JPS58194870A - Oxadiazolinone derivative, its preparation and insecticide and acaricide containing the same as active constituent - Google Patents

Abstract

NEW MATERIAL:An oxadiazolinone derivative expressed by formula I (X is O or methylene; R1, R2 and R4 are H or CH3; R3 is 1-3C alkyl). EXAMPLE:3-(2,2-Dimethylindan-4-yl)-5-methoxy-1,3,4-oxadiazolin-2-one. USE:An insecticide and acaricide, having a wide insecticidal spectrum and a high efficacy, and effective against insects, e.g. leafhoppers of the family Detocephalidae or Delphacidae in paddy fields or diamondblack moth, cabbage armyworm or grasshopper damaging vegetables, fruit trees, wood, etc. mosquitoes, flies, cockroaches, mites of the family Ixodidae or injurious insects of stored grains. PROCESS:Phosgene is reacted with a hydrazinocarboxylate derivative expressed by formula II to give a 2-chlorocarbonylhydrazinocarboxylate derivative expressed by formula III, which is then reacted in the presence of a base, e.g. triethylamine, in an organic solvent, e.g. methylene chloride, at -20-+100 deg.C to afford the compound expressed by formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is based on the general formula (■) 1R2 [wherein, X represents an oxygen atom or a methylene group]. R, R2, and R4 are the same or different.

Represents a hydrogen atom or a methyl group, where R3 is the number of carbon atoms/
Represents 3 to 3 alkyl groups. ] The present invention relates to an oxadiazolione derivative represented by the following, a method for producing the same, and an insecticide and acaricide containing the same as an active ingredient.

an oxadiazolione derivative having a 3-dihydrobenzofuran ring and an alkyl group at the position of the phenyl nucleus,
It is reported in U.S. Patent No. 1I3θB92 and Kaisho J/-/θ/RIl1 that oxadiazolinon derivatives having an alkoxyl group or an alkylthio group or a trifluoromethyl group are effective against certain pests. This is known from the official gazette.

The present inventors have conducted various studies on the substituents on the phenyl nucleus in oxadiazolinone derivatives, and have found that the compounds of the present invention have a wide insecticidal spectrum and high efficacy, and in particular, in general formula (I), R It has been found that a compound in which both Yo and R3 are methyl groups and R3 is a methyl group or an ethyl group has high insecticidal efficacy.

The compound of the present invention can be obtained by reacting a hydrazinocarboxylate derivative represented by the general formula (1) [wherein, X%R, R1, R3, and R4 are as described above] with phosgene, ): 1 "In the formula, X, R,,1,: Ro, Ro and r
, This is the same as mentioned above. ] It can be produced by using a 3-hydroluponyl hydrazino-lupochelate derivative represented by the formula (It) and cyclizing it in the presence of a base. The reaction between the dinocarboxylate derivative and phosgene is carried out by cyclization of the 1-chlorocarbonylhydrazinocarboxylate derivative represented by the general formula (1) using methylene chloride, chloroform, tetramerized carbon. 1. In an organic solvent such as henzene, toluene, or tetrahydrofuran, in the presence of a tertiary amine such as pyridine, trimethylamine, or triethylamine, an alkali metal hydroxide such as sodium hydroxide, or a base such as ammonia, 1 reaction site - 1 θ°C ~ / θθ” C 0 hydrazinolytic force represented by the general formula (If) [wherein R3 is O as defined above] and the chloroformate represented by the general formula (V) [In the formula, X, R, R2 and R4 are as defined above.] The reaction obtained by reacting with the hydrazine derivative shown by A production example is shown below, which is carried out in an organic solvent such as chloroform or carbon tetrachloride in the presence of a base such as pyridine, triethylamine, or an aqueous sodium hydroxide solution.

Production example/(Production of invention compound (1)) Methyl --(
,2,2-dimethylindan-guyl)hydrazinocarboxylate-13 (0.01 mol) in concentrated [/θ
, θ% (wt/vol) of phosgene in toluene solution 3θd
After stirring for an hour at room temperature, gradually warm the mixture.
The reaction mixture was stirred under reflux for / hour and concentrated under reduced pressure.
Methylene chloride Jθd was added to the obtained oil, and then triethylamine/, 2/fcO, θ/, 2 mol) was added, stirred for 3 hours in a 0 room mixture, washed with water, and the methylene chloride solution was concentrated under reduced pressure. did. The obtained oil was purified using methylene chloride as a developing solvent and a nine column filled with silica gel joP to obtain J-(,2,,2-dimethylindan-guyl)-j-methoxy-/.

J, +-oxadiazoline-coon J, 4t1. f(
A free yield (a%) was obtained as white crystals. mp7/~
7-℃ Note that methyl --(,2,2-dimethylindan-l
-yl) hydrazinocarboxylate is 2. ．． Can be produced by reacting 2-dimethyl-derhydrazinoindan and methyl chloroformate in tetrahydrofuran in the presence of triethylamine. Some of the compounds of the present invention produced by such a method are shown in Table 1.

The compound of the present invention can be mixed with solid carriers, liquid carriers, surfactants, and other formulation auxiliaries to form preparations, such as emulsions, powders, granules, wettable powders, oils, etc., and can be used for various purposes. Each preparation can contain the compound of the present invention as an active ingredient in a weight ratio of θ, preferably - to θ.

These preparations can be prepared according to conventional methods.◇In this case, clays (for example, kaolin,
Fine powders or powders such as bentonite, acid clay, pyrophyllite, sericite), talcs, and their inorganic minerals (such as hydrated silicon dioxide, pumice, algae, sulfur powder, and activated carbon) can be mentioned.

Liquid carriers include alcohols (eg methyl alcohol, ethyl alcohol), ketones (eg acetone, methyl ethyl ketone), ethers (eg ethyl ether, dioxane, cellosolve, tetrahydrofuran).

Aromatic hydrocarbons (e.g. benzene, toluene, xylene, methylnaphthalene) [manufactured hydrocarbons (e.g. gasoline, kerosene, kerosene), esters, nitriles, acid amides (e.g. methylformamide, dimethylacetamide) , halogenated hydrocarbons (eg dichloroethane, trichloroethylene, carbon tetrachloride), and the like.

Next, as surfactants, alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates,
Examples include polyethylene glycol ethers and polyhydric alcohol esters. In addition, usable fixing agents and dispersants include casein, gelatin, starch powder, O
M.O.

gum arabic, alginic acid, lignin sulfonate,
bentonite, molasses, polyvinyl alcohol, pine oil,
As a stabilizer, for example, 'PAP' is used as a stabilizer.
(isopropyl phosphate).

TCP (tricresyl phosphate), tall oil,
Examples include epoxidized oils, various surfactants, various fatty acids or their esters, etc. These compounds include fenitrothion (0,0-dimethyl-〇-(3-methyl-goonitrophenyl) phosphorothioate), (8-(/ ,,!-bis(ethoxylecarbonyl)ethyl)0.0-dimethylphosphorothioate], dimethoate (OIO-dimethyl5
-(N-methylcarbamoylmethyl)phosphorodithioate), salithion (-1methoxy-4H-/, 3
ex-penzodioxaphosphorine-cosulfide),
Diazinon (0,0-diethyl o-(2-inopropyl-6-methylda-pyrimidinyl) phosphorothioate), dibuterex (s,, 2..2-trichloro-
Organophosphorus insecticides such as 7-hydroxyethyl) 0.0-dimethylphosphonate), dichlorvos (0-(,2,,2-dichlorovinyl) 0.0-dimethylphosphate), MPMO (J, &-dimethylphenyl) N-
Carbamate insecticides such as methyl carbamate), MTMO (m-tolyl N-methyl carbamate), BPMO (2-6θC-butylphenyl N-methyl carbamate), and carbaryl (/-naphthyl N-methyl carbamate).

Vermethrin (3-phenoxybenzyl d.

! -cis, trans-3-(J,,2-dichlorovinyl)-1,,2-dimethylcyclopropanecarboxylate), fenvalerate (α-cyano-m-phenoxybenzyl α-isopropyl-p-chlorophenylacetate), etc. It can be mixed with pyrethroid insecticides, acaricides, nematicides, fungicides, herbicides, plant growth regulators, fertilizers, soil conditioners, etc. in any proportion, especially when mixed with insecticides. We can expect stability in their respective efficacy and synergistic effects.

The compounds of the present invention can be used to protect against lepidoptera such as planthoppers, leafhoppers, stink bugs, and cutworms that damage vegetables, fruit trees, wood, etc. in rice paddies, etc.
Insects belonging to the order Orthoptera such as grasshoppers, as well as spider mites,
Pathogens such as insects, flies, cockroaches, ticks,
It is effective as an insecticide and acaricide against fleas, lice, and grain pests.

When the compound of the present invention is used in rice fields, fields, orchards, forests, etc., the amount used is /θθyAa ~〃θθ, /ha
◇When used as an emulsion or a wettable powder diluted with water, the appropriate concentration is /θppm to /θθθpyn.

Next, some formulation examples are shown.

Formulation Example / 0 part of each of the compounds (1) to (I) of the present invention, and an emulsifier (a mixture of polyoxyethylene styrenated phenyl ether, a polymer of polyoxyethylene styrenated phenyl ether, and an alkylaryl sulfonate). ), and 1,260 parts of filtrate were added, and these were thoroughly stirred and mixed to obtain each type 10 emulsion.

Formulation Example 1 Emulsifier (
5 parts of sodium lauryl sulfate) are mixed thoroughly, ±7j parts of 3θθmelle didiatoms are added, and the mixture is thoroughly stirred and mixed in a crusher to obtain each 2θ hydrating powder.

Formulation Example 3 Three parts of each of the compounds (1) to <tr> of the present invention were dissolved in an appropriate amount of acetone, and 3 parts of each of the compounds (1) to <tr> of the present invention were dissolved in a suitable amount of acetone. Add 7 parts,
After thorough stirring and mixing in a crusher, acetone is removed by evaporation to obtain each 3% powder.

Formulation Example: 5 parts each of the compounds (1) to (Ir) of the present invention, 2 parts each of a dispersant (calcium lignin sulfonate), and 3 parts of Crater.
of the mixture and stir thoroughly in a crusher to mix. Next, water is added to the mixture in an amount of /θ%, and the mixture is stirred and mixed, granulated using a granulator, and dried through ventilation to obtain each SS granule.

Formulation Example S By dissolving 0.7 parts of each of the compounds (1) to (lr) of the present invention in white kerosene to make a total of 700 parts, a 0.7% oil solution is obtained.

Formulation Example B Add θ part to the compound (1) of the present invention, 70 parts of an emulsifier (a mixture of polyoxyethylene styrenated phenyl ether, polyoxyethylene styrenated phenyl ether polymer, and alkylaryl sulfonate), and xylene/θ part. Then, by stirring and mixing them well, a θ-chi emulsion is obtained.

Next, test examples demonstrate that the compounds of the present invention are useful as insecticides and acaricides. Note that, as control compounds, preparations obtained in the same manner as described above for the following compounds (A), (B), (0), and (D) were used.

Compound symbol Chemical structural formula Remarks Test example/Formulation example - 70 of the hydrating powder of the present compound obtained by
Rice stems (length approximately/θm) were immersed in the 0-fold water dilution for 7 minutes. After air-drying, the rice stems were placed in a test tube, and 70 adult brown planthoppers were released.After 7 days, the dead or dead was examined to determine the mortality rate (repeat II).

Test compound Mortality rate ((6) (1), /θθ (p2)/θθ (3)/θθ (lI) /θθ) /θθ (6)/θθ Obtained by Test Example Co-Formulation Example Aqueous dilutions of the water conservancy of the compound of the present invention and a control compound obtained in the same manner were mixed at Sθθ~θ
,? diluted within the ppm range, and in the same manner as in the test example, determine the mortality rate of brown-bottomed planthopper at each concentration, Sθ
The lethal concentration (IJO5o value) was determined (repeated).

Test Example 3 Formulation Example/900% of emulsion of the compound of the present invention obtained by
Rice stems (length approximately/θm) were immersed in the diluted solution for 7 minutes. After air-drying, the rice stems were placed in a test tube, and Nakagawara type leafhopper, (organophosphorus agent, - carbamate agent resistant line)
Seventy-six adult insects were released, and 7 days later, they were examined to see if they were alive or dead, and the mortality rate was calculated (repetition).

Test Example: A water diluted emulsion of the compound of the present invention and a control compound was diluted with Sθ.
θ~7. U I) 1) diluted in the range of m, and in the same manner as Test Example 3, the mortality rate of the Nakagawara leafhopper at each concentration was determined, and the jθchi lethal concentration (L05o value) was determined (lI repetition).

(／　9　) 544- (,2θ)

Claims (1)

[Claims] [In the formula, or represents an oxygen atom or a methylene group. Ro
, R2 and R4 are the same or different and represent a hydrogen atom or a methyl group, and R3 represents an alkyl group having 1 to 3 carbon atoms. ] An oxadiazolinone derivative represented by (P2) General formula [In the formula, X represents an oxygen atom or a methylene group. R1
, R2 and R4 are the same or different and represent a hydrogen atom or a methyl group, and R3 represents an alkyl group having 1 to 3 carbon atoms. [In the formula, xlRl, R2, R3 and R4 are as described above. ] A method for producing an oxadiazolinone derivative represented by (3) Phosgene and the general formula [wherein, X represents an oxygen atom or a methylene group]. R, R2 and R4 are the same or different and represent a hydrogen atom or a methyl group, and R3 represents an alkyl group having 1 to 3 square atoms. ] by reacting with a hydrazinocarboxylate derivative represented by the general formula. 1 [In the formula, xSR1, R2, R3 and R4 are as described above] A general formula characterized by cyclizing it in the presence of a base [In the formula, xSR1, R2, R3 and R4 are as described above. ] A method for producing the oxadiazolinone derivative shown in the following. (da) General formula [in the formula, or represents an oxygen atom or a methylene group. Ro
, R2 and R4 are the same or different and represent a hydrogen atom or a methyl group, and R3 represents an alkyl group having 1 to 3 carbon atoms. ] An insecticide and acaricide characterized by containing an oxadiazolinone derivative represented by the following as an active ingredient.