JP2556363B2 - Optically active organophosphorus compounds, their production method and pest control agents containing them - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an optically active (−) S-sec-butyl O-ethyl (2-oxo-3-thiazolidinyl) phosphonothiolate, a method for producing the same, and them. The present invention relates to a pest control agent containing as an active ingredient.

(Prior Art) S-alkyl-O-ethyl- (2-oxo-3-thiazolidinyl) phosphonothiolate is disclosed in JP-A-60-136590.
The publication discloses that the compound is useful as an insecticide, acaricide, nematicide, and contains optical isomers.

However, there is no specific disclosure of the optical isomer of the compound.

[Disclosure of Invention]

The present inventors have found that optically active (-) S-sec-butyl O-
It was found that ethyl- (2-oxo-3-thiazolidinyl) phosphonothiolate has a higher control effect as a pest control agent than the corresponding racemate or (+) optical isomer.

That is, the present invention has the general formula (I): (In the formula, * means an asymmetric phosphorus atom), an optically active (−) S-sec-butyl O-ethyl (2-oxo-3-thiazolidinyl) phosphonothiolate, a method for producing them and the The present invention relates to a pest control agent to be contained.

The (−) optical isomer represented by the general formula (I) generally has the general formula (II): It can be produced by optically resolving the racemate represented by As the optical resolution method, for example, as described in the production examples below, 1,4-
Poly-2,3,6-tri-O-phenylcarbamoyl-β-
Chiralcel Aucy (Ch
iralcel OC) can be separated into the (−) optical isomer and the (+) optical isomer by high performance liquid chromatography (solvent: a mixture of n-hexane and 2-propanol) using a column.

Production Example (-) S-sec-Butyl O-ethyl (2-oxo-3-thiazolidinyl) phosphonothiolate (Compound
No.1) Synthesis of S-sec-butyl O-ethyl (2-oxo-3-thiazolidinyl) phosphonothiolate racemic compound, Chiralcel OC (manufactured and sold by JASCO Corporation) (inner diameter 4.6) mm x length 25 cm) was used for the column and split. As a resolving agent for the column 1,
4-poly-2,3,6-tri-O-phenylcarbamoyl-β
-D-Glucoside supported on silica gel is filled. This racemic compound was dissolved in n-hexane / 2-propanol (9/1), and this mixed solvent was used as a mobile phase for high performance liquid chromatography at a flow rate of 1.0 ml / min. When analyzed using an instrument (220 nm), a peak with a retention time of 32 minutes (peak 2)
And a peak at 37 minutes (peak 1) was obtained.

Each peak component was converted from 1 mg of racemate to peaks 1 and 2
Each component was repeatedly sampled in an amount of 0.4 mg, and the luminosity thereof was measured. The peak 1 component was [α] _D ^{27 °} = + 42.6 (C = 5.02 /
Methanol), the component of peak 2 is [α] _D ^{27 °} = -42.6 (C = 4.96 /
(Methanol). The peak 2 has the desired (-) S-sec-butyl O-ethyl-
(2-oxo-3-thiazolidinyl) phosphonothiolate (Compound No. 1). To test the insecticidal activity of this product, the components divided through the above steps were used as they were.

The (−) optical isomer of the present invention is an insecticide, acaricide, nematicide,
It exhibits excellent activity as an active ingredient of soil pesticides.

For example, phytoparasitic mites such as scab spider mite, spider mites, citrus spider mite, burrowing mite, diamondback moth, bollworm, common worm, codling moth, ball worm, tobacco bat worm, mime moth, colorado beetle, urchin beetle, ball weevil, aphids, planthopper Agricultural insect pests such as insects, leafhoppers, scale insects, stink bugs, whitefly, thrips, grasshoppers, grasshoppers, chafers, Tamanayaga, Kaburagaga, ants, etc., such as house dust mites, cockroaches, house flies, and house mosquitoes. Sanitary pests, stored-grain pests such as stag beetles, adzuki bean weevils, stag beetles, and bedbugs, clothing such as squid, velvet beetle, termites, house pests, and fleas and lice that parasitize livestock. And flies It is also effective against etc., and even cat-flops nematodes, cyst nematodes,
It is also effective against plant parasitic nematodes such as Negusta nematodes, rice garlic nematodes, strawberry nematodes, and pine wood nematodes. It is also effective against soil pests. The soil pests mentioned here include slugs, gastropods such as snails, pill bugs,
Examples include isopods such as woodworms. Further, it is also effective against pests such as dicofol (trade name: manufactured by Takeda Pharmaceutical Co., Ltd.), organophosphorus agent-resistant plant parasitic mites, organophosphorus agent-resistant aphids, and house flies. Furthermore, since the (-) optical isomer of the present invention has an excellent permeation migration property, soil harmful insects, mites, nematodes, gastropods, etc. can be treated by treating the compound of the present invention in soil. At the same time as the control of the legs, the pests of the foliage can also be controlled.

Insecticidal, acaricidal, nematicidal, (-) optical isomer of the present invention,
When used as an active ingredient of a soil-killing insect pest composition, in the same manner as in the case of conventional pesticide formulations, various agricultural chemicals such as emulsions, powders, granules, wettable powders, liquids, aerosols, pastes and the like are used. It can be formulated into a form. The compounding ratio thereof is usually 0.5 to 0.9 part by weight of the active ingredient and 10 to 99.5 parts by weight of the agricultural chemical 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. As the solid carrier, starch, activated carbon, soy flour, wheat flour, wood flour, fish flour,
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 teirahydrofuran, kerosene,
Aliphatic hydrocarbons such as kerosene, aromatic hydrocarbons such as xylene, trimethylbenzene, tetramethylbenzene, cyclohexane, and solvent naphtha, 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, insecticides, acaricides, or nematicides include O- (4-bromo-2-chlorophenyl) O-ethyl S-propyl phosphorothioate, 2,2-dichlorovinyl, dimethyl phosphate, ethyl 3-methyl. -4-
(Methylthio) phenylisopropyl phosphoramidate, O, O-dimethyl O-4-nitro-m-tolyl phosphorothioate, O-ethyl O-4-nitrophenylphenylphosphonothioate, O, O-diethyl O-2-isopropyl -6-Methylpyrimidin-4-yl phosphorothioate, O, O-dimethyl O- (3,5,6-trichloro-2
-Pyridyl) phosphorothioate, O, S-dimethylacetylphosphoramidothioate, O- (2,4-dichlorophenyl) O-ethyl S-propylphosphorodithioate, an organic phosphate compound; 1-naphthylmethyl Carbamate, 2-isopropoxyphenylmethyl carbamate, 2-methyl-2- (methylthio) propionaldehyde O-methylcarbamoyl oxime,
2,3-Dihydro-2,2-dimethylbenzofuran-7-ylmethylcarbamate, dimethyl N, N '-[thiobis [(methylimino) carbonyloxy]) bisethaneimidothioate, S-methyl N- (methylcarbamoyloxy) ) Thioacetimidate, N, N-dimethyl-2-
Methylcarbamoyloxyimino-2- (methylthio)
Acetamide, 2- (ethylthiomethyl) phenylmethylcarbamate, 2-dimethylamino-5,6-dimethylpyrimidin-4-yldimethylcarbamate, S, S'-
Carbamate compounds such as 2-dimethylaminotrimethylene bis (thiocarbament); 2,2,2-trichloro-1,1-bis (4-chlorophenyl) ethanol, 4-
Organochlorine compounds such as 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 (1
R) -cis-3- (2,2-dipromovinyl) -2,2-dimethylcyclopropanecarboxylate, (RS) -α-cyano-3-phenoxybenzyl (1RS) -cis, trans-3- (2- Chloro-3,3,3-trifluoropropenyl) -2,2-dimethylcyclopropanecarboxylate, 2,3,5,6-tetrafluoro-4-methylbenzyl (Z)-(1RS, 3RS) -3- Pyrethroid compounds such as (2-chloro-3,3,3-trifluoroprop-1-enyl) -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-2,4-difluorophenyl) -3- Benzoylurea compounds such as (2,6-difluorobenzoyl) urea; 2-tert-butylimino-3-isopropyl-5-phenyl-3,4,5,6-tetrahydro-2H-1,3,5-thiadiazine Compounds such as -4-one, trans- (4-chlorophenyl) -N-cyclohexyl-4-methyl-2-oxothiazolidinone-3-carboxamide, N-methylbis (2,4-xylyliminomethyl) amine Isopropyl (2E, 4E) -1
Juvenile hormone-like compounds such as 1-methoxy-3,7,11-trimethyl-2,4-dodecadienoate; as other compounds, dinitro compounds, organic sulfur compounds, urea compounds, triazine compounds A compound etc. are mentioned. Furthermore, 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, aluminum ethyl hydrogen phosphonate;
Organochlorine compounds such as 4,5,6,7-tetrachlorophthalide and tetrachloroisophthalonitrile; Manganese ethylene bis (dithiocarbamate) polymer, zinc Ethylene bis (dithiocarbamate) polymer, zinc And manneb complex compounds, dizinc bis (dimethyl dithiocarbamate) ethylene bis (dithiocarbamate), dithiocarbamate compounds such as zinc propylene bis (dithiocarbamate) polymer; 3a, 4,7,7a
-Tetrahydro-N- (trichloromethanesulfenyl) phthalimide, 3a, 4,7,7a-tetrahydro-N-
N-halogenothioalkyl compounds such as (1,1,2,2-tetrachloroethanesulfenyl) phthalimide and N- (trichloromethylsulfenyl) phthalimide;
(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, N- (3,
5-Dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide-containing dicarboximide compounds; methyl 1- (butylcarbamoyl) benzimidazol-2-ylcarbamate, dimethyl 4,4'-
Benzimidazole compounds such as (o-phenylene) bis (3-thioallophanate); 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazole-1- Ill) 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] -1
Azole compounds such as H-1,2,4-triazole, 1- [2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole; 2,4'-dichloro-α- (Pyrimidin-5-yl) benzhydryl alcohol, (±)-
2,4'-Difluoro-α- (1H-1,2,4-triazole-
Carbinol compounds such as 1-ylmethyl) benzhydryl alcohol; benzanilide compounds such as 3'-isopropoxy-o-trianilide, α, α, α-trifluoro-3'-isopropoxy-o-toluanilide Methyl N- (2-methoxyacetyl) -N- (2,6
-Xylyl) -DL-alaninate, an acylalanine compound; 3-chloro-N- (3-chloro-2,6-dinitro-4-α, α, α-trifluorotolyl) -5-trifluoromethyl 2-Pyridinamine compounds such as pyridinamine; and as other compounds, piperazine compounds, morpholine compounds, anthraquinone compounds, quinoxaline compounds, crotonic acid compounds, sulfenic acid compounds, urea compounds, antibiotics And so on.

The pest control agent of the present invention is effective for controlling various harmful insects, harmful mites, harmful nematodes, harmful soil pests, and its application is generally 1 to 20,000 ppm, preferably 20 to 2,000 pp.
Perform with an active ingredient concentration of m. The concentration of these active ingredients is
It can be appropriately changed depending on the form of the preparation, the method of application, the purpose, the time, the place, the occurrence status of the pest 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 1 as an active ingredient compound per 10 a.
0-1,000g is used. However, it is possible to deviate from these ranges in special cases.

The application of various preparations containing the (-) optically active isomer of the present invention, or a dilution thereof, is generally applied, that is, spraying (for example, spraying, spraying, misting, atomizing, granulation). , Water surface application, etc., soil application (mixing, irrigation, etc.), surface application (application, dressing, coating, etc.), immersion bait, etc. It is also possible to feed livestock with the above-mentioned active ingredient mixed with it to control the development and growth of harmful insects, especially harmful insects, in the excrement thereof. In addition, the so-called ultra-high-concentration small-volume spray method (ultr
a low volume) can also be applied. In this way it is possible to contain 100% of the active ingredient.

Test Example 1 A 1 / 5,000 are pot was filled with soil contaminated with Necob, and a predetermined amount of a chemical solution adjusted so that the active ingredient had a predetermined amount was algae-injected.
Tomato seedlings at the 4-leaf stage were transplanted, and the degree of fecundity of the cats was examined 28 days after the liquid drug treatment, and the results shown in Table 1 were obtained.

 The degree of Necob engraftment complied with the following criteria.

Test Example 2 Each formulation of the active ingredient compound was dispersed in water,
The concentration was adjusted to a predetermined level. What was left only one primary leaf of kidney bean was transplanted to a cup (diameter 7 cm, height 4 cm),
This was inoculated with about 30 larvae of Dichofol and organophosphorus drug-resistant flesh mites. This was immersed in the above-mentioned chemical solution adjusted to a predetermined concentration for about 10 seconds, air-dried, and then left in a 28 ° 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 2 were obtained.

Test Example 3 Only one primary leaf of kidney bean was left in a cup and transplanted into a cup, which was inoculated with adults of Dicofol and an organophosphorus agent-resistant flesh mite, and the eggs were removed to remove the adults. Next, the formulation of the active ingredient compound was dispersed in water, the kidney bean was immersed in a drug solution adjusted to a predetermined concentration for about 10 seconds, air-dried, and then left in a 28 ° C illuminated thermostat. 5
After a day, the hatching condition of the eggs was investigated, the ovicidal rate was calculated by the following formula, and the results shown in Table 3 were obtained.

Test Example 4 Dispersing each formulation of the active ingredient compound in water,
The concentration was adjusted to a predetermined level. Seedlings of two primary leaves of common bean were transplanted into a cup (diameter 7 cm, height 4 cm), and 10 ml of the chemical solution adjusted to the above-mentioned predetermined concentration was soil-irrigated. Process 2
After 30 days, about 30 larvae of Dicofol- and organophosphorus-resistant flesh mites were inoculated into the leaves 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 determined in the same manner as in the case of Test Example 2 above, and the results shown in Table 4 were obtained.

Test Example 5 Rice seedlings were immersed in a chemical solution adjusted to a concentration of 100 ppm for 10 seconds, air-dried, and the roots were 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. After 2 days, the life and death of the insects were investigated, and the mortality rate was obtained in the same manner as in Test Example 2, and the results shown in Table 5 were obtained.

Test Example 6 Each formulation of the active ingredient compound was dispersed in water,
The leaf pieces of cabbage were soaked in a chemical solution adjusted to 100 ppm for about 10 seconds and air dried. A 9 cm diameter Petri dish was lined with moist filter paper, and air-dried leaf pieces were placed thereon. Two to three instar larvae of Spodoptera litura were released there, covered, and allowed to stand in a 26 ° C illuminated thermostat. On the 2nd day after the release of insects, life or death was determined, and the mortality rate was obtained in the same manner as in the case of Test Example 2, and the results shown in Table 6 were obtained.

Formulation Example 1 (a) Compound No. 1 20 parts by weight (b) N, N'-dimethylformamide 32 parts by weight (c) Xylene 40 parts by weight (d) Polyoxyethylene alkylphenyl ether 8 parts by weight Mix and dissolve to prepare an emulsion.

Formulation Example 2 (a) Compound No. 1 5 parts by weight (b) Bentonite 45 parts by weight (c) Kaolin 50 parts by weight The above ingredients are kneaded with a small amount of water, extruded into granules, and dried to obtain granules. .

Formulation Example 3 (a) 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) Fine silica 1.0 part by weight (e) Granular carbonic acid 98.25 parts by weight of calcium (a) to (c) are uniformly mixed in advance, diluted with an appropriate amount of acetone, and then sprayed on the mixture of (d) and (e) to remove acetone to obtain granules.

Formulation Example 4 (a) Compound No. 1 50 parts by weight (b) Fine silica 15 parts by weight (c) Fine clay 25 parts by weight (d) Naphthalene sulfonate sodium soda formalin condensate 2 parts by weight (e) Dialkylsulfosuccinate 3 Parts by weight (f) Polyoxyethylene alkylaryl ether sulfate 5 parts by weight The above ingredients are uniformly pulverized and mixed to obtain a wettable powder.

Formulation Example 5 (a) Compound No. 1 1 part by weight (b) Talc 99 parts by weight The above components are uniformly mixed to obtain a powder.

Formulation Example 6 (a) Compound No. 1 50 parts by weight (b) Methyl cellosolve 30 parts by weight (c) Polyoxyethylene alkylphenyl ether 20 parts by weight The above ingredients are uniformly mixed to obtain a liquid preparation.

Formulation Example 7 (a) Compound No. 1 75 parts by weight (b) Polyarylphenol ethoxylate 15 parts by weight (c) Ethoxylated polyarylphenol 10 parts by weight The above ingredients are uniformly mixed to obtain a liquid preparation.

Front page continuation (72) Inventor Masayuki Morita 2-3-1, Nishi-Shibukawa, Kusatsu-shi, Shiga Ishihara Sangyo Co., Ltd. Central Research Laboratory Examiner Satoru Fukui (56) Reference JP-A-60-136590 (JP, A) )

Claims (3)

(57) [Claims] 1. General formula (I): (In the formula, * means an asymmetric phosphorus atom) An optically active (−) S-sec-butyl O-ethyl (2-oxo-3-thiazolidinyl) phosphonothiolate. 2. General formula (I): (In the formula, * means an asymmetric phosphorus atom) containing an optically active (−) S-sec-butyl O-ethyl (2-oxo-3-thiazolidinyl) phosphonothiolate as an active ingredient. Characteristic pest control agent. 3. General formula (II): The racemic compound represented by the resolving agent 1,4-poly-2,3,6
General formula (I) characterized by optical resolution with -tri-O-phenylcarbamoyl-β-O-glucoside: (In the formula, * means an asymmetric phosphorus atom) A method for producing optically active (-) S-sec-butyl O-ethyl (2-oxo-3-thiazolidinyl) phosphonothiolate.