JPS5942396A - Phosphoric acid amide derivative and insecticidal, miticidal and nematocidal agent containing the same - Google Patents

Abstract

NEW MATERIAL:The compound of formula I [X is halogen, alkyl(thio), alkoxy, cyano, nitro or trifluoromethyl; Y is H or alkyl; Z<1> and Z<2> are O or S; R<1> is alkyl; R<2> is alkyl(thio), alkoxy, or phenyl; A is =CH or =N-; n is 0-4, provided that when A is =N-, n is 0-3]. EXAMPLE:O, O-Diethyl-N- 3-chloro-5- trifluoromethylpyridin- 2- yl -phosphoramide thioate. USE:An insecticidal, miticidal and nematocidal agent. PROCESS:The ojective compound can be prepared e.g. by reacting the compound of formula II (e.g. 2-amino-3-chloro-5-trifluoromethylpyridine) with the compound of formula III (HAL is halogen) (e.g. O,O-diethylchlorothiophosphate) in a solvent such as THF in the presence of an acid acceptor preferably at -30-+50 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides novel phosphoric acid amide derivatives that exhibit effective control action against harmful insects, mites, and nematodes, and insecticidal, acaricidal, and acaricidal agents containing the derivatives as active ingredients. Regarding nematicides.

The compound of the present invention is a novel phosphoric acid amide derivative represented by the following general formula (I).

2- In the formula, X is a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, a cyano group, a nitro group, or a trifluoromethyl group;
1 and Z2 are oxygen atoms or sulfur atoms, R1 is an alkyl group, R2 is an alkyl group, alkoxy group, alkylthio group, or phenyl group, A is a group =CH- or =N-, and n is It is 0 or an integer from 1 to 4. However, when A is M=N-, n is O or an integer from 1 to 3.

Examples of the halogen atom represented by X in the general formula (1) include fluorine, chlorine, bromine and iodine;
Alkyl group represented by R1 and R2 or X and R2
Examples of the alkyl moiety of the alkoxy group and alkylthio group represented by the above include methyl, ethyl, propyl, butyl, and the like.

The compound of the present invention can be produced, for example, by the following method.
Z', Z2, R', R2, A and 11 are as described above. ) The reactions of [A] and [r3) above are usually -1
00=150°C, preferably in a temperature range of -80 to 50°C.

In addition, these reactions take place in the presence of acid acceptors,
As acid acceptors, trialkylamines, pyridine, N
, tertiary amines such as N-dialkylaniline, alkali metal or alkaline earth metal hydrides, hydroxides,
Inorganic bases such as carbonates or bicarbonates, alkali metal or alkaline earth metal salts of alcohols such as sodium methoxide and potassium-1-butoxide, organic bases such as n-butyllithium, phenyllithium, lithium diisopropylamide, etc. Examples include lithium. Furthermore, these reactions are preferably carried out in the presence of a solvent, and examples of solvents include ethers such as diethyl ether and tetrahydrofuran, and aprotic solvents such as acetonitrile, dimethylformamide, dimethyl sulfoxide, and hexamethylphosphoric triamide. Polar solvents, acetone, ketones such as methyl ethyl ketone, benzene,
Examples include R hydrogenated compounds such as toluene and chloroform.

4- Synthesis Example 1 Synthesis of o,n-diethyl-N-3-chloro-5-trifluoromethylpyridin-2-yl-phosphoramidothioate 2 g of 2-amino-3-chloro-5-trifluoromethylpyridine , and the solution was cooled to -78°C. There, 7.2 m of a rhohexane solution (1.7 molar concentration) of n-butyllithium was added.
ρ was gradually added dropwise while stirring, and stirring was continued for 15 minutes after the addition. Next, 2.2 g of (), 0-diethylchlorothiophos 7-) was gradually added dropwise, and stirring was continued for 30 minutes. Thereafter, the temperature of the solution was gradually returned to room temperature, and the reaction was carried out at room temperature for 12 hours. After the reaction was completed, the product was poured into ice water, extracted with methylene chloride, and the extracted layer was washed with brine. Next, it was dried with sodium sulfate, the solvent was distilled off, and the refractive index was purified by silica gel column chromatography. 1p
1.3 g of the target product 2301.5051 was obtained.

Synthesis Example 2 Synthesis of 0-ethyl-8-propyl-N-5-iodopyrimidin-2-ylphosphoramitothiolet 1. a In the above Synthesis Example 1, 30 mρ of tetrahydrofuran,
2-Amino-3 was added to a mixed solvent of 30 mρ of tetrahydrofuran and 10 nρ of hexamethylphosphoric triamide.
-Chloro-5- 2 g of 5-trifluoromethylpyridine was added to 2-amino-
To 2.2 g of 5-iodopyrimidine was added 2 g of O,O-diethylchlorothiophos 7-2), and 2 g of Q-ethyl-8-propylphosphorochloride thiole) 2.4. The reaction and purification treatments were carried out in the same manner as in Synthesis Example 1 except that H was used instead, to obtain 0.3 g of the target product having a melting point of 88 to 93°C.

Table 1 shows typical examples of the compounds of the present invention produced by the above-mentioned Synthesis Examples 1 and 2 or by general production methods.

6--7 The compound of the present invention exhibits excellent activity as an active ingredient of insecticides, acaricides, and nematicides, as shown in the test examples below.

For example, plant parasitic mites such as two-spotted spider mite, false red spider mite, citrus spider mite, etc., external parasitic mites such as house dust mite, diamondback moth, armyworm, Japanese armyworm, Colorado'8- potato beetle, Japanese ladybug, and green leaf mite. Agricultural pests such as aphids, leafhoppers, red hoppers, etc., sanitary pests such as cockroaches, houseflies, Culex mosquitoes, termites, etc., grain storage pests such as the bean weevil, brown weevil, etc., clothing pests such as the cutworm, etc. It is also effective against fleas, lice, flies, etc. that parasitize livestock, etc. It is also effective against harmful plant parasitics such as the sweet potato nematode, and nematodes1.

When using the compound of the present invention as an active ingredient in insecticides, acaricides, and nematicides, it can be used in emulsions, powders, wettable powders, liquids, and granules together with pesticide adjuvants, as in the case of conventional pesticide formulations. In addition to being formulated into various forms, these formulations can be used as they are, or diluted with a diluent to a predetermined concentration.

The pesticide adjuvants mentioned here include solid carriers such as talc, kaolin, bentonite, diatomaceous earth, white carbon, clay, and starch; liquid diluents such as water, xylene, toluene, dimethyl sulfoxide, dimethylformamide, acetonitrile, and alcohol; Examples include emulsifiers, dispersants, and spreading agents. In addition, if necessary, it can be mixed or used in combination with other agricultural chemicals such as 9-insecticides, acaricides, fungicides, plant growth regulators, etc., and in this case some products may exhibit even better effects.

For example, insecticides or acaricides include polyphosphate compounds, carbamate compounds, dithio (or thiol) carbamate compounds, organic chlorine compounds,
dinitro compounds, organic sulfur or metal compounds, antibiotics, substituted diphenyl ether compounds, urea compounds,
Examples include triacyl compounds, benzoyl urea compounds, and pyrethroid compounds.More specifically, N-(
2,6-difluorobenzoyl)-N'-(p-chlorophenyl)urea, N-(2,6-difluorobenzoyl)-N'-[3,5-dichloro-4-(3-chloro-5- Benzoylurea compounds such as trifluoromethyl-2-pyridyloxy)phenyl]urea, a-
Examples include pyrethroid compounds such as cyano-3-phenoxybenzyl-2-(4-chlorophenyl)isovalerate.

The insecticide, acaricide, and nematocide of the present invention are effective for controlling various harmful insects, harmful mites, and harmful nematodes, and the application is generally 1-10', 000 pp+n, preferably H20-
2. Perform at an active ingredient concentration of OOOppm. In the case of aquatic harmful insects, a chemical solution with a concentration in the above-mentioned -H)- concentration range can be sprayed to the place where the pests occur to control them, so it is effective even if the concentration range in water is below the above-mentioned range. In addition, some of the compounds of the present invention have the property of being absorbed from the roots of plants and translocating within the plant body, and these are distributed on the soil surface at 1 to 500 g/a, preferably 10 to 500 g/a.
It is also possible to spray or mix 2Or1g/a into the soil to control harmful insects parasitic on plants or soil pests.

Test Example 1 Each formulation of active ingredient compound was dispersed in water,
The concentration was adjusted to 0.00 ppm. A cup (7cm in diameter, 4cm in height) of kidney bean with only one first leaf remaining.
About 30 young adult two-spotted spider mites were inoculated into this and immersed in this chemical solution for about 10 seconds, and then air-dried for 2 hours.
Illuminated at 8°C (=t%) The insects were left in a constant temperature chamber, and on the third day after release, they were determined whether they were alive or dead.The dead weight percentage was calculated using the following formula, and the results shown in Table 2 were obtained. .

Table 2 Test Example 2 Only the roots of rice seedlings were immersed in a chemical solution adjusted to a concentration of 800 ppII for 48 hours. After thoroughly washing the roots of the treated bacteria with water, the stems were wrapped with absorbent cotton and placed in a test tube. Nymphs of the brown planthopper were released into this test tube, and the tube 1 was covered with gauze.

After 48 hours, the insects were examined to see if they were alive or dead, and the dead weight ratio was determined in the same manner as in Test Example 1, and the results shown in Table 3 were obtained.

Table 3 Test Example 3 Only the roots of kidney bean seedlings were immersed for 48 hours in a chemical solution adjusted to a concentration of 200p. After thoroughly washing the roots of the treated bacteria with water, they were transplanted into a small pot, and inoculated with about 15 young adult mites, and after 648 hours, the survival of the insects was investigated. Calculate the dead weight rate in the same way as
The results shown in Table 4 were obtained.

Table 4 Test Example 4 Cabbage leaf pieces were immersed for about 10 seconds in a chemical solution in which the active ingredient compound was dispersed in water and adjusted to a concentration of 800 ppm.
It was taken out and air-dried. A wet filter paper was placed in a 9 cm diameter veterinary dish, and a leaf piece was placed on top of the moist filter paper. Kona larvae of 2nd or 3rd instar were released into the container, and the container was placed in a lighted incubator at 28° C. with a lid. On the 5th day after release, the dead weight percentage was determined in the same manner as in Test Example 1, and the results shown in Table 5 were obtained.

13- Test Example 5 A test was conducted in the same manner as in Test Example 4 above, except that the 2nd to 3rd instars of Funaga were replaced with 2nd to 3rd instars of Spodoptera japonica, and the results shown in Table 6 were obtained.

Table 6 Test Example 6 No. 1.5 to 9.14.15 as active ingredient compound.
18.20.21 and 24-26 were used. In a cup (diameter 7 cm, height 4 cm), powdered feed 14- (product of Oriental Yeast Co., Ltd.), wheat bran, and chemical solutions of each compound were mixed in a weight ratio of 1:1:3 as a medium for house fly larvae. was added so that the concentration of each compound was 200 ppm. Third instar larvae of house flies were released into the container, covered with gauze, and left there.

When the number of eclosion was investigated after 10 days, 100% eclosion inhibition effect was observed in all test plots.

Test Example 7 Concentration 21) Add 1 ml of drug solution adjusted to Oppm to a test tube.
Take the mθ and add the second part of the sweet potato nematode into it.
Add 1 mρ of nematode solution containing about 100 stage larvae and heat at 25°C.
It was left for 24 hours. Thereafter, the nematodes were examined to see if they were alive or dead under a microscope, and the dead weight percentage was determined in the same manner as in Test Example 1, and the results shown in Table 7 were obtained. Test Example 8 10 mff of a chemical solution adjusted to a concentration of 400 ppm was poured therein and mixed uniformly. After 24 hours of mixing, onion pieces were buried in the soil as bait, and 10-day-old onion fly larva 1 was placed there.
0 were released.

After 48 hours, the insects were examined to see if they were alive or dead, and the dead weight ratio was determined in the same manner as in Test Example 1.

Test Example 9 A kidney bean with only one primary leaf left was transplanted into a cup, inoculated with adult two-spotted spider mites to spawn, and the adult was removed. Next, the kidney beans were immersed in each chemical solution of Compound No. 1.3 to 7.12.20.21.25 and 26 adjusted to a concentration of 800 ppm for 10 seconds, air-dried, and then kept at a constant temperature of 28° C. for illumination. It was left in the container. As a result of investigating the hatching status after 7 days, all were 100%.
Test Example 10: Rice seedlings were immersed in a chemical solution adjusted to a concentration of 800 ppm for 10 seconds, air-dried, the roots were wrapped with absorbent cotton, and the seedlings were placed in a test tube.

Next, I left 10 adult brown planthoppers inside.
The tube opening was covered with zeolite. After 3 days, the insects were examined to see if they were alive or dead, and the dead weight percentage was determined in the same manner as in Test Example 1, and the results shown in Table 9 were obtained.

Table 9' Test Example 11 The test was carried out in the same manner as in Test Example 10 above, except that the adults of the brown leafhopper were replaced with the adults of the leafhopper, and the results shown in Table 10 were obtained.

-17 = Table 10 Test Example 12 One tangerine seedling was added to a chemical solution adjusted to a concentration of 800 ppm.
After being immersed in 0 sand and air-dried, 15 adult citrus beetles were inoculated. After 48 hours, the insects were trimmed to see if they were alive or dead, and the dead weight percentage was determined in the same manner as in Test Example 1, and the results shown in Table 11 were obtained.

Table 11 Formulation Example 1 (a) Compound No. 3 20 parts by weight (
b) N,N-dimethylformamide 70 parts by weight - 18 = (c) Polyoxyethylene alkylphenyl ether 1
0 parts by weight or more were uniformly mixed and dissolved to form an emulsion.

Formulation Example 2 - (a) Compound No. 12 5 parts by weight (b) Talc 95 parts by weight or more of 1- was uniformly ground and mixed to form a powder.

Formulation Example 3 (a) Compound No. 1 50 parts by weight (
b) Fine powder silica 15 parts by weight (c)
Fine clay 25 parts by weight (d) Naphthalene sulfonic acid sodium formalin condensate 2 parts by weight (e) Dialkyl sulfosuccine-1.31fL
Part R (f) Polyoxyethylene alkyl allyl ether sulfate 5 parts by weight 2 were uniformly crushed and mixed to prepare a wettable powder.

Formulation Example 4 (a) Compound No. 26 5 parts by weight (b) Bentonite 45 parts by weight 19- (c) Kaolin 50 parts by weight or more are kneaded with a small amount of water, extruded into granules, and dried to form granules. And so.

Patent application hole Ishihara Sangyo Co., Ltd. 120 complete

Claims (1)

[Claims] (In the formula, X is a halogen atom, an alkyl group, an alkoxy group,
It is an alkylthio group, a cyano group, a 21.4 group or a trifluoromethyl group, Y is a hydrogen atom or an alkyl group, Zl and Z21J are an oxygen atom or a sulfur atom, and R'
is an alkyl group, R2 is an alkyl group, alkoxy group, alkylthio group, or phenyl group, and A is a group =CH
- or =N-, and n is 0 or an integer from 1 to 4. However, when 1tJ=N-, n is O or an integer of 1 to 3). 1- (wherein X is a halogen atom, an alkyl group, an alkoxy group,
an alkylthio group, a cyano group, a nitro group or a trifluoro□methyl group, Y is a hydrogen atom or an alkyl group, Zl and Z2 are an oxygen atom or a sulfur atom, R1
is an alkyl group, R2 is an alkyl group, an alkoxy group, an alkylthio group, or a phenyl group, and A is a group = C
tl- or 2N-1, where n is 0 or an integer from 1 to 4. However, if A is [=N-, +1 is 0 or 1
1. An insecticide, acaricide, or nematocide, which contains as an active ingredient at least one kind of phosphoric acid amide derivative represented by (an integer of 3 to 3).