JP3392912B2 - Carbohydroxymoylazole derivatives or their salts and insecticides - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a carbohydroxymoylazole derivative or a salt thereof and an insecticide containing the same as an active ingredient.

[0002]

2. Description of the Related Art Benzohydroxymoylazole derivatives are known to have activity against harmful insects (for example, Japanese Patent Application Laid-Open No. 1-308260 and WO9209581). Further, regarding carbohydroxymoylazole derivatives of alkanecarboxylic acid or cycloalkanecarboxylic acid, US Pat.
Only the bactericidal activity of the pivalic acid derivative is known in the specification of JP 99348, but the insecticidal activity is not known.

[0003]

In recent years, the use of existing commercial insecticides has been restricted due to problems such as residue, accumulation, and environmental pollution, and resistant insects have been generated due to long-term use, and some have become less effective. ing. Therefore, there is a demand for the development of an insecticide that has high efficacy even at a low dose, is highly safe, and is useful for resistant pests.

[0004]

The present inventors have synthesized carbohydroxymoylazole derivatives of various alkanecarboxylic acids and cycloalkanecarboxylic acids which may be substituted with an alkyl group, and investigated their physiological activity. Overlaid. As a result, the compounds of the present invention, various harmful insects, especially susceptible and resistant planthoppers and leafhoppers,
Against hemiptera pests such as aphids and stink bugs,
The inventors have found that they have extremely excellent insecticidal activity and completed the present invention. That is, the present invention has the general formula [I]

[0005]

[Chemical 2] (In the formula, R ¹ represents an alkyl group having 5 to 17 carbon atoms, or a cycloalkyl group having 6 carbon atoms which may be substituted with an alkyl group, R ² represents a hydrogen atom, and 1 to 6 carbon atoms. of <br/> alkyl group or the number of carbon atoms represents 3-6 cycloalkyl group, a is shows the nitrogen atom or a methine group. carbo hydroximoylpyrazole azole derivative or represented by) the effective salt thereof and these It is an insecticide contained as an ingredient.

In the present invention, the alkyl group having 5 to 17 carbon atoms includes n-pentyl group, isopentyl group and se.
c-pentyl group, n-hexyl group, isohexyl group, s
ec-hexyl group, n-heptyl group, isoheptyl group,
n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-
Tetradecyl, n- pentadecyl, n- hexadecyl group, n- heptadecyl group, group _{(CH 2)} m C _(C
H ₃ ) ₃ (m represents an integer of 1 to 13), group (CH ₂ ).
_n CH (CH ₃ ) CH ₂ C (CH ₃ ) ₃ (n represents 0 and an integer of 1 to 10), a group CH (CH ₃ ) (C
_{H 2) p CH (CH 3} ) CH 2 C (CH 3) 3 (p is 0
And an integer of 1 to 8), a group CH (CH ₃ ) (CH
₂ ) _q CH ₃ (q represents an integer of 2 to 14) and a group (C
_{H 2) s CH (CH 3} ) 2 (s can be exemplified.) Or the like representing an integer of 4 to 14, as the cycloalkyl group which may be substituted by an alkyl group a cyclohexyl group,
A 4-tert-butyl cyclohexyl group etc. can be illustrated.

The alkyl group represented by R ² is a linear or branched alkyl group having 1 to 6 carbon atoms, for example,
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
Examples thereof include a tert-butyl group, n-pentyl group and n-hexyl group, and examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group. As salt,
Examples thereof include sulfates, hydrochlorides, nitrates and phosphates.

In the above-mentioned general formula [I], preferred compounds include (R ¹ represents an alkyl group having 7 to 12 carbon atoms, R ² represents an ethyl group, a propyl group, an isopropyl group or a sec-butyl group, A represents a nitrogen atom).

The carbohydroxymoylazole derivative represented by the general formula [I] has two stereoisomers, an entgegen body and a tumen semen body, but the present invention includes these isomers and any of these isomers. It also includes a mixture of ratios. Further, in the case of the cycloalkyl group substituted with an alkyl group in the general formula [I], two or more kinds of stereoisomers may exist, but the compound of the present invention may have any ratio of these isomers. Also includes mixtures.

Next, typical examples of the compounds of the present invention represented by the general formula [I] are shown in Tables 1 to 3. Regarding the stereoisomerism of alkenes in the table, the entgegen form is abbreviated as E, the tsugemen form is Z, and the mixture of the entgegen form and the tsumen form is abbreviated as EZ. In addition, the compound numbers are referred to in the following description.

[0011]

[Table 1]

[0012]

[Table 2]

[0013]

[Table 3] The compound of the present invention represented by the general formula [I] can be produced, for example, according to the following production method. In the compound of the present invention, when R ² is an alkyl group or a cycloalkyl group, it can be produced by the methods shown in the production methods A and B, and when R ² is a hydrogen atom, the production method C Can be manufactured by the method shown in. Manufacturing method A

[0014]

[Chemical 3] (In the formula, D represents a halogen atom or a paratoluenesulfonyloxy group, and R ¹ , R ² and A have the same meanings as described above.) The compound of the present invention represented by the general formula [I] has the formula [II] Can be produced by reacting a carbohydroxymoylazole compound represented by the formula (I) with a halogen compound or a sulfonate compound represented by the formula [III] in the presence of a base. In this reaction, the halogen compound or the sulfonate compound can be used in an equivalent amount or more. As the base that can be used, hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, hydroxides of alkaline earth metals such as magnesium hydroxide and calcium hydroxide, sodium carbonate, Inorganic bases such as alkali metal carbonates such as potassium carbonate, sodium hydrogen carbonate, alkali metal bicarbonates such as potassium hydrogen carbonate, metal hydrides such as sodium hydride and potassium hydride, or triethylamine,
Organic bases such as N, N-dimethylaniline, pyridine, and 1,8-diazabicyclo [5.4.0] undec-7-ene can be mentioned.

The reaction can be carried out in the presence of a suitable diluent if necessary. Diluents that can be used include water or inert organic solvents, for example, ketones such as acetone and butanone, aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene that may be halogenated, petroleum ether, ligroin, etc. Of aliphatic hydrocarbons, ethers such as diethyl ether, tetrahydrofuran, dioxane, nitriles such as acetonitrile and propionitrile, or N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, An aprotic polar solvent such as sulfolane may, for example, be mentioned. The reaction temperature is any temperature from 0 ° C to the reflux temperature in the reaction system, preferably 40 ° C to 10 ° C.
It is 0 ° C. The reaction time varies depending on the compound, but is 1 to 6
Let them react for a time. Manufacturing method B

[0016]

[Chemical 4] (In the formula, E represents a halogen atom, R ¹ , R ² and A
Represents the same meaning as described above. The compound of the present invention represented by the general formula [I] is produced by reacting the carbohydroxymoyl halide compound represented by the formula [IV] with an imidazole or triazole represented by the formula [V] in the presence of a base. You can In this reaction, imidazole or triazole acts as a base and can be used in an equivalent amount or more. Further, as the base, the same bases as exemplified in the production method A can be used.

The reaction can be carried out in the presence of a suitable diluent if necessary. Examples of the diluent that can be used include the same diluents as those exemplified in the production method A.
The reaction temperature is any temperature from room temperature to the reflux temperature in the reaction system, preferably 80 to 150 ° C. The reaction time varies depending on the compound, but if the reaction is carried out for 2 to 5 hours, the desired product can be produced in good yield.

The carbohydroxymoyl halide compound represented by the general formula [IV] can be produced by the method represented by the following reaction formula.

[0019]

[Chemical 5] (In the formula, R ¹ , R ² and E have the same meanings as described above.) The hydroxamic acid compound represented by the general formula [VII] is
React with a halogenating agent such as phosphorus pentachloride or thionyl chloride in the presence of an inert solvent such as aromatic hydrocarbons such as benzene and toluene or halogenated hydrocarbons such as chloroform and carbon tetrachloride, or acetonitrile. React with a halogenating agent consisting of triphenylphosphine and carbon tetrachloride or carbon tetrabromide in the presence of an inert solvent such as nitriles such as propionitrile or aromatic hydrocarbons such as benzene and chlorobenzene. It can be manufactured. In this case, carbon tetrachloride and carbon tetrabromide can also serve as a solvent. The reaction temperature is any temperature from 0 ° C. to the reflux temperature in the reaction system, and preferably 50 to 50 ° C.
It is 80 ° C. The reaction time varies depending on the compound, but is 1
It may be allowed to react for ~ 6 hours.

The hydroxamic acid compound represented by the general formula [VII] is prepared by converting the corresponding carboxylic acid by a known method.
It can be produced by preparing an acid halide or 1-acylimidazole and reacting it with an alkoxyamine. Manufacturing method C

[0021]

[Chemical 6] (In the formula, R ³ represents a benzyl group or a tert-butyl group, and R ¹ and A have the same meanings as described above.) The compound represented by the general formula [II] is an ether represented by the formula [VI]. Are aromatic hydrocarbons such as benzene and chlorobenzene or halogenated hydrocarbons such as dichloromethane and 1,2-dichloroethane, ethers such as tetrahydrofuran, diethyl ether and methyl ethyl ether, or nitriles such as acetonitrile and propionitrile. Of the ethers represented by the formula [VI] in which R ³ is a benzyl group, for example, water, acetic acid, alcohols. Or in acetic acid esters,
It can be produced by hydrogenolysis using palladium carbon as a catalyst. The reaction temperature is any temperature from −60 ° C. to the reflux temperature in the reaction system, and preferably −60 ° C. to 80 ° C. The reaction time varies depending on the compound, but the reaction may be performed for 1 to 12 hours. Further, the compound represented by the formula [VI] can be produced by a method according to the production method B. Production Method D The compound of the present invention represented by the general formula [I] can be converted into its salt by reacting a strong acid such as hydrogen chloride, sulfuric acid, nitric acid and phosphoric acid according to a conventional method.

After dissolving the compound of the present invention represented by the general formula [I] in a solvent, adding 1 to 1.5 equivalents of an acid as a gas or an aqueous solution under ice cooling or room temperature, and leaving it for 10 minutes to 1 hour. After that, post-treatment such as vacuum concentration is performed, and if necessary, recrystallization or the like is performed. The reaction solvent, methanol, lower alcohols such as ethanol, toluene, aromatic hydrocarbons such as benzene, halogenated hydrocarbons such as ethyl ether, tetrahydrofuran, dioxane, ketones such as acetone, esters such as ethyl acetate, Hydrocarbons such as hexane, water, or a mixture thereof can be used.

Next, the production method of the compound of the present invention will be specifically described with reference to examples.

[0024]

【Example】

Production Example 1 1- (O-hexyl-decanehydroxymoyl) -1H-1,2,4-triazole (Compound No. 4
2) Preparation 1- (decanehydroxymoyl) -1H-1,2,4-
Dissolve 0.4 g (1.7 mmol) of triazole in 50 ml of tetrahydrofuran, add 0.08 g (2.0 mmol) of 60% sodium hydride and 0.4 g (2.4 mmol) of hexyl bromide, and stir to react at 60 ° C. for 3 hours. It was The reaction mixture was concentrated and the residue was extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The residue was purified by column chromatography and the refractive index at 20 ° C was 1.
0.24 g (yield 44%) of the desired product of 4730 was obtained.

Production Example 2 Production of 1- (O-sec-butyl-decanehydroxymoyl) -1H-1,2,4-triazole (Compound No. 41) O-sec-butyl-decanehydroxymoyl chloride 9.0 g ( 34 mmol), 1,2,4-triazole 3.6 g (52 mmol) and potassium carbonate 5.6 g.
(41 mmol) was added to 200 ml of dimethyl sulfoxide, and the mixture was heated with stirring at 140 ° C. for 3 hours. The reaction mixture was naturally cooled to room temperature, poured into water, and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, the residue was purified by column chromatography, and the refractive index at 20 ° C. was 1.4665.
3.9 g (yield 39%) of the target product of

Production Example 3 1- (O-isopropyl-6,6
6-dimethylheptanehydroxymoyl) -1H-1,
Production of 2,4-triazole (Compound 26) O-isopropyl-6,6-dimethylheptanehydroxymoyl chloride 6.0 g (26 mmol), 1,2,
2.7 g (39 mmol) of 4-triazole and 4.3 g (31 mmol) of potassium carbonate were added to 150 ml of dimethyl sulfoxide, and the mixture was heated and stirred at 140 to 150 ° C for 3 hours. The reaction mixture was naturally cooled to room temperature, poured into water, and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, the residue was purified by column chromatography, and 1.1 g of the desired product having a refractive index of 1.4699 at 20 ° C. (yield 17
%) Was obtained.

Production Example 4 1- (O-isopropyl-decanehydroxymoyl) imidazole (Compound No. 14)
Preparation of O-isopropyl-decanehydroxymoyl chloride 4.0 g (16 mmol), imidazole 1.6 g (2
4 mmol) and 2.7 g of potassium carbonate (19 mmo
l) was added to 100 ml of dimethyl sulfoxide, and added to 140
The mixture was heated and stirred at 0 ° C for 3 hours. The reaction mixture was naturally cooled to room temperature, poured into water, and extracted with ethyl acetate. The organic layer is washed with water, dried over anhydrous magnesium sulfate, the solvent is removed under reduced pressure, the residue is purified by column chromatography, and the target product having a refractive index of 1.4791 at 20 ° C. of 1.0
g (yield 22%) was obtained.

Production Example 5 Z-decane hydroxymoyl-
1,2,4-triazole (Compound No. 44) and E-
Preparation of decanehydroxymoyl-1,2,4-triazole (Compound No. 45) O-benzyl-decanehydroxymoyl-1,2,4-
10 g (30 mmol) of triazole was added to 300 ml of dichloromethane, and 15.3 g (60 mmo) of boron tribromide was added to this solution at -50 ° C under cooling with dry ice-acetone.
l) was added dropwise. After the dropping, the refrigerant was removed, and after stirring for 2 hours, 50.5 g (370 g) of potassium carbonate dissolved in 100 ml of water was added.
(mmol) was added at room temperature over 1 hour and the layers were separated. The organic layer was washed with water, dried over anhydrous magnesium sulfate, the solvent was removed under reduced pressure, the residue was purified by silica gel column chromatography (n-hexane: ethyl acetate = 6: 1), and the melting point was 39 to 42 ° C. 1.0 g of Z-isomer (14% yield) and 1.1 g of E-isomer (melting point 54-58) (15% yield) were obtained.

The insecticide of the present invention comprises a carbohydroxymoylazole derivative represented by the general formula [I] as an active ingredient. In order to use the compound of the present invention as an insecticide, the compound of the present invention may be used by itself, but a carrier generally used for formulation, a surfactant, a dispersant, an auxiliary agent or the like is added, and a powder formulation, It can also be used by formulating it into a wettable powder, an emulsion, a fine granule or a granule. As the carrier used in the formulation, Sieglite, talc, bentonite, clay, kaolin, diatomaceous earth, white carbon,
Examples thereof include solid carriers such as vermiculite, slaked lime, silica sand, ammonium sulfate and urea, and liquid carriers such as isopropyl alcohol, xylene, cyclohexane and methylnaphthalene.
As the surfactant and the dispersant, an alkylbenzenesulfonic acid metal salt, a dinaphthylmethanedisulfonic acid metal salt,
Examples thereof include alcohol sulfate ester salts, alkylaryl sulfonates, lignin sulfonates, polyoxyethylene glycol ethers, polyoxyethylene alkylaryl ethers and polyoxyethylene sorbitan monoalkylates. Examples of the auxiliary agent include carboxymethyl cellulose, polyethylene glycol, gum arabic and the like. Before use, dilute to an appropriate concentration and spray or apply directly.

The insecticide of the present invention can be used by foliage spraying, soil application, nursery box application or water surface application. The blending ratio of the active ingredient is appropriately selected as necessary, but in the case of powder or granule, it is 0.03 to 30.
% (Weight), preferably from 0.05% to 20% (weight). When it is used as an emulsion or wettable powder, 0.5 to 85% (weight) is suitable. It is preferable to appropriately select from the range of 1 to 50% (weight).

The application rate of the insecticide of the present invention varies depending on the type of compound used, target pest, development tendency, degree of damage, environmental conditions, dosage form used, etc., but it is used as it is as in powder and granules. If you do, 10 as the active ingredient
0.05 g to 5 kg per are, preferably 0.1 g to
It is preferable to appropriately select from the range of 1 kg. When it is used as a liquid such as an emulsion and a wettable powder, it is 0.1
~ 5,000 ppm, preferably 1-1,000 ppm
It is preferable to appropriately select from the range.

The insecticide of the present invention includes other insecticides, fungicides,
Fertilizers and plant growth regulators can also be mixed and used.

Next, the formulation method will be specifically described with reference to typical formulation examples. The types and compounding ratios of the compounds and additives are not limited to these, and can be changed in a wide range. In the following description,% indicates weight percentage.

Formulation Example 1 Emulsion compound (9) 30%, cyclohexanone 20%, polyoxyethylene alkylaryl ether 11%, calcium alkylbenzene sulfonate 4% and methylnaphtha
Was emulsion homogeneously dissolved 35% les down.

Formulation Example 2 Wettable powder compound (29) 40%, diatomaceous earth 15%, clay 15%,
White carbon 25%, dinaphthylmethane disulfonate sodium 2% and lignin sulfonate sodium 3
% Was uniformly mixed and pulverized to obtain a wettable powder.

Formulation Example 3 2% of powder compound (32), 5% of diatomaceous earth and 93% of clay were uniformly mixed and pulverized to obtain a powder.

Formulation Example 4 Granule compound (44) 5%, sodium salt of lauryl alcohol sulfate 2%, sodium lignin sulfonate 5
%, Carboxymethylcellulose 2% and clay 86%
Are uniformly mixed and pulverized. 100 parts by weight of this mixture are mixed with 2 parts of water.
Add 0 parts by weight and knead.
It was processed into 32 mesh granules and then dried to obtain granules.

Next, the effects of the compound of the present invention will be described with reference to test examples. The comparative drug a used was the compound described in US Pat. No. 4,599,348. This comparative drug was formulated and used in the same manner as the test compound. Comparative drug a: 1- (O-methyl-t-butylhydroxymoyl) imidazole Test Example 1 Toroid planthopper insecticidal test A wettable powder prepared according to Formulation Example 2 was diluted with water to a concentration of 500 ppm. Rice foliage was soaked in the drug solution, air-dried, and then allowed to stand in a test tube. Five brown planthopper larvae in it
The head was released and plugged with absorbent cotton. Then, the cells were placed in a constant temperature room at 25 ° C., and after 6 days, the number of dead insects was investigated, the dead insect rate was calculated, and evaluation was performed according to the criteria shown in Table 4. The test was conducted in two consecutive cycles. The results are shown in Table 5.

[0039]

[Table 4]

[0040]

[Table 5] Test Example 2 A wettable powder prepared according to Formulation Example 2 of the leafhopper leafhopper insecticidal test was diluted with water to a concentration of 500 ppm. Rice foliage was soaked in the drug solution, air-dried, and then allowed to stand in a test tube. Five larvae of the leafhopper leafhoppers were released therein and capped with absorbent cotton. Then, put it in a constant temperature room at 25 ° C, and after 6 days, check the number of dead insects and calculate the dead rate.
Evaluation was made according to the criteria shown in Table 4. The test was conducted in two consecutive cycles. The results are shown in Table 6.

[0041]

[Table 6] Test Example 3 Cotton aphid insecticidal test A wettable powder prepared according to Preparation Example 2 was diluted with water to a concentration of 100 ppm. Cucumber seedlings, which had been inoculated with cotton aphid nymphs in advance, were immersed in the drug solution and air-dried. The cucumber seedlings after the treatment were placed in a constant temperature room at 25 ° C., and after 3 days, the number of dead insects was investigated, the dead insect rate was calculated, and evaluated according to the criteria shown in Table 4. The test was conducted in two consecutive cycles. The results are shown in Table 7.

[0042]

[Table 7]

[0043]

INDUSTRIAL APPLICABILITY The carbohydroxymoylazole derivative of the present invention exhibits a particularly excellent controlling effect against hemiptera pests. Especially useful planthoppers (crops, flowering trees, etc.) that damaging planthoppers such as brown planthoppers, sedge brown planthoppers, and planthopper leafhoppers, leafhoppers such as leafhopper leafhoppers, leafhopper leafhoppers, leaf aphids, and green peach aphids,
Aphids such as Japanese radish aphid, whitefly such as whitefly whitefly, stag beetle, scale insects such as stag beetle, stag beetle, stink bugs such as spider helicopter beetle, chaetophoridae, etc. Effective against psyllids.

In addition, lepidopteran pests such as diamondback moth, white-spotted armyworm, Spodoptera litura, diptera pests such as housefly and mosquito, rice weevil, weevil weevil, corn leafworm, and pests of the cockroach, Dermatogidae It also has insecticidal activity and shows a controlling effect.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ryo Kudo 3353 Kamo, Kikugawa-cho, Ogasa-gun, Shizuoka (72) Inventor Yuki Nakano 6 2356 Shimouchida, Kikugawa-cho, Ogasa-shi, Shizuoka (72) Inventor Hiroshi Kurihara Shizuoka 4-6, 1-6 Aobadai, Kikugawa-cho, Ogasa-gun (72) Inventor Tadami Hirano 3-9-2, Katsurugaoka, Kakegawa-shi, Shizuoka (58) Fields investigated (Int.Cl. ⁷ , DB name) C07D 233/56 C07D 249/08 CA (STN)

Claims (2)

(57) [Claims] 1. A general formula: (In the formula, R ¹ represents an alkyl group having 5 to 17 carbon atoms, or a cycloalkyl group having 6 carbon atoms which may be substituted with an alkyl group, R ² represents a hydrogen atom, and 1 to 6 carbon atoms. An alkyl group or a cycloalkyl group having 3 to 6 carbon atoms, and A represents a nitrogen atom or a methine group.) Is a carbohydroxymoylazole derivative or a salt thereof. 2. An insecticide containing the carbohydroxymoylazole derivative or the salt thereof according to claim 1 as an active ingredient.