JPH066600B2 - 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): [Wherein, X ₁ and X ₂ are a hydrogen atom or an alkyl group, Y ₁ and Y ₂ are a hydrogen atom, and Z ₁ , Z ₂ and Z are
₃ is an oxygen atom, and R ₁ and R ₂ are alkyl groups.] In the general formula (I), the alkyl group represented by X ₁ , X ₂ , R ₁ and R ₂ is a methyl group, an ethyl group, Examples thereof include n-propyl group, iso-propyl group, n-butyl group, iso-butyl group and sec-butyl group.

The compounds of the present invention have 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 , Z ₃ R
₁ and R ₂ are as described above] Both of the reactions are usually −100 to 50 ° C., preferably −100 ° C.
It is carried out in the temperature range of 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, 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), the substituted oxazolidin-2-one (thione) is easily obtained by a ring-forming reaction between a substituted β-amino alcohol and urea or thiophosgene, and a substituted thiazolidine-2 -Thion is easily obtained by a ring-forming reaction between a substituted β-amino alcohol sulfate and carbon disulfide, and further substituted thiazolidin-2-one is (1) a ring-forming reaction between a substituted β-aminomercaptan and urea. , (2) substituted thiazolidine-2-
It can be easily obtained by oxidation reaction of thione, (3) ring-forming reaction of substituted β-aminoalcohol sulfate and carbonyl sulfide, and the like.

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

Synthesis Example Synthesis of S-sec-butyl Sn-propyl (2-oxo-3-oxazolidinyl) phosphonodithiolate.

[1] 5.0 g of 2-oxazolidinone was dissolved in 100 ml of tetrahydrofuran and cooled to -78 ° C. There n
-Butyllithium in hexane (1.55 molar) 36.8
ml was added dropwise over 10 minutes, followed by stirring at the same temperature for 15 minutes. Next, 13.1 g of sec-butyl phosphorodichloride thiolate was added dropwise over 10 minutes, the temperature was gradually returned to room temperature and the mixture was stirred for 10 minutes, and S- (sec-butyl 2-
Oxo-3-oxazolidinyl) phosphonochloride thiolate was synthesized.

[2] The reaction product obtained in the above step [1] was cooled to −78 ° C., and a solution of 6.2 ml of n-propylmercaptan and 6.9 g of triethylamine dissolved in 10 ml of tetrahydrofuran was added dropwise over 10 minutes while stirring.

After completion of the dropping, the temperature was returned to room temperature and stirred for 2 hours, then tetrahydrofuran was distilled off under reduced pressure, ethyl acetate was added to the residue, washed with saturated brine and dried over anhydrous sodium sulfate, and ethyl acetate was distilled off under reduced pressure. I left. The obtained crude product was purified by silica gel chromatography to obtain a refractive index (▲
n ^30.0 _D ▼) is 1.5286 S-sec-butyl Sn
0.37 g of -propyl (2-oxo-3-oxazolidinyl) phosphonodithiolate was obtained.

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

Compound NO.1 S-methyl Sn-propyl (4,4
-Dimethyl-2-oxo-3-oxazolidinyl) phosphonodithiolate ▲ n ^17.4 _D ▼ = 1.5389 Compound NO.2 S-sec-butyl S-methyl (2-oxo-3-oxazolidinyl) phosphonodithiolate
▲ n ^24.8 _D ▼ = 1.5416 Compound NO.3 S-sec-butyl Sn-propyl (2
-Oxo-3-oxazolidinyl) phosphonodithiolate ▲ n ^30.0 _D ▼ = 1.5286 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 described 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),
Daba Kobat 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 ants, scarab beetles, Tamanagaga, Kaburagaga, house dust mites, cockroaches, house flies, sanitary pests such as Culex pipiens, storage pests such as Azuki bean weevils, Kokunusutomodoki, squid,
It is also effective against clothing such as scabbard beetles, termites, house pests, and other humans, fleas parasitic on livestock, lice, flies, and root-knot nematodes, cyst nematodes, It is also effective against plant parasitic nematodes such as Negusta nematodes, rice garlic nematodes, strawberry nematodes, and pine wood nematodes. Also, Dicofol
It is also effective against pests such as organophosphorus-resistant plant parasitic mites, organophosphorus-resistant aphids, and house flies. 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. It is also effective against molluscs belonging to pulmonary gastropods such as slugs and snails, which cause human discomfort and sometimes damage to agricultural crops, and crustaceans belonging to the isosceles such as pill bugs and woodworms. 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-m-
Tolyl phosphorothioate, O-ethyl O-4-nitrophenyl phenylphosphonothioate, O, O-
Diethyl O-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate, O, O-dimethyl O- (3,5,6-trichloro-2-pyridyl) phosphorothioate, O, S-dimethyl acetylphosphoramidothioate , O- (2,4-dichlorophenyl)
Organic phosphate compounds such as O-ethyl S-propyl phosphorodithioate: 1-naphthyl methyl carbamate, 2-isopropoxyphenyl methyl carbamate, 2-methyl-2- (methylthio) propionaldehyde O-methyl Carbamoyl oxime, 2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate, 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, S, S'-2-dimethylaminotrimethylenebis (thiocarbamate) Carbamate compounds such as: 2,2,2-trichloro-1,1-bis (4-
Chlorophenyl) ethanol, 4-chlorophenyl
Organochlorine compounds such as 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-dimethylcyclopropane Carboxylate, (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- (2-chloro-3,
Pyrethroid compounds such as 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- (2,6-difluorobenzoyl) urea, 1- (3,5-dichloro-
Benzoyl urea compounds such as 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-like compound: Isopropyl (2E, 4E)-
11-methoxy-3,7,11-trimethyl-2,4-
Juvenile hormone-like compounds such as 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: 4,5,6,7-Tetrachlorophthalide, organochlorine compounds such as tetrachloroisophthalonitrile: Manganese ethylene bis ( Dithiocarbamate)
Polymers of zinc, ethylene bis (dithiocarbamate), zinc and manneb complex compounds, dizinc bis (dimethyldithiocarbamate) ethylenebis (dithiocarbamate), zinc propylenebis (dithiocarbamate) Carbamate compound: 3a, 4,7,7a-tetrahydro-N-
(Trichloromethanesulfenyl) phthalimide, 3
a, 4,7,7a-tetrahydro-N- (1,1,2,
2-tetrachloroethanesulfenyl) phthalimide,
N-halogenothioalkyl compounds such as N- (trichloromethylsulfenyl) phthalimide: 3- (3,3
5-dichlorophenyl) -N-isopropyl-2,4-
Dioxoimidazolidine-1-carboxamide, (R
S) -3- (3,5-Dichlorophenyl) -5-methyl-5-vinyl-1,3-oxazolidine-2,4-dione, N- (3,5-dichlorophenyl) -1,2-dimethylcyclo Dicarboximide compounds such as propane-1,2-dicarboximide: methyl 1- (butylcarbamoyl) benzimidazol-2-yl carbamate, dimethyl 4,4 '-(O-phenylene) bis (3-thioallophanate ) Benzimidazole compounds such as: 1- (4-chlorophenoxy) -3,3-
Dimethyl-1- (1H-1,2,4-triazole-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-propoxyacetimidoii] 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-dioxolane-2
-Ylmethyl] -1H-1,2,4-triazole, 1
-[2- (2,4-dichlorophenyl) pentyl] -1
Azole compounds such as H-1,2,4-triazole: 2,4'-dichloro-α- (pyrimidin-5-yl) benzhydryl alcohol, (±) -2,4'-difluoro-α- (1H-1,2,4-triazole-1
A carbinol-based compound such as -ylmethyl) benzhydryl alcohol: 3 '. 3'-isopropoxy-O-
Benzanilide compounds such as toluanilide and α, α, α-trifluoro-3′-isopropoxy-O-toluanilide: methyl N- (2-methoxyacetyl) -N
Acyl alanine-based compound such as-(2,6-xylyl) -DL-alaninate: 3-chloro-N- (3-chloro-2,6-dinitro-4-α, α, α-trifluorotolyl)- Pyridinamine compounds such as 5-trifluoromethyl-2-pyridinamine: As other compounds, piperazine compounds, morpholine compounds, anthraquinone compounds, quinoxaline compounds, crotonic acid compounds, sulfenic acid compounds, urea compounds , Antibiotics, etc.

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, 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 a so-called ultra low volume small amount application method (ultra low volume). In this way it is possible to contain 100% of the active ingredient.

Test Example 1. Each formulation of the 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 larvae of N. spp. This was immersed in the chemical solution adjusted to the above predetermined concentration for about 10 seconds, air-dried, and then left in a constant temperature oven with lighting at 26 ° C. On the 2nd day after the release of the insects, it was judged whether they were live or dead, and the mortality rate was calculated by the following formula.
In all of the above, it was 100%.

Test example 2. Each formulation of the active ingredient compounds NO. 1 and 2 was dispersed in water, and cabbage leaf pieces were immersed in each chemical solution adjusted to a concentration of 800 ppm 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. Release a few larvae of the diamondback moth,
The lid was closed and left in a 26 ° C. illuminated incubator. On the 2nd day after the release of insects, the survival rate was determined in the same manner as in Test Example 1 above, and the percentage of dead insects was 100% for all the active ingredient compounds No. 1 and 2.

Test example 3. Rice seedlings were soaked in a chemical solution adjusted to a concentration of 800 ppm for the active ingredient compound No. 1 for 10 seconds, air-dried, and the root portion was wrapped with absorbent cotton and placed in a test tube. Next, 10 adult brown planthoppers were released into this, and the tube mouth was covered with gauze. Two days later, the life and death of insects was investigated, and Test Example 1. When the mortality rate was calculated in the same manner as in the above case, it was 100%.

Test example 4. Filling the soil contaminated with sweet potato root-knot nematodes into 1/14000 are pots, the active ingredient compounds No. 1 and 2 250
A predetermined amount of each drug solution adjusted to have g / a was irrigated. Two days after chemical solution treatment, the treated soil is mixed in all layers and
Four tomato seedlings 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 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. The active ingredient compound No. 1 preparation 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. On the second day after the insect was released, it was judged whether it was alive or dead,
Test Example 1. The mortality is calculated in the same manner as in
The results in the table were obtained.

Test example 6. Disperse the active ingredient compound No.1 formulation in water and
The concentration was adjusted to pm. 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, about 30 larvae of Dicofol- and organophosphorus-drug-resistant spider mites were inoculated on the leaves and left in a 26 ° C. illuminated thermostat. On the 2nd day after the release of the insects, life or death was determined, and the test example 1. When the mortality rate was calculated in the same manner as for
It was 00%.

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 components were uniformly mixed and dissolved to obtain an emulsion.

Formulation example 2. (A) 5 parts by weight of compound NO.2 (b) 95 parts by weight of talc The above ingredients were uniformly mixed to obtain a dust.

Formulation example 3. (B) Compound NO.1 0.50 part by weight (b) Polyoxyethylene octyl phenyl 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 4. (B) Compound NO.3 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 sulphate 5 parts by weight The above ingredients were uniformly mixed and pulverized to obtain a wettable powder.

Formulation example 5. (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 ingredients were kneaded uniformly to obtain a paste.

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

Claims (3)

[Claims] 1. A general formula: [Wherein, X ₁ and X ₂ are a hydrogen atom or an alkyl group, Y ₁ and Y ₂ are a hydrogen atom, and Z ₁ , Z ₂ and Z are
₃ is an oxygen atom, and R ₁ and R ₂ are alkyl groups]. 2. A general formula: [Wherein, X ₁ and X ₂ are a hydrogen atom or an alkyl group, Y ₁ and Y ₂ are a hydrogen atom, and Z ₁ , Z ₂ and Z are
₃ is an oxygen atom, and R ₁ and R ₂ are alkyl groups], and an insecticidal, acaricidal or nematicidal agent containing at least one organic phosphorus compound as an active ingredient. . 3. A general formula: [Wherein, X ₁ and X ₂ are a hydrogen atom or an alkyl group, Y ₁ and Y ₂ are a hydrogen atom, and Z ₁ , Z ₂ and Z are
₃ is an oxygen atom] and a compound represented by the general formula: [Wherein Z ₃ is an oxygen atom and R ₁ is an alkyl group] to react with a compound represented by the general formula: [Wherein X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , Z ₂ , Z ₃ and R ₁ are as described above] is produced, and then this compound and the general formula: R ₂ SH [wherein R ₂ is an alkyl group] is reacted with a mercaptan represented by the general formula: [In the formula, X ₁ , X ₂ , Y ₁ , Y ₂ , Z ₁ , Z ₂ , Z ₃ R
₁ and R ₂ are as described above], the method for producing an organophosphorus compound, comprising producing an organophosphorus compound represented by