JPS58124795A - Organophosphoric ester derivative and insecticide, acaricide, nematocide and germicide containing the same - Google Patents

Abstract

NEW MATERIAL:A compound of formulaI[R<1> and R<2> are lower alkyl; R<3> is 5-12C alkyl or formula II (X is halogen)]. USE:An insecticide, acaricide, nematocide and germicide. PROCESS:A compound of formula III, e.g. O-methyl-S-sec-butylchloride phosphorothiolate of formula IV, is reacted with a compound of formula V, e.g. 2,2,2- trichloro-1-iso-pentylthioethanol, in the presence of an acid acceptor, e.g. triethylamine.

Description

[Detailed description of the invention] The present invention is based on the general formula [However, in formula 1, R1 and R''G are replaced by a lower alkyl group.

R1 is an alkyl group having 5 to 12 carbon atoms or an organic phosphate ester conductor represented by the formula -CH, (wherein X represents a halogen atom.) and contains this as an active ingredient. This invention relates to insecticides, acaricides, nematicides, and fungicides characterized by V.

Protecting agricultural crops from pests and diseases is essential for stabilizing yields, maintaining quality, and increasing yields, and various insecticides and fungicides are used for this purpose. on the other hand,
Recently, environmental pollution caused by these drugs has become a problem, and there is a desire for a drug that is effective against pests and diseases at low doses and does not pollute the environment.

The object of the present invention is to solve the above points by providing an organophosphate ester derivative represented by the general formula (IIK) and an insecticide, acaricide, nematocide, and fungicide characterized by containing the same as an active ingredient. I am trying to provide a solution.

Compounds represented by the general formula (In) of the present invention are illustrated in Table 1. The compound numbers will be referred to in the following description.

Table t The compounds of the present invention were synthesized according to the first reaction formula (wherein R1, R1, and R1 are the same as above).

Y represents a halogen atom. ) In the above reaction formula, the acid acceptor is a tertiary amine,
For example, trialkylamine, dialkylaniline, N-
Alkylaliphatic cyclic amine, pyridine or 1,8-diazabicyclo(5,4,0)-7-undecene (hereinafter DB
It is called U. ) and other organic bases.

Inorganic bases such as alkali metal or alkaline earth metal hydrides, hydroxides, carbonates or bicarbonates can be used.

Suitable solvents include diethyl ether, dipropyl ether, dioxane, tetrahydrocarbon ethers or ethereal compounds, and compounds such as N,N-dialkylated carboxamides, and benzene.

Aromatic hydrocarbons such as toluene or xylene, aromatic or aliphatic halogenated hydrocarbons such as chloroform dichloromethane or chlorobenzene, nitriles such as acetonitrile, alkyl sulfoxides such as dimethyl sulfoxide, ketones such as acetone or methyl ethyl ketone. ,
Alcohols such as methanol or ethanol or water can be used.

Next, a specific synthesis example will be shown.

Synthesis example 1. Synthesis of compound 4 SC@Hll-is.

2.2.2-) Lichloro-1-1so-pentylthioethanol 1h5fc0.026 mole) Triethylamine 5.5ft0.052 mole) after dissolving in benzene 100-.

While stirring at 40 to 50°C, O-methyl-8@@e-butyl chloride phosphorothiole) ``>3f (α026)- was gradually added. After the dropwise addition, stirring was continued for 4 hours, and the reaction was completed. The precipitated salt is divided into 5 parts, the penzene is concentrated and removed, and then distilled under reduced pressure to remove low boiling point substances, the boiling point)
o'c/α015+o+HjL, refractive index n'o = t
A brown liquid &3P (yield: $8&81G) showing 5460 was obtained.

Synthesis Example 2 Synthesis of compound 6 S -C@Hll -5ee 2.2.2- ) dichloro-1-easily C-benthioethanol 6, QjL (α024 mol) and Q-ethyl -
g-n-globyl chloride phosphorothiolate 49?
(0,024 mol) was dissolved in 100% of benzene under stirring.

Pyridine 38? (α04B mol)' (I- Gradually added dropwise at the 0-dropping edge, and stirred in an Il flow for 3 hours to complete the reaction.

After the reaction was completed, the precipitated salt was separated into three parts and benzene was distilled off.

The residual liquid was distilled under reduced pressure to give a pale yellow liquid with a yield of 57.
1%).

Boiling point 12B-155℃/L01mHf, refraction 11chi=
15120 Synthesis Example 5 Synthesis of Compound 13 8-C1゜-1-n 2.2.2-) dichloro-1-n-decylthioethanol 6.4fCcLo 2%) and Q-ethyl-g
-n-propyl chloride phosphorothiolate 411P
(0.02 mol) was dissolved in 100 ml of benzene, and while stirring, DBU41y-((1.04 mol) was gradually added.
After that, stirring was performed for 4 hours to complete one reaction. After the reaction is completed, the precipitated salt is separated into 6 parts, the benzene is distilled off, and low-boiling substances are removed by distillation under reduced pressure.
V[101M)l f , refractive index n20=t5048
A brown liquid 7.5 f (yield 8t1) was obtained.

Synthesis Example 4 Synthesis of Compound 21 0 2.2.2-) Lichloro 1-n-heptylthioethanol 28? (101 mol), leg number potassium 2.8? (
102 mol), a mixture of methyl ethyl ketone 50-4
0-Ethyl-8-$ec while keeping at 0~50℃ without stirring
-butyl chloride phosphorothiolate 2.2P (α01
mol) was gradually added dropwise to 1 wM, and the mixture was stirred and heated for 3 hours to complete the reaction. After cooling.

The precipitated inorganic salt v5 was separated, and the three liquids of methyl ethyl ketone were distilled off. If the residual liquid is distilled under reduced pressure to remove low-boiling substances, the boiling point>110℃/Q, 02■HP, refractive index n20=
t5045. 17jL of brown liquid (yield a &
, 111) are obtained.

Synthesis Example 5 Synthesis of Compound 24 2.2.2-Trichloro-t-n-dodecylthioethanol ZO? (102 mol) and 〇-ethyl-8-He-
7' tyl chloride phosphorothiole) 44f (α02
An aqueous solution (50) containing 4 moles of caustic soda (t6fcαo) was gradually added dropwise to a mixed solution of 50 moles of caustic soda dissolved in dipropyl ether with stirring. After completion of the dropwise addition, stirring was performed at room temperature for 4 hours to complete the reaction. The dipropyl ether layer was washed with water until it showed C1, dried over anhydrous magnesium sulfate, and then evaporated under reduced pressure. If the residual liquid is distilled under reduced pressure to remove low-boiling substances, the boiling point will be 110℃/αOO5
8.2 JP (yield: 82 J%) of a brown liquid having a fiH7 and a refractive index r=t496B was obtained.

Other compounds of the present invention can also be synthesized in accordance with the above Synthesis Examples (1) to (6)K.

Examples of pests that can be effectively controlled by the compounds of the present invention include the following.

Two paddy field pests, the brown borer moth and the rice beetle.

Black leafhopper, brown planthopper, brown planthopper,
rice weevil, rice weevil, rice weevil,
Rice leafminer fly, rice nematode, field crop pests: Spodoptera 1M caterpillar, : I-naga, warpworm.

Green caterpillars, bead armyworms, bead armyworms (
Be@t armY wow), Antlcarsia
i4) Turkish Prusiani (Tri@oplusia
n1l) Aphids, scarab beetles, cucumber beetles.

Coconut weevils, seed flies, and locusts.

Crickets, cat nematodes, thurilapsid tea Harmful insects: tea leafhopper, tea leafhopper, tea leafhopper, tea thrips, green leafhopper.

Pests of fruit trees that cause pests of the Japanese white-spotted tree: peach moth, white-spotted moth, American white-winged wigeon, white-spotted moth, aphid, peach leafminer moth, peach weevil, yellow moth.

Stink bug, Citrus leafminer moth, and Gomadara longhorn beetle.

Cotton Pest Two Ball Weeple (B611W...mile),
Ball worm (Boll wem), Pink boll worm ('etton 1saf worm)
Mites: two-spotted spider mite, two-spotted spider mite, Kanzawa/- mite.

Orange spider mite, apple spider mite, and bed mite.

Hygiene IF insects: flies, cockroaches, insects Livestock pests: ticks Wood pests: termites, wood beetles.

Paddy disease: Rice blast disease The characteristics of the compound of the present invention are as follows.

(1) Coccinella moth, including Spodoptera japonica, /1 Makia
.

It is highly effective against lepidopteran pests such as the goldenrod moth and the black beetle.

(2) Since it has a wide insecticidal spectrum, it can simultaneously control pests in various crops, which is labor-saving and economical. For example, it is possible to simultaneously control armyworms, diamondback moths, aphids, apple leafhoppers, tea leafhoppers, tea leafhoppers, tea leafhoppers, rice leafhoppers, paddy rice leafhoppers, brown borer moths, and brown planthoppers.

(3) Whiteflies, which are highly effective against phosphorus-resistant scallops, diamondback moths, brown planthoppers, houseflies, spider mites, etc., are also considered difficult to control pests.

It is also effective against Thurilapsidae.

(41II) It has low toxicity to mammals and fish and shellfish and can be used with confidence.

(5) The compound of the present invention can also be used by emulsion, wettable powder, direct spraying with powder, soil treatment with granules, and water surface application, such as cabbage and tomatoes.

It is easy to use and has no harmful effects on harvested vegetables such as eggplant, citrus fruits, apples, paddy rice, beets, cotton, and tea.

The insecticide, acaricide and fungicide of the present invention contain 1 as an active ingredient.
Containing the compound of the present invention, only one compound of the present invention, or each auxiliary agent, such as a diluent.

By blending solvents, surfactants, etc., it is made into IK formulations such as emulsions, wettable powders, single powder tablets, and oil solutions.

Examples of diluents include clay, talc, bentonite,
Examples of solvents include diatomaceous earth, white carbon, etc., and examples of solvents include xylene, toluene, methyl ethyl keto/,
Ingbanol, dimethylnaphthalene, etc. are mentioned.

Examples of the surfactant include alkylbenzene k fonic acid gold layer salt, polyoxyethylene alkyl allyl ether, alkyl sodium sulfate, alkylnaphthalene sulfone sulfone f, I) Kunin sulfo/acid soda, and the like.

Next, examples of the insecticide, acaricide, and fungicide of the present invention will be explained, but it goes without saying that the S additives and the blending ratio are not limited to these and can be changed within a wide range. Nor.

In the following formulation examples, all parts indicate parts by weight.

Formulation example t (emulsion) 3.50 parts of compound, xylene 401 [1, Tulpol 8
NX (trade name Ni-Toho Chemical Co., Ltd.) 1oIS is uniformly dissolved to form an emulsion.

Formulation example 2. (Emulsion) 5.40 parts of compound, 35 parts of xylene, 1011 parts of inpropanol. A solubilized emulsion was prepared by uniformly dissolving 15 parts of Tsurupol 8TX (51flFm mark: manufactured by Toho Chemical Industry Co., Ltd.).

Formulation example & (aqueous phase agent) 6.40 parts of compound, 15 parts of diatomaceous matter, 15 parts of clay,
25 parts of white carbon, Ninykol 564 (manufactured by Tokama Trademark Nippon Emulsifier), 5 parts, Sunextract P 252 (
Two parts (registered trademark Nisanyo Kokusaku Pulp ■) are mixed and ground to make a wettable powder.

Formulation example 4. (Powder) 16.2 parts of the compound, 4 parts of talc, 47 parts of clay, and 5 parts of white carbon are mixed and ground to obtain a powder.

Formulation example s, (granules) 19.5 parts of compound, 15 parts of bentonite, Merck 47.
5 parts, clay 5 parts, lignin sulfonic acid salt/211S
, 5 parts of dodecylbenzenesulfonic acid so fα was uniformly mixed and pulverized, 25 parts of water was added and mixed, and extrusion granulation 4! ! The mixture is made into granules, dried and sieved to obtain granules.

Next, the effects of the compounds of the present invention will be explained using test examples. The comparative drugs used in the test are the following compounds.

Digterex: 2,2.2-) Dichlor-1
A
-Vinylphos 7ate erthane: 0.0-dimethyldithiophosphorylphenylacetate ethyl lanate: S-methyl N-(methylcarbamoyloxy)-thioacetimidate EM Example 1 <Insecticidal efficacy test against Spodoptera trifoliata) Prepared according to Formulation Example 1 The emulsion was diluted with water to 500 PPm, cabbage leaves were immersed in it for 10 seconds, and after air drying,
It was placed in a 0-vinyl chloride cup, and 3rd instar larvae of Heno1 Spodoptera were released into it.

After treatment, the plants were kept in a constant temperature room at 25°C for 48 hours, and the number of live and dead insects was determined.

The test was conducted with 5 repetitions per section, and 50 animals were tested.

The results are shown in Table 2.

Table 2 Test Example 2 Insecticidal efficacy test against diamondback moth An emulsion prepared according to Formulation Example t was diluted with water to 1100 ppt K, cabbage collection was immersed in it for 10 seconds, and after air drying, it was placed in a 60-inch vinyl chloride cup and placed there. The 3rd instar larvae of Hekonaga were released. After the immersion treatment, the insects were kept in a constant temperature room at 25° C. for 72 hours and examined for dead insect scars. The test was conducted with 6 repetitions per section, and 3011V was used. The results are shown in Table 3.

Table 3 Test Example & Control Effect Test on Phosphate-Resistant Kanzawa Spider Mites An emulsion prepared according to Formulation Example 1 was mixed with water at 500 ppmK.
The diluted solution was thoroughly sprayed with a spray gun to soybeans planted in 4-inch pots that were infested with Kanzawa spider mites. After spraying, the pots were placed in a greenhouse.

Thereafter, the number of #C resident adults was checked every predetermined day, and the control efficiency was calculated using the formula shown below.

The test was conducted with 5 repetitions per section. The results are shown in Table 1.

ΣTh1 Cb: Number of insects in untreated area before treatment Tb: Historical number of insects in treated area before treatment α type: Number of insects in untreated area immediately after treatment 1 day after treatment Th1 = Number of insects 1 day after treatment in treatment area Table 4 Test example Against Chanoko kawamon hamaki - Insecticidal efficacy test An emulsion prepared according to Formulation Example 1 was mixed with water at 1100 ppK.
Dilute it and soak the tea leaves in it for 10 seconds.

After air drying, it was placed in a 60-inch vinyl chloride cup.

Next, release the 5th instar larvae of Chanokokakumonhamaki there, and
After keeping it in a constant temperature room at 5°C for 72 hours, the dead weight rate was examined. The test was conducted with three repetitions per section, and go@ was used. -The results are shown in Table 5.

Table 5 Test Example & Insecticidal Power Test against Brown Planthopper A wettable powder prepared according to Preparation Example 3 was diluted with water to 100 PPai, and rice seedlings were immersed in it. The head was released and a cotton plug was placed. After keeping it in a constant temperature room at 25°C for 48 hours, the number of live and dead insects was counted to determine the dead weight percentage. The test was conducted three times per section and 30 animals were tested. The results are shown in Table 6. Table 6 Test Example 4 Insecticidal efficacy test against the goldenrod moth A hydrating powder prepared according to Formulation Example 5 was diluted with water to 500 ppmK, and immediately after hatching, it was planted in a pot infested with larvae. The apple seedlings were thoroughly sprayed with a spray gun and placed in a greenhouse. 14 days after spraying, decompose the damaged leaves and
Live and dead insects were examined to determine the dead weight percentage. The test consisted of 5 bottles in 1 area. The results are shown in Table 7.

Table 7 Test Example 7 Nematicidal effect test of N6 on sweet potato nematodes Sand loam containing sweet potato nematodes raised on tomatoes and sand were mixed at a ratio of 1:1 using a stirrer and placed in a 4-inch clay pot. Next, an emulsion prepared in accordance with Formulation Example 1 was diluted with water, and the emulsion was mixed so that the amount of active ingredient was L15 hours/IQa. 5 tomato seedlings per pot 1 day after treatment
The plants were transplanted, placed in a greenhouse, and watered for 4 hours. In the investigation, the number of root nodules was counted 20 days after treatment, and the control rate was calculated using the method shown below. The test was conducted with 5 repetitions per section.

The results are shown in Table 8.

Table 8 Test Example 6 Control effect test on rice blast disease Example S
The wettable powder prepared in accordance with K was diluted with water to SOOppm K, and sufficiently sprayed with a spray gun to 20 rice seedlings at the 4-leaf stage planted in 3-inch pots, and after air-drying, they were inoculated with the blast fungus. For inoculation, measure the spore concentration by measuring 50 spores per field of view (15x10x) using a microscope.
The prepared suspension was sprayed at a rate of 3 parts per pot. After inoculation, the plants were kept in a vinyl greenhouse (saturated humidity 25°C) for 24 hours, and then moved into a room and kept at a high temperature to allow lesions to develop. Seven days after inoculation, 10 leaves per pot were counted and the number of lesions was calculated (control value was calculated).

The results are shown in Table 9.

Table 9 Test Example 9 Emulsion prepared according to Example IK of phytotoxic formulation for various crops was added to SonppvmK with water.
It was diluted and thoroughly sprayed on each test plant using a spray gun, and placed in a greenhouse. Ten days after spraying, the presence or absence of chemical damage was examined. The test was conducted with 1 section and 3 repetitions.

The results are shown in Table 10.

Table 10 In Table 9, - indicates no chemical damage at all.

Figure 1 shows compound 1, -2 shows compound 2, and Figure 6 shows compound em
1 of 3 Figure 4 is Compound 4 1 Figure 5 is Compound 8 1 Figure 6 is Compound 10, Figure 7 is Compound 15 1 Figure 8 is Compound 14 1 Figure 9 is Compound 17 1 Figure 10 is Compound 1B ,Figure 11
is Compound 20 1 Figure 12 is Compound 21 1 Figure 15 is Compound 22 1 Figure 14 is Compound 23 1 Figure 15 is Compound 24
Figure 16 shows Compound 25. Figure 17 shows Compound 26. Figure 18 shows Compound 27. Figure 19 shows Compound 28. Figure 20 shows Compound 29. .

patent applicant Kumiai Chemical Industry Co., Ltd. Director and President Tsuki Nozobe

Claims (1)

[Claims] (II General formula [However, in the formula, W and R are lower alkyl groups. Rs is an alkyl group having 5 to 12 carbon atoms or a formula -CH, (
However, in the formula, X represents a halogen atom. ) is shown. ] An organic phosphate ester derivative represented by +21 General formula [However, in formula 1, R1 and V represent a lower alkyl group. ) V is shown. An insecticide, acaricide, nematocide, or insecticide comprising an organic phosphate derivative represented by the following as an active ingredient.