JPS63211293A - Organophosphorus based compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (X and Y are H, alkyl, phenyl or join together to form alkylene; Z<1> and Z<2> are O or S; R<1> and R<2> are alkyl provided that when either one of X and Y is methyl and other is phenyl, Z<1> and Z<2> are both O or S). EXAMPLE:S-sec.-Butyl O-ethyl(2-oxo-3-thiazolidinyl)phosphonothiolate. USE:A controlling agent to harmful insecticides, acarids and nematodes. PREPARATION:The compound expressed by formula I is obtained by reacting a compound expressed by formula II with a compound expressed by formula III (HAL is halogen) preferably in the presence of an acid acceptor (e.g. n- butyllithium, sodium hydroxide, etc.) at -80-30 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel organophosphorus compounds that exhibit effective control action against harmful insects, mites, and nematodes, and methods for producing them.

The present invention is a novel organic phosphorus compound represented by the following general formula (1), which includes stereoisomers such as optical isomers.

In the formula, X and Y are a hydrogen atom, an alkyl group, a phenyl group, or X and Y together form an alkylene group,
Zl and 2m are oxygen atoms or sulfur atoms, and R' and R2 are alkyl groups.

(However, when one of X and Y is a methyl group and the other is a phenyl group, Zl and Z2 are both oxygen atoms or sulfur atoms.) In the general formula (1), represented by X, Y, R' and R2 Examples of the alkyl group include methyl, ethyl, propyl, butyl, and the like.

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

(In the formula, 11AL is a halogen atom, and X, Y, Z'
.

ZZ, R1 and R2 are as described above. ) The reaction is usually -100 to 50'' C1, preferably -80 to 30
It is carried out in the temperature range of ℃.

In addition, this reaction is carried out in the presence of an acid acceptor, and examples of acid acceptors include organic lithium compounds such as n-butyllithium, tert-butyllithium, and phenyllithium, sodium hydroxide, potassium hydroxide, and hydrogen. Examples include inorganic bases such as sodium chloride and potassium hydride, and organic bases such as triethylamine and pyridine. Furthermore, these reactions are preferably carried out in the presence of a solvent, and examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; cyclic or acyclic aliphatic hydrocarbons such as hexane and cyclohexane; Ethers such as Nidiethyl ether, Methyl ethyl ether, Dioxane, Tetrahydrofuran etc. Niacetonitrile,
Examples include nitriles such as propionitrile and acrylonitrile, aprotic polar solvents such as dimethylformamide, dimethyl sulfoxide, sulfolane, and hexamethylphosphoric triamide.

Synthesis Example I Synthesis of 5-sec-butyl 〇-ethyl (2-oxo-3-thiazolidinyl) phosphonothiolate 1.5 g of thiazolidin-2-one was added to 30 mj of tetrahydrofuran! and cooled to -78°C.

Thereto, n-butyllithium (1,65M), 11 m
1 was gradually added dropwise, and the mixture was stirred for 15 minutes. Then, 5-
10 ml of a tetrahydrofuran solution containing 5 g of see-butyl 0-ethylthiophosphoric acid chloride was gradually added dropwise,
After stirring for 30 minutes and reacting at room temperature for 3 hours, the product was poured into water, extracted with ethyl acetate, the extracted layer was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. As a result, 2.3 g of the target product (compound light 2 described later) having a refractive index of 1.5334 (19.6° C.) was obtained.

Synthesis Example 2 Synthesis of 5-see-butyl 〇-ethyl (5-methyl-2-oxo-3-oxazolidinyl) phosphonothiolate 2.0 g of 5-methyloxazolidin-2-one was added to 40 mj of tetrahydrofuran! and cooled to -78°C. There, 12mj of n-butyllithium (1,65M)
! was gradually added dropwise and stirred for 15 minutes. Then, 5-
sec-butyl 0-ethylthiophosphoric acid chloride 4.3
After gradually adding 5 ml of tetrahydrofuran solution containing g, stirring for 30 minutes, and reacting at room temperature for 2 hours. After drying with sodium, the solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to obtain 1.6 g of the target product (Compound No. 6, described below) having a refractive index of 1.4923 (20.5° C.).

Synthesis example 30-ethyl 5-n-propyl (4-ethyl-2
Synthesis of -oxo-3-oxazolidinyl)phosphonothiolate 2.5 g of 4-ethyloxazolidin-2-one was dissolved in tetrahydrofuran 401I11 and cooled to -78°C. There n-butyllithium (1,55M) 14+
After gradually dropping nl, the mixture was stirred for 10 minutes. Next, 4.3 g of 〇-ethyl 5-n-propylthiophosphoric acid chloride
was gradually added dropwise, the temperature was returned to room temperature, and the mixture was allowed to react for 2.5 hours.

After the reaction, the solvent was distilled off, the residue was poured into water, extracted with ethyl acetate, the extracted layer was washed with saturated brine, dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was subjected to silica gel chromatography. Refractive index: 1.4948
(22.6°C) 3.84 g of the target product was obtained.

Note that diastereomers exist in the above compound due to the asymmetric carbon atom and the asymmetric phosphorus atom at the 4-position of the oxazolidine ring. The above compound was separated by silica gel column chromatography, and the refractive index was 1.4956 (19,8
°C) and the compound 17a with a refractive index of 1.4950 (20,
Compound 17b was isolated at 3°C.

In addition, 4-ethyloxazolidine-2- of Synthesis Example 3
(+)-4-ethyloxazolidin-2-one [(α) ” + 4.29” (C1,86, Cl
Synthesis and separation were carried out in the same manner as in Synthesis Example 3, except that ICl3)) was used as a raw material, and the refractive index was 1.4.
Compound m17a-■ (one component of compound magnetic 17a, [α)''-46,19° (C4
, 55, ClICl 3) ) and refractive index 1.4978
Compound 17b-1 (compound 17b) at (16,2℃)
One component of (α) “-2,12” (C20,28,
ClICl3)) was obtained.

Furthermore, (-)-4-ethyloxazolidin-2-one ((
α) “-2,48” (C2,82, ClIC123
) ) as a raw material, synthesized and separated in the same manner to obtain a compound NQ17 a with a refractive index of 1.4990 (14.8°C)
-TI (one component of compound cation 17a, [α) 3o+62
．． 33” (C9,45, Cl1(1,)) and a refractive index of 1.
4966 (17,2°C) compound NQ17b-IF (
One component of compound 11h17b, [α) ”+ 4.53
(C11,70, CICII 3) ) was obtained.

Typical specific examples of the compounds of the present invention produced by the synthesis examples 1 to 3 or the production method of the present invention described above are listed in Table 1.

Table 1 (Note) In Table 1 above, compound magnets have the same number a and b; a-
1 and b-I, b-n: or a-U and b-r, b-n,
are in a diastereomeric relationship with each other, and a-I
and a-11 or b-1 and b-n are enantiomeric with each other.

As shown in the test examples described later, the compound of the present invention exhibits excellent activity as an active ingredient of insecticides, acaricides, and nematicides. For example, plant parasitic mites such as two-spotted spider mite, false red spider mite, orange spider mite, etc., ectoparasitic mites such as house dust mite, diamondback moth, fall armyworm, fall armyworm, Colorado spider mite, red spider mite, peach aphid, black leafhopper, brown leafhopper, onion fly,
Agricultural pests such as scarab beetles, cutworms, etc.
Sanitary pests such as cockroaches, houseflies, Culex mosquitoes, termites, etc., grain storage pests such as adzuki bean weevils, blackberry beetles, etc., clothing pests such as bonito beetles, fleas, lice, flies, etc. that parasitize livestock, etc. It is also effective against plant-parasitic nematodes such as Nematodes, cyst nematodes, Negusare nematodes, and rice nematodes. It is also effective against plant parasitic mites that are resistant to Dicofol and organophosphates.

When using the compound of the present invention as an active ingredient in insecticides, acaricides, and nematocides, it can be used in various forms such as emulsions, powders, wettable powders, and liquids together with pesticide adjuvants, as in the case of conventional pesticide formulations. It can be formulated into When these preparations are actually used, they can be used as they are or diluted to a predetermined concentration with a diluent such as ζ or water.

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

For example, as insecticides or acaricides, organic phosphate compounds, carbamate compounds, dithio (or thiol) carbamate compounds, organic chlorine compounds,
Dinitro compounds, organic sulfur or organometallic compounds, antibiotics, substituted diphenyl ether compounds, urea compounds, triazine compounds, benzoyl urea compounds,
Examples include pyrethroid compounds, more specifically, N-
(2,6-difluorobenzoyl)-N'-(p-chlorophenyl)urea, N-(2,6-difluorobenzoyl)-N'-(3,5-dichloro-4-(3-chloro-5-tri fluoromethyl-2-pyridyloxy)
Benzoylurea compounds such as phenyl)urea, α
Examples include pyrethroid compounds such as -cyano-3-phenoxybenzyl-2-(4-chlorophenyl)isovalerate.

Insecticides, acaricides, and nematicides containing the compound of the present invention as an active ingredient are effective for controlling various harmful insects, harmful mites, and harmful nematodes, and are generally applied in a range of 1 to io or oo.

ppm, preferably at an active ingredient concentration of 20 to 2.000 ppm. In the case of harmful aquatic insects, it is possible to control them by spraying a chemical solution in the above concentration range to the place where they occur, so it is effective even if the concentration range of the chemical solution in water is less than the above range.

Test Example 1 Each formulation of active ingredient compound was dispersed in water and adjusted to a predetermined concentration. Only one primary leaf of the common bean was transplanted into a cup (diameter: 7 cm, height: 4 cm), and about 30 young adult red spider mites were inoculated into the cup.

This product was immersed in the chemical solution adjusted to the predetermined concentration for about 10 seconds, air-dried, and then left in an illuminated incubator at 28°C.

The survival rate was determined at the second molar after adulthood, and the mortality rate was calculated using the following formula, and the results shown in Table 2 were obtained.

Table 2 Test Example 2 Each formulation of the active ingredient compound was dispersed in water and adjusted to a predetermined concentration. Cabbage leaf pieces were immersed in the drug solution for about 10 seconds and air-dried. A Petri dish with a diameter of 9ea+ was lined with moist filter paper, and the air-dried leaf pieces were placed on top of it. There 2
~3rd instar diamondback moth larvae were released, covered, and left in a lighted incubator at 26°C. The survival rate was determined in the second mortar after adulthood, and the mortality rate 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 The test was carried out in the same manner as in Test Example 2, except that the 2nd to 3rd instar diamondback moth was replaced with the 2nd to 3rd instar Spodoptera japonica, and the results shown in Table 4 were obtained.

Table 4 Test Example 4 One primary leaf of common bean was transplanted into a cup, inoculated with adult two-spotted spider mites to spawn, and the adult was removed. The kidney beans were immersed in the dispersed chemical solution adjusted to a predetermined concentration for about 10 seconds, air-dried, and then left in a thermostat with lighting at 28°C. After 5 days, we investigated the hatching status of the eggs.
The ovicidal rate was calculated using the following formula and the results shown in Table 5 were obtained.

Table 5 Test Example 5 10 rice seedlings were added to a chemical solution adjusted to a concentration of 800 ppm+.
After soaking for a second and air-drying, the roots were wrapped with absorbent cotton and placed in a test tube.Next, 10 adult brown planthoppers were released into the test tube, and the mouth of the tube was covered with gauze. Two days later, the insects were examined to see if they were alive or dead, and the mortality rate was determined in the same manner as in Test Example 1, and the results shown in Table 6 were obtained.

Table 6 Test Example 6 Pack contaminated soil into a 115,000 are pot,
A chemical solution adjusted to have an active ingredient content of 250 g/a was irrigated at a predetermined ffi. Two days after the chemical solution treatment, tomato seedlings at the 3- to 4-leaf stage were transplanted, and 20 days after the chemical solution treatment, the degree of Nekkob settlement was investigated, and the results shown in Table 7 were obtained.

The degree of Nekopu settlement was determined according to the following criteria.

O Nekobu no adhesion 1 〃 Slight 2 〃 Medium 3 〃 Large 4 〃 Very large Table 7 Test Example 7 Each formulation of the active ingredient compound was dispersed in water, and cabbage leaf pieces were added to the chemical solution adjusted to a predetermined concentration. It was immersed for 10 seconds and air dried. A Petri dish with a diameter of 9 cm was lined with moist filter paper, and the air-dried leaf pieces were placed on top of it. Wingless viviparous female larvae of the green peach aphid were released into the flask, and the flask was placed in a lighted incubator at 26° C. with a lid. The survival rate was determined in the second mortar after release, and the mortality rate was determined in the same manner as in Test Example 1, and the results shown in Table 8 were obtained.

Table 8 Test Example 8 Each formulation of active ingredient compound was dispersed in water and adjusted to a predetermined concentration. Only one primary leaf of common bean was transplanted into a cup (diameter 7 cm, height 4 cm), and about 30 young adult two-spotted spider mites resistant to dicofol and organophosphorus were inoculated into the cup. This product was immersed in the chemical solution adjusted to the predetermined concentration for about 10 seconds, and after being air-dried at 28°C.
It was left in a thermostat with lighting. The survival rate was determined on the second day after the release of the insects, and the mortality rate was determined in the same manner as in Test Example 1.
The results shown in Table 9 were obtained.

Table 9 Test Example 9 Air-dried ±40 g was placed in an ice cream cup, and 10 mJ of the chemical solution adjusted to a concentration of 200 ppm was poured into it and mixed uniformly. After 24 hours of mixing, onion pieces were buried in the soil as bait, and 10 10-day-old onion fly larvae were placed there.
! I released a. After 48 hours, the insects were examined to see if they were alive or dead, and the mortality rate was determined in the same manner as in Test Example 1, and the results shown in Table 10 were obtained.

Table 10 Formulation Example 1 (a) Compound positive 1 20 parts by weight (b)
N,N'-dimethylformamide 70! Part (c) Polyoxyethylene alkyl 10 parts by weight or more of phenyl ether were uniformly mixed and dissolved to prepare an emulsion.

Formulation Example 2 (a) 5 parts by weight of compound 11h2 (
b) Talc 95 parts by weight or more were uniformly mixed to form a powder.

Formulation Example 3 (a) Compound N16 50 parts by weight (b) Finely powdered silica 15 parts by weight (c) Finely powdered clay 25 parts by weight (e) Dialkyl sulfosuccinate 3 parts by weight or more are uniformly ground, mixed and hydrated. It was used as a drug.

Formulation Example 4 (a) Compound 13 5 parts by weight (b) Bentonite 45 parts by weight (c) Kaolin 50 t-1 part or more was kneaded with a small amount of water, extruded into granules, and dried to form granules. .

Claims (1)

[Claims] 1. General formula▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, X and Y are a hydrogen atom, an alkyl group, a phenyl group, or X and Y together form an alkylene group) and Z^1 and Z^2 are oxygen atoms or sulfur atoms, and R
^1 and R^2 are alkyl groups. However, when one of X and Y is a methyl group and the other is a phenyl group, Z^1 and Z^2 are both an oxygen atom or a sulfur atom). 2. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X and Y are hydrogen atoms, alkyl groups, phenyl groups, or X and Y together form an alkylene group, and Z^2 is an oxygen atom or a sulfur atom.However, when one of X and Y is a methyl group and the other is a phenyl group, Z^1 and Z^2 are both an oxygen atom or a sulfur atom). It is characterized by reacting a compound represented by the general formula ▲Mathematical formula, chemical formula, table, etc.▼ (in the formula, R^1 and R^2 are an alkyl group, and HAL is a halogen atom). A method for producing an organic phosphorus compound represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. .