JPH066599B2 - Organic phosphorus compounds and pest control agents containing them - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to novel organophosphorus compounds having an effective control action against harmful insects, mites, and nematodes, a method for producing the same, and a method for producing the same. The present invention relates to insecticides, acaricides, and nematicides containing the compound as an active ingredient.

(Disclosure of the Invention) The compound of the present invention is a novel organophosphorus compound represented by the following general formula (I).

General formula (I): [In the formula, X ₁ and Y ₁ are a hydrogen atom or an alkyl group, and X ₂ and Y ₂ are a hydrogen atom, a cyano group, or —CH ₂ Q.
(Q is a phenylsulfinyl group, an alkylsulfonyloxy group, an alkylcarbonylmethylthio group, a dialkylamino group, an alkoxycarbonyloxy group or a dialkoxydithiophosphonomethyl group), and Z ₁ is an oxygen atom or a sulfur atom. , Z ₂ is an oxygen atom,
R ₁ and R ₂ are alkyl groups, and one of X ₂ and Y ₂ is a cyano group or a —CH ₂ Q group] In the general formula (I), X ₁ , Y ₁ , R ₁ and R ₂ are The alkyl group represented by, and the alkylsulfonyloxy group represented by Q, the alkylcarbonylmethylthio group, the dialkylamino group, the alkoxycarbonyloxy group and the alkyl moiety of the dialkoxyphosphonomethyl group,
Methyl, ethyl, n-propyl, iso-propyl, n-
Butyl, iso-butyl, sec-butyl and the like can be mentioned.

The compound of the present invention has isomers due to asymmetric carbon, and all of these isomers have effects as insecticides, acaricides and nematicides, and are included in the present invention.

The compound of the present invention can be produced, for example, by the following method.

(In the formula, X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , Z ₂ , R ₁ and R ₂ are as described above.) The reaction is usually −100 to 50 ° C., preferably −80 ° C. ~ It is performed in the temperature range of room temperature.

Further, this reaction is carried out in the presence of an acid acceptor, and as the acid acceptor, organic lithium compounds such as n-butyllithium, tert-butyllithium, phenyllithium, sodium hydroxide, potassium hydroxide, hydrogenation sodium,
Examples thereof include inorganic bases such as potassium hydride and organic bases such as triethylamine and pyridine. Furthermore, these reactions are preferably carried out in the presence of a solvent, and as the solvent, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene: cyclic or non-cyclic aliphatic hydrocarbons such as hexane and cyclohexane. Kinds: Ethers such as diethyl ether, dioxane and tetrahydrofuran: Nitriles such as acetonitrile, propionitrile and acrylonitrile: Aprotic polar solvents such as dimethylformamide, dimethylsulfoxide, sulfolane and hexamethylphosphoric triamide.

Among the starting materials represented by the general formula (II), A. A compound in which _one of X ₁ and Y ₁ is a hydrogen atom or an alkyl group, one of X ₂ and Y ₂ is substituted with a cyano group, Z ₁ is an oxygen atom or a sulfur atom, and Z ₂ is an oxygen atom is , For example, the method described in Journal of Organic Chemistry, Vol. 33, p. 766 (1968).

B. One of X ₁ and Y ₁ is a hydrogen atom or an alkyl group, one of X ₂ and Y ₂ is a —CH ₂ Q group, Q is substituted with an alkoxycarbonyloxy group or an alkylsulfonyloxy group, and Z ₁ is A compound which is an oxygen atom or a sulfur atom and Z ₂ is an oxygen atom is described in British Patent No. 93.
It can be easily obtained by reacting a compound described in No. 8424 in which one of X ₂ and Y ₂ is substituted with a hydroxymethyl group, with a substituted sulfonyl chloride or an acyl chloride.

C. One of X ₁ and Y ₁ is an oxygen atom or an alkyl group, one of X ₂ and Y ₂ is a —CH ₂ Q group, and Q is an alkylcarbonylmethylthio group, a dialkylamino group or a dialkoxydithiophosphonomethyl group. In which Z ₁ is an oxygen atom or a sulfur atom and Z ₂ is an oxygen atom, one of X ₂ and Y ₂ described in British Patent No. 938424 is substituted with a chloromethyl group. It is easily obtained by reacting a compound with an alkali salt of a substituted mercaptan or a dialkylamine. D. A compound in which _one of X ₁ and Y ₁ is an oxygen atom or an alkyl group, one of X ₂ and Y ₂ is substituted with a phenylsulfinyl group, Z ₁ is an oxygen atom or a sulfur atom, and Z ₂ is an oxygen atom. Is _one of X ₁ and Y ₁ is an oxygen atom or an alkyl group, one of X ₂ and Y ₂ is substituted with a phenylsulfenyl group, Z ₁ is an oxygen atom or a sulfur atom, and Z ₂ is an oxygen atom. It is easily obtained by oxidizing a known compound of

Next, synthetic examples relating to the compound of the present invention will be described.

Case example. O-ethyl S-n-propyl (4-cyano-
Synthesis of 2-oxo-3-thiazolidinyl) phosphonothiolate 1.1 g of 5-cyanooxazolidin-2-one was dissolved in 30 ml of tetrahydrofuran and cooled to -78 ° C. To there
7 ml of a hexane solution of n-butyllithium (1.55 molar concentration) was gradually added dropwise, and stirring was continued at the same temperature for 15 minutes. Next, 2.4 g of S-sec-butyl O-ethyl phosphorochloride thiolate was gradually added dropwise, and the reaction was allowed to proceed for 2 hours while gradually returning to room temperature.

After completion of the reaction, the reaction product was put into ice water, and ethyl acetate was added for extraction. The extract layer was dried over anhydrous sodium sulfate, the solvent was distilled off, and the obtained crude product was purified by silica gel chromatography to obtain a refractive index (▲ n ^25.4 _D ▼) of 1.4.
901 O-ethyl Sn-propyl (4-cyano-2
-Oxo-3-thiazolidinyl) phosphonothiolate.
5 g was obtained.

Examples of representative compounds of the present invention are given below. Compound NO.
1 S-sec-butyl O-ethyl (5-phenylsulfinylmethyl-2-oxo-3-oxazolidinyl)
Phosphonothiolate ▲ n ^21.2 _D ▼ = 1.5484 Compound NO.2 S-sec-butyl O-ethyl (4-methylsulfonyloxymethyl-2-oxo-3-oxazolidinyl) phosphonothiolate ▲ n ^25.0 _D ▼ = 1.4962 Compound NO .3 S-sec-butyl O-ethyl (4-methyl-4-methylsulfonyloxymethyl-2-oxo-
3-oxazolidinyl) phosphonothiolate
▲ n ^19.2 _D ▼ = 1.5002 Compound NO.4 S-sec-butyl O-ethyl (5-ethylcarbonylmethylthiomethyl-2-oxo-3-oxazolidinyl) phosphonothiolate ▲ n ^27.6 _D ▼ = 1.5056 Compound NO.5 S -Sec-Butyl O-ethyl (5-diethylaminomethyl-2-oxo-3-oxazolidinyl) phosphonothiolate ▲ n ^27.6 _D ▼ = 1.4860 Compound NO.6 S-sec-butyl O-ethyl (4-methyl-4-) Acetoxymethyl-2-oxo-3-oxazolidinyl) phosphonothiolate ▲ n ^19.4 _D ▼ = 1.4880 Compound NO.7 S-sec-butyl O-ethyl {4-methyl-4- (0,0-diethyldithiophosphorylmethyl) −
2-oxo-3-oxazolidinyl} phosphonothiolate ▲ n ^17.1 _D ▼ = 1.5202 Compound NO.8 S-sec-butyl O-ethyl (5-cyano-2-oxo-3-oxazolidinyl) phosphonothiolate ▲ n ^25.4 _D ▼ = 1.4901 Compound NO.9 O-ethyl S-n-propyl (4-cyano-2-oxo-3-thiazolidinyl) phosphonothiolate The compound of the present invention is insecticidal, acaricidal, and nematicidal, as seen in Test Examples below. It exhibits excellent activity as an active ingredient of insect repellents.

For example, phytoparasitic mites such as scab spider mites, spider mites, citrus spider mites, etc., diamondback moth, weevil, Lotus japonicum, codling moth, ball worms (no Japanese name), Daba kobat worms (no Japanese name), mai maiga, Colorado potato beetle, ball wee Agricultural pests such as Bill (no Japanese name), aphids, planthoppers, leafhoppers, scale insects, stink bugs, whiteflies, thrips, grasshoppers, scabbards, ants, chafers, tamanagaga, cabbage moths, etc. , Sanitary pests such as, house dust mites, cockroaches, house flies, mosquitoes,
Against stored-product insects such as adzuki bean weevils and dwarf beetles, clothes such as squid, scabbard beetles, termites, house pests, and fleas, lice and flies that parasitize humans and livestock. Is also effective, and further, root-knot nematodes, cyst nematodes, negusare nematodes, rice singale nematodes,
It is also effective against plant parasitic nematodes such as strawberry nematodes and pine wood nematodes. It is also effective against pests such as dicofol and organophosphorus-resistant plant parasitic mites, organophosphorus-resistant aphids, and house flies. Furthermore, the compound of the present invention is
Since it has an excellent osmotic transfer property, by treating the soil with the compound of the present invention, it is possible to control soil pests and nematodes as well as pests on foliage. It is also effective against molluscs belonging to pulmonary gastropods such as slugs and snails, which cause human discomfort and sometimes damage to agricultural products, and crustaceans belonging to the isosceles such as pill bugs and platypus. is there.

Insecticide, acaricide, when using the compound of the present invention as an active ingredient of nematicides, emulsions, powders, granules, wettable powders, liquids, together with pesticide adjuvants as in the case of conventional pesticide formulations,
It can be formulated into various forms such as an aerosol and a paste. The mixing ratio of these is usually 0.5 to 0.5
90 parts by weight is 10 to 99.5 parts by weight of pesticide adjuvant. In the actual use of these preparations, they can be used as they are or diluted with a diluent such as water to a predetermined concentration and used.

Examples of the agrochemical adjuvant include a carrier, an emulsifier, a suspending agent, a dispersing agent, a spreading agent, a penetrating agent, a wetting agent, a thickener, a stabilizer, and the like, which may be appropriately added if necessary. The carrier is divided into a solid carrier and a liquid carrier, and the solid carrier includes starch, activated carbon, soybean flour, wheat flour, wood flour, fish meal,
Animal and plant powders such as milk powder, talc, kaolin, bentonite, calcium carbonate, zeolite, diatomaceous earth, white carbon, clay, alumina, mineral powders such as sulfur powder, and the like, and the liquid carrier includes water, methyl alcohol, ethylene. Alcohols such as glycols, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane and tetrahydrofuran, kerosene,
Kerosene and other aliphatic hydrocarbons, xylene, trimethylbenzene, tetramethylbenzene, cyclohexane, solvent naphtha and other aromatic hydrocarbons, chloroform,
Halogenated hydrocarbons such as chlorobenzene, acid amides such as dimethylformamide, ethyl acetate,
Examples thereof include esters such as glycerin esters of fatty acids, nitriles such as acetonitrile, and sulfur-containing compounds such as dimethyl sulfoxide.

In addition, if necessary, other pesticides, such as insecticides, acaricides, nematicides, fungicides, antiviral agents, attractants, herbicides, plant growth regulators, etc., can be mixed and used in combination,
In this case, a more excellent effect may be exhibited.

For example, as an insecticide, acaricide, or nematicide,
O- (4-bromo-2-chlorophenyl) O-ethyl
S-propyl phosphorothioate, 2,2-dichlorovinyl dimethyl phosphate, ethyl 3-methyl-
4- (methylthio) phenyl isopropyl phosphoramidate, O, O-dimethyl O-4-nitro-n-tolyl phosphorothioate, O-ethyl O-4-nitrophenyl phenylphosphonothioate, O, O-diethyl O-2 -Isopropyl-6-methylpyrimidin-4-yl phosphorothioate, O, O-dimethyl
Such as O- (3,5,6-trichloro-2-pyridyl) phosphorothioate, O, S-dimethyl acetylphosphoramidothioate, O- (2,4-dichlorophenyl) O-ethyl S-propyl phosphorodithioate. Organic phosphate compounds; 1-naphthyl methyl carbamate, 2-isopropoxyphenyl methyl carbamate, 2-methyl-2- (methylthio) propionaldehyde O-methylcarbamoyl oxime, 2,3-
Dihydro-2,2-dimethylbenzofuran-7-yl
Methyl carbamate, dimethyl N, N '-[thiobis [(methylimino) carbonyloxy]] bisethaneimidothioate, S-methyl-N- (methylcarbamoyloxy) thioacetimidate, N, N-dimethyl-
2-methylcarbamoyloxyimino-2- (methylthio) acetamide, 2- (ethylthiomethyl) phenyl methylcarbamate, 2-dimethylamino-5,6-dimethylpyrimidin-4-yl-dimethylcarbamate,
Carbamate compounds such as S, S′-2-dimethylaminotrimethylene bis (thiocarbamate); 2,2,2-
Organochlorine compounds such as trichloro-1,1-bis (4-chlorophenyl) ethanol and 4-chlorophenyl 2,4,5-trichlorophenylsulfone; organometallic compounds such as tricyclohexyltin hydroxide;
(RS) -α-Cyano-3-phenoxybenzyl (RS) -2
-(4-chlorophenyl) 3-methylbutyrate, 3-
Phenoxybenzyl (1RS) -cis, trans-3- (2,2
-Dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate, (RS) -α-cyano-3-phenoxybenzyl (1RS) -cis, trans-3- (2,2-dichlorovinyl) -2,2- Dimethylcyclopropanecarboxylate, (S) -α-cyano-3-phenoxybenzyl
(1R) -cis-3- (2,2-dibromovinyl) -2,2-dimethylcyclopropanecarboxylate, (RS) -α-cyano-3-phenoxybenzyl (1RS) -cis, trans-3- ( Pyrethroid compounds such as 2-chloro-3,3,3-trifluoropropenyl) -2,2-dimethylcyclopropanecarboxylate; 1- (4-chlorophenyl) -3- (2,6-difluorobenzoyl) urea ,
1- [3,5-dichloro-4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenyl] -3-
Benzoylurea compounds such as (2,6-difluorobenzoyl) urea and 1- (3,5-dichloro-2,4-difluorophenyl) -3- (2,6-difluorobenzoyl) urea; 2-tert- Butylimino-3-isopropyl-
5-phenyl-3,4,5,6-tetrahydro-2H-1,3,5-
Thiadiazin-4-one, trans-S- (4-chlorophenyl) -N-cyclohexyl-4-methyl-2-oxothiazolidinone-3-carboxamide, N-methylbis (2,4-xylyliminomethyl) amine Compounds such as isopropyl (2E, 4E) -11-methoxy-3,7,1
Juvenile hormone-like compounds such as 1-trimethyl-2,4-dodecadienoate; other compounds include dinitro compounds, organic sulfur compounds, urea compounds, triazine compounds and the like. Further, they can be mixed and used in combination with microbial agents such as BT agents and insect pathogenic virus agents.

For example, germicides include S-benzyl O, O-diisopropyl phosphorothioate, O-ethyl S, S-
Organophosphorus compounds such as diphenyl phosphorodithioate and aluminum ethyl hydrogen phosphonate; Organochlorine compounds such as 4,5,6,7-tetrachlorophthalide and tetrachloroisophthalonitrile; Manganese ethylenebis (dithio Carbamate) polymer,
Zinc ethylene bis (dithiocarbamate) polymer, zinc and manneb complex compound, dizinc bis (dimethyldithiocarbamate) ethylene bis (dithiocarbamate), zinc propylene bis (dithiocarbamate) polymer dithiocarbamate compound; 3
a, 4,7,7a-tetrahydro-N- (trichloromethanesulfenyl) phthalimide, 3a, 4,7,7a-tetrahydro-
N-halogenothioalkyl compounds such as N- (1,1,2,2-tetrachloroethanesulfenyl) phthalimide and N- (trichloromethylsulfenyl) phthalimide; 3- (3,5-dichlorophenyl) -N- Isopropyl-2,4-dioxoimidazolidine-1-carboxamide, (RS) -3- (3,5-dichlorophenyl) -5-methyl-5-vinyl-1,3-oxazolidine-2,4-dione, Dicarboximide compounds such as N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide; methyl 1- (butylcarbamoyl) benzimidazol-2-yl carbamate, dimethyl Benzimidazole compounds such as 4,4 '-(O-phenylene) bis (3-thioallophanate);
1- (4-chlorophenoxy) -3,3-dimethyl-1-
(1H-1,2,4-triazol-1-yl) butanone,
1- (biphenyl-4-yloxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) butan-2-ol, 1- [N- (4-chloro-2 -Trifluoromethylphenyl) -2-propoxyacetimidoyl] imidazole, 1- [2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-ylmethyl] -1H-1,2, 4-triazole, 1- [2- (2,4
-Dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl] -1H-1,2,4-triazole, 1- [2- (2,4-dichlorophenyl) pentyl]
Azole compounds such as -1H-1,2,4-triazole; 2,4'-dichloro-α- (pyrimidin-5-yl)
Carbinol compounds such as benzhydryl alcohol, (±) -2,4'-difluoro-α- (1H-1,2,4-triazol-1-ylmethyl) benzhydryl alcohol; 3'3'- Benzanilide systems such as isopropoxy-O-toluanilide, α, α, α-trifluoro-3′-isopropoxy-O-toluanilide; methyl N- (2-methoxyacetyl) -N- (2,6-xylyl) An acylalanine-based compound such as -DL-alaninate; 3-chloro-N- (3-chloro-2,6-dinitro-4-α, α, α-trifluorotolyl) -5-trifluoromethyl-2- Pyridinamine compounds such as pyridinamine; other compounds such as piperazine compounds, morpholine compounds, anthraquinone compounds, quinoxaline compounds, crotonic acid compounds, Rufen acid compounds, urea compounds, and the like antibiotics.

The insecticidal, acaricidal, and nematicidal agents of the present invention are effective for controlling various harmful insects, harmful mites, and harmful nematodes, and the application is generally 1 to 20000 ppm, preferably 20 to 2000 ppm of the active ingredient concentration. To do. The concentrations of these active ingredients can be appropriately changed depending on the form of the preparation, the method of application, the purpose, the time, the place, the state of occurrence of harmful insects and the like. For example, in the case of aquatic pests, it can be controlled even by spraying a drug solution having the above-mentioned concentration range to the place of occurrence, and therefore the active ingredient concentration range in water is below the above. The amount applied per unit area is about 0.1 to 5000 g, preferably 10 to 1000 g as the active ingredient compound per 10 a. However, it is possible to deviate from these ranges in special cases.

The application of various preparations containing the compound of the present invention, or a dilution thereof, is a generally applied application method, that is, spraying (for example, spraying, spraying, misting, atomizing, granulating, water surface application, etc.) Soil It can be carried out by application (mixing, irrigation, etc.), surface application (application, dressing, coating, etc.), immersion bait, etc. It is also possible to feed livestock by mixing the above-mentioned active ingredient with feed to control the development and growth of harmful insects, especially harmful insects, in the excrement. It can also be applied by the so-called ultra low volume application method. In this way it is possible to contain 100% of the active ingredient.

Test Example 1. Acarid mite killing test Each formulation of active ingredient compounds No. 1 to 8 was dispersed in water and adjusted to a concentration of 800 ppm. A cup (diameter 7 cm, height 4 c) that leaves only one primary leaf of kidney bean
m) and were inoculated with about 30 larvae of N. spp. This was immersed in the above-mentioned chemical solution having a predetermined concentration for about 10 seconds, air-dried, and then left in a 26 ° C. illuminated thermostat. On the second day after the treatment, life or death was judged, and the mortality was calculated by the following calculation, and it was 100% for all the compounds.

Test example 2. Diamondback moth insecticidal test Each of the active ingredient compounds NO. 1 to 4 and 6 to 8 was dispersed in water to prepare a drug solution adjusted to a concentration of 200 ppm,
The leaf pieces of cabbage were soaked for about 10 seconds and air dried. Diameter 9
A cm petri dish was lined with moist filter paper and air-dried leaf pieces placed on it. Two to three instar larvae of Plutella xylostella were released there, covered with a lid, and allowed to stand in a 26 ° C illuminated thermostat. On the second day after the release of the insects, life or death was determined, and the mortality rate was calculated by the following formula, and the results shown in Table 1 were obtained.

Test example 3. Hasmonyoto test 2 for active ingredient compounds NO. 1-3 and 6-8
Tests were carried out in the same manner as in the above-mentioned Test Example 2 except that the 2nd to 3rd order diamondback moth was replaced with the 2nd to 3rd order Lotus japonicus, and the active ingredient concentration of 200ppm was changed to 800ppm and 200ppm. It was

Test example 4. Namihadani egg-killing test The leaves of the kidney bean, which had only one primary leaf left, were transplanted into a cup, and adults of the Namihadani mite were inoculated into the cup. The eggs were laid for 24 hours to remove the adults. Then, the active ingredient compound N
The formulation of O.2 was dispersed in water, and the kidney bean was soaked in a drug solution adjusted to a concentration of 800 ppm for about 10 seconds, air-dried, and then left in a 26 ° C. illuminated thermostat. After 5 days from the treatment, the hatching condition of the eggs was investigated and the ovicidal rate was calculated by the following formula, and it was 100%.

Test example 5. Black-necked planthopper insecticidal test Each formulation of active ingredient compounds NO.2 and 8 is dispersed in water, and rice seedlings are dipped in a chemical solution adjusted to an active ingredient concentration of 800 ppm and 200 ppm for about 10 seconds, air-dried, and then moistened absorbent cotton. The root part was wrapped with and put in a test tube. Then, 10 adult brown planthoppers were released into this, the tube mouth was capped with gauze, and left in a 26 ° C. illuminated incubator.
On the 2nd day after the release of the insects, life or death was determined, and the mortality rate was determined in the same manner as in Test Example 2, and the results shown in Table 3 were obtained.

Test example 6. Sweetpotato Nematode nematode nematode test Sweetpotato Nematode nematode contaminated soil was packed in 1/14000 are pots and the active ingredient compounds No. 1-3 and 6-8 were 2
The drug solution adjusted to be 50 g / a was irrigated. On the second day after the treatment, all layers of the treated soil were mixed and tomato seedlings at the 3-4 leaf stage were transplanted. After 20 days from the treatment with the chemical solution, the degree of cat globule colonization was investigated and the results shown in Table 4 were obtained. The degree of Necob engraftment complied with the following criteria.

Test Example 7. Green peach aphid insecticidal test Each formulation of active ingredient compounds NO. 1 to 4 and 6 to 8 was dispersed in water, and cabbage leaf pieces were immersed in a drug solution adjusted to a predetermined concentration for about 10 seconds and air dried. A wet filter paper was laid on a Petri dish with a diameter of 9 cm, and air-dried leaf pieces were placed on it. The peach peach aphid, a non-progressive female nymph, is released there,
The lid was closed and left in a 26 ° C. illuminated incubator. On the second day after the release of the insects, life or death was determined, and the mortality rate was calculated in the same manner as in the case of Test Example 2, and the results shown in Table 5 were obtained.

Test Example 8. Resistant Acarid Acaricide Test Each formulation of active ingredient compounds NO. 2 and 5 to 8 was dispersed in water and adjusted to a predetermined concentration. The leaves of only one initial leaf of common bean were transplanted into a cup (diameter: 7 cm, height: 4 cm) and inoculated with about 30 larvae of Dicofol- and organophosphorus-resistant fleshworm mites. This was immersed in the chemical solution adjusted to the above predetermined concentration for about 10 seconds, air-dried, and then left in a 26 ° C. illuminated thermostat. 2 after release
On the day, life and death were judged, and the mortality rate was obtained in the same manner as in the case of Test Example 1, and the results in Table 6 were obtained.

Test Example 9. Resistance mitid mites migration test Each formulation of active ingredient compounds NO. 1, 2 and 8 was dispersed in water and adjusted to a concentration of 800 ppm. Seedlings of two primary leaves of common bean were transplanted to a cup (diameter 7 cm, height 4 cm), and 10 ml of the chemical solution adjusted to the predetermined concentration was soil-irrigated. Two days after the treatment, the leaves were inoculated with about 30 larvae of Dicofol- and organophosphorus drug-resistant worms, 2
It was left to stand in a 6 ° C. illuminated thermostat. On the second day after the release of the insects, the life or death was determined, and the mortality rate was obtained in the same manner as in the case of Test Example 1, and the results shown in Table 7 were obtained.

Next, formulation examples of the compound of the present invention are described below.

Formulation Example 1. (B) Compound No. 1 20 parts by weight (b) N, N-dimethylformamide 72 parts by weight (c) Polyoxyethylene alkylphenyl ether 8 parts by weight The above ingredients were uniformly mixed and dissolved to obtain an emulsion.

Formulation example 2. (A) Compound NO.2 50 parts by weight (b) Tetramethylbenzene 38 parts by weight (c) Mixed emulsifier of alkylbenzene sulfonate, polyoxyethylene alkylphenol ether and polyoxyethylene phenylphenol ether (trade name Agrisol p-311 Kao Soap Co., Ltd.) 12 parts by weight or more The above ingredients were uniformly mixed and dissolved to obtain an emulsion.

Formulation example 3. (B) Compound No. 3 85 parts by weight (b) 15 parts by weight or more of the mixed emulsifier used in Preparation Example 2 The above ingredients were uniformly mixed to obtain a high-concentration emulsion.

Formulation example 4. (A) 5 parts by weight of compound No. 8 (b) 95 parts by weight of talc The above ingredients were uniformly mixed to obtain a powder.

Formulation example 5. (B) Compound No. 1 5 parts by weight (b) Bentonite 45 parts by weight (c) Kaolin 50 parts by weight The above components were kneaded with a small amount of water, extruded into granules, and dried to give granules.

Formulation example 6. (A) Compound NO.8 0.50 part by weight (b) Polyoxyethylene octylphenyl ether 0.15 part by weight (c) Polyoxyethylene phosphate ester 0.10 part by weight (d) Granular calcium carbonate 99.25 parts by weight (b)-(c) Was uniformly mixed in advance, diluted with an appropriate amount of acetone, and then sprayed on (d) to remove acetone to obtain a granule.

Formulation Example 7. (B) Compound NO.4 50 parts by weight (b) Fine silica 15 parts by weight (c) Fine clay 25 parts by weight (d) Naphthalene sulfonic acid sodium formalin condensate 2 parts by weight (e) Dialkylsulfosuccinate 3 parts by weight ( F) Polyoxyethylene alkylallyl ether sulfate 5 parts by weight or more The above ingredients were uniformly mixed and pulverized to obtain a wettable powder.

Formulation Example 8. (A) Compound No. 6 5 parts by weight (b) Glycerin 5 parts by weight (c) Powdered milk 3 parts by weight (d) Fish meal 87 parts by weight The above ingredients were kneaded uniformly to form a paste.

Formulation Example 9. (A) Compound No. 7 10 parts by weight (b) Polyoxyethylene octyl phenyl ether 3 parts by weight (c) Kerosene 87 parts by weight The above components are uniformly mixed and dissolved to obtain a spray agent sprayed with compressed air. .

 ─────────────────────────────────────────────────── ─── Continuation of front page Examiner Tetsuo Tsukanaka (56) References JP-A-60-136590 (JP, A)

Claims (3)

[Claims] 1. A general formula: [In the formula, X ₁ and Y ₁ are a hydrogen atom or an alkyl group, and X ₂ and Y ₂ are a hydrogen atom, a cyano group, or —CH ₂ Q.
(Q is a phenylsulfinyl group, an alkylsulfonyloxy group, an alkylcarbonylmethylthio group, a dialkylamino group, an alkoxycarbonyloxy group or a dialkoxydithiophosphonomethyl group), and Z ₁ is an oxygen atom or a sulfur atom. , Z ₂ is an oxygen atom,
R ₁ and R ₂ are alkyl groups, and one of X ₂ and Y ₂ is a cyano group or a —CH ₂ Q group]. 2. A general formula: [In the formula, X ₁ and Y ₁ are a hydrogen atom or an alkyl group, and X ₂ and Y ₂ are a hydrogen atom, a cyano group, or —CH ₂ Q.
(Q is a phenylsulfinyl group, an alkylsulfonyloxy group, an alkylcarbonylmethylthio group, a dialkylamino group, an alkoxycarbonyloxy group or a dialkoxydithiophosphonomethyl group), and Z ₁ is an oxygen atom or a sulfur atom. , Z ₂ is an oxygen atom,
R ₁ and R ₂ are alkyl groups, and one of X ₂ and Y ₂ is a cyano group or a —CH ₂ Q group], and at least one organic phosphorus compound represented by the formula is contained as an active ingredient. Let's say insecticide, acaricide, nematicide. 3. A general formula: [In the formula, X ₁ and Y ₁ are a hydrogen atom or an alkyl group, and X ₂ and Y ₂ are a hydrogen atom, a cyano group, or —CH ₂ Q.
(Q is a phenylsulfinyl group, an alkylsulfonyloxy group, an alkylcarbonylmethylthio group, a dialkylamino group, an alkoxycarbonyloxy group or a dialkoxydithiophosphonomethyl group), and Z ₁ is an oxygen atom or a sulfur atom. , Z ₂ is an oxygen atom,
One of X ₂ and Y ₂ is a cyano group or a —CH ₂ Q group], and a compound represented by the general formula: [Wherein R ₁ and R ₂ are alkyl groups] is reacted with a phosphodiester chloride compound to give a compound of the general formula: [Wherein X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , Z ₂ , R ₁ and R ₂ are as described above] to produce an organophosphorus compound, A method for producing an organic phosphorus compound.