JPH068309B2 - Organophosphorus compounds and insecticides, acaricides and nematicides 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 is a methyl group, X ₂ is a 2,4-dichlorophenyl, 4-methoxyphenyl or thienyl group, Y is a sulfur atom, Z is an oxygen atom, R ₁ and R ₂ Is an alkyl group] The compound of the present invention can be produced, for example, by the following method.

(In the formula, X ₁ , X ₂ , Y, Z, R ₁ and R ₂ are as described above.) The reaction is usually carried out in a temperature range of −100 to 50 ° C., preferably −80 ° C. to 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 and 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, acrylonitrile, etc .: Aprotic polar solvents such as dimethylformamide, dimethylsulfoxide, sulfolane, hexamethylphosphoric triamide, etc.

Among the starting materials represented by the general formula (II), substituted thiazolidin-2-one is described in, for example, JP-A-57-1751.
80, JP-A-58-29775 or JP-A-58-297.
And the substituted oxazolidin-2-ones are easily obtained by the method described in Chemical Review, 67.
Volume, p. 197 (1967).

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

Synthesis example 1. O-ethyl Sn-propyl [4-methyl-5- (2,4-dichlorophenyl) -2-oxo-3-
Synthesis of thiazolidinyl] phosphonothiolates.

After dissolving 0.89 g of 4-methyl-5- (2,4-dichlorophenyl) -thiazolidin-2-one in 10 m of tetrahydrofuran, the mixture was cooled to -78 ° C and n-butyllithium n was added.
-Hexane solution 2.8 m (1.55 mol concentration) was gradually added dropwise, and the mixture was stirred at the same temperature for 15 minutes. Next, O-ethyl S-
A tetrahydrofuran solution (5 m) containing 1.03 g of n-propylthiophosphoric acid chloride was gradually added dropwise, and then the liquid temperature was gradually returned to room temperature and reacted for 2 hours. After completion of the reaction, the reaction solution was poured into ice water and extracted with ethyl acetate. The extract layer is dried over anhydrous sodium sulfate, the solvent is distilled off under reduced pressure,
The residue is purified by silica gel chromatography, melting point
101-103 ° C. O-ethyl Sn-propyl [4-methyl-5- (2,4-dichlorophenyl) -2-oxy-3
1.0 g of -thiazolidinyl] phosphonothiolate was obtained.

Examples of specific compounds of the present invention are given below.

Compound NO.1. O-ethyl Sn-propyl [4-methyl-5- (2,4-dichlorophenyl) -2-oxo-
3-thiazolidinyl] phosphonothiolate
Melting point 101-103 ° C. Compound NO.2. O-ethyl Sn-propyl [4-methyl-5- (4-methoxyphenyl) -2-oxo-3
-Thiazolidinyl] phosphonothiolate Melting point 128-132 ° C Compound NO.3. O-ethyl Sn-propyl [4-methyl-5- (thienyl-2) -2-oxo-3-thiazolidinyl] phosphonothiolate ▲ n ²⁶ _D ▼ = 1.5238 The compound of the present invention exhibits excellent activity as an active ingredient of insecticides, acaricides and nematicides, as will be seen in the test examples below. For example, phytoparasitic mites such as scab spider mite, moss spider mite, citrus spider mite, etc., diamondback moth, weevil, Lotus japonicum, codling moth, ball worm (no Japanese name),
Tobacco bat worm (no Japanese name), gypsy moth, Colorado potato beetle, Boleweville (no Japanese name), aphids, planthoppers, leafhoppers, scale insects, stink bugs, whitefly, thrips, grasshoppers, leaf flies, Agricultural pests such as chafers, Tamanaaga, Kaburagaiga, house dust mites, cockroaches, house flies,
Sanitary pests such as Culex pipiens, storage grain pests such as adzuki bean weevils and cornworms, clothing such as squid, scabbard beetles, termites, house pests, and fleas and lice that parasitize humans and livestock. , Is also effective against flies and the like, and further, root-knot nematodes, cyst nematodes, nebulae nematodes, rice garle nematodes, strawberry nematodes,
It is also effective against plant parasitic nematodes such as pine wood nematodes. It is also effective against harmful insects such as dicofol and organophosphorus agent-resistant plant parasitic mites, organophosphorus agent-resistant aphids, and houseflies. Furthermore, since the compound of the present invention has an excellent osmotic migration property, by treating the compound of the present invention in soil, soil pests and nematodes can be simultaneously controlled, and at the same time, pests of foliage can be controlled. be able to.

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.

Further, if necessary, it can be mixed and used in combination with other pesticides such as insecticides, acaricides, nematicides, fungicides, antiviral agents, attractants, herbicides, and plant growth regulators. ,
In this case, it may exhibit a further superior effect.

For example, as an insecticide, acaricide, or nematicide, O- (4-bromo-2-chlorophenyl) O-ethyl can be used.
S-propyl phosphorothioate, dimethyl 2,2-dichlorovinyl phosphate, ethyl-3-methyl-4-
(Methylthio) phenyl (isopropyl) phosphoramidate, O, O-diethyl O- (4-nitro-m-tolyl) phosphorothioate, O-ethyl O-4-nitrophenyl phenylphosphonothioate, O, O-dimethyl O -(2-isopropyl-6-methyl-
Pyrimidin-4-yl) phosphorothioate, O, O-dimethyl O- (3,5,6-trichloro-2-pyridyl) phosphorothioate, O, S-dimethyl acetylphosphoramidothioate, O- (2,4-dichlorophenyl ) O-ethyl S-propyl phosphorodithioate, organic phosphoric acid ester compounds such as, 1-naphthyl methyl carbamate, 2- (1-isopropoxy) phenyl methyl carbamate, 2-methyl-2- (methylthio) propion Aldehyde O- (methylcarbamoyl) oxime, 2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate, bis [{N- (1-methylthio) ethylideneaminooxycarbonyl} -N-methylamino] sulfide , S-methyl N-[(methylcarbamoyl) oxy] thio Setoimideto, N, N-dimethyl-2-methylcarbamoyl-oximino-2- (methylthio) acetamide, 2 - [(ethylthio) methyl] phenyl methylcarbamate, 2-dimethylamino-5,6-dimethyl-4-
Ile-dimethyl carbamate, carbamate-based compound such as 2,2,2-trichloro-1,1-bis (4-chlorophenyl)
Organochlorine compounds such as ethanol, 4-chlorophenyl-2,4,5-trichlorophenyl sulfone, organometallic compounds such as tricyclohexyl hydroxide, α-cyano-3-phenoxybenzyl 2- (4- Chlorophenyl) -3-methylbutyrate, 3-phenoxybenzyl (+ or-) cis trans-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropane carboxylate, (±) α-cyano-3 -Phenoxybenzyl (±) cis / trans 3- (2,2-dichlorovinyl)-
2,2-Dimethylcyclopropane carboxylate, (S) -α-cyano-m-phenoxybenzyl (1R, 3
R) -3- (2,2-Dibromonovinyl) -2,2-dimethylcyclopropane carboxylate, (RS) -α-cyano-3-phenoxybenzyl (IR
S) -cis-3- (2-chloro-3,3,3-trifluoropropenyl) -2,2-dimethylcyclopropane carboxylate, a pyrethroid compound such as 1- (4-chlorophenyl) -3- (2,6-Difluorobenzoyl) urea, 1- (3,5-dichloro-4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenyl) -3-
(2,6-Difluorobenzoyl) urea, 1- (3,5-dichloro-2,4-difluorophenyl) -3
-(2,6-difluorobenzoyl) urea, benzoylurea-based compounds such as, 2-tert-butylimino-3-isopropyl-5
-Phenyl-3,4,5,6-tetrahydro-2H-1,3,5-thiadiazin-4-one, 4-methyl-5- (4-chlorophenyl) -3-cyclohexyl-carbamoyl-2-thiazolidone, N -Methylbis (2,4-xylyliminomethyl) amine, a compound such as: isopropyl (2E, 4E) -11-methoxy-3,7,11-
Juvenile hormone-like compounds such as trimethyl-2,4-dodecadienoate, and other compounds include dinitro compounds, organic sulfur compounds, urea compounds, triazine compounds and the like. Furthermore, they can be mixed and used in combination with biological pesticides such as BT agents.

For example, as a bactericide, organophosphorus compounds such as S-benzyl O, O diisopropyl phosphorothiolate, O ethyl S, S-diphenyl phosphorodithioate, aluminum ethyl hydrogenphosphonate, 4, 5, 6, Organochlorine compounds such as 7-tetrachlorophthalide, tetrachloroisophthalonitrile; Manganese ethylene bis (dithiocarbamate), zinc ethylene bis (dithiocarbamate), complex compound of zinc and manneb, dizinc bis (dimethyldithiocarbamate) ) Ethylene bis (dithiocarbamate), propylene bis (dithiocarbamate) zinc polymer, N- (trichloromethylthio) cyclohexene-1,2-dicarboximide, N-
N-halogenothioalkyl compounds such as (1,1,2,2-tetrachloroethylthio) -4-cyclohexene-1,2-dicarboximide and N- (trichloromethylthio) phthalimide; 3- (3,5- Dichlorophenyl) -N-
Isopropyl-2,4-dioxoimidazolidine-1-carboxamide, 3- (3,5-dichlorophenyl) -5-
Methyl-5-vinyloxazolidine-2,4-dione, N
A dicarboximide-based compound such as-(3,5-dichlorophenyl) -1,2-dimethyl-cyclopropane-1,2-dicarboximide; methyl 1- (butylcarbamoyl)-
2-benzimidazole carbamate, dimethyl 4,
Benzimidazole compounds such as 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- (1
H-1,2,4-triazol-1-yl) butan-2-ol, 1- [N- (4-chloro-2-trifluoromethylphenyl) -2-propoxyacetimidoyl] imidazole, (±) -1- [2,4-dichlorophenyl)-
4-Ethyl-1,3-dioxolan-2-ylmethyl]-
1H-1,2,4-triazole, 1- [2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolane-2
-Ylmethyl] -1H-1,2,4-triazole, 1-
[2- (2,4-dichlorophenyl) pentyl] -1H-
Azole compounds such as 1,2,4-triazole;
(±) -2,4'-Dichloro-α- (pyrimidin-5-yl) benzhydryl alcohol, (±) -2,4'-difluoro-α- (1H-1,2,4-triazole-1 Carbinol-based compounds such as -ylmethyl) benzhydryl alcohol; benzanilide-based compounds such as 3'-isopropoxy-2-methylbenzanilide, 3'-isopropoxy α, α, α-trifluoro-O-toluanilide Methyl N- (2-methoxyacetyl) -N- (2,6
-Xylyl) -DL-alaninate, dimethyl-N-acylanilide compound, 3-chloro-N- (3-chloro-2,6-dinitro-4-α, α, α-trifluorotolyl) 5-trifluoro Aniline compounds such as methyl-2-pyridinamine, and other compounds Compounds Piperazine compounds; Morpholine compounds; Anthraquinone compounds; Quinoxaline compounds; Crotonic acid compounds; Sulfenic acid compounds; Urea compounds; Antibiotics Examples include substances.

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 20,000 ppm, preferably 20 to 2,000 ppm. Perform at the component concentrations. 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 5,000 g, preferably 10 to 1,000, as the active ingredient compound per 10 a.
g is used. However, it is possible to deviate from these ranges in special cases.

Application of various formulations 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, granulation, water surface application, etc.), It can be carried out by soil 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. Each formulation of active ingredient compounds No. 1 to 3 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 adult larvae of Nicaria spp. Apply this to a drug solution adjusted to the prescribed concentration.
It was soaked for 10 seconds, air-dried, and then left in a 26 ° C. illuminated constant temperature chamber. On the second day after the release of the insects, the life or death was judged, and the mortality rate was calculated by the following formula, and it was 100% in all of the active ingredient compounds NO.

Test Example 2. The active ingredient compounds NO. 1 and 3 were dispersed in water, and cabbage leaf pieces were dipped in a drug solution adjusted to a concentration of 800 ppm for 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. 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, the life and death was determined, and the mortality rate was determined in the same manner as in Test Example 1 above.
The mortality of active ingredient compounds NO. 1 and 3 was 100%.

Test Example 3. Rice seedlings were immersed in a chemical solution adjusted to a concentration of 800 ppm for the active ingredient compound NO.3 for 10 seconds, air-dried, and the roots were wrapped with absorbent cotton and placed in a test tube. Next, ten adult brown planthoppers were released into the plant, and the tube mouth was covered with a case. Two days later, the life and death of the insects was examined, and the mortality rate was calculated in the same manner as in Test Example 1. The result was 100%.

Test Example 4. Sweetpotato rootworm nematode-contaminated soil was packed in 1 / 5,000 R pots and 250 g of active ingredient compounds NO.2 and NO.3
A predetermined amount of each drug solution adjusted to be / a was irrigated. Two days after the treatment with the chemical solution, the treated soil was mixed in all layers, and tomato seedlings in the 3 to 4 medicinal period were transplanted. Twenty days after the treatment with the chemical solution, the degree of growth of cats was investigated and the results shown in Table 1 were obtained.

The degree of Necob engraftment complied with the following criteria.

0 No cattle epidemic 1 〃 Small 2 〃 Medium 3 〃 Large 4 〃 Very large Test Example 5. A formulation of active ingredient compound No. 1 was sprayed on water to adjust the concentration to a predetermined level. What left only one primary leaf of common bean was transplanted into a cup (diameter 7 cm, height 4 cm), and this was inoculated with 30 larvae of the larvae mite which are resistant to dicofol and organophosphorus agents. This product was immersed in the drug solution adjusted to the above-mentioned predetermined concentration for 10 seconds, air-dried, and then left in a 26 ° C. illuminated thermostat. Two days after the release of the insects, life and death were determined, and the mortality rate was obtained in the same manner as in Test Example 1. The results shown in Table 2 were obtained.

Test Example 7. Active ingredient compound NO.2 formulation was dispersed in water to give 800ppm
The concentration was adjusted to. The leaves of only one primary leaf of kidney bean were transplanted into a cup (7 cm in diameter and 4 cm in height), and about 30 female adults of Dicofol and organophosphorus-resistant scabbard mites were inoculated into the cup. Place this in a 26 ° C illuminated thermostat
It was left for 24 hours to lay eggs. After removing this female imago,
It was immersed in the chemical solution adjusted to the predetermined concentration for about 10 seconds, air-dried, and then left in the thermostat. On the 5th day after the treatment, the viability of eggs and hatched larvae was determined, and the ovicidal / larvicidal rate was calculated by the following formula, and the results shown in Table 3 were obtained.

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

Formulation Example 1. (a) Compound NO.2 50 parts by weight (b) Tetramethylbenzene 38 〃 (c) Mixed emulsifier of alkylbenzene sulfonate, polyoxyethylene alkylphenol ether and polyoxyethylene phenylphenol ether (trade name Agrisol p -311, manufactured by Kao Soap Co., Ltd. 12 parts by weight or more The above ingredients were uniformly mixed and dissolved to obtain an emulsion.

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

Formulation Example 3. (a) Compound No. 2 5 parts by weight (b) Talc 95 parts by weight The above ingredients were uniformly mixed to obtain a powder.

Formulation Example 4. (b) Compound NO.3 0.05 parts by weight (b) Polyoxyethylene octyl phenyl ether 0.15 parts by weight (c) Polyoxyethylene phosphate ester 0.10 parts by weight (d) Granular calcium carbonate 99.25 parts by weight (b) ~ (C) were previously uniformly mixed, diluted with an appropriate amount of acetone, and then sprayed on (D) to remove acetone to obtain granules.

Formulation Example 5. (b) Compound NO.3 50 parts by weight (b) Fine silica 15 parts by weight (c) Fine clay 25 parts by weight (d) Sodium formalin condensate naphthalenesulfonate 2 parts by weight (e) Dialkylsulfosuccinate 3 parts by weight (f) Polyoxyethylene alkylallyl ether sulfate 5 parts by weight Formulation Example 6. (a) Compound NO.1 5 parts by weight (b) Glycerin 5 parts by weight (c) Milk powder 3 parts by weight (d) Fish meal 87 parts by weight The above parts were uniformly kneaded to obtain a paste.

Formulation Example 7. (a) Compound NO.2 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, and sprayed with compressed air. It was used as a spray.

Continuation of front page Examiner Tetsuo Tsukanaka (56) References JP-A-60-104096 (JP, A)

Claims (3)

[Claims] 1. A general formula: [In the formula, X ₁ is a methyl group, X ₂ is a 2,4-dichlorophenyl, 4-methoxyphenyl or thienyl group, Y is a sulfur atom, Z is an oxygen atom, R ₁ and R ₂ Is an alkyl group]. 2. A general formula: [In the formula, X ₁ is a methyl group, X ₂ is a 2,4-dichlorophenyl, 4-methoxyphenyl or thienyl group, Y is a sulfur atom, Z is an oxygen atom, R ₁ and R ₂ Is an alkyl group]. An insecticide, acaricide, or nematicide, which comprises at least one organic phosphorus compound represented by the formula [1] as an active ingredient. 3. A general formula: [Wherein X ₁ is a methyl group, X ₂ is a 2,4-dichlorophenyl, 4-methoxyphenyl or thienyl group, and Y is a sulfur atom], and a compound represented by the general formula: [Wherein, Z is an oxygen atom, and R ₁ and R ₂ are alkyl groups] and reacted with a phosphodiester chloride compound to give a compound represented by the general formula: [Wherein X ₁ , X ₂ , Y, Z, R ₁ and R ₂ are as described above], and a method for producing an organophosphorus compound, comprising producing the organophosphorus compound .