JPS6058995A - Dithiol phosphate, production thereof and controlling agent against soil injurious insect containing the same as active constituent - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (A is sec-butyl or tert-butyl; B is iso- propyl, n-butyl, iso-butyl, sec-butyl or tert-butyl). EXAMPLE:O-Methyl S-sec-butyl S-iso-butyl phosphorodithiolate. USE:A controlling agent against soil injurious insects applicable to paddy fields, upland fields, orchards, tea gardens and mulberry fields, etc. without exhibiting phytotoxicity to plants. PREPARATION:A thiophosphoric acid derivative of formula II (R is iso-propyl, n-butyl, iso-butyl, sec-butyl or tert-butyl; X is halogen), e.g. O-methyl S-sec-butyl phosphorochloridothioate, is reacted with an alkyl mercaptan of the formula R'SH (R' is B when R is A, and A when R is B), e.g. isobutyl mercaptan.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides compounds of the general formula (1) [wherein A represents a 5ec-butyl group or a tert-butyl group, and B represents a 1so-propyl group, a n-butyl group,
1so-butyl group, 5ec-butyl group or tert-
Represents a butyl group. The present invention relates to a dithiol phosphate ester (hereinafter referred to as the compound of the present invention) represented by the formula (hereinafter referred to as the compound of the present invention), a method for producing the same, and a soil pest control agent containing the same as an active ingredient.

Certain dithiol phosphates, such as O-edyl S dithiol phosphate, S-di-n-butyl, etc., are insecticidal,
It is used as an active ingredient in acaricides and nematocides, as specified in 1 Landa Patent No. 261789, Japanese Patent Publication No. 1973-2.
No. 9047 discloses dithiol phosphate 〇-ethyl S-
International Publication No. WO83100870 describes that 5ec-butyl-s-tert-butyl and the like can be used as active ingredients in nematicides and soil pest control agents. However, these compounds cannot always be said to be sufficient as effective ingredients for soil pest control agents.

On the other hand, the compound of the present invention has a superior insecticidal effect compared to these known compounds, and it lives in the soil, including paddy rice, spring vegetables, flowers, lawns, etc.
It has a control effect against soil pests that damage fruit trees, tea, mulberry, etc., and does not cause any problematic phytotoxicity to these plants.

Therefore, the compound of the present invention can be used as an active ingredient of a soil pest control agent for paddy fields, fields, orchards, pastures, tea gardens, mulberry gardens, and the like.

Soil pests include pests of the genus Diabrolica such as Western corn rootworm, northern corn root I worm, and corn rootworm, pests of the genus Phyllotreta such as the Japanese red beetle, Japanese scarlet beetle, cherry beetle, and striped flea beetle, and the common corn rootworm. Melanotus pj4 pests, such as Agrioies x pests, such as onion fly, taikon fly, and seed fly, Agrotis pests, mole crickets, etc. a) Li s *Orliopt ru rich genus pests, Pratylen such as northern nematode, walnut nematode, southern nematode, etc.
Pests of the genus Chus, soybean cyst nematode, etc.
Rodera genus pests, Meloidogyne genus pests, such as the northern nematode, sweet potato nematode, Javanese nematode, 乎T car 4-a-1-Jt-y-chi 1-u τ arenaria genus pest, rice sinew. There are pests of the genus Aphelenchoidem such as the nematode.

The compound of the present invention has the general formula [1s] [wherein R is 1so-propyl group, n-butyl group, 1s
It represents an o-butyl group, a 5ec-butyl group or an Iert-butyl group, and X represents 10 gen atoms. ] and 1 to 5 equivalents of the halogenated theophosphoric acid derivative represented by the general formula [R'SH] [In the formula, when K represents A, 〆 represents B, and when K represents 8
When representing A, O), 8 and B have the same meanings as above. ] in a solvent or without a solvent, in the presence of a 1.0 to 1.5 equivalent dehydrohalogenating agent and a phase transfer catalyst or a copper-based catalyst, at a temperature of about -10°C to about 50°C. It can be produced by reacting for about 30 minutes to 5 hours.

Solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, and dichlorobenzene, and aromatic carbons such as benzene, toluene, and xylene. Hydrogens, n-
Examples include aliphatic hydrocarbons such as hexane, n-hebutane, and cyclohexane, nitrites such as acetonitrile and isobutyronitrile, water, and mixtures thereof.

Examples of the dehydrohalogenation agent include organic bases such as pyridine, triethylamine, and N,N-diethylaniline, and inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. Phase transfer catalysts include tetraalkylammonium halides such as butrabutylammonium bromide and triethylbenzylammonium chloride. Copper-based catalysts include copper powder, cupric chloride, and the like.

After the reaction is completed, usual post-treatments are carried out, and if necessary, purification is carried out by chromatography, distillation, etc.

Furthermore, the compound of the present invention has the general formula [1v] [where λ is 1
so-propyl group, n-butyl group, 1so-butyl group,
Represents a 5ec-butyl group or a te-butyl group, and H
represents an alkali metal atom. ] Dithiophosphate represented by and 1 to 10 equivalents of the general formula (V
) Me Y (V) [In the formula, k represents B when K represents A;
When it does not represent A, A and B have the same meanings as above, and Y represents a halogen atom. ] It can also be produced by reacting an alkyl halide represented by the formula in a solvent or without a solvent at temperatures from around 20° C. to Bθ° C. for about 30 minutes to 3 hours.

Solvents include the aforementioned ketones, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons, nitriles, water, etc., as well as methanol, ethanol, isopropanol,
Examples include alcohols such as rt-phthanol and methyl cellosolve, and mixtures thereof.

After the reaction is completed, post-treatment is carried out in the same manner as above, and purification is carried out if necessary.

Next, production examples of the compounds of the present invention will be shown.

Production Example 1 (Production of Compound (4) of the Present Invention) 3. Ov potassium, 0-methyl S-5ec-butyl phosphorodithioate was dissolved in acetin 50-, and 3.52 bromide n- Butane was added, and the mixture was stirred and refluxed for 3 hours. After the reaction, acetone was distilled off under reduced pressure, toluene was added to the residue, and 3
After washing with % sodium bicarbonate and water, rough
O-methyl S-5ec is purified by zeta and is a colorless oil.
-Butyl S -n-butyl phosphorodithiolate 1.
I got 81.

nDl, 5022 Production Example 2 (11! Preparation of Compound (1) of the Present Invention) 9, OF
0-/Til S-5ec-butyl phosphorochloride thiony 1. to a 15-solution in toluene 4. After adding OF isobutyl mercaptan and a catalytic amount of tetrabutylammonium bromide, a 3.6F 50% aqueous sodium hydroxide solution was stirred for 1 hour while cooling so that the internal temperature of the reaction solution was 0 to IO℃. and then add it dropwise at room temperature for 1 hour.
Stir for hours. After the reaction was completed, the toluene was distilled off under reduced pressure after washing with sodium trihydroxide and water, and the oily substance obtained as a residue was subjected to silica gel column chromatography ↓-
0-Methyl/l/5-s as a pale yellow oil
6.32 of ec-buty/L/S-i*o-butyl phosphorodithiolate was obtained.

1 nDl, 5015 Table 1 shows the compounds of the present invention that can be produced by such a production method.

When the compound of the present invention is used as an active ingredient in a Soil II pest control agent, it is usually mixed with a solid carrier, liquid carrier, or gaseous carrier, and if necessary, a surfactant and other formulation auxiliaries are added. Formulated into oils, emulsions, wettable powders, granules, powders, aerosols, etc.

These preparations suitably contain the compound of the present invention as an active ingredient in a weight ratio of 0.1 to 99.9%, preferably 1 to 80%.

Solid carriers include clays (e.g. kaolin, diatomaceous earth, synthetic hydrous silicon oxide, fubasamiclay, bentonite, acid clay), talcs, and other inorganic minerals (e.g. sericite, quartz powder, sulfur powder, activated carbon, calcium carbonate,
hydrated silica), chemical fertilizers (e.g. ammonium sulfate, ammonium phosphorus, ammonium nitrate,
Liquid solvents include water, alcohols (e.g., methanol, ethanol), ketones (e.g., acetone, methyl edyl ketone), aromatic carbonization, etc. -1U11M1. -14
．． Lxrj-a*ly+Ij++, +++a, +, +n, ethylbenzene, methylnaphthalene), aliphatic hydrocarbons (e.g. n-hexane, cyclohexanone, kerosene, kerosene), esters (e.g. ethyl acetate, butyl acetate), nitriles (e.g. acetonitrile, isobutyronitrile), ethers (e.g. dioxane,
diisopropyl ether), acid amides (e.g. dimethylacetamide, dimethylacetamide), halogenated hydrocarbons (e.g. dichloroethane, trichloroethylene, tetracarbon 1), etc. Gaseous carriers, i.e. propellants, include chlorofluorocarbon gas, butane gas, etc. , carbon dioxide gas, etc.

Surfactants include alkyl nisder sulfates, alkyl sulfonates, alkylaryl sulfonates, alkylaryl ethers and their polyoxyethylenic products, polyethylene glycol ether, polyhydric alcohol esters, sugar alcohol derivatives, and the like.

Fixing and dispersing agents include casein, gelatin, polysaccharides (such as starch powder, gum arabic, cellulose derivatives,
alginic acid), lignin derivatives, bentonite, sugars,
There are synthetic water-soluble polymers (for example, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids), etc., and stabilizers include PAP (isopropyl acid phosphate), B
HT (2,6-tert-butyl-4-methyl7
．． Examples include BHA (a mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oil, mineral oil, surfactant, fatty acid or its ester.

The above-mentioned preparations are sprayed on the soil surface either as they are or diluted with water, and if necessary, after spraying, they are mixed with the soil or poured onto the soil, and sometimes they are sprayed on the leaves. It can also be used simultaneously with or without mixing with other insecticides, acaricides, nematicides, fungicides, seed disinfectants, fertilizers, soil conditioners, etc.

Next, examples of formulations of the compounds of the present invention will be shown.

The compounds of the present invention are indicated by compound numbers in Table 1.

Formulation Example 1 Emulsion 40 parts each of the compounds (1) to (9) of the present invention were added to 5 parts of xylene.
Add 10 parts of the emulsifier Tsurupol SM-200 (registered trademark of Toho Chemical, 9 compounds of alkylphenol and dodecylbenzenesulfonic acid) and stir and mix thoroughly to obtain a 40% emulsion.

Formulation Example 2 Wettable powder Add 75 parts of Trupol SM-2000 to 40 parts each of the compounds of the present invention (1) to (9), mix well, and Carplex #80 (registered trademark of Geotsugi Pharmaceutical, synthetic hydrated silicon oxide fine powder) Add 20 parts and 35 parts of 300 mesh diatomaceous earth,
Stir and mix with a juice mixer to obtain a 40% wettable powder.

Formulation Example 3 Granules Toyolignin CT (registered trademark of Toyobo, lignin sulfonate) 5 parts each of the compounds (1) to (9) of the present invention
Department and OEM Clay (Sieglite Ishimotogyo registered trademark name,
Add 90 parts of quartz powder) and mix thoroughly with stirring in a crusher. Then add water equivalent to 10% of these mixtures,
The mixture is further stirred, granulated using a granulator, and dried through ventilation to obtain 5-inch granules each.

Additive Example 4 Powder 5 parts each of the compounds (1) to (9) of the present invention were mixed with 20 parts of acetone.
803 parts of Carplex, 0.0 parts of PAP.
3 parts and 91.7 parts of 300 mesh units were added, stirred and mixed using a juice mixer, and the acetone was removed by evaporation to obtain 5% powders.

Late Form Example 5 Oil Agent 20 parts each of the compounds (1) to (9) of the present invention are dissolved in 80 parts of kerosene to obtain a 20% oil agent.

When the compound of the present invention is used as an active ingredient of a soil pest control agent, the application amount is usually from IOP to 1000 jl per 10 are, preferably from 50 to 500 f, and the application concentration is in the form of an emulsion, a wettable powder, etc. When diluted, the amount is from 0.01% to 30%.

The amount and concentration of these applications depend on the type of formulation, application time, application location, application method, type of soil pest, damage,
It also depends on other circumstances, such as the degree, and can increase or decrease without regard to the above range.

Next, the control efficacy of the compound of the present invention against soil pests was not shown in a test example. In addition, unless otherwise specified, each test example was repeated three times. Among the test compounds, the compounds of the present invention are shown by the compound numbers in Table 1, and the compounds used for comparison are shown by the compound symbols in Table 2.

Test Example 1 A water-diluted solution 5 of an emulsion of a test compound prepared according to Formulation Example 1 was mixed with 50 f of soil Ill (J Omeah) to adjust the concentration of the active ingredient in the soil to i ppm. This soil was packed in a polyethylene cup with a diameter of 5.6QIl and a height of 5.8cm, and two kernels of rooted corn were planted at a height of 2 to 30m.
tica undecimpun-ctata how
ardi BARBER) 3 10 total larvae were released. Two days later, the number of living and dead larvae was investigated, and the survival rate (%) was calculated.

The results are shown in Table 3.

−′～＼＼＼＼Table 2 Measurement 2 A 50% water dilution of the emulsion of the test compound prepared according to Formulation Example 1 was added to soil! I! (1 (imesh)) Mix with 5002 to reduce the concentration of active ingredients in soil to 0.5 or 0.25.
It was set to ppm. This soil is 12G in diameter and 8a in height.
Four seeds of germinated corn were planted at 5 to 6c11, and 20 southern corn roux I worm 3 + larvae were released. After 20 days, the number of living and dead larvae was investigated, and the mortality rate (chi) was calculated.

The results are shown in Table 4.

Table 4 Test Example 3 Meloidgyne sp. contaminated soil was packed into a polyethylene cup with a diameter of 12 cm and a height of 8011 cm, and three tomatoes at the 3-4 leaf stage were planted.

One day later, an emulsion of the test compound prepared according to Formulation Example 1 was diluted with water to give an active ingredient concentration of 500 PPm, and 30-mg was poured into a cup. After 18 days, the degree of colonization was observed with the naked eye and evaluated in 6 grades: 5.4, 3, 2, and 1.0 according to the following classification. The results are shown in Table 5.

Evaluation value Level of cat-kub settlement 5 No settlement 4 Graining less than 10% compared to untreated area 3 〃 10
~30% 〃 〃 〃 30-50% 〃 1 Close to the untreated plot, with a large amount of cat-kub settling 0 〃 Same or even more settling

Claims (1)

Scope of Claims (1) In the general formula c, A represents a 5ec-butyl group or a tert-butyl group, and B represents a 1so-propyl group, n-butyl group, fso-butyl group, 5e(- butyl group or tert
-Represents a butyl group. ] Nisdel dithiol phosphate. [In the formula, 1 is 1so-propyl group, n-butyl group, 1s
It represents an o-butyl group, a 5ec-butyl group or a tert-butyl group, and X represents a halogen atom. ] A halogenated thiophosphoric acid derivative represented by the general formula [wherein K represents 8] represents B, and when represents B represents A. A represents a 5ec-butyl group or a tert-butyl group, and B represents a 1so-propyl group, an i-butyl group, a 130-
Represents a butyl group, a 5ec-butyl group or a tert-butyl group. [wherein A and B represent the same meanings as above]. ] A method for producing dithiol phosphate ester shown by. (3) General formula [wherein K is tso-propyl group, n-butyl group, 1a
It represents an o-butyl group, a 5ec-butyl group or a tert-butyl group, and M represents an alkali metal atom. ] A dithiophosphate represented by the general formula [wherein, when R represents A, represents B, and when R represents B
When A is not expressed, it is expressed as A. Δ represents a 5ec-butyl group or a terj-butyl group, B represents a 1so-propyl group, n-butyl group, 1so-butyl group, 5ec-butyl group or tirt-butyl group, and Y represents a halogen atom. represents. [In the formula, A, B and k have the same meanings as above. ] A method for producing a dithiol phosphate ester shown by (4) General formula [wherein A represents a 5ec-butyl group or a tert-butyl group, B represents a 1so-propyl group, a n-butyl group,
110-butyl group, 5ec-butyl group or tert-
Represents a butyl group. ] A soil pest control agent characterized by containing a dithiol phosphate ester represented by the following as an active ingredient.