JPH021828B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the formula () The present invention relates to a carboxylic acid ester represented by the following formula and an insecticide containing the carboxylic acid ester as an active ingredient. Pesticides are used to eradicate various pests that damage agricultural crops, and are essential production materials for maintaining agricultural production at a high level. In addition, many infectious diseases are transmitted by insects, and exterminating them is very effective in preventing the spread of diseases, and the use of insecticides is the most effective way to achieve this goal. It is a practical means. In this way, pesticides play an extremely important role in maintaining the high standard of living that humanity has currently achieved and is expected to achieve in the future. In order to meet these objectives, many excellent insecticides have been created in the past and have been used with success in various fields. However, organochlorine insecticides such as BHC and DDT are no longer used due to the emergence of pests that are resistant to them, as well as problems such as environmental pollution and toxicity to various organisms that are not targeted for extermination. severely restricted. Furthermore, there are signs that the problem of resistant pests is becoming more serious in various fields with organic phosphate ester and carbamate insecticides, which should replace them, and against this background, there is a need to create new and better insecticides. It's long awaited. If we think about the properties that a good insecticide should have, it goes without saying that it should have high insecticidal power, but today it is also important that it has low toxicity to non-target organisms such as humans and animals, is non-residual, and is environmentally friendly. Low contamination is strongly desired. Although natural pyrethrins have some of the properties required for insecticides as mentioned above, as they have low toxicity to humans and livestock and are easily decomposed under outdoor environmental conditions, they are relatively less toxic than organic phosphates and carbamates. Its use is limited to fields such as household insecticides because it has poor insecticidal power, decomposes too quickly, has little residual effect, and is expensive. In order to compensate for these shortcomings of natural pyrethrins, the present inventors conducted many studies and found that
The carboxylic acid ester represented by the above formula () is 1.
It has extremely high insecticidal efficacy and is fast-acting. 2.Although it has a long-lasting effect, it does not have the same environmental persistence as organic chlorine pesticides. 3.Low toxicity to humans and animals. 4.Excellent effectiveness against pests that are resistant to organic phosphorus agents or carbamate agents. They discovered that it has excellent properties such as, and completed the present invention. Specific insect pests for which the compounds of the present invention are particularly effective include the following. 1 Hemiptera (1) Delphacidae: For example,
Sogatella furcifera,
Nilaparvata lugens,
Laodelphax striatellus (2) Deltocephalidae: e.g.
Nephotettix cincticeps, Tettigella viridis,
Inazuma dorsalis (3) Aphididae: e.g.
Rhopalosiphum padi (4) Pentatomidae: e.g.
Nezara antennata,
Eysarcaris ventralis 2 Lepidoptera: e.g. Archips
fumiferana (Spruce Budworm), Chilo
suppressalis, Cuapha
Iocrocis medinalis, Galleria
mellonella, Dendrolimus
spectabilis, Malacosoma
neustria 3 Coleoptera (Coleoptera): For example, Onlema
oryzae, Echinocnemus
squameus (rice weevil) 4 Diptera (Diptera): e.g. Aedes aegypti
(Aedes aegypti), Anopheles sp. (Anopheles sp.), Culex pipiens pallens (Culex pipiens pallens),
Agromyza oryzae 5 Orthoptera: For example, Oxya
yezoensis The compound of the present invention has the formula () A carboxylic acid or its reactive derivative represented by the formula () or by a method of reacting with an alcohol of the formula () or its reactive derivative; The aldehyde represented by and the formula () [In the formula, Y represents a chlorine atom or a bromine atom. ] It can be obtained in good yield by the method of reacting the carboxylic acid halide shown below with an alkali metal cyanide. Examples of the reactive derivative of the carboxylic acid represented by the formula () herein include carboxylic acid halides, carboxylic acid anhydrides, salts of tertiary organic bases of carboxylic acids, and alkali metal salts of carboxylic acids. The raw material α-cyanobenzyl alcohol is “Preparative Organic” than aldehyde.
The halide can be easily obtained by the method described in "Chemistry" (C. Hilgetay et al.), page 875, and the halide can be easily obtained by the method described in Organic Synthesis Col. Vol.
It can be obtained by the method described on page 793. The carboxylic acid and carboxylic acid chloride used as raw materials are disclosed in JP-A-53-40743 and JP-A-53-101340.
The acid anhydride can be obtained by the method described in JP-A No. 53-40744, etc., and the acid anhydride can be obtained from these methods using "Synthetic Organic Chemistry" (RB
It can be obtained in good yield by the method described on page 558 of Wagner et al. Note that the compounds of the present invention include optical isomers based on asymmetric carbon atoms of alcohol components and acid components, and all of these are included in the present invention. Hereinafter, among the methods for producing the compounds of the present invention, aldehydes,
The method of reacting an alkali metal cyanide and an acid halide will be explained in more detail. An aldehyde represented by the formula (), an alkali metal cyanide, and a carboxylic acid halide represented by the formula () are mixed with a phase transfer catalyst (such as tetra- n-butylammonium bromide,
(benzyltriethylammonium chloride, etc.) at an internal temperature of 0°C to 100°C for 30 minutes to 10 hours to obtain the desired compound. The obtained compound can be purified by means such as chromatography, if necessary. Next, the method for synthesizing the compound of the present invention will be explained in further detail using production examples. Production example: Dissolve 0.37 g of sodium cyanide and 0.25 g of benzyltriethylammonium chloride in 5 mg of water, and add 1.08 g of 3-anilino-4-fluorobenzaldehyde and dl-cis at room temperature with stirring.
Add dropwise to a solution of 1.19 g of trans-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid chloride dissolved in 10 ml of toluene. After completion of the dropwise addition, stirring was continued for 5 hours at the same temperature. The resulting reaction solution is washed with saturated brine and then dried over anhydrous magnesium sulfate. By distilling off the solvent, 1.73 g of 3-anilino-4-fluoro-
α-cyanobenzyl dl-cis, trans-2,
2-dimethyl-3-(2,2-dichlorovinyl)
Cyclopropane carboxylate was obtained as a pale yellow liquid. n _D ^24.7 1.5763 The compound of the present invention thus obtained has low toxicity to humans and livestock, and can be used in a wide range of applications, including for epidemic prevention purposes targeting flies, mosquitoes, and cockroaches, and for controlling stored grain pests such as the white-breasted moth and the black elephant. These include planthoppers, leafhoppers, armyworms, diamondback moths, leafhoppers, aphids, beetles,
It is extremely effective in controlling agricultural, horticultural and forest pests such as chestnut beetles, as well as animal parasitic lice, and can also control a wide variety of other pests. The compound of the present invention not only knocks pests down and kills them, but also has repellent properties,
It also has the effect of repelling pests from the host.
It can be put to practical use in various dosage forms. When preparing the compound of the present invention as an insecticide, it is possible to prepare emulsions, wettable powders, Powders, granules, fine granules, oils, aerosols, heated fumigants (mosquito coils, electric mosquito repellents, etc.), fogging agents such as fogging, non-heated fumigants,
It can be prepared into any dosage form, such as poison bait, and can be used for various purposes by using the form and carrier as required. Furthermore, α-[2-
(2-butoxyethoxy)ethoxy]-4,5-
Mixed with other known synergists effective against allethrin and pyrethrin, such as methylenedioxy-2-propyltoluene {referred to as piperonyl butoxide}, octachlorodipropyl ether {referred to as S-421} By doing so, the insecticidal effect can also be enhanced. Although the compounds of the present invention are relatively stable against photo-oxidation, antioxidants or ultraviolet absorbers, such as
Phenol derivatives like BHT, BHA, bis-
By adding an appropriate amount of phenol derivatives or 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. can be obtained. In addition, other physiologically active substances, such as allethrin,
N-Chrysansemoxymethyl-3,4,5,6-
Tetrahydrophthalimide {referred to as tetramethrin}, 5-benzyl-3-furylmethyl chrysanthemate {referred to as resmethrin}, 3-phenoxybenzyl chrysanthemate, and their d-trans primary chrysanthemum esters, d-cis , trans primary chrysanthemum acid ester or insect repellent chrysanthemum extract,
In addition to d-trans primary chrysanthemum acid or d-cis, trans primary chrysanthemum acid ester of d-allethrone, and other known pyrethroid compounds, O,O-dimethyl-O-(3-methyl-4-nitrophenyl) phosphorothioate {referred to as fenitrothion},
O,O-dimethyl-O-(4-cyanophenyl)
Phosphorothioate {referred to as cyanophos},
Organophosphorus insecticides such as O,O-dimethyl-O-(2,2-dichlorovinyl)phosphorothioate {referred to as dichlorovos}, 1-naphthyl-N
-Methyl carbamate, 3,4-dimethylphenyl-N-methyl carbamate {referred to as MPMC}
carbamate insecticides such as, other insecticides,
Or fungicides, nematicides, acaricides, herbicides,
A multi-purpose composition with even better efficacy can be made by mixing plant growth regulators, fertilizers, microbial pesticides such as BT agents and BM agents, insect hormone agents, and other agricultural chemicals, and the efficacy of these combinations can be increased. A synergistic effect 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. First, a formulation example will be shown. Formulation Example 1 0.2 part of the compound of the present invention was dissolved in white kerosene, and the whole
If it is 100 parts, you will get an oil solution. Formulation Example 2 10 parts of the compound of the present invention, 15 parts of Solpol 3005X (emulsifier manufactured by Toho Chemical Co., Ltd.), and 75 parts of xylene are added and mixed with thorough stirring to obtain an emulsion. Formulation Example 3 Mix and dissolve 0.2 parts of the compound of the present invention, 0.2 parts of tetramethrin, 7 parts of xylene, and 7.6 parts of deodorized kerosene, fill it into an aerosol container, and attach the valve part, and then spray the propellant (liquefied petroleum gas) through the valve part. An aerosol can be obtained by filling 85 parts under pressure. Formulation Example 4 5-propargylfurfuryl dl-cis, trans-chrysanthemate to 0.1 g of the compound of the present invention
Add 0.1 g of BHT and 0.1 g of BHT, dissolve in an appropriate amount of chloroform, and uniformly adsorb onto a 3.5 cm x 1.5 cm, 0.3 cm thick filter paper. A fiber fumigation composition heated on an electric heating plate is thus obtained. Formulation Example 5 10 parts of fenitrothion was added to 20 parts of the compound of the present invention, and Solpol 5029-0 (emulsifier manufactured by Toho Chemical Co., Ltd.) was added.
Mix 5 parts well, add 65 parts of 300 mesh diatomaceous earth, and stir and mix thoroughly in a grinder to obtain a wettable powder. Formulation Example 6 Add 2 parts of 1-naphthyl-N-methyl carbamate to 1 part of the compound of the present invention, dissolve it in 20 parts of acetone, add 97 parts of 300 ml of turquoise, mix well with stirring in a grinder, and then evaporate the acetone. If you remove it, you will get a powder. Formulation Example 7 To 5 parts of the compound of the present invention, 5 parts of Toyolignin CT (emulsifier manufactured by Toyobo Co., Ltd.) and 90 parts of GSM clay (Clay manufactured by Sieglite Co., Ltd.) are added, and the mixture is sufficiently stirred and mixed in a grinder. Then water is added in an amount of 10% of the mixture,
The mixture is further stirred and mixed, granulated using a granulator, and dried through ventilation to obtain granules. Formulation Example 8 Add 2 parts of Cyanox, 5 parts of Toyolignin CT, and 91 parts of GSM clay to 2 parts of the compound of the present invention,
Thoroughly stir and mix in a crusher. Next, water is added in an amount of 10% of the mixture, and the mixture is stirred and mixed, granulated using a granulator for fine granules, and dried through ventilation to obtain fine granules. Next, a test example will be shown. The control compounds used in the following test examples are indicated by compound symbols in Table 1.

【table】

[Table] Test Example 1 Place a filter paper of the same size at the bottom of a polyethylene cup with a diameter of 5.5 cm. 0.7 ml of a 200-fold dilution (equivalent to 500 ppm) of the emulsion obtained in Formulation Example 2 with water is dropped onto a filter paper, and 30 mg of sucrose is added uniformly as bait. Ten female adult house flies were released into the container, the lid was closed, and 48 hours later, the mortality rate was determined (4 repetitions).

[Table] Test Example 2 The compound of the present invention and the control compound were diluted with acetone to a prescribed concentration, and food and water were placed in a plastic cup that was applied topically to the thoracic dorsal plate of an adult female susceptible house fly (CSMA strain) 4 days after emergence. After 1 day, the animals were examined to see if they were alive or dead, and the LD ₅₀ value (50% lethal dose) was determined.

【table】

[Table] Test Example 3 2 ml of a 200-fold dilution with water of the emulsion of the compound of the present invention obtained in Formulation Example 2 is soaked into 15 g of artificial feed for Spodoptera spp. and placed in a polyethylene cup with a diameter of 11 cm. Ten 3rd instar Spodoptera larvae were released into the larvae, and 6 days later, their survival and death were examined (4 times).

[Table] Test Example 4 Rice stems (about 10 cm in length) are immersed for 1 minute in a water dilution of the emulsions of the present compound and control compound obtained in Formulation Example 2 at a predetermined concentration. After air drying,
A rice stem was placed in a test tube and 10 adult leafhoppers of a resistant strain were released, and after one day, the survival and death were examined.
The LC ₅₀ value (50% lethal dose) was determined (4 replicates).

【table】

[Table] Test Example 5 The insecticidal efficacy of the aerosol obtained in Formulation Example 3 against adult house flies was evaluated using an aerosol test method using a peat gradient chamber (6 feet cubic) [Soap & Chemical Specialties] Method described in Blue Book (1965)]
Tested by. As a result, we were able to knock down over 80% of the flies within 15 minutes of injection, and the next day we were able to kill over 70% of the flies.

Claims (1)

[Claims] 1 formula Carboxylic acid ester represented by 2 formulas An insecticide characterized by containing a carboxylic acid ester represented by as an active ingredient.