JPH02264785A - O,o-diethyl o-1-(n-methoxyimino)ethyl phosphorothioate geometric isomer and soil pest preventive with same as active ingredient - Google Patents

Abstract

NEW MATERIAL:Such a geometric isomer, among those involving the C = N bond of a compound of formula I, that the C-signal for the C = N bond in <13>C-NMR spectra (non-chloroform solution) appear in lower magnetic field side. USE:Soil pest preventives. PREPARATION:A reaction is carried out between O,O-diethylthiophosphoryl chloride of formula II and N-methoxyacetamide of formula III in the presence of a base.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention relates to the geometric isomer of 0,0-diethyl 0-1-(N-methoxyimino)ethyl phosphorothioate represented by formula (I) and its use as an active ingredient. This invention relates to soil pest control agents.

<Prior art and problems to be solved> The compound represented by the above formula (I) is disclosed in Japanese Patent Application Laid-open No. 68-810.
Although it is described in Japanese Patent Application No. 896, it does not disclose anything about the syn and anti geometric isomers regarding the C;N bond, and it cannot be said that it is necessarily sufficient for practical use as a pest control agent for earthen walls.

Means for Solving the Problems> As a result of intensive studies to develop an excellent soil pest control agent, the present inventors found that among the geometric isomers regarding the C=N bond of the compound represented by the above formula (I), ``The geometric isomer (hereinafter referred to as compound CA) in which the signal of the carbon atom of the C=N bond in the C-NMR spectrum (deuterated chloroform solution) appears more on the lower magnetic field side is the one in which the signal is more The geometric isomer that occurs on the high magnetic field side (hereinafter, compound CB
). ), it has been found that acute toxicity and fish toxicity are lower than those of the previous method, leading to the present invention.

Generally, compounds of formula (I) are of formula 0 (CtHsO
)! PCI ([0 denoted by D,
O-diethylthiophosphoric acid chloride and the formula surface CHsCNHOCHs ([1
JP-A-6B-81089 shows that it can be obtained by reacting N-methoxyacetamide represented by 0 in the presence of a base.
It is stated in Publication No. 6. The present inventors found that compounds manufactured according to the production example in the publication are compound CB) and compound (A).
) and that a highly toxic compound represented by Ohdan's formula a) is produced as a by-product.
A selective manufacturing method for compound (A) was also developed by improving this manufacturing method.

Compound (A) is obtained by combining 01O-diethylthiophosphoric acid chloride represented by formula O and N-methoxyacetamide represented by formula (2) in the presence of a deoxidizing agent such as aqueous sodium hydrogen carbonate.
Using monohard copper ions such as cupric chloride and a phase transfer catalyst, the pH of the reaction solution is adjusted to 7.5 to 8 in a two-phase system of organic solvent and water.
．． By carrying out the reaction while maintaining the temperature of 5, it can be produced selectively in high yield.

The amount of the reagent used in the reaction is usually 1 to 2 equivalents of the compound represented by formula (2) and 1 to 2 equivalents of the deoxidizing agent per 1 equivalent of the compound represented by formula (2). The amount of water relative to the deoxidizing agent is about 1 to 2 times the weight. Examples of the deoxidizing agent include sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, and sodium hydroxide. Examples of sources of hard copper ions as catalysts include cuprous chloride, cuprous oxide, etc., and examples of phase transfer catalysts include tetrabutylammonium bromide, penzyltriethylammonium (M), etc. Examples include quaternary phosphonium salts such as quaternary ammonium salt of parrot, tetrabutylphosphonium bromide, and butyltriphenylphosphonium chloride. - Hard copper ions and phase transfer catalysts are each usually used in an amount of 0.01 to 0.8 equivalents per equivalent of the compound represented by formula 0. Examples of organic solvents used in the reaction include aromatic hydrocarbons such as toluene and benzene. The reaction temperature and reaction time vary depending on the catalyst and solvent used, but
Generally, the temperature is 50 to 80°C for about 2 to 5 hours. The reaction solution has a pH of 7.5 to 8.5, preferably 8.5. The pH in the reaction system is maintained at around 0, and in some cases, a deoxidizing agent is added dropwise to
It is better to adjust H. After the reaction is completed, usual post-treatment is carried out.

Compound (A) can be used, for example, to pests of the genus Diabrotica such as Western corn rootworm, northern corn rootworm, and southern corn rootworm;
A genus pests, Au1acophora genus pests such as cucurbit beetles, Phyllotreta genus pests such as leaf beetles, and Melanotus g
Agr io of pests, tobiiromunabosoko plating, etc.
Pests of the genus Hylemya, such as onion fly, radish fly, and seed fly; pests of the genus Agrotis, such as Kaburaya moth and Tamanaya moth; Gryl 1o, such as mole crickets;
Li5sor of talpa genus pests, rice weevils, etc.
Pests of the genus hoptrus, pests of the genus Pratylenchus such as northern nematode, walnut nematode, and southern nematode; pests of the genus Heterodera such as soybean cyst nematode; Meloi of Sencheu et al.
Ap of dogyne pests, rice nematode, etc.
It is highly effective against various soil pests such as the genus Helienchoides.

When the compound (A) of the present invention is used as an active ingredient of 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. Then, it is formulated into oils, emulsions, wettable powders, granules, powders, aerosols, etc. for use.

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%.

Examples of solid carriers include clays (such as kaolin, diatomaceous earth, synthetic hydrous silicon oxide, fubasamiclay, bentonite, and acid clay), talcs, and other inorganic minerals (such as sericite, quartz powder, sulfur powder, activated carbon, calcium carbonate, hydrated silica), chemical fertilizers (e.g. ammonium sulfate,
Examples of liquid carriers include water, alcohols (e.g., methanol, ethanol), ketones (e.g., acetone, methyl ethyl ketone), and aromatic carbons. Hydrogens (e.g. benzene, toluene, xylene, ethylbenzene, methylnaphthalene), aliphatic hydrocarbons (e.g. n-hexane, cyclohexanone, kerosene, kerosene), esters (e.g. ethyl acetate, butyl acetate)
, nitriles (e.g. acetonitrile, imbutyronitrile), ethers (e.g. dioxane, diisopropyl ether), acid amides (e.g. dimethylformamide, dimethylacetamide), halogenated hydrocarbons (e.g. dichloroethane, trichloroethylene,
Examples of the gaseous carrier, ie, propellant, include chlorofluorocarbon gas, butane gas, carbon dioxide gas, and the like.

Examples of surfactants include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, alkylaryl ethers and their polyoxyethylenic products, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives, etc. can give.

Examples of fixing agents and dispersants include casein, gelatin, polysaccharides (such as starch powder, gum arabic, cellulose derivatives, and alginic acid), lignin derivatives, bentonite, sugars, and synthetic water-soluble polymers (such as polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylics). acids)
Examples of stabilizers include PAP (isopropyl acid phosphate), BHT (2,6-tert
-butyl-4-methylphenol), BHA (2-te
rt-butyl-4-methoxy7znort8-ter
(mixtures with t-butyl-4-methoxyphenol), botanical oil, mineral oil, surfactants, fatty acids or esters thereof, and the like.

The above 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 irrigated, and sometimes they are sprayed on stem vegetables. It can also be used simultaneously with or without mixing with other insecticides, acaricides, nematicides, fungicides, mild disinfectants, fertilizers, or soil conditioners.

<Examples> Hereinafter, the present invention will be explained in more detail with reference to production examples, formulation examples, and test examples, but the present invention is not limited to these examples.

First, a production example of compound [A] will be given.

Production Example 1 251 parts of water was added to 16.8 F of sodium hydrogen carbonate, and 2.5 parts of tetrabutylammonium was added. Of.

Cuprous chloride 2. Of, N-methoxyacedo [do 9.8
f and 85 f of toluene were added. 0.0 at room temperature under stirring.
18.9F of 0-diethylthiophosphoric acid chloride was added, heated and maintained at 80"C for 8 hours.

After cooling, it was filtered through Celite, and the toluene counterfeit separated from the P liquid was washed with saturated brine and dried over anhydrous magnesium sulfate.

After removing the solvent, compound [A] 22.61C (yield 98%)
I got it.

Gas chromatography analysis (column: 10% Salmon 8000.1.5 m, inlet temperature 260°C, column temperature 1
As a result, it was confirmed that 97.1% of compound 6(A) and 0.794 of the compound represented by formula (5) were contained. .

In addition, analysis by high performance liquid chromatography (column; SUMIPAX R-618, Lichrosor
bRP-8,4m13X25z1 expansion a; itanol/
Water = 8/2, V/V) As a result, the production ratio of compound (A) and metal compound (B) was 99/1.

Compound (A) was purified by silica gel chromatography to obtain the following physical property data.

n21°"1.4665 uv; ,! evening'-" 205nm (g-460
0)ax IR(51-'); 2992(m), 2944(f
i), 2914 (m), 1659 (m, C=N), 14
46 (m), 1877 (m), 1280 (S), 118
g(m), 1164(m), 1068(s), 1028
(s), 972(s), 888(m), 825(s)
, 780(8)MS 'H-NMR (60MHz); δ (ppm)D
C1m 1.80 (6H, t, J=6Hz), 2.00 (IH,
s), 8.72 (8H, s), 8.90-4.45 (4
H, m) MS ”C-NMR (22,5 MHz); δ (pp
m) CDCA! 11 14.24 (d, Jcp=4.2Hz), 15.81
(d, Jcp=7.6Hz), 62.08.65.
07 (d, Jcp=5.5Hz), 155.7
1(d=J(p=8.8H2)gPO4 SIP-NMR(109MHz); δ(CDs)x
co (ppm) -60,40 Elemental analysis value theoretical value (CyHrsNO4PS= 241.27)C
:84.84, H;6.70. N; 5.81, P;
12.84, S; 1 B, 29 (96) Actual value C; 84.70, H; 6.65, N; 5.92, P
; 12.50, S; 18.40 (%) Production Example 2 Potassium hydrogen carbonate was used instead of sodium hydrogen carbonate in Production Example 1 to cause a reaction (reaction time was 4 hours). As a result, compound (A) was reduced to 91 % yield.

As a result of gas chromatography analysis, the compound (A
) 98.2%, compound O, S 9 represented by formula (2)
It was confirmed that 6 was included.

In addition, as a result of analysis by high performance liquid chromatography,
Combine with compound (A)! The production ratio with fi ('B) is 99
/1.

Production Example 8 The reaction was carried out using sodium carbonate instead of sodium hydrogen carbonate in Production Example 1 (reaction temperature: 60-60°C, reaction time: 4 hours). As a result, compound (A) was produced in a yield of 88.6%. Obtained.

As a result of gas chromatography analysis, the compound (A
) 98.2%, compound represented by formula (2) 0.6%
was confirmed to be included.

Next, the production of compound (3) for use in the test examples described below will be described in reference examples. Compound CB) is disclosed in JP-A-68-8
In the method described in Publication No. 10896, by using sodium hydroxide as a base and tetrahydrofuran as a solvent, or by using calcium oxide as a base and methyl isobutyl ketone as a solvent, almost no by-product of the compound represented by formula (2) is produced. and selectively for compound CB) (compound [A]: compound CB) at about 1:99)
can get.

Reference Example N-Methoxyacedeamide 11.6jF was dissolved in methyl isobutyl ketone 6o-, and calcium oxide 7.6jF was dissolved therein.
Added 8g. While keeping the reaction solution at 60-70°C,
Add 18.9jF of 0-diethylthiophosphoric acid chloride,
After being kept at 80'C for 7 hours, the mixture was allowed to cool and filtered through Celite. F[ was concentrated under reduced pressure, water and toluene were added, and the toluene layer was separated. The toluene solution was washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was removed to obtain Te compound (B) 22.801 (yield 94.5%).

Gas chromatography analysis (column: 10% Salmon 8000, 1.5 m, inlet temperature 26011c, column temperature raised from 100°C to 200°C at a rate of 7.5°C/min)
As a result, it was confirmed that 99.6% of compound CB) and 0.2% of the compound represented by formula (2) were contained.

In addition, analysis by high performance liquid chromatography (column; SUMIPAX R-618, Lichrosor
As a result of bRP-8,4- ×26 tan, developing solution; methanol/water = 8/2, V/V), compound (A) and compound (
The production ratio with B) was 1/99.

Compound CB) was purified by silica gel chromatography to obtain the following physical property data.

21.0 nD 1.4640 Uv; λ1ri'-" 205 nm (g=4
700) ax IR (cWA'); 2986 (m), 2988 (m
), 2860 (m), 1659 (m, C=N), 146
7(m), 1448(m), 1886(8), 1254
(8), 1188 (m), 1164 (m), 1028 (
8), 975(8), 972(8), 908(S),
825 (S), 758 (S) 1.85 (6H,t,
J=6Hz), 2.05 (8H, d, J=2Hz)
, 8.75 (8H, S), 8.90-4.45 (4H.

m) 15.81 (d, Jo, = 7.6 Hz), 1 'i, 7
1.61.88.65.00 (d, JCP=5.5H
z), 145.01 (d, JcP=9.9Hz) -58,60 Elemental analysis value theoretical value (Cy) ItsNOt PS = 241.27
) C:;84.84, H;6.70, N;5.
81, P; 12.84, S; 1B, 29 (%) Actual value C; 84.65, )l; 6.91, N; 5.701P
; 12.60, S; 18.05 (%) Next, formulation examples are shown. Note that parts represent parts by weight.

Formulation Example 1 40 parts of emulsion compound (A) was dissolved in 50 parts of xylene, and 10 parts of emulsifier Tsurupol 5M-200 (registered trademark of Toho Chemical, a mixture of polyoxyethylene alkylaryl ether, etc. and dodecylbenzenesulfonic acid) was added. Add and stir well to obtain a 40% emulsion.

Formulation Example 2 Add 5 parts of Tsurupol 5M-200 (above) to 40 parts of the wettable powder compound (A), mix well, and prepare a carpre.

Add 20 parts of #80 (registered trademark of Geotsugi Pharmaceutical, synthetic hydrated silicon oxide fine powder) and 85 parts of 800 mesh diatomaceous earth, and stir and mix with a juice mixer to obtain a 40% hydrating powder.

Formulation Example 8 Granules To 5 parts of compound [A], 5 parts of Toyolignin CT (registered trademark of Toyobo, lignin sulfonate) and 90 parts of GSM clay (registered trademark of Sieglite Mining Co., Ltd., quartz powder) were added, and the mixture was placed in a pickling vessel. Stir thoroughly to combine. Next, an amount of water equivalent to 10% of the mixture is added, and the mixture is further stirred, granulated using a granulator, and dried with ventilation to obtain 5% granules.

Formulation Example 4 Powder Dissolve 5 parts of compound [A] in 20 parts of acetone, add 8 parts of Carplex $80 (above), 08 parts of PAPO, and 80 parts of PAPO.
Add 91.7 parts of 0 Metsstarck, stir and mix using a juice mixer, and remove acetone by evaporation to obtain a 5% powder.

Formulation Example 5 20 parts of oil compound (A) was dissolved in 80 parts of kerosene to obtain 20 parts of oil.
Obtain % oil solution.

[ω] When used as an active ingredient in the present invention compound Usuiwadosan pest control agent, the application amount is usually from 109 to 100 per 10 are, preferably from 50 to 500, and the application concentration is emulsion, When diluting with water, such as a permanent agent, the amount is 0.01% to 80%.

These application amounts and concentrations will vary depending on other circumstances such as the type of formulation, application time, application location, application method, type of soil-destroying pest, degree of damage, etc., and may increase without regard to the above range. can be reduced.

Next, the control efficacy of compound (A) against soil pests will be shown in test examples. The test was repeated 8 times. Among the test compounds, the compounds used for comparison are indicated by compound symbols in Table 1.

Table 1 The active ingredient concentration in the soil was adjusted to 0.5, 0.25 or 0.125 ppm by mixing.

This soil has a diameter of 5.6 ant and a height of 5.8 cm.
Fill a polyethylene cup with 2 roots, plant 2 kernels of corn with roots 2 to 8 cm in height, and add Southern corn rootworm (D
iabrotica undecimpunctata
Ten 8th instar larvae (howardiBARBER) were released. Two days later, the number of living and dead larvae was investigated to determine the mortality rate (%). The results are shown in Table 2.

Table 2 Test Examples A water diluted solution 5- of the emulsion of the test compound prepared according to Formulation Example 1 was added to soil (16 mesh) 501. Compound 1'A) and Compound ['B'') The results of the acute toxicity test and the fish toxicity test on carp are shown in Table 8.

In the table, LD6 (l indicates the 60% lethal dose, and TLM4g indicates the 60% lethal concentration after 48 hours.

<Effects of the Invention> Compound (A) is a compound that is highly effective against soil pests and has excellent safety, and is useful as a soil pest control agent.

Claims (2)

[Claims] (1) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Among the geometric isomers regarding the C=N bond of the compound shown by, the carbon atom of the C=N bond in the ^1^3C-NMR spectrum (deuterated chloroform solution) The geometric isomer in which the signal appears on the lower magnetic field side. (2) Among the geometric isomers related to the C=N bond of the compound shown by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. A soil pest control agent characterized by containing as an active ingredient a geometric isomer whose signal appears on the lower magnetic field side.