JPH0714950B2 - Phosphate ester derivative and insecticide and acaricide containing the derivative - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel phosphoric acid ester derivative and an insecticidal and acaricidal agent containing the derivative.

2. Description of the Related Art Among the conventionally known organophosphate ester derivatives, compounds having acaricidal activity are known, but the compounds have a strong insecticidal activity against Coleoptera such as ladybug which is a natural enemy of mites. Since it also possesses, it is unavoidable to kill the natural enemies of these mites, and the selectivity of killing only mites is poor. Moreover, the compound has a short duration of effect of acaricidal activity and is highly toxic to warm-blooded animals. Therefore, among the conventionally known organophosphate derivatives, those compounds which have been put to practical use as acaricides. Does not exist yet.

DISCLOSURE OF THE INVENTION The present inventors have made efforts to develop compounds that can be put to practical use as insecticides and acaricides, and as a result, the phosphoric acid ester derivative of the following general formula (I) is extremely powerful without killing the natural enemies of mites. Has acaricidal activity and insecticidal activity against harmful insects such as Lepidoptera, Hemiptera, Thysanoptera, and has a long duration of effect of these activities, and also has extremely low toxicity to warm-blooded animals, insecticide, They have found that they can be suitably used as an acaricide, and have completed the present invention.

The phosphoric acid ester derivative of the present invention is a novel compound not described in the literature and is represented by the following general formula (I).

[In the formula, R ¹ and R ² represent a lower alkyl group. R ³ represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or a lower alkylthio group. X ¹ and X ² are the same or different and each represents a hydrogen atom or a halogen atom. Y represents an oxygen atom or a sulfur atom. In the present specification, each group represented by R ¹ , R ² , R ³ , X ¹ and X ² is specifically as follows.

Examples of the lower alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, amyl and hexyl groups.

As the lower alkoxy group, methoxy, ethoxy, n-
Examples include propoxy, isopropyloxy, n-butoxy, isobutyloxy, sec-butyloxy groups and the like.

Examples of the lower alkylthio group include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio and n-hexylthio groups.

Examples of the halogen atom include chlorine atom and bromine atom.

The phosphoric acid ester derivative represented by the general formula (I) can be produced by various methods, and a typical method thereof is, for example, the method shown in the following reaction formula 1.

Reaction formula 1 [In the formula, R ¹ , R ² , R ³ , X ¹ and X ² are the same as defined above. That is, the compound of the present invention is produced by reacting the phenol derivative represented by the general formula (II) with the phosphoric acid chloride represented by the general formula (III) in the presence of an acid binder.

The above reaction is carried out in an organic solvent or a two-phase system of an organic solvent and water. Examples of the organic solvent used include ethers such as ethyl ether, butyl ether, tetrahydrofuran and dioxane, nitriles such as acetonitrile and propionitrile, ketones such as acetone and methyl ethyl ketone, and aromatic hydrocarbons such as benzene and toluene. , Halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform and carbon tetrachloride. The ratio of the phenol derivative represented by the general formula (II) to the phosphoric acid chloride represented by the general formula (III) is not particularly limited and may be appropriately selected from a wide range. 0.5 to 2 times mole,
It is preferably about 1 to 1.5 times the molar amount. As the acid binder, conventionally known ones can be widely used, and specific examples thereof include tertiary amines such as triethylamine and pyridine, alkali metal carbonates such as sodium carbonate and potassium carbonate, sodium hydroxide and potassium hydroxide. And the like, and alkali metal hydrides such as sodium hydride and potassium hydride. The amount of such an acid binder used is usually about 1 to 2 times the molar amount of the compound (II), preferably about 1 to 1.2 times the molar amount. The reaction normally proceeds suitably at 0 to 50 ° C. and is generally completed in about 1 to 5 hours.

In the above Reaction Scheme 1, the compound (III) used as a starting material is a known compound and is industrially available at low cost. In addition, the other one of the starting materials, compound (II), can also be prepared, for example, by the following reaction formulas 2, 3, and 4
It can be easily produced according to the known method shown in.

Reaction formula 2 Reaction formula 3 Reaction formula 4 [In the above formulas, R ³ , X ¹ and X ² are the same as defined above. The reaction of reaction formula 2 is carried out in the presence of a base, for example, using potassium carbonate, and the details thereof are disclosed in JP-A-57-146736.

The reaction of Reaction Scheme 3 is carried out in the presence of a suitable condensing agent such as sulfuric acid, and the details thereof are disclosed in US Pat. No. 2,766,293.

The reaction of Reaction Scheme 4 is carried out in the presence of a base such as sodium hydroxide and sodium methylate, and the details are described in J-Pract chem., 323.
(4), 637-646 (1981)].

The compound of the present invention obtained by the above method is easily isolated and purified from the reaction mixture by a conventional separation means such as solvent extraction method, solvent dilution method, distillation method, recrystallization method, column chromatography and the like. . According to the above production method, the compound of the present invention can be produced in high yield and high purity.

The representative examples of the compound of the present invention thus obtained are as follows.

O-ethyl S-n-propyl O- [4- (β, β
-Dichloro-α-phenyl) vinyl] phenylphosphorothioate (Compound 1) O-ethyl Sn-propyl O- {4- [β, β
-Dichloro-α- (p-methoxy) phenyl] vinyl}
Phenyl phosphorodithioate (compound 2) O-ethyl S-isobutyl O- [4- (β, β-
Dichloro-α-phenyl) vinyl] phenyl phosphorothioate (Compound 3) O-ethyl Sn-propyl O- {4- [β, β
-Dichloro-α- (p-ethoxy) phenyl] vinyl}
Phenyl phosphorothioate (Compound 4) O-ethyl Sn-propyl O- {4- [β, β
-Dichloro-α- (p-methyl) phenyl] vinyl} phenyl phosphorothioate (Compound 5) O-ethyl Sn-propyl O- {4- [β, β
-Dichloro-α- (p-isopropyl) phenyl] vinyl} phenyl phosphorothioate (Compound 6) O-ethyl Sn-propyl O- [4- (β, β
-Dichloro-α-phenyl) vinyl] -2-chlorophenyl phosphorothioate (Compound 7) O-ethyl Sn-propyl O- {4- [β, β
-Dichloro-α- (p-methoxy) phenyl] vinyl}
2-Chlorophenyl phosphorothioate (Compound 8) O-ethyl S-isobutyl O- {4- [β, β-
Dichloro-α- (p-methyl) phenyl] vinyl} phenyl phosphorothioate (Compound 9) O-ethyl Sn-propyl O- [4- (β, β
-Dichloro-α-phenyl) vinyl] -2,6-dichlorophenyl phosphorothioate (Compound 10) O-ethyl Sn-propyl O- [4- (β, β
-Dichloro-α-phenyl) vinyl] -2,6-dibromophenyl phosphorothioate (Compound 11) O-ethyl S-isobutyl O- [4- (β, β-
Dichloro-α-phenyl) vinyl] -2,6-dichlorophenyl phosphorothioate (Compound 12) O-ethyl Sn-propyl O- {4- [β, β
-Dichloro-α- (p-chloro) phenyl] vinyl}-
2,6-Dichlorophenyl phosphorothioate (Compound 1
3) O-ethyl Sn-propyl O- {4- [β, β
-Dichloro-α- (p-methyl) phenyl] vinyl}-
2,6-Dichlorophenyl phosphorothioate (Compound 1
4) O-ethyl Sn-propyl O- {4- [β, β
-Dichloro-α- (p-isopropyl) phenyl] vinyl} -2,6-dichlorophenylphosphorothioate (Compound 15) O-ethyl Sn-propyl O- {4- [β, β
-Dichloro-α- (p-methoxy) phenyl] vinyl}
-2,6-Dichlorophenyl phosphorothioate (Compound 1
6) O-ethyl S-isobutyl O- {4- [β, β-
Dichloro-α- (p-methoxy) phenyl] vinyl}-
2,6-Dichlorophenyl phosphorothioate (Compound 1
7) O-ethyl Sn-propyl O- {4- [β, β
-Dichloro-α- (p-ethoxy) phenyl] vinyl}
-2,6-Dichlorophenyl phosphorothioate (Compound 1
8) O-ethyl Sn-propyl O- {4- [β, β
-Dichloro-α- (p-methylthio) phenyl] vinyl} phenyl phosphorodithioate (Compound 19) O-ethyl Sn-propyl O- {4- [β, β
-Dichloro-α- (p-methylthio) phenyl] vinyl} -2,6-dichlorophenyl phosphorothioate (Compound 20) O-ethyl Sn-propyl O- {4- [β, β
-Dichloro-α- (p-ethyl) phenyl] vinyl} phenyl phosphorothioate (Compound 21) O-ethyl Sn-propyl O- [4- (β, β
-Dichloro-α-phenyl) vinyl] phenyldithiophosphate (Compound 22) O-methyl Sn-propyl O- [4- (β, β
-Dichloro-α-phenyl) vinyl] phenyl phosphorothioate (Compound 23) O-methyl S-isobutyl O- [4- (β, β-
Dichloro-α-phenyl) vinyl] phenyl phosphorothioate (compound 24) O-methyl Sn-propyl O- {4- [β, β
-Dichloro-α- (p-methoxy) phenyl] vinyl}
Phenyl phosphorothioate (compound 25) O-methyl S-isobutyl O- {4- [β, β-
Dichloro-α- (p-methoxy) phenyl] vinyl} phenyl phosphorothioate (Compound 26) O-ethyl S-isobutyl O- {4- [β, β-
Dichloro-α- (p-methyl) phenyl] vinyl} phenyl phosphorothioate (Compound 27) O-methyl S-isobutyl O- [4- (β, β-
Dichloro-α-phenyl) vinyl] phenylphosphorodithioate (Compound 28) The compound of the present invention has a strong acaricidal activity and kills Coleoptera such as ladybug which is a natural enemy of mites. Since it has no residual effect and has a long residual effect and low toxicity to warm-blooded animals, it can be suitably used as a tick control agent for vegetables, fruit trees and the like. In addition, the compound of the present invention has insecticidal activity against insect pests such as Lotus japonicus, Plutella xylostella, Pteridophyta such as Anoectochilus spp., Aphids, Hemiptera such as leafhoppers, Thrips such as Thrips palmi, etc. And can also be used as an insecticide for these pests.

When the compound of the present invention is used as an insecticide or acaricide, an emulsion, a wettable powder, a suspension, a fine granule, a powder, a wettable powder, a coating agent, a foam spray formulation, a microcapsule formulation, an aerosol formulation, It can be used in various forms such as a preparation for impregnation with a natural or synthetic substance, a preparation for fumigation, and a preparation for spraying a concentrated small amount. In preparing these formulations, various surfactants can be used for emulsification, dispersion, suspension and foaming. Examples of such a surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, sorbitan alkyl ester and the like as a nonionic surfactant, and alkylbenzene sulfonate, alkyl as an anionic surfactant. Examples thereof include sulfosuccinate, alkyl sulphate, polyoxyethylene alkyl sulphate, allyl sulphonate and lignin sulfite. As the solubilizer, diluent and carrier, various organic solvents, various aerosol propellants, various natural minerals and plants, and various synthetic compounds can be used. Particularly preferred among the organic solvents are benzene, toluene, xylene, ethylbenzene, chlorobenzene, alkylnaphthalene, dichloromethane, chloroethylene, cyclohexane, cyclohexanone, acetone, methyl ethyl ketone, methyl isobutyl ketone, alcohols, dimethylformamide, diethyl sulfoxide, Acetonitrile, mineral oil fraction, etc. can be illustrated. Examples of aerosol propellants include propane, butane, halogenated hydrocarbons, nitrogen, carbon dioxide and the like. Examples of mineral substances include kaolin, talc, bentonite, diatomaceous earth, clay, montmorillonite, chiyoke, calcite, pumice, sepiolite and dolomite. Examples of plants include walnut shells, tobacco stems, sawdust, and the like. Examples of synthetic compounds include alumina, silicates, sugar polymers and the like. Examples of the adhesive include carboxymethyl cellulose, gum arabic, polyvinyl alcohol, polyvinyl acetate and the like. It is also possible to color these preparations with an organic or inorganic dye. In the present invention, in producing the above various preparations, the compound of the present invention is contained in an amount of about 0.1 to 95% by weight, preferably about 0.5.
It may be formulated so as to contain ˜90% by weight.

The prepared preparation may be used as it is or diluted with a carrier or water, and is used in an amount of about 0.00001 to 100% by weight depending on the purpose.
It can be freely diluted within the range of, preferably about 0.
It is preferable to use it after diluting it so that it contains 0001 to 10% by weight of the compound of the present invention. The amount of spray is based on the occurrence of ticks,
The amount of the compound of the present invention is generally about 0.1 to 10 kg, and preferably about 0.1 to 1 kg per hectare, although it varies depending on the weather and the like and cannot be generally stated.

Examples The present invention will be further clarified below with reference to production examples and test examples.

Production Example 1 4- (β, β-dichloro-α-phenyl) vinylphenol 2.65 g and triethylamine 1.05 g were added to methylene chloride 20.
The mixture was placed in ml and stirred under ice-cooling with O-ethyl S-n.
-2.03 g of propylphosphoric acid chloride was added dropwise. After dropping
After stirring at room temperature for 1 hour, the reaction solution was washed with a 5% aqueous solution of hydrochloric acid, then a 5% aqueous solution of sodium hydrogen carbonate, and finally with a saturated saline solution, and then dried over anhydrous magnesium sulfate. The solvent was distilled off to obtain 4.10 g of pale yellow oily O-ethyl S-propyl O- [4- (β, β-dichloro-α-phenyl) vinyl] phenylphosphorothioate.

IR (neat); 1260 cm ⁻¹ (P═O) NMR (CDCl ₃ ); δppm 0.8 to 1.80 (m, 8H, alkyl) 2.56 to 3.10 (m, 2H, CH ₂ S) 3.90 to 4.32 (m, 2H, CH ₂ O) 7.0-7.40 (m, 9H, aromatic H) The compounds obtained from the above results are Was confirmed.

Production Example 2 4- [β, β-dichloro-α- (p-methoxy) phenyl] vinylphenol 2.95 g and anhydrous potassium carbonate 1.35 g
Was placed in 30 ml of acetonitrile and heated with stirring at 40-45 ° C for 1 hour. Then, after cooling to room temperature, O-ethyl S-
2.18 g of n-propyldithiophosphoric acid chloride was added dropwise.
The reaction mixture was stirred at 50-60 ° C for 4 hr, the precipitated salt was separated, and the liquid was concentrated. The residue was purified on a silica gel column (benzene-ethyl acetate = 10: 1) to give O-methyl Sn-propyl O- {4- as a pale yellow oil.
[Β, β-dichloro-α- (p-methoxy) phenyl]
5.25 g of vinylphenyl} dithiophosphate was obtained.

IR ^{(neat); 663,790cm -1 (P = S} ) NMR (CDCl 3); δppm 0.70~1.90 (m, 8H, alkyl) 2.60~3.15 (m, 2H, CH 2 S) 3.90~4.30 (m, 2H, CH ₂ O) 3.80 (s, 3H, CH ₃ O) 6.68 to 7.38 (m, 8H, aromatic H) The compounds obtained from the above results are Was confirmed.

Production Examples 3 to 28 In the same manner as in Production Example 1 or 2 above, the compounds shown in Table 1 below were obtained. Table 1 also shows the physical properties of the compound.

In the above table, Me is a methyl group, Et is an ethyl group, ▲
P ⁿ _r ▼ means n-propyl group, ▲ P ^iso _r ▼ means isopropyl group, and ▲ B ^iso _u ▼ means isobutyl group.

Test Example 1 (Namidani test) 2 parts by weight of the compound of the present invention was dissolved in 98 parts by weight of acetone.
This was diluted to a predetermined concentration with an aqueous solution containing 0.04% spreader (using Nippon Pesticides Shin-Reno) to prepare a liquid preparation. Potted green beans were inoculated with adult worms, then sprayed with the solution prepared as described above until the drops dripped. The mortality of insects after 3 days was measured, and the results are shown in Table 2. In addition, the test compound No. in Table 2 is the same as Example N.
Corresponds to o.

Test Example 2 (aphid test) 2 parts by weight of the compound of the present invention was dissolved in 98 parts by weight of acetone.
This was diluted to a predetermined concentration with an aqueous solution containing 0.04% spreader (using Nippon Pesticides Shin-Reno) to prepare a liquid preparation. Aphids on cotton seedlings (2 to 3 true leaves) planted in pots
Ten of them were bred, and after breeding for 2 days, the liquid preparation prepared as described above was sprayed. Seven days after the drug was sprayed, the number of parasites was examined, and the mortality rate was measured by comparison with the untreated plot. The result is the third
Shown in the table. In addition, the test compound No. in Table 3 is
Corresponds to Example No.

Test Example 3 (Similar Thrips test) 2 parts by weight of the compound of the present invention was dissolved in 98 parts by weight of acetone.
This was diluted to a predetermined concentration with an aqueous solution containing 0.04% spreader (using Japan Pesticides Shin-Reno) to prepare a liquid agent. Ten Southern Thrips thrips were released on potted cucumber seedlings (2 to 3 true leaves), and after breeding for 2 days, the liquid preparation prepared as described above was sprayed. Seven days after the drug was sprayed, the number of parasites was examined, and the mortality rate was measured by comparison with the untreated plot. The results are shown in Table 4. The test compounds in Table 4
No. corresponds to Example No.

Claims (2)

[Claims] 1. A general formula [In the formula, R ¹ and R ² represent a lower alkyl group. R ³ represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or a lower alkylthio group. X ¹ and X ² are the same or different and each represents a hydrogen atom or a halogen atom. Y represents an oxygen atom or a sulfur atom. ] The phosphoric acid ester derivative represented by these. 2. General formula [In the formula, R ¹ and R ² represent a lower alkyl group. R ³ represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or a lower alkylthio group. X ¹ and X ² are the same or different and each represents a hydrogen atom or a halogen atom. Y represents an oxygen atom or a sulfur atom. ] An insecticidal and acaricidal agent containing a phosphoric acid ester derivative represented by the following as an active ingredient.