JPH01197494A - Organic phosphorus compound, production thereof and soil insect pest controlling agent containing said compound as active ingredient - Google Patents

Abstract

PURPOSE:To obtain the title compound capable of exhibiting excellent effects as a soil insect pest controlling agent, by reacting a thiophosphoric acid amide (thiophospboric acid) chloride with N-methoxyacetamide in the presence of a base. CONSTITUTION:(A) One equiv. thiophosphoric acid amide (thiophosphoric acid) chloride expressed by formula I [R<1> is methyl or ethyl; R<2> is alkyl or mono(di) alkylamino] is reacted with (B) 1-2 equiv. N-methoxyacetamide expressed by formula II in the presence of (C) 1-2 equiv. base, such as pyridine or NaOH, in (D) a solvent, such as toluene or acetone, at 0-100 deg.C for 0.5-24hr. The resultant reaction product is then subjected to treatment, such as extraction with an organic solvent, to afford the aimed compound expressed by formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to an organophosphorus compound, a method for producing the same, and a soil pest control agent containing the same as an active ingredient.

<Prior art> Until now, compounds similar to the compound of the present invention include:
For example, JP-A-47-9149, JP-A-58-39
No. 692 and U.S. Patent No. 4,473,562
There is a compound described in the specification of No.

<Problems to be Solved by the Invention> However, it cannot be said that the compounds disclosed in the above-mentioned publications are necessarily sufficient as active ingredients for insecticides, especially soil pest control agents.

Means for Solving the Problems> The present inventors have conducted intensive studies to find a control agent that is effective against so-called soil pests that live in the soil and cause great damage to crops. [In the formula, R1 represents a methyl group or an ethyl group, and R2 represents an alkyl group, a monoalkylamino group, or a dialkylamino group. ) (hereinafter referred to as the compound of the present invention) is
It was found that it has extremely excellent efficacy.

By the way, the compound of the present invention is disclosed in U.S. Patent No. 4.473.
．． Although it is included in the general formula described in Specification S of No. 562, there is no specific description or even suggestion of the compound of the present invention in the specification, and there is no description of test examples against soil pests. On the other hand, as shown in the test examples, it was confirmed that the compound of the present invention has extremely superior insecticidal efficacy against soil pests compared to known compounds with extremely similar chemical structures, leading to the present invention. .

The compound of the present invention can be produced, for example, by the following method.

General formula (II) [In the formula, R1 and R2 represent the same meanings as above.

] Thiophosphoric acid amide (thiophosphonic acid) chloride represented by the formula (I[I) CH,CN HOCH, (III) is reacted with N-methoxyacetamide represented by the formula (I[I) CH,CN HOCH, (III) in a solvent in the presence of a base.

This production method is usually carried out under the following reaction conditions.

The amounts of reagents used in the reaction are 1 to 2 equivalents of N-methoxyacetamide (■) and 1 to 2 equivalents of base per 1 equivalent of thiophosphonic acid chloride (I[). Examples of the base include inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, and potassium carbonate, and organic bases such as pyridine and triethylamine. different, but - each 0 to 100 in the membrane
'C130 minutes to 24 hours. Examples of solvents include aromatic hydrocarbons such as toluene and benzene, ketones such as methyl ethyl ketone and acetone, diethyl ether,
Ethers such as tetrahydrofuran, acetonitrile,
Examples include water and mixtures thereof.

After completion of the reaction, the desired compound of the present invention can be obtained by performing usual post-treatments such as extraction with an organic solvent, and purification by column chromatography or the like is also possible if necessary.

The compounds of the present invention are suitable for use in pests of the genus D 1abrotica such as Western corn rootworm, northern corn rootworm, and southern corn rootworm;
Pests of the genus A, such as cucumber beetles, P hyllotreta of the genus Aulacophora, such as the leaf beetle
Pests of the genus MelanoLus
Agrio such as ll'll, Tobiiromunabosoko plating etc.
tes 16 Insects such as onion fly, radish fly, seed fly, Hylemya genus pests, Agrotis genus pests such as Capraya moth, Kumanaya moth, Gryl such as mole crickets, etc.
L 1s of 1otalpa genus pests, rice weevils, etc.
Pests of the genus sorhoptrus, pests of the genus Pratylenchus such as Aster nematode, walnut nematode, and southern nematode; pests of the genus Heterodera such as soybean cyst nematode; M of
It is highly effective against various soil pests such as eloidogyne pests and A phelenchoides pests such as the nematode.

When the compound of the present invention is used as an active ingredient in a soil 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. , emulsions, wettable powders, granules, powders, aerosols, etc.

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

Examples of solid carriers include clays (kaolin clay,
Diatomaceous earth, synthetic hydrated silicon oxide, bentonite, fusamiclay, acid clay, etc.), talc, other inorganic minerals (sericite, quartz, sulfur, activated carbon, calcium carbonate, hydrating acid, etc.), chemical fertilizers (ammonium sulfate, ammonium phosphorus, etc.) , ammonium nitrate, urea, ammonium chloride, etc.), and examples of liquid carriers include water, alcohols (methanol,
, ethanol, etc.), ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (benzene, toluene,
xylene, ethylhenzene, methylnafculene, etc.), aliphatic hydrocarbons (hexane, cyclohexane, kerosene, kerosene, etc.), esters (ethyl acetate, butyl acetate, etc.)
, nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopylether, dioxane, etc.)
, acid amides (dimethylformamide, dimethylacetamide, etc.), halogenated hydrocarbons (dichloroethane,
(trichloroethylene, carbon tetrachloride, etc.), and gaseous carriers, ie, propellants, include, for example, chlorofluorocarbon gas, butane gas, carbon dioxide gas, and the like.

Examples of surfactants include alkyl sulfates,
Examples include alkyl sulfonates, alkylaryl sulfonates, alkylaryl ethers and polyoxyethylenized products thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives, and the like.

Examples of formulation auxiliaries such as fixing agents and dispersants include casein, gelatin, polysaccharides (starch powder, gum arabic,
cellulose derivatives, alginic acid, etc.), lignin derivatives,
Examples of stabilizers are PAP (isopropyl acid phosphate), BIT (2,6-tert-butyl-4 -methylphenol), BHA (2-ter
t-butyl-4-methoxyphenol and 3 tert
-butyl-4-methoxyphenol), vegetable oils, mineral oils, surfactants, fatty acids or esters thereof, and the like.

The preparation thus obtained is used as it is or diluted with water, etc., and sprayed on the soil surface, and if necessary, after spraying, it is mixed with the soil or irrigated, and sometimes it is used by spraying on the foliage. In addition, other insecticides, nematicides, acaricides,
It can also be used simultaneously with or without mixing with fungicides, herbicides, plant growth regulators, fertilizers, and soil conditioners.

When the compound of the present invention is used as an active ingredient of a soil insect control agent, the application amount is usually 10 to 10 per 10 are.
00 g, preferably 50 to 500 g, and when applying emulsions, wettable powders, etc. diluted with water, the application concentration is 0.00 g, preferably 50 to 500 g.
01 to 30%, and powders, granules, oils, aerosols, etc. are applied as they are without any dilution.

These application amounts and concentrations vary depending on the type of formulation, application time, application location, application method, pest species11, degree of damage, etc., and may be increased or decreased regardless of the above range. You can

<Examples> The present invention will be explained in more detail below using production examples, formulation examples, and test examples, but the present invention is not limited thereto.

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

Production Example 1 1.61 g of N-methoxyacetamide and 1.01 g of powdered potassium hydroxide were suspended in 100 ml of acetonitrile and stirred at 50°C for 1 hour. To this, 3.12 g of 0-ethyl ethylthiophosphonic acid chloride was added dropwise. After the dropwise addition was completed, the mixture was further stirred at 80'C for 5 hours. After the reaction is complete, acetonitrile is distilled off under reduced pressure, 50 m2 of Hensen and water are added to separate the layers, and the organic layer is added with 50 m2 of a 2% aqueous sodium hydroxide solution. Then, after washing twice with 50 m2 of water, drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the resulting residue was subjected to silica gel column chromatography to obtain 0-ethyl 0-1
-(N-Methoxyimino)ethyl 0.2 g of ethylthiophosphonic acid ester [the compound (1) of the present invention] was obtained.

Production Example 2 1.73 g of 60% sodium hydride was suspended in 100 mj2 of tetrahydrofuran, and while stirring at room temperature, N
-3.84 g of methoxyacetamide was added dropwise. After the addition was completed, the mixture was further stirred for 1 hour, and then 5.0 g of O,N-dimethyl thiophosphoric acid amide chloride was added dropwise at room temperature.

After the dropwise addition was completed, the reaction solution was heated and refluxed for 2 hours. After the reaction, tetrahydrofuran was distilled off under reduced pressure, 50 ml of chloroform and water were added to separate the layers, and the organic layer was washed twice with water, dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The resulting residue was subjected to silica gel column chromatography, and O,N-dimethyl 0
0.2 g of -1-(N-methoxyimino)ethylthiophosphoric acid amide ester [the compound (2) of the present invention] was obtained.

The compounds of the present invention obtained according to these production examples are summarized in Table 1.

1st Compound of the Invention Displayed Next, a formulation example is shown below, where parts represent parts by weight. Formulation Example 1
Emulsion 40 parts each of compounds (1) to (3) of the present invention were added to 5 parts of xylene.
Dissolve in 0 parts of emulsifier Tsurupol 5M-200 (registered trademark of Toho Chemical, mixture of polyoxyethylene alkylaryl ether, etc. and dodecylbenzenesulfonic acid) 1
Add 0 parts and stir and mix thoroughly to obtain each 40% emulsion.

Formulation Example 2 Wettable powder 5 parts of the emulsifier Tsurupol 5M-200 were added to 40 parts each of the compounds of the present invention (1) to (3), mixed well, and Carplex #80 (registered trademark of Shionogi & Co., Ltd. , synthetic hydrated silicon oxide fine powder) and 35 parts of 300 mesh diatomaceous earth were added and stirred and mixed with a juice mixer to obtain each 40% permanent agent.

Formulation Example 3 Granules To 5 parts each of the compounds (1) to (3) of the present invention, 5 parts of Toyolignin CT (registered trademark of Toyobo, lignin sulfonate) and 90 parts of 03M clay (registered trademark of Zeekrite Mining, quartz powder). Add 100% and mix thoroughly in a crusher.

Next, water equivalent to 10% of these mixtures was added, further stirred, granulated with a granulator, and dried with ventilation to give 5% of each.
Obtain granules.

Formulation Example 4 Powder 5 parts each of the compounds (1) to (3) of the present invention were mixed with 20 parts of acetone.
3 parts of Carplex #8°, 0.3 parts of P A P and 91.9 parts of 300 ml of Carplex #8°.
Add 7 parts, stir and mix using a juice mixer, and remove acetone by evaporation to obtain each 5% powder.

Formulation Example 5 Oil Solution 20 parts of each of the compounds (1) to (3) of the present invention are dissolved in 80 parts of kerosene to obtain a 20% oil solution.

Next, test examples demonstrate that the compounds of the present invention are useful as active ingredients for soil pest control agents. Compounds used for comparison are indicated by compound symbols in Table 2.

Table 2 Test Examples 5mf of the water diluted emulsion of each test compound prepared in Formulation Example 1 was mixed with 50g of soil (16 mesh) to bring the concentration of the active ingredient in the soil to 1.0.0. .5 or 0.25
I made it ppm.

This soil was packed into a polyethylene camp with a diameter of 5.6 cm and a height of 5.8 cm, and two roots of corn were planted at a height of 2 to 3 cm, and southern corn rootworm (D1
abrotica undecim unctata
10 3rd instar larvae were released. After 20 days, the survival rate of the larvae (%) was determined.
was calculated (2 repetitions). The results are shown in Table 3.

Table 3 <Effects of the Invention> The compounds of the present invention exhibit extremely excellent insecticidal efficacy against soil pests that live in the soil and damage various crops, flowers, lawns, etc.

Claims (3)

[Claims] (1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 represents a methyl group or an ethyl group, and R
^2 represents an alkyl group, a monoalkylamino group or a dialkylamino group. ] An organic phosphorus compound represented by (2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1 represents a methyl group or an ethyl group, and R
^2 represents an alkyl group, a monoalkylamino group or a dialkylamino group. ] Thiophosphoric acid amide (thiophosphonic acid) chloride represented by the formula ▲ Numerical formula, chemical formula, table, etc. are available ▼ is reacted with N-methoxyacetamide in the presence of a base. A method for producing an organic phosphorus compound represented by the general formula described in item 1. (3) A soil pest control agent characterized by containing an organic phosphorus compound represented by the general formula according to claim 1 as an active ingredient.