JPH0190A - O-ethyl S-t-butyl O-phenylphosphorothiolate and insecticides, nematicides, and acaricides containing it as an active ingredient - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention relates to 〇-ethyl 5-t-butyl 0-phenyl small sulforothiolate (hereinafter referred to as the compound of the present invention) represented by formula (I), and its production. law and insecticides, nematicides, and acaricides containing the same as an active ingredient.

<Prior art> Conventionally, this system of organophosphorus insecticidal, nematicidal, and acaricidal compounds has been disclosed in Japanese Patent Publication No. 46-14759 and Japanese Unexamined Patent Publication No. 48-22
446 and Japanese Patent Publication No. 49-21768, general formula (6) (wherein R is n-propyl group, i-propyl group or 5
Represents an ec-butyl group. ) are described.

<Problems to be Solved by the Invention> However, these compounds are not necessarily satisfactory in that they have insufficient efficacy, especially against soil pests, and are highly acutely toxic to bleeding animals.

Means for Solving the Problems> In view of the hot situation, the present inventors have developed a compound with excellent insecticidal, nematocidal, and acaricidal effects (As a result of various studies, the present invention compound has been developed). It shows excellent insecticidal, nematicidal, and acaricidal effects against insects, nematodes, and mites that live in the soil and damage various volatile crops, flower petals, lawns, etc. As is clear from the test examples, it was confirmed that the compound not only has a remarkable difference in efficacy compared to conventional compounds, but also has very low toxicity to mice, leading to the completion of the present invention.

The compound of the present invention can be produced, for example, by widening 〇-ethyl 〇-phenylphosphorine chloride and t-butyl mercaptan in a solvent in the presence of a base. It can be manufactured under such conditions.

That is, all the reagents used in the reaction are 〇-ethyl O-
The amount is 1 to 2 equivalents of t-butylmercapkun per equivalent of phenylphosphoryl chloride, and these are reacted in a solvent in the presence of a base at a reaction temperature of -20°C to 40°C for 1 to 24 hours.

Examples of the solvent include aromatic hydrocarbons such as benzene and toluene, and ethers such as diethyl ether and tetrahydrofuran. Examples of the base include sodium hydride and potassium hydride.

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

When the compound of the present invention is used as an active ingredient for insecticides, nematocides, and acaricides, it may be used as is without adding any other ingredients, but it is usually used as a solid carrier, liquid carrier, gaseous carrier, or surfactant. , and other formulation auxiliaries can be added to formulate into granules, powders, wettable powders, emulsions, oils, aerosols, and the like.

These preparations can contain 0.1 to 99.9% by weight of the metal of the present invention as an active ingredient.

Solid carriers used in formulation include, for example, clays (e.g. kaolin clay, attapulgite clay, 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 (
Examples include fine powders or granules of ammonium sulfate, ammonium phosphorus, ammonium nitrate, urea, ammonium chloride, etc. Liquid carriers include alcohols (for example, methanol, ethanol),
ketones (e.g. acetone, methyl ethyl ketone),
Aromatic hydrocarbons (e.g. benzene, toluene, xylene, ethylbenzene, methylnaphthalene), aliphatic hydrocarbons (e.g. n-hexane, cyclohexane, kerosene, kerosene), esters (e.g. ethyl acetate, butyl acetate), nitriles (e.g. acetonitrile, isobutyronitrile), ethers (e.g. dioxane, diisopropyl ether), acid amides (e.g. dimethylformamide, dimethylacetamide), halogenated hydrocarbons (e.g. dichloroethane, trichloroethylene, carbon tetrachloride), etc. Examples of gaseous carriers include chlorofluorocarbon gas, butane gas, carbon dioxide gas, and the like.

Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, alkylaryl ethers and their polyoxyethylene compounds, polyethylene glycol ether KA,
Examples include polyhydric alcohol esters, sugar alcohol: A conductor, and the like.

Examples of fixing agents and dispensing agents include casein, gelatin, polysaccharides (for example, starch powder, gum arabic, cellulose derivatives, alginic acid), lignin-conducting conductors, bentonite, sugars, synthetic water-soluble polymers (for example, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acids)
Examples of stabilizers include PAP (isopropyl acid phosphate), BHT (2,6-tert
-butyl-4-methylphenol), BHA (2-te
rt-butyl-4-methoxyphenol and 8-ter
Examples include mixtures of t-butyl-4-methoxyphenol), vegetable oils, mineral oils, surfactants, fatty acids or esters thereof, and the like.

The obtained formulation can be used as it is or diluted with water. It can also be used in combination with other insecticides, acaricides, nematicides, fungicides, herbicides, plant growth regulators, fertilizers, soil conditioners, etc.

When the compound of the present invention is used as an active ingredient for insecticides, nematicides, and acaricides, the application rate is usually 1 per 10 ares.
0F to 10002, and the application concentration is 10 ppm to 1000 ppm when diluting with water such as emulsions and wettable powders.
It is pm.

These application amounts and concentrations vary depending on the situation, such as the type of formulation, application time, application location, application method, type of pest, and degree of damage, and may increase or decrease regardless of the above months. Can be done.

<Examples> The present invention will be described in more detail below with reference to production examples, formulation examples, and test examples, but the present invention is of course not limited to these.

First, a production example of the compound of the present invention will be given.

Production Example t-Butyl mercaptan at 20-26°C with stirring under a nitrogen stream 9. Of (0,1 mol) sodium hydride 4.0r (6o91) of tetrahydrofuran (80
mJ) was added dropwise into the mixed solution. The resulting mixture was heated to 86-4
After keeping it at 0℃ for 2 hours, it was brought to 0 to 5℃, and this is the number.
Ethyl 0-phenylphosphoryl chloride22. Oy
(0.1 mol) notoluene solution (30 mJ) was added.

After the resulting reaction solution was maintained at 20 to 25°C for 6 hours, the solvent was distilled off under reduced pressure. Then methylene chloride 150mJ
The organic layer was washed with water (100 mJ x 2), and the organic layer was dried over anhydrous magnesium sulfate. After filtering this, solution F was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 0-ethyl
5-tert-butyl 〇-phenyl phosphorothiolate 22
．． yr (yield 88.0*) was obtained. 1%, F-'
1.5122 Next, formulation examples of the compounds of the present invention will be shown.

Formulation Example 1 Emulsion 40 parts of the compound of the present invention was dissolved in 50 parts of xylene, and emulsifier Tsurupol 5M-200 (registered trademark of Toho Chemical, mixture of alkylphenol and dodecylbenzenesulfonic acid) was added.
Add 10 parts and stir and mix thoroughly to obtain 40 g6 of emulsion.

Formulation Example 2 Wettable powder Add 76 parts of Tsurpol 5M-200 to 40 parts of the compound of the present invention, mix well, and add 20 parts of Carplex φ80 (registered trademark of Geotsugi Pharmaceutical, synthetic hydrated silicon oxide fine powder) and 80 parts of the compound of the present invention.
Add 85 parts of 0 mesh diatomaceous earth and stir and mix with a jet mixer to obtain a 40% wettable powder.

Formulation Example 8 Granules Add 6 parts of the compound of the present invention, 5 parts of Toyolignin CT (registered trademark of Toyobo, lignin sulfonate) and 90 parts of GSM clay (registered trademark of Zeeklite Co., Ltd., quartz powder),
Stir and mix thoroughly in a crusher. Next, water in an amount equivalent to 104 parts of these mixtures is added, and the mixture is further stirred, granulated using a granulator, and dried through ventilation to obtain 6% granules.

Formulation Example 4 Powder 6 parts of the compound of the present invention were dissolved in 20 parts of A7Tone, 808 parts of Carplexna, 0.8 part of P A P and 80 G
Add 91.7 parts of mesh talc, mix with stirring using a jet mixer, and remove acetone by evaporation to obtain a 6% powder.

Formulation Example 5 Oil Solution 20 parts of the compound of the present invention is dissolved in 80 parts of kerosene to obtain a 20% oil solution.

Next, the insecticidal, nematicidal, acaricidal efficacy and toxicity tests of the compounds of the present invention will be shown in test examples. In addition, unless otherwise specified, each test example was repeated 8 times. In addition, the comparative compounds listed in Table 1 were used.

Table 1 (2): Compounds described in Japanese Patent Publication No. 49-21768 (
g): Japanese Patent Publication No. 48-22446 〃0: Special Publication No. 4
No. 6-14759〃Test Example 1 414mJ of the water diluted spray solution of the compound of the present invention and the comparative compound 414m(El,
ne$p,) After mixing with the contaminated soil Boot to reach a predetermined concentration in the soil, 8 tomatoes at the 8-4 leaf stage were planted. After 8 weeks, the degree of colonization was observed and evaluated according to the following classifications.

Degree of Nekobu settlement - No settlement 1 to 10 Less than 10% settlement compared to untreated area
# 10-40% epiphyte + #
Table 2 shows the results of settlement of 40 to 804, which are equivalent to those of the untreated plot.

Table 2 Test Example 2 6 mJ of diluted water solution of each of the emulsions of the present compound and comparative compound A, @, formulated according to Formulation Example 1, was mixed with 50F soil to adjust the concentration of the active ingredient in the soil to tppm. . This soil was placed in a polyethylene cup with a diameter of 5.6 mm and a height of 5.85 mm, and two roots of corn 2~8511 were planted at the same time.
brotica undecim unctata ho
wardi BARBER) Ten 8th instar larvae were released. Two days later, the survival and death of the larvae and the number of writhing insects were investigated, and the rate of young dead insects (@) was determined. The results are shown in Table 8.

Table 8 Test Example 8 Sowing 1ff! Potted green beans after 7 days (first leaf stage)
Ten female adult spider mites were infested per vegetable and stored in a constant temperature room at 25°C.

After 6 days, a diluted solution of the emulsion of the present compound and the control compound prepared according to IJ Formulation Example 2 with water (equivalent to 500 ppm) was sprayed at 15 mj per pot on a turntable.
At the same time, 2 ml of soil was injected. Eight days later, the degree of damage caused by spider mites to each plant was investigated.

The effectiveness criteria are −: Hardly any damage is observed.

+: Slight damage is observed.

+: The same damage as in the untreated area is observed.

Closed. The results are shown in Table 4. Table 4 Test Example 4 The weight of 6-week-old ICR mice that had been fed approximately 24 hours a day was measured using an electronic balance. A mouse gastric tube was attached to a syringe filled with the test preparation, the tip was inserted into the stomach by sliding it in the back of the throat, and a predetermined amount of liquid was injected. After 4 hours g+W of administration, the animals were given food and water, and observations were made for 7 days to determine where they died (5 animals per group). , the results are shown in Table 5.

Table 5 <Effects of the invention> The compounds of the present invention live in soil electrification and are useful in various crops, flower plants,
It is an effective compound against soil-destroying pests, nematodes, and mites that feed on grass plants.

Claims (3)

[Claims] (1) Formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ O-ethyl S-t-butyl O -Phenylphosphorothiolate. (2) A formula characterized by reacting O-ethyl O-phenylphosphoryl chloride and t-butyl mercaptan represented by the formula ▲ Numerical formulas, chemical formulas, tables, etc. in the presence of a base ▲ Numerical formulas, chemical formulas, There are tables etc. ▼ Production method of O-ethyl S-t-butyl O-phenylphosphorothiolate. (3) Insecticides, nematocides, and nematicides characterized by containing O-ethyl S-t-butyl O-phenylphosphorothiolate as an active ingredient, represented by the formula ▲ Numerical formulas, chemical formulas, tables, etc.▼ Mite agent.