JPH0372614B2 - - Google Patents

Description

[Detailed Description of the Invention] The present invention is based on the following general formula [] [In the formula, R ₁ represents a hydrogen atom, and R ₂ represents a hydrogen atom or a methyl group. R ₃ represents a 2,2-difluorovinyl group and a 2,2-dichloro-1,2-dibromoethyl group. ] The present invention relates to a carboxylic acid ester represented by (hereinafter referred to as the compound of the present invention) and an insecticide containing the same as an active ingredient. It is known that certain cyclopropane carboxylic acid esters can be used as insecticides; for example, Nature,
246, 169-170 (1973), Nature, 207, 938-940
(1965) and others. However, these compounds are not always sufficient as insecticides. The compound of the present invention has the general formula [] [In the formula, R ₃ has the same meaning as above. ] Carboxylic acid or its reactive derivative represented by the general formula [] [In the formula, R ₁ and R ₂ have the same meanings as above. ] It can be produced by reacting the alcohol represented by the following in an inert solvent in the presence or absence of a suitable reaction aid, if necessary. In this case, examples of reactive derivatives of carboxylic acids include acid chlorides, acid bromides, and acid anhydrides, and examples of inert solvents include toluene, benzene, xylene, tetrahydrofuran, hexene, and the like. In addition, as reaction aids, when using carboxylic acid itself, acid catalysts such as mineral acids and dehydrating agents such as dicyclohexylcarbodiimide can be mentioned, and when using acid chlorides and acid bromides, dehalogenators such as pyridine and triethylamine can be mentioned. Hydrogenation agents can be mentioned. Further, when using an acid anhydride, no particular reaction aid is required. Usually, this objective can be easily achieved by reacting an acid chloride and an alcohol with pyridine in benzene or toluene at room temperature to 40°C. Incidentally, the carboxylic acid represented by the general formula [] and its reactive derivative, and the alcohol represented by the general formula () are all well-known compounds,
Methods for their production are also known. Next, a manufacturing example will be shown. Production Example 1 (Reaction between alcohol and acid chloride) α-1-propynylbenzyl alcohol 1.0g
Dissolve and 0.8g of pyridine in 20ml of dry toluene,
Cool with cold water, below 20℃ (1R)-Trans-3
A solution of 1.3 g of -(2,2-difluorovinyl)-2,2-dimethylcyclopropanecarboxylic acid chloride in 5 ml of dry toluene was added dropwise. After stirring at room temperature for 4 hours, the mixture was poured into 20 ml of 2% hydrochloric acid solution to separate the layers, the oil layer was taken, washed with 20 ml of saturated brine, dried over magnesium sulfate, and the solvent, toluene, was distilled off under reduced pressure. The residue was purified by chromatography using a chromatography column packed with about 20 g of silica gel using a hexane-ethyl acetate mixture (10:1) as an elution solvent. α-(1-propynyl) as a pale yellow oil
1.7 g of benzyl (1R)-trans-3-(2,2-difluorovinyl)-2,2-dimethylcyclopropanecarboxylate (the compound (1) of the present invention) was obtained. n ^22.5 _D 1.4850 Table 1 shows some examples of the compounds of the present invention that can be produced in a similar manner. [Table] [Table] The compound of the present invention represented by the general formula () is used to kill insects,
When preparing it as an acaricide, it can be prepared as an emulsion, wettable powder, powder, or granule by a method well known to those skilled in the art, using a dilution aid for general insecticides in the same way as conventional pyrethroids. , fine granules, oils, aerosols,
It can be prepared into any dosage form such as heating fumigants (mosquito coils, electric mosquito repellents, etc.), fumigants such as fogging, non-heating fumigants, poison baits, etc., and can be used for various purposes by using the form and carrier according to your needs. It can be served. Furthermore, α-[2-
(2-butoxyethoxy)ethoxy]-4,5
- Mixed with other synergists known to be effective against allethrin and birethrin, such as methylenedioxy-2-propyltoluene {referred to as piperonyl butoxide}, octachlorodipropyl ether {referred to as S-421}, etc. Its use can also enhance its insecticidal effect. In general, chrysanthemum acid ester compounds are exposed to light, heat,
Since they tend to lack stability against oxidation, antioxidants or ultraviolet absorbers such as BHT and BHA are used.
By adding an appropriate amount of phenol derivatives such as bis-phenol derivatives or arylamines such as phenyl-α-naphthylamine, phenyl-β-naphthylamine, condensates of phenetidine and acetone, or benzophenone compounds as stabilizers, A composition with more stable effects can be obtained. Also, other physiologically active substances, such as allethrin,
N-(chrysansemoxymethyl)-3,4,5,6
-tetrahydrophthalimide {hereinafter referred to as tetramethrin}, 5-benzyl-3-furylmethylchrysansemate {hereinafter referred to as resmethrin},
3-phenoxybenzyl chrysansemate, and their d-trans primary chrysanthemum esters, d-
d-trans primary chrysanthemum acid ester or pyrethrum extract, d-trans primary chrysanthemum acid or d-cis trans primary chrysanthemum ester of d-arethrolone,
In addition to other known pyrethroid compounds, O,
O-dimethyl-O-(3-thymel-4-nitrophenyl) phosphorothioate {referred to as phenitrothion}, O,O-dimethyl-O-4-cyanophenyl phosphorothioate {referred to as cyanophos}, O,O-dimethyl-O- Organophosphorus insecticides such as (2,2-dichlorovinyl)-phosphate {referred to as dichlorovos}, 1-naphthyl-
Carbamate insecticides such as N-methylcarbamate, 3,4-dimethylphenyl-N-methylcarbamate (referred to as MPMC), other insecticides or fungicides, nematicides, acaricides, herbicides, plants Multi-purpose compositions with even better efficacy can be made by mixing them with growth regulators, fertilizers, microbial pesticides such as BT agents, BM agents, insect hormone agents, and other agricultural chemicals. Synergistic effects can also be expected. Next, the preparation and effects of the insecticide of the present invention will be explained using formulation examples and test examples. Formulation Example 1 Add 20 parts each of the compounds (1) to (3) of the present invention, 10 parts emulsifier {Solpol 3005X (registered trademark of Toho Chemical)}, and 70 parts xylene, stir well, and mix and dissolve. Obtain each emulsion. Formulation Example 2 Add 0.3 parts of PAP (isopropyl acid phosphate) to 1 part of the compound of the present invention (1), dissolve it in 20 parts of acetone, add 98.7 parts of 300 mesh clay, stir and mix thoroughly, and then remove the acetone by evaporation. Get the powder. Formulation Example 3 By dissolving 0.1 part of each of the compounds (1) to (3) of the present invention in white kerosene to make a total of 100 parts, each oil solution is obtained. The compounds of the present invention are effective as insecticides against sanitary pests such as flies, mosquitoes, and cockroaches, and against agricultural and horticultural pests such as brown planthoppers, brown planthoppers, leafhoppers, and armyworms. Therefore, the compounds of the present invention can be used as pesticidal insecticides, household insecticides, and agricultural and horticultural insecticides. Next, test examples will show that the compounds of the present invention are effective as insecticides. Incidentally, unless otherwise specified, the test compounds are indicated by the compound numbers shown in Table 1. In addition, the test results are expressed as insect mortality rate (%). Test Example 1 Insecticidal effect on house flies Place a filter paper of the same size at the bottom of a polyethylene cup with a diameter of 5.5 cm. With water of the emulsion obtained in Formulation Example 1
Drop 0.7 ml of the 400-fold diluted solution (equivalent to 500 ppm) onto the filter paper. Place 30 mg of sucrose on the filter paper as bait. Ten female adult house flies were released into the container, the lid was placed on the container, and 48 hours later, their survival and death were determined to determine the mortality rate. (2 repetitions) [Table] Test Example 2 Insecticidal effect on the brown planthopper The 20% emulsion of the compound of the present invention obtained in Formulation Example 1 was diluted 400 times (equivalent to 500 ppm) with water. Rice seedlings were immersed in each chemical solution for 1 minute, air-dried, placed in test tubes, and adult brown planthoppers were released, and their survival was examined 24 hours later. 【table】

Claims (1)

[Claims] 1. General formula [In the formula, R ₁ represents a hydrogen atom, and R ₂ represents a hydrogen atom or a methyl group. R ₃ is 2,2-difluorovinyl group or 2,2-dichloro-1,2
-represents a dibromoethyl group. ] A carboxylic acid ester represented by 2 General formula [In the formula, R ₁ represents a hydrogen atom, and R ₂ represents a hydrogen atom or a methyl group. R ₃ represents a 2,2-difluorovinyl group or a 2,2-dichloro-1,2-dibromoethyl group. ] An insecticide characterized by containing a carboxylic acid ester represented by the following as an active ingredient.