JPH0449537B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula () [In the formula, R ₁ and R ₂ are the same or different,
It represents a hydrogen atom or a lower alkyl group, R ₃ represents a hydrogen atom or a methyl group, and R ₄ represents a hydrogen atom or a methyl group. When R ₄ represents a hydrogen atom, R ₅ and R ₆ are the same or different,
It represents a halogen atom or a methyl group, and when R ₄ represents a methyl group, R ₅ and R ₆ are the same or different and represent a hydrogen atom, a halogen atom or a methyl group. n represents an integer from 1 to 4. ] The present invention relates to an oxime ether derivative represented by (hereinafter referred to as the compound of the present invention), a method for producing the same, and an insecticide containing the same as an active ingredient. In the compound of the present invention represented by the above general formula (), halogen atom means chlorine atom, fluorine atom or bromine atom, and lower alkyl group means methyl group, ethyl group, n-propyl group or iso-propyl group. means. The compound of the present invention represented by the general formula () can be produced by the following method. (Manufacturing method A) General formula () [In the formula, R ₃ , R ₄ , R ₅ , R ₆ and n have the same meanings as above, and A ₁ represents a halogen atom, mesyloxy group or tosyloxy group. ] Compounds shown by and general formula () [In the formula, R ₁ and R ₂ have the same meanings as above. ] A method of reacting a compound represented by or an alkali metal salt thereof. (Manufacturing method B) General formula () [In the formula, R ₄ , R ₅ , R ₆ and n have the same meanings as above]. The compound represented by or its alkali metal salt and the general formula () [In the formula, R ₁ , R ₂ and R ₃ have the same meanings as above, and A ₂ represents a halogen atom, mesyloxy group or tosyloxy group. ] A method of reacting with a compound shown in The reactions according to Preparation A and Preparation B are conveniently carried out in the presence of an inert organic solvent and an acid binder. Suitable solvents include dimethylformamide,
Examples include dimethyl sulfoxide, tetrahydrofuran, dimethoxyethane, toluene, and combinations of two or more of these solvents. Suitable acid binders include alkali metals, especially sodium, potassium, alkali metal hydrides, alkali metal amides, alkali metal hydroxides such as alkali metal carbonates, especially potassium carbonate, and organic bases. Moreover, in this reaction, when using a phase transfer catalyst such as benzyltriethylammonium chloride or tetra n-butylammonium bromide, water may be used as a solvent. The temperature at which production methods A and B are carried out is not particularly limited, but generally ranges from -30°C to the boiling point of the reaction mixture, preferably from room temperature to
Carry out at a temperature of 100°C. Generally the reaction is complete in 0.5 to 24 hours. Compounds represented by general formula () and general formula ()
The molar ratio with the compound represented by is usually 1:1 to 3
and preferably 1:1.1-1.2. Also,
The molar ratio of the compound represented by the general formula () and the compound represented by the general formula () is usually 1:0.33 to 3.
and preferably 1:0.8 to 1.2. (Manufacturing method C) General formula () [In the formula, R ₃ , R ₄ , R ₅ , R ₆ and n have the same meanings as above. ] The compound represented by or the reactive derivative and the general formula () [In the formula, R ₁ and R ₂ have the same meanings as above. ] A method of reacting a compound represented by these or the reactive derivative thereof. Here, the compound represented by the general formula () includes mineral acid salts such as hydrochloride and sulfate,
It includes organic acid salts, oxime ethers contained in the compounds of the present invention, other oxime ethers, etc., and includes all derivatives of general formula () that can form general formula () in the reaction system. Needless to say. In addition, the compound represented by the general formula () includes all derivatives thereof such as acetal, ketal, hemiacetal, hemiketal, hydrate, etc., and all compounds that can form the general formula () in the reaction system. Needless to say, it includes derivatives of the general formula (). The reaction according to Production Method C may be carried out in the presence or absence of an inert solvent, and may be carried out in the presence or absence of an acid or alkali. Suitable solvents include water, benzene, toluene, carbon tetrachloride, chloroform, ethylene chloride, methylene chloride, and combinations of two or more thereof. Suitable acids include hydrochloric acid, sulfuric acid, and p-toluenesulfonic acid, and suitable alkalis include inorganic bases such as sodium hydroxide, potassium hydroxide, and potassium carbonate, and organic bases such as triethylamine and pyridine. The temperature at which production method C is carried out is not particularly limited, but
The reaction is generally carried out at a temperature of -30°C to the boiling point of the reaction mixture, preferably room temperature to 100°C. Generally the reaction is complete in 0.5 to 24 hours. Compounds represented by general formula () and general formula ()
The molar ratio with the compound represented by is usually 1:1 to 20
and preferably 1:1.1-1.2. The obtained compound of the present invention can be purified by means such as column chromatography and distillation, if necessary. Note that the compound of the present invention includes geometric isomers based on R ₁ and R ₂ and optical isomers based on R ₃ , and it goes without saying that all of these are included in the present invention. Next, a manufacturing example will be shown. Production example 1 Production of compound (1) by (Production method A) 0.59 g (10.0 mmol) of acetaldoxime was dissolved in 10 ml of dimethylformamide, and the solution was heated to internal temperature under ice cooling.
0.24g of sodium hydride while stirring below 10℃
(10.0 mmol) was added. After continuing stirring for 2 hours after completion, 3.02 g of 1-bromo-2-[4-(3,5-dichlorophenoxy)phenoxy]ethane
(8.33 mmol) dissolved in 10 ml of dimethylformamide was applied. After completion of the dropwise addition, the mixture was stirred at room temperature overnight, and then the reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with water and concentrated, and the residue was purified by silica gel column chromatography using benzene as a developing solvent to obtain 1.43 g of the target compound (1) as a colorless oil (yield: 50.5 %, n ^24.0 _D
1.5781). Production Example 2 Production of Compound (6) by (Production Method B) 2.22 g (10.0 mmol) of 4-(3,5-difluorophenoxy)phenol was dissolved in 10 ml of dimethylformamide, and the temperature was lowered to 10°C or less under ice cooling. While stirring, 0.24 g (10.0 mmol) of sodium hydride was added. After continuing stirring for 2 hours after completion, 3-
(p-Toluenesulfonyloxy)propylpropionaldoxime ether 2.28g
(8.0 mmol) dissolved in 10 ml of dimethylformamide was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature overnight, and then heated and stirred at 80 to 100°C for 1 hour. The resulting reaction solution was poured into water and extracted with ethyl acetate. The extract was washed with water and concentrated, and the residue was purified by silica gel column chromatography using benzene as a developing solvent to obtain 0.92 g of the target compound (6) as a colorless oil (yield 35.8%). , n ^25.0 _D
1.5364). Production Example 3 Production of compound (2) by (Production method C) O-2-[4-(3,5-dichlorophenoxy)
Phenoxy]ethylhydroxylamine 0.31g
(1.0 mmol) dissolved in 5 ml of chloroform, 0.58 g (10.0 mmol) of propionaldehyde
was added dropwise over a period of 10 minutes. After the addition was completed, the mixture was stirred at room temperature overnight, washed with water, dried over anhydrous sodium sulfate, and concentrated. The obtained oil was purified by silica gel column chromatography using methylene chloride as a developing solvent to obtain 0.28 g of the target compound (2) as a colorless oil (yield 79.0%, n ^24.0 _D 1.5718). Next, Table 1 shows some of the compounds of the present invention produced according to the production methods shown in these production examples.

[Table] Organophosphate insecticides, organochlorine insecticides, and carbamate insecticides have played a very important role in pest control, but some of these are highly toxic and have a negative impact on the ecosystem due to their persistence. This is an extremely worrying situation as it is disturbing the situation. Also,
In recent years, resistance to insecticides has become a problem in certain pest insects, such as houseflies, planthoppers, leafhoppers, and insects. In order to cope with such a situation, the present invention aims to control agricultural, forestry, and horticultural pests, grain storage pests, sanitary pests, etc. using a compound having juvenile hormone-like activity that exhibits extremely excellent control effects at low concentrations. . Currently, methoprene (U.S. Pat. Nos. 3,904,662 and 3,912,815) has a juvenile hormone-like activity and is used as an insecticide, but this also has sufficient insecticidal activity. The reality is that it is not. As a result of intensive research, the present inventors found that the compound represented by the general formula () has juvenile hormone activity. It was found that it has an extremely high insect control effect. The compound of the present invention can be mixed with solid carriers, liquid carriers, surfactants, and other auxiliary materials for formulations to prepare formulations, such as emulsions, powders, granules, wettable powders, and fine granules, and can be used for various purposes. I can offer it. Each formulation contains the compound of the present invention as an active ingredient in a weight ratio of 0.1 to 99.9%.
Preferably, it can be contained in an amount of 2.0 to 80.0%. These formulations can be prepared according to conventional methods. In this case, solid carriers include fine powders such as clays (e.g. kaolin, bentonite, acid clay, pyrophyllite, sericite), talcs, and other inorganic minerals (e.g. hydrated silicon dioxide, pumice, diatomaceous earth, sulfur powder, activated carbon). Or powdered substances can be given. Liquid carriers include alcohols (e.g. methyl alcohol, ethyl alcohol), ketones (e.g. acetone, methyl ethyl ketone), ethers (e.g. ethyl ether, dioxane,
cellosolve, tetrahydrofuran), aromatic hydrocarbons (e.g. benzene, toluene, xylene, methylnaphthalene), aliphatic hydrocarbons (e.g. gasoline, kerosene, kerosene), esters,
Nitriles, acid amides (for example, methylformamide, dimethylacetamide), halogenated hydrocarbons (for example, dichloroethane, trichloroethylene, carbon tetrachloride), and the like. Next, as surfactants, alkyl sulfate esters,
Examples include alkyl sulfonates, alkylaryl sulfonates, polyethylene glycol ethers, and polyhydric alcohol esters. Fixing agents and dispersing agents that can be used include casein, gelatin, starch powder, CMC, gum arabic, alginic acid, lignin sulfonate, bentonite, molasses, polyvinyl alcohol, pine oil, agar, etc. Stabilizers include: for example
Examples include PAP (isopropyl phosphate), TCP (tricresyl phosphate), tall oil, epoxidized oil, various surfactants, and various fatty acids or their esters. In addition, these compounds include phenitrothion {O,O-dimethyl-O-(3-methyl-4-nitrophenyl)phosphorothioate}, marathon [S-{1,2-bis(ethoxycarbonyl)ethyl}O,O-dimethylphosphorothioate ], dimethoate {O,O-dimethyl S-(N-methylcarbamoylmethyl)phosphorodithioate},
Salithion (2-methoxy-4H-1,3,2-
benzodioxaphosphorine-2-sulfide),
Diazinon {O,O-diethyl O-(2-isopropyl-6-methyl-4-pyrimidinyl)phosphorothioate}, dipterex {2,2,2
-trichloro-1-hydroxyethyl)O,O
-dimethylphosphonate}, dichlorvos {O-
Organophosphorus insecticides such as (2,2-dichlorovinyl)O,O-dimethylphosphate}, MPMC
(3,4-dimethylphenyl N-methylcarbamate), MTMC (m-tolyl N-methylcarbamate), BPMC (2-sec-butylphenyl N-methylcarbamate), carbaryl (1-naphthyl N-methylcarbamate), etc. Carbamate insecticides, permethrin {3-phenoxybenzene d,l-cis, trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate}, phenvalerate (α-cyano -m-phenoxybenzyl α-isopropyl-
It can be mixed in any proportion with pyrethroid insecticides such as p-chlorophenyl acetate, acaricides, nematicides, fungicides, herbicides, plant growth regulators, fertilizers, soil conditioners, etc. Particularly when mixed with insecticides, stability in the efficacy of each and synergistic action can be expected. Next, some formulation examples and test examples will be shown, but the present invention is of course not limited to these. Formulation Example 1 20 parts each of the compounds (1) to (9) of the present invention, each emulsifier (polyoxyethylene styrenated phenyl ether, polyoxyethylene styrenated phenyl ether polymer, alkylaryl sulfonate mixture) ) and 60 parts of xylene and stir and mix well to obtain each emulsion. Formulation Example 2 20 parts of each of the compounds (1) to (9) of the present invention are thoroughly mixed with 5 parts of an emulsifier (sodium lauryl sulfate), 75 parts of 300 mesh diatomaceous earth are added, and the mixture is sufficiently stirred in a crusher. , to obtain each hydrating agent. Formulation Example 3 Dissolve 3 parts each of the compounds (5) and (6) of the present invention in 20 parts of acetone, add 97 parts of 300 ml of turquoise, stir thoroughly and mix in a grinder, and then evaporate and remove the acetone. Obtain each powder. Formulation Example 4 5 parts each of compounds (5) and (6) of the present invention, 2 parts each of a dispersant (calcium lignin sulfonate) and clay.
Add 93 parts of the mixture and mix well with stirring in a crusher. Next, water is added in an amount of 10% of the mixture, and the mixture is stirred and mixed, granulated using a granulator, and dried through ventilation to obtain each granule. Formulation Example 5 To 2 parts of the compound of the present invention (5), 2 parts of a dispersant (calcium lignin sulfonate) and 96 parts of clay are added, and the mixture is thoroughly stirred and mixed in a grinder. Next, water is added in an amount of 10% of the mixture, and the mixture is stirred and mixed, granulated using a granulator for fine granules, and dried through ventilation to obtain each fine granule. Test Example 1 The emulsion obtained in Formulation Example 1 was diluted 400 times with water, and 0.7 ml of the solution was added to 10.0 ml of distilled water.
Culex Culex last-instar larvae were released into the larvae, fed, and reared for about 7 days until emergence. The results are shown in Table 2 (2 replicates).

[Table] Compound Test Example 2 Among the emulsions obtained in Formulation Example 1, the emulsion containing the compounds listed in Table 3 was diluted with water to the specified concentration, and 0.5 ml of the solution was added to 100 ml of distilled water. In addition, 20 last-instar Culex Culex larvae were released into the larva, fed, and reared for approximately 7 days until emergence, and the concentration of 50% inhibition of emergence (IC ₅₀
(ppm)) was determined (2 repetitions). The result is given by the following formula
It is shown in Table 4 as pI ₅₀ . pI ₅₀ = −logIC ₅₀

[Table] *Same test example as above 3 14 g of wheat bran and 2 g of powdered feed were thoroughly mixed. A chemical solution obtained by diluting an emulsion containing the compounds listed in Table 7 with water to a predetermined concentration with water among the emulsions obtained in Formulation Example 1 was added thereto, and the mixture was stirred and mixed. Thirty final instar house fly larvae were released into the artificial medium for house flies, and pupated therein. The formed pupae were transferred to new plastic cups, the emergence rate was determined, and the emergence inhibition rate was determined using the following formula. Inhibition rate of emergence (%) = (1 - emergence rate in treated area/emergence rate in untreated area) x 100 The results are shown in Table 7.

[Table] *Same as above

Claims (1)

[Claims] 1. General formula [In the formula, R ₁ and R ₂ are the same or different,
It represents a hydrogen atom or a lower alkyl group, R ₃ represents a hydrogen atom or a methyl group, and R ₄ represents a hydrogen atom or a methyl group. When R ₄ represents a hydrogen atom, R ₅ and R ₆ are the same or different,
It represents a halogen atom or a methyl group, and when R ₄ represents a methyl group, R ₅ and R ₆ are the same or different and represent a hydrogen atom, a halogen atom or a methyl group. n represents an integer from 1 to 4. ] An oxime ether derivative represented by 2 General formula [In the formula, R ₃ represents a hydrogen atom or a methyl group, and R ₄ represents a hydrogen atom or a methyl group. _R4
represents a hydrogen atom, R ₅ and R ₆ are the same or different and represent a halogen atom or a methyl group, and when R ₄ represents a methyl group, R ₅ and R ₆
are the same or different and represent a hydrogen atom, a halogen atom or a methyl group. n represents an integer of 1 to 4, and A ₁ represents a halogen atom, mesyloxy group or tosyloxy group. ] Compound and general formula shown by [In the formula, R ₁ and R ₂ are the same or different,
Represents a hydrogen atom or a lower alkyl group. ] A general formula characterized by reacting with a compound represented by or an alkali metal salt thereof [In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and n have the same meanings as above. ] A method for producing an oxime ether derivative shown in the following. 3 General formula [In the formula, R ₄ represents a hydrogen atom or a methyl group, and when R ₄ represents a hydrogen atom, R ₅ and R ₆ are the same or different and represent a halogen atom or a methyl group, and R ₄ represents a methyl group. In this case, R ₅ and R ₆ are the same or different and represent a hydrogen atom, a halogen atom or a methyl group. n represents an integer from 1 to 4. ] The compound represented by or its alkali metal salt and the general formula [In the formula, R ₁ and R ₂ are the same or different,
It represents a hydrogen atom or a lower alkyl group, R ₃ represents a hydrogen atom or a methyl group, and A ₂ represents a halogen atom, mesyloxy group or tosyloxy group. ] A general formula characterized by reacting with a compound represented by [In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and n have the same meanings as above. ] A method for producing an oxime ether derivative shown in the following. 4 General formula [In the formula, R ₃ represents a hydrogen atom or a methyl group, and R ₄ represents a hydrogen atom or a methyl group. _R4
represents a hydrogen atom, R ₅ and R ₆ are the same or different and represent a halogen atom or a methyl group, and when R ₄ represents a methyl group, R ₅ and R ₆
are the same or different and represent a hydrogen atom, a halogen atom or a methyl group. n represents an integer from 1 to 4. ] The compound represented by or the reactive derivative and the general formula [In the formula, R ₁ and R ₂ are the same or different,
Represents a hydrogen atom or a lower alkyl group. ] A general formula characterized by reacting with the compound represented by or the reactive derivative thereof [In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and n have the same meanings as above. ] A method for producing an oxime ether derivative shown in the following. 5 General formula [In the formula, R ₁ and R ₂ are the same or different,
It represents a hydrogen atom or a lower alkyl group, R ₃ represents a hydrogen atom or a methyl group, and R ₄ represents a hydrogen atom or a methyl group. When R ₄ represents a hydrogen atom, R ₅ and R ₆ are the same or different,
It represents a halogen atom or a methyl group, and when R ₄ represents a methyl group, R ₅ and R ₆ are the same or different and represent a hydrogen atom, a halogen atom or a methyl group. n represents an integer from 1 to 4. ] An insecticide characterized by containing an oxime ether derivative represented by the following as an active ingredient.