JPH07103079B2 - Para-aryloxyaralkylamine derivatives and insecticides and acaricides - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Object of the Invention (Field of Industrial Application) The present invention relates to a novel paraaryloxyaralkylamine derivative. More specifically, the present invention relates to a novel paraaryloxyaralkylamine derivative represented by the following general formula (I), and an insecticidal and acaricidal agent containing the derivative. Therefore, the present invention is useful in the chemical industry as well as agriculture, especially in the agricultural manufacturing field.

(Prior Art) Up to now, regarding aryloxyaralkylamine derivatives, Pharmaceutical Bulletin Vol. 5,
Pages 397-400 (1957) describe N-acetyl derivatives of 4-phenoxybenzylamine. However, it is not known whether they have insecticidal and acaricidal activity.
Further, there is no literature description about the derivative as seen in the present invention.

(Problems to be solved by the invention) Until now, as agricultural and horticultural insecticides and acaricides, organic phosphorus compounds, carbamate compounds, organic chlorine compounds,
Many types are used, including pyrethroids. However, the emergence of more safe drugs has been desired, and drugs that are highly toxic to humans, drugs that have residual problems, etc. are gradually being used. For this reason, limited drugs are frequently used. As a result, pests and mites have become resistant to these drugs, and the reduction of insecticidal or acaricidal effects has become a problem. In particular, many leafhoppers, which are important pests for paddy fields in Japan, have emerged that show strong resistance to organophosphorus insecticides and carbamate insecticides. In addition, mites showing resistance to dicofol (Kelsen) have emerged worldwide, which has become a major problem in control measures. Therefore, with respect to agricultural and horticultural insecticides and acaricides, it has been earnestly desired to develop a compound having a new structure, which is safe for humans and animals and has a strong effect on conventional drug-resistant pests and mites.

The present invention is to provide a novel insecticidal and acaricidal agent that satisfies these needs.

Structure of the Invention (Means for Solving the Problems) The present inventors have synthesized a large number of aryloxyaralkylamine derivatives in order to achieve the above-mentioned object, and have conducted intensive studies on their usefulness. As a result, the para-aryloxyaralkylamine derivative represented by the general formula (I) described later is a novel compound not described in the literature, and high insecticidal activity
Has acaricidal activity and safety for useful crops, livestock, etc.,
It has been found that the above object is achieved.

Therefore, the gist of the first aspect of the present invention lies in the following general formula (I): (In the formula, X represents a halogen atom or a lower haloalkyl group, n represents 1 or 2, Y represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower haloalkyl group or a lower alkoxy group, and A represents a lower alkylene. Group or a lower alkenylene group), which is a paraaryloxyaralkylamine derivative.

The gist of the second aspect of the present invention is an insecticidal and acaricidal agent characterized by containing the above-mentioned paraaryloxyaralkylamine derivative of the general formula (I) as an active ingredient.

Next, Table 1 shows typical examples of the compound of the present invention represented by the general formula (I). However, the compound No. is also referred to in the following examples and test examples.

Although not particularly mentioned in the present specification, the compound of the present invention has at least one asymmetric carbon atom, and the number of asymmetric carbon atoms may be further increased depending on the kind of the substituent such as A. There are several types of optical isomers. When A is an alkenylene group, geometric isomers exist. The present invention includes a single isomer or a mixture of isomers in any kind and ratio.

Action The compound of the general formula (I) of the present invention is a novel compound.
The compound of the general formula (I) acts as an insecticidal and acaricidal active ingredient in the field of agriculture and horticulture.

(Example) Method for Producing Compound of the Present Invention The compound of the general formula (I) according to the first present invention is represented by the general formula (III) in the paraaryloxyaralkylamine derivative represented by the general formula (II). It can be produced by reacting a carboxylic acid halide.

(In the formula, X, n, Y, and A are the same as described above, and Z represents a halogen atom.) This condensation reaction is usually performed in an organic solvent. Usable solvents include hydrocarbons such as benzene, toluene and hexane, halogenated hydrocarbons such as chloroform and chlorobenzene, ethers such as ethyl ether, dioxane and tetrahydrofuran, esters such as methyl acetate and ethyl acetate, Examples thereof include ketones such as acetone and methyl isobutyl ketone, nitriles such as acetonitrile and propionitrile, alcohols such as methyl alcohol and ethyl alcohol, amides such as dimethylformamide and dimethylacetamide, and dimethyl sulfoxide.

As the acid binder, an inorganic base such as sodium hydride, sodium amide, sodium hydroxide or potassium carbonate,
Alternatively, an organic base such as triethylamine or pyridine can be used.

Although the reaction proceeds even at room temperature, the reaction time can be shortened by heating in the range up to the boiling point of the solvent. After the completion of the reaction, if salts of the acid binder, etc., are present, they are filtered off and the solvent is distilled off to obtain the desired product. The compound of the present invention can also be obtained by adding water and an organic solvent such as benzene, toluene, tetrahydrofuran, or chloroform to fractionate the desired product and distill off the solvent. An example of producing the compound of the present invention by such a method is shown in Example 1-2.

The starting compound (II) compound is a known compound or a method similar to a known compound, for example, British Patent No. 720,59.
According to the production method described in Japanese Patent Publication No. 3 (1954), it can be easily produced by reacting a corresponding halide with methylamine. An example of producing the compound of formula (II) by this method is shown in Reference Production Example. The compound of formula (II) produced by the method is shown in Table 2. The compound of formula (III) is a known compound.

(Example 1) N-methyl N-α-methyl-p- (4-
Preparation of tolufluoromethylphenoxy) benzylphenylacetamide (Compound No. 12) Methyl α-methyl-P- (4-trifluoromethylphenoxy) benzylamine 29.5 g, triethylamine
15.5 g of phenylacetyl chloride was added dropwise to a mixture of 10.1 g and 100 ml of toluene under water cooling, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the precipitated salt was filtered off and the concentrated solution was concentrated to obtain 38.8 g of the title compound as a pale yellow oily substance. This product was purified by silica gel column chromatography using a hexane-acetone mixed solvent to give a colorless oily substance, and the result was (n ²³ _D) = 1.5546.

(Example 2) N-methyl N-α-methyl-p- (2-
Preparation of chlor-4-trifluoromethylphenoxy) benzylphenylacetamide (Compound No. 26) Methyl α-methyl-p- (2-chloro-4-trifluoromethylphenoxy) benzylamine 33.0 g, triethylamine 10.1 g, chloroform When 100 ml and 15.5 g of phenylacetyl chloride were used and the reaction and treatment were carried out in the same manner as in Example 1, 41.2 g of the title compound was obtained as a pale yellow oil. This product was purified by silica gel column chromatography using a mixed solvent of hexane-ethyl acetate to give a colorless oil, ▲ n ²³ _D ▼ = 1.5.
It showed 532.

(Reference Production Example) Production of methyl α-methyl-p- (4-trifluoromethylphenoxy) benzylamine α-methyl- (4-trifluoromethylphenoxy) benzyl chloride 30.1 g, 40% aqueous methylamine solution 1
A mixture of 5.5 g and 100 ml of ethanol is stirred at 60 ° C. for 3 hours. After completion of the reaction, toluene and water are added to disperse the toluene layer, and dried with anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the title compound was obtained as a pale yellow oily substance.
1.7 g was obtained. This product was purified by silica gel column chromatography using a hexane-acetone mixed solvent to give a colorless oily substance, and showed a value of (n ²³ _D) = 1.5136.

(Example) Formulation method of insecticidal and acaricidal agent In addition, the insecticidal and acaricidal agent of the second aspect of the present invention comprises an emulsion, a wettable powder, a liquid formulation, and Flowable (sol) agent, powder, driftless (DL)
It can be prepared in an appropriate form such as powder, granules, fine granules and tablets. The carrier used here may be either solid or liquid as long as it is commonly used for agricultural and horticultural chemicals, and is not limited to a particular carrier. For example, as a solid carrier, mineral powder (kaolin, bentonite, clay, montmorillonite, talc, diatomist,
Mica, vermiculite, gypsum, calcium carbonate, apatite, white carbon, slaked lime, silica sand, ammonium sulfate, urea, etc., vegetable powder (soybean flour, wheat flour, wood flour, tobacco powder,
Examples include starch, crystalline cellulose, etc., polymer compounds (petroleum resin, polyvinyl chloride, ketone resin, dammal gum, etc.), alumina, silicates, sugar polymers, highly dispersible silicic acid, waxes and the like. The liquid carrier may be water, alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, iso-propyl alcohol, butanol, ethylene glycol, benzyl alcohol, etc.), aromatic hydrocarbons (toluene, benzene, xylene, ethylbenzene). , Methylnaphthalene, etc.), halogenated hydrocarbons (chloroform, carbon tetrachloride, dichloromethane, chloroethylene, monochlorobenzene, trichlorofluoromethane, dichlorodifluoromethane, etc.), ethers (ethyl ether, ethylene oxide, dioxane, tetrahydrofuran) Etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, isophorone, etc.), esters (ethyl acetate, butyl acetate, ethylene glycol) Cetate, amyl acetate, etc.), acid amides (diketylformamide, dimethylacetamide, etc.), nitriles (acetonitrile, propionitrile, acrylonitrile, etc.), sulfoxides (dimethylsulfoxide, etc.), alcohol ethers (ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, etc.), aliphatic or alicyclic hydrocarbons (n-hexane, cyclohexane, etc.), industrial gasoline (petroleum ether, solvent naphtha, etc.), petroleum fraction (paraffins, kerosene, light oil, etc.) , And so on.

In the preparation of emulsions, wettable powders, flowable agents, various surfactants or emulsifiers are used for the purpose of emulsification, dispersion, solubilization, wetting, foaming, lubrication, spreading and the like.
As such a surfactant, nonionic type (polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, sorbitan alkyl ester, etc.), anionic type (alkylbenzene sulfonate, alkyl sulfosuccinate, Alkyl sulphate, polyoxyethylene alkyl sulphate, aryl sulphonate, etc.), cationic type [alkyl amines (lauryl amine, stearyl trimethyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, etc.), polyoxyethylene alkyl amines)] amphoteric type Acid (betaine type), sulfate ester salt, etc.),
However, the present invention is not limited to these examples. In addition to these, various auxiliary agents such as polyvinyl alcohol, carboxymethyl cellulose, gum arabic, polyvinyl acetate, gelatin, casein, sodium alginate, and tragacanth gum can be used.

In the present invention, when producing the various preparations described above, the compound of the present invention may be formulated so as to contain 0.001% to 95% (wt%: the same hereinafter), preferably 0.01% to 90%. it can. For example, normally, 0.01% to 5% for powders, DL powders, and several powders (F), 0.01% to 10% for granules, 1% to 75% for wettable powders, emulsions, and liquids.
It can be contained in the range of%.

For example, in the case of a wettable powder, an emulsion and a sol, the preparation thus prepared is diluted with water or a suitable solvent so that the amount of the active ingredient is about 0.3 to 300 g per 10 are. Just scatter.

Further, when using the compound of the present invention as an insecticidal and acaricidal agent, it is possible to expand the applicability by mixing it with a known insecticide, acaricide or fungicide in any proportion.
In some cases, a synergistic effect can be expected.

A method for formulating the compound of the present invention represented by the general formula (I) as an insecticidal and acaricidal agent will be described in Examples 3-6. However, the present invention is not limited to these examples, and various other additives can be mixed in an arbitrary ratio.

In the examples, all parts are parts by weight.

Example 3 (Emulsion) 40 parts of the compound of Compound No. 12, 20 parts of Solpol 700H (trade name of emulsifier manufactured by Toho Chemical Industry Co., Ltd.) and 40 parts of xylene are uniformly mixed to obtain an emulsion.

Example 4 (Wettable powder) 15 parts of compound No. 26, white carbon 15
Parts, calcium lignin sulfonate 3 parts, polyoxyethylene nonylphenyl ether 2 parts, diatomaceous earth
Evenly mix 5 parts and 60 parts of clay with a pulverizing mixer,
Obtain a wettable powder.

Example 5 (Dust) 1.5 parts of the compound of Compound No. 32 and 98.5 parts of clay are uniformly mixed and pulverized to obtain a powder.

Example 6 (Granule) Compound No. 5 Compound 5 parts, lauryl sulfate 1.
5 parts, 1.5 parts of calcium lignin sulfonate, 25 parts of bentonite and 67 parts of white clay were mixed with 15 parts of water and kneaded with a kneader, then granulated with a granulator and dried with a fluid dryer to obtain granules. obtain.

(Effect of the Invention) The compound of the present invention exhibits a high control effect against various pest boxes such as sucking pests, chewing pests, and mites. It is also useful for controlling plant parasitic pests, stored grain pests and sanitary pests. Among them, extremely high insecticidal activity against organophosphorus insecticides, carbamate insecticides such as leafhopper leafhoppers and dicofol resistant mites.
Has acaricidal action. Moreover, the compound of the present invention hardly causes phytotoxicity to useful crops. Therefore, it can be used for the control of a wide range of pests and mites as shown below.

Coleoptera Pest Weevil (Coleoptera) Weevil Weevil, Weevil Weevil, Pleurotus communis, Nebula serrata, Tobiiromunabokometsukii, Douganebububu, Himeboshi, Kisugominomushi, Weevil Weevil, etc.

Lepidoptera Lepidoptera such as gypsy moth, caterpillars, Lotus japonicus, Nikameichu, apple cockroach beetle, Cobra moth, cabbage moth, tamanagaya, diamondback moth.

Hemiptera pests (Hemiptera) leafhopper, brown planthopper, brown planthopper,
Aphis gossypii, green peach aphid, cotton aphid, ring aphid, etc.

Orthoptera pests such as German cockroaches, American cockroaches, kerula, and Kobaneago.

Diptera Pests such as house flies, Aedes aegypti, Aedes mosquitoes, Culex tritaeniorhynchus, Onion flies.

Tick (Acarina), such as spider mites, kanzawa mites, mites, citrus mites, apple mites, citrus rust mites, etc.

Next, specific examples of usefulness and action of the compound of the present invention will be shown in Test Examples 1 and 2.

Test Example 1 Control effect test against resistant leafhopper Green rice plant was planted in a square pot made of black vinyl having a side of 6 cm, and when the plant height was about 40 cm, the powder preparation of the present invention prepared according to Example 5 was used. A fixed amount was sprayed on the foliage of rice with a midget duster. After spraying, the rice seedlings were covered with a vinyl chloride cylinder having a diameter of 11 cm, and 20 adult females of the leafhopper leafhopper leafhopper (3 days after emergence), which are resistant to organophosphorus intermediates and carbamate insecticides, were released in the cylinder. . Then, this pot was placed under a constant temperature of 25 ° C., and 48 hours later, the supine rate (%) was obtained.

This test was carried out in a three-pot system per one drug concentration group, and the average elevation rate (%) was calculated. The results are shown in Table 2.

Test Example 2 One side of the control effect test for resistant mites
Plant kidney bean seedlings in a 6 cm-sized black vinyl square pot and inoculate 20 dicofol-resistant adult female adults of the genus Dicorfol that were in the process of breeding during the first true leaf development period, and settled in each pot. I laid the eggs. Then, 24 hours after that, 30 ml of a predetermined concentration diluted solution of the wettable powder of the present invention prepared according to Example 4 was sprayed per pot. Then the pot
It was kept at a constant temperature of 25 ° C, and 14 days later, the number of female adults of Nami-dani, which had parasitized, was examined to determine the control value (%).

This test was carried out in a 3-pot system for each concentration of the chemical solution, and the average control value (%) was calculated. The results are shown in Table 3.

Claims (2)

[Claims] 1. A general formula (In the formula, X represents a halogen atom or a lower haloalkyl group, n represents 1 or 2, Y represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower haloalkyl group or a lower alkoxy group, and A represents a lower alkylene group. Or a lower alkenylene group), which is a paraaryloxyaralkylamine derivative. 2. General formula (In the formula, X represents a halogen atom or a lower haloalkyl group, n represents 1 or 2, Y represents a hydrogen atom, a halogen atom, a lower alkyl group, a lower haloalkyl group or a lower alkoxy group, and A represents a lower alkylene group. Or a lower aryl alkenylene group), which is contained in the composition as a paraaryloxyaralkylamine derivative as an active ingredient.