JPH0122255B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula () The present invention relates to a novel 3-substituted-1-indenyl ester represented by the following formula and an insecticide containing the same as an active ingredient. However, in the above general formula (), R ¹ is a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group; a lower alkenyl group such as an allyl group or a methylpropenyl group; a chlorpropenyl group, a dichloropropenyl group, or a bromine group; It represents a halo lower alkenyl group such as a propenyl group; a lower alkynyl group such as a propargyl group or a methylpropargyl group; or an arylmethyl group such as a benzyl group, a 4-chlorobenzyl group, or a tolylmethyl group. R ² is the general formula () represents a group represented by In the group represented by the general formula (), R ³ represents a hydrogen atom or a methyl group; R ⁴ represents a cyclopentylidenemethyl group, XC≡C- group, when R ³ is a hydrogen atom;

[Formula] Motomata teeth

[Formula] represents a group, and when R ³ is a methyl group, it represents a methyl group. Here, X is a chlorine atom,
represents a halogen atom such as a bromine atom or a fluorine atom; Y represents a halogen atom such as a chlorine atom, a bromine atom, a fluorine atom, or a methyl group; Z represents a hydrogen atom or a halogen atom such as a chlorine atom or a bromine atom . As a result of extensive research in search of new and excellent pyrethroid insecticides, the present inventors found that 3-substituted-1-indenyl ester represented by the general formula () has excellent insecticidal efficacy; In addition, it is fast-acting, has relatively low toxicity to humans, livestock, and fish, has a long-lasting effect, but has no environmental persistence, and is an organophosphorus insecticide and/or carbamate insecticide. The present inventors have discovered that it has various excellent properties, including being highly effective against pests that are resistant to insects, leading to the completion of the present invention. 3-Substituted-1-indenyl esters represented by the general formula () are harmful to leafhoppers, planthoppers, etc. that cause damage to paddy rice, field crops, cotton, fruit trees, forests, etc.
stink bugs, stink bugs, aphids, green caterpillars, fall armyworms, diamondback moths,
It not only exhibits excellent insecticidal efficacy against agricultural, horticultural and forest pests such as bed bugs, scale insects, leaf beetles, spider mites, silver beetles, white beetles, gypsy moths, bark beetles, but also grain storage pests such as grain weevils and corn weevils, flies,
It also shows strong insecticidal effects against sanitary pests such as mosquitoes and cockroaches. In addition, 3 represented by the general formula ()
-Substituted-1-indenyl ester has extremely low toxicity to humans, livestock, and fish compared to other pyrethroid insecticides, so it can be used safely. The 3-substituted-1-indenyl ester of the present invention represented by the general formula () is characterized by being composed of a substituted cyclopropanecarboxylic acid component and a novel 3-substituted-1-indenol component. Typical esters are listed below. Note that the compounds of the present invention are not limited to the compounds listed below, and further include geometric isomers and optical isomers.

【table】

【table】

【table】

【table】

[Table] 3-substituted-1-indenyl esters represented by the general formula () are [In the formula, R ¹ has the same meaning as in the general formula (). ] 3-substituted-1-indenol or its reactive derivative represented by the general formula () R ² COOH ... () [wherein R ² has the same meaning as in the general formula (). ] It can be easily produced by reacting with the carboxylic acid shown in the following formula or a reactive derivative thereof. Here, examples of reactive derivatives of 3-substituted-1-indenol include halides and arylsulfonates. Reactive derivatives of carboxylic acids include lower alkyl esters, acid halides, acid anhydrides, mixed acid anhydrides, alkali metal salts or salts of organic tertiary bases. Below, the above-mentioned typical manufacturing method will be specifically explained. (Manufacturing method a) Method by reaction of alcohol and carboxylic acid halide 3-substituted-1-indenol represented by the general formula () and the general formula R ² COX' [wherein R ² is the general formula ()]
has the same meaning as in, and X′ represents a halogen atom. ] in an inert solvent such as benzene, toluene, ether, hexane, etc. in the presence of a tertiary amine such as pyridine or triethylamine in an amount of 1 to 3 molar equivalents relative to the indenol. The desired 3-substituted-1-indenyl ester is obtained by reacting at a temperature of -30°C to 100°C for about 30 minutes to 24 hours. (Production method b) Method by reaction of alcohol and carboxylic acid anhydride 3-substituted-1-indenol represented by the general formula () and the general formula (R ² CO) ₂ O [wherein R ² is the general formula ( ) has the same meaning as in ). ] in an inert solvent such as benzene, toluene, hexane, acetone, etc., preferably in the presence of an acid such as sulfuric acid, p-toluenesulfonic acid, or a tertiary amine such as pyridine or triethylamine. The desired 3-substituted-1-indenyl ester is obtained by reacting at a temperature of -20°C to 100°C for about 1 to 24 hours. (Production method C) Method by reaction of alcohol and carboxylic acid 3-substituted-1-indenol represented by the general formula () and a carboxylic acid represented by the general formula () are mixed in an inert solvent such as benzene, toluene, or xylene. in the presence of a dehydration condensation agent such as dicyclohexylcarbodiimide or 2-chloro-1-methylpyridinium iodide and triethylamine.
The desired 3-substituted-1-indenyl ester is obtained by reacting at a temperature of 30 minutes to 24 hours at a temperature of 150°C to 150°C. The 3-substituted-1-indenyl ester obtained by the above production method can be purified by means such as chromatography and distillation, if necessary. The alcohol component 3-substituted-1-indenol represented by the general formula () can be easily produced, for example, by the following method. [In the formula, R ¹ has the same meaning as in the general formula (). ] In other words, 3-substitution- shown in the general formula ()
By reacting 1-indenone with an equivalent or more amount of sodium borohydride in ethanol, 3-substituted-1-indenol represented by the general formula () can be easily produced in good yield. On the other hand, substituted cyclopropanecarboxylic acids as acid components are known, and their carboxylic acid halides and carboxylic acid anhydrides can be prepared from the corresponding free acids by conventional methods. When the compound of the present invention is actually applied, it can be used alone without adding other ingredients, but in order to make it easier to use as an insecticide, a carrier may be added to form a preparation. It is generally applied after dilution. For formulation, we use emulsions, wettable powders, powders, granules, fine granules, oils, aerosols, heated fumigants (mosquito coils, electric mosquito repellents, etc.), follicles, etc. in accordance with conventional techniques for agricultural chemical formulations. It can take any form such as aerosols, non-heated fumigants, poison baits, etc., and these can be used for various purposes depending on the purpose. In addition, unlike general chrysanthemum acid ester compounds,
The compounds of the present invention have high stability against light, heat, oxidation, etc., but if it is particularly necessary under extremely oxidative conditions, antioxidants or ultraviolet absorbers, such as
Phenol derivatives such as BHT, BHA, bis-
By adding appropriate amounts of phenol derivatives, arylamines such as phenyl-α-naphthylamine, phenyl-β-naphthylamine, condensates of phenetidine and acetone, or benzophenone compounds as stabilizers, compositions with more stable effects can be obtained. Obtainable. The formulation generally contains 0.01 to 95% by weight of the compound of the present invention.
It is preferably contained in an amount of 0.1 to 90% by weight. The compounds of the present invention may be used in the form of the various types of preparations mentioned above, or these preparations may be further formulated into usage forms. The content of the compound of the present invention in the usage form can be appropriately selected within a very wide range such as 0.0000001 to 100% by weight, but is preferably 0.001 to 10% by weight. The insecticides according to the invention are used in the customary manner appropriate to the particular use type. Synthesis examples, formulation examples, and effect examples of the compounds of the present invention are shown below, but the present invention is not limited thereto. In addition, "parts" in the formulation examples mean parts by weight. The compound numbers correspond to the 3-substituted-1-indenyl esters (1) to (25) represented by the above-mentioned general formula (). Synthesis reference example 1 Sodium borohydride 0.40g and ethanol 30
3-benzyl-1-indenone in a solution consisting of ml
A solution consisting of 10 mmol and 50 ml of methylene chloride was added dropwise, and the mixture was stirred at room temperature for 2 hours. Thereafter, the reaction solution was poured into dilute hydrochloric acid and extracted with ethyl ether. The extract was washed with saturated brine and dried over anhydrous magnesium sulfate, and then low-boiling substances were distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 1.70 g of 3-benzyl-1-indenol having the following NMR spectrum. NMR spectrum (90MHz) δ ^TMS _CDCl3 : 2.67 (br.s,
1H); 3.6 (br.s, 2H); 4.83-4.96 (m,
1H); 5.72-5.83 (m, 1H); 6.8-7.4 (m,
9H) Synthesis Examples 1 to 4 In a solution consisting of 5 mmol of 3-substituted-1-indenol, 0.5 ml of pyridine and 10 ml of dry benzene, add 2,
2-dimethyl-3-(2,2-dichlorvinyl)
A solution consisting of 1.25 g of cyclopropanecarboxylic acid chloride and 5 ml of dry benzene was added dropwise, and after the addition, the mixture was stirred overnight at room temperature. Pour the obtained reaction solution into water,
It was extracted with ether, and the extract was washed with saturated brine. After drying the organic layer over anhydrous magnesium sulfate, low-boiling substances were distilled off under reduced pressure, and the resulting residue was subjected to silica gel high performance liquid chromatography [solvent:
3-substituted-1-indenyl ester was obtained by purification with n-hexane/isopropylether=95/5 volume ratio]. In the above method, as 3-substituted-1-indenol, 3-allyl-1-indenol, 3-methyl-1-indenol, 3-n-butyl-1-
By using indenol and 3-benzyl-1-indenol, the corresponding 3-allyl-1-indenyl 2,2-dimethyl-3-
(2,2-dichlorvinyl)cyclopropanecarboxylate [compound (1)], 3-methyl-1-indenyl 2,2-dimethyl-3-(2,2-dichlorvinyl)cyclopropanecarboxylate [compound (10)] , 3-n-butyl-1-indenyl 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate [compound (16)] and 3-benzyl-1-indenyl 2,2
-Dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate [Compound (22)]
I got it. The respective yields and NMR spectra are shown in Table 1.

[Table] Formulation Example 1 0.2 part of compound (1) was stirred and dissolved in white kerosene to make the total 100 parts to obtain an oil solution. Formulation example 2 By adding 50 parts of xylene and 20 parts of surfactant Solpol SM-200 (Toho Chemical Industry Co., Ltd., trade name) to 30 parts of compound (1) and stirring and mixing well.
A 30% emulsion was obtained. Combination example 3 20 parts of compound (1) and surfactant Solpol SM-
200 (same as above) were thoroughly mixed, 75 parts of talc was added, and the mixture was sufficiently stirred in a grinder to obtain a wettable powder. Formulation example 4 0.5 parts of compound (1) was dissolved in 20 parts of acetone, then 99.5 parts of clay was added and thoroughly stirred, the acetone was removed by evaporation, and the mixture was further stirred thoroughly in a grinder to make a 0.5% powder. I got it. Effect Example 1 Compound (1) produced in the same manner as Formulation Example 2
Each of the emulsions (25) was diluted with water to increase the compound concentration.
Each drug solution was prepared to have a concentration of 400 ppm.
Spray 7 ml/pot of the above chemical solution on rice planted in pots (6 cm diameter pot, 7 rice seedlings) 4 weeks after sowing, air dry, cover with a wire mesh cage, and incubate 20 female adult leafhoppers in the cage. Released. The pots were stored in a constant temperature room at 25°C, and 24 hours later, the test insects were observed to see if they were alive or dead, and the mortality rate was determined. The mortality rate for all compounds was over 90%. Effect Example 2 Compounds (1), (2), produced in the same manner as Formulation Example 2
A chemical solution was prepared by diluting the emulsions (10), (11), and (17) with water to give a compound concentration of 80 ppm. Rice planted in pots 4 weeks after sowing (pots with a diameter of 6 cm,
Spray 7 ml/pot of the above chemical solution on 7 rice seedlings,
After air-drying, the cage was covered with a wire mesh cage, and 20 female adult leafhoppers were released into the cage. Pot at 25℃
After 24 hours, the test insects were observed to see if they were alive or dead, and the mortality rate was determined. The mortality rate was over 80%. Effect Example 3 An emulsion of compound (1) produced in the same manner as in Formulation Example 2 was diluted with water to prepare a drug solution so that the compound concentration was 40 ppm. Spray 7 ml/pot of the above chemical solution on rice planted in pots (pots with a diameter of 6 cm, 7 rice seedlings) 4 weeks after sowing, and after air-drying, cover with a wire mesh cage and release 30 adult brown planthoppers into the cage. I kept it. The pots were stored in a constant temperature room at 25°C, and 24 hours later, the test insects were observed to see if they were alive or dead, and the mortality rate was determined.
The mortality rate was over 80%.

Claims (1)

[Claims] 1. General formula [In the formula, R ¹ represents a lower alkyl group, a lower alkenyl group, a halo-lower alkenyl group, a lower alkynyl group, or an arylmethyl group, and R ² represents a general formula represents a group represented by Here, R ³ represents a hydrogen atom or a methyl group; R ⁴ represents a cyclopentylidenemethyl group, XC≡C- group, when R ³ is a hydrogen atom;
It represents a [Formula] group or a [Formula] group, and when R ³ is a methyl group, it represents a methyl group. X
represents a halogen atom, Y represents a halogen atom or a methyl group, and Z represents a hydrogen atom or a halogen atom. ] A 3-substituted-1-indenyl ester represented by the following. 2 General formula [In the formula, R ¹ represents a lower alkyl group, a lower alkenyl group, a halo-lower alkenyl group, a lower alkynyl group, or an arylmethyl group, and R ² represents a general formula represents a group represented by Here, R ³ represents a hydrogen atom or a methyl group; R ⁴ represents a cyclopentylidenemethyl group, XC≡C- group, when R ³ is a hydrogen atom;
It represents a [Formula] group or a [Formula] group, and when R ³ is a methyl group, it represents a methyl group. X
represents a halogen atom, Y represents a halogen atom or a methyl group, and Z represents a hydrogen atom or a halogen atom. ] An insecticide containing a 3-substituted-1-indenyl ester shown as an active ingredient.