily synthesized according to the method described in JP-A-57-74'18.

In addition, the isoxazole derivative represented by the above general formula (III) is derived from the inoxazole derivative represented by the following general formula (IV) ((■) in the formula, X and Y are the same as X and Y in the formula (III), and Mal is represents a halogen atom) De16pine reaction [e.g. 5ynthesis,
161 (1976)] or Gabriel synthesis [e.g. J. Chem. Soc.

2348 (1926)]. Among the compounds represented by general formula (IV),
Some of the compounds are known in the literature, but other compounds are described by Zh, 0bshch, Khim, 2
8.2736 (1958), Org-syn, Co1
1. , vol. VI, P2S5 (1988)
It can be synthesized by the method described in or a method similar thereto.

[Action] The compound represented by the general formula (I) has remarkable control activity against the following insects of the orders Coleoptera, Lepidoptera, Hemiptera, Orthoptera, Diptera, etc., but is of course limited to these insects. isn't it.

1 Hemiptera: Planthoppers such as the brown planthopper, brown planthopper, and brown planthopper, leafhoppers such as the black leafhopper and giant leafhopper, and aphids such as the green peach aphid 2 Hiptera: Spodoptera: Spodoptera nigricans, the Japanese brown planthopper, the brown borer moth, etc. 3 Coleoptera: Azuki bean weevil, etc. 4 Ptera: House fly, Aedes aegypti, Culex mosquito, etc. When the compound of the present invention represented by the general formula (I) is used as an insecticide, it may be used alone, but it is usually used with an adjuvant as with conventional agricultural chemicals. It can be formulated into emulsions, powders, water preparations, granules, etc., and used as is or diluted. As adjuvants, those commonly used in insecticide formulations can be used. For example, solid carriers such as talc, kaolin, diatomaceous earth, viscosity, starch, water, hydrocarbons such as cyclohexane, benzene, xylene, and toluene, halogenated hydrocarbons such as chlorobenzene, ethers, amides such as dimethylformamide, Solvents such as ketones, alcohols, nitriles such as acetonitrile,
Other known surfactants include emulsifiers and dispersants.

In addition, other insecticides, acaricides, fungicides,
It can also be mixed or used in combination with insect growth regulating substances, plant growth regulating substances, and the like.

The concentration of the active ingredient in the formulated insecticide is not particularly limited, but is usually 0.1 to 20% by weight for powders, preferably 0.2 to 10% by weight, and 1 to 90% by weight for irrigation agents.
Preferably it contains 10 to 80% by weight of the active ingredient, emulsions contain 1 to 90% by weight, preferably 10 to 40% by weight, granules contain 0.5 to 30% by weight, preferably 1 to 10% by weight.

When the compound represented by the above general formula (I) is used as an insecticide, the active ingredient is usually used in a concentration range of 5 to 1000 ppm, preferably 10 to 500 ppm.

[Examples] Next, the present invention will be explained in more detail with reference to production examples, formulation examples, and test examples of the compounds of the present invention, but the present invention is not limited to the following examples unless the gist thereof is exceeded.

Example I N-(5-methylisoxazol-4-yl)methyl-N'-methyl-2-nitro-1,1-ethenodiamine 4-aminomethyl-5-methylisoxazole 0.2
A mixture of 0.26 g of 1N-methyl-1-methylthio-2-nitroethenamine and 2 ml of water was heated and stirred at 50°C for 6.5 hours. Next, 50 ml of acetone was added, and after drying over anhydrous magnesium sulfate, the solvent was distilled off. The residue was purified using a silica gel column to obtain 0.32 g of the compound (No. 3) listed in Table 2. Melting point 163
-164°C (decomposition) Example 2 N-(3-methylisoxazol-4-yl)methyl-N', N'-dimethyl-2-nitro-1,1-ethenediamine 4-aminomethyl-3- Methyl isoxazole 1.1
2 g of N,N-dimethyl-1-methylthio-2-nitroethenamine and 5 ml of water.
The mixture was heated and stirred at 0°C for 3 hours. Next, 60ml of acetone
was added and the solvent was distilled off. The remaining amount is 100% acetonitrile.
ml, dried over anhydrous magnesium sulfate, filtered, distilled off the solvent, and purified the residue using a silica gel column to obtain 1.15 g of the compound listed in Table 2 (No. 2).
I got it. Melting point: 111-114°C0 Representative compounds of the present invention produced in the same manner are shown in Table 2.

Next, examples of formulations of the compounds of the present invention will be shown. In addition, below is [section],
"1%" means "part by weight" and "% by weight", respectively.

Formulation Example 1: Irrigation Table 2 20 parts of the compound of the present invention, Carplex #80
(Shionogi Pharmaceutical Co., Ltd., trade name) 20 copies, Kunilite 201 (
Kunimine Kogyo Co., Ltd., trade name) 55 parts, higher alcohol sulfate ester surfactant Tsurupol 8070 (Toho Chemical Co., Ltd., trade name) 5 parts are mixed and ground uniformly to form a hydrated product containing 20% of the active ingredient. obtained the drug.

Formulation Example 2: Powder 0.5 parts of the compound of the present invention in Table 2, 94.3 parts of clay (manufactured by Nippon Talc Co., Ltd.), 5 parts of white carbon, and 0.2 parts of isopropyl acid phosphate (PAP) were added. The mixture was uniformly mixed and ground to produce a 0.5% powder.

Formulation Example 3: Emulsion 20 parts of the compound of the present invention in Table 2 is dissolved in a mixed solvent consisting of 32.5 parts of Kawakazole (trade name, Kawasaki Kasei Co., Ltd.) and 32.5 parts of dimethylformamide, and polyoxy Ethylene surfactant Tsurupol 3005X
(Toho Chemical Co., Ltd., trade name) 15 parts and 20 parts of active ingredient
An emulsion was obtained containing %.

Formulation Example 4: Flowable agent 30 parts of the compound of the present invention listed in Table 2, 8 parts of ethylene glycol mixed in advance, Tsurpol AC30
32 (Toho Chemical Co., Ltd., trade name) 5 parts, xanthan gum 0.
1 part was well mixed and dispersed in 56.9 parts of water. Next, this slurry-like mixture was wet-pulverized using Dyno Mill (Shinmaru Enterbrizes Co., Ltd.) to obtain a flowable agent containing 30% of the active ingredient.

Test Example 1 Effective formulation example 1 against brown planthopper larvae
A hydrating agent containing the compound of the present invention prepared according to the recipe of
Diluted with water containing 0 ppm to give an active ingredient concentration of 500 ppm.
Adjusted to pm. Diameter 2.5 cm, height 1
Five 3rd instar larvae of brown planthopper and rice seedlings were placed in an 8 cm glass cylinder, covered with a cap covered with mesh, and the above aqueous solution was sprinkled from the top at a rate of 0.5 ml/cylinder, and 25 parts were heated at 1°C. It was left in a constant temperature room. Five days after release, the number of live and dead insects in each cylinder was investigated, and the death and death rate was calculated using the following formula.

In addition, 20 3rd instar larvae of brown planthopper were used in each test. The results are shown in Table-3. In addition, each compound N in Table-3
o corresponds to compound No. in Table-2.

00 00 00 00 00 00 00 00 00 00 00 00 00 00 No treatment test example 2 Effect on leafhopper larvae A water conservancy containing the compound of the present invention formulated according to the formulation of Preparation Example 1 was used as a spreading agent (Tsurpol 3005X, Toho Kagakusha)
It was diluted with water containing 200 ppm to adjust the active ingredient concentration to a predetermined concentration. 3 whole larvae of leafhopper 5 in a glass cylinder with a diameter of 2.5 cm and a height of 18 cm
Put in the rice seedlings and the heads, cover with a cap with a mesh,
The above aqueous solution was sprinkled from the top at a rate of 0.5 ml/cylinder and left in a thermostatic chamber at 25±1°C. Hojo 4
Days later, the number of live and dead insects in each cylinder was investigated, and the mortality rate was calculated using the following formula.

Note that 20 insects were used in each test. Display the results -
4. In addition, each compound No. in Table-4 corresponds to compound No.- in Table-2.

Table 4 Example 3 (Compound 3) of JP-A No. 2-171 [Effects of the Invention] The compound of the present invention has excellent insecticidal activity even at a low dose, and its value is high.

Claims (2)

[Claims] (1) An isoxazole derivative represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (In the above formula, A represents an alkyl group of C_1 to C_4, E represents a hydrogen atom or an alkyl group of C_1 to C_4, and X is a hydrogen atom. or represents an alkyl group of C_1 to C_6, and Y represents a hydrogen atom or an alkyl group of C_1 to C_6.) (2) An insecticide containing the isoxazole derivative according to claim 1 as an active ingredient.