JPS6332070B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel heterocyclic ether urea compound, a method for producing the same, and an insecticide containing the compound. As a result of many years of research and development into insecticides, a wide variety of insecticides have been put into practical use, and these insecticides have contributed to improving the productivity of agricultural and horticultural crops. However, even today, there is a demand for the development of new drugs with more outstanding insecticidal properties, and the present inventors have been diligently researching the insecticidal properties of various heterocyclic compounds with the aim of developing new and useful insecticides. As a result of research, the following formula: (In the formula, A represents CH or a nitrogen atom, X ¹ represents a hydrogen atom, a halogen atom, or a trifluoromethyl group, X ² represents a hydrogen atom or a halogen atom, and R ¹ and R ² are each independently R ³ represents a halogen atom or a lower alkoxy group, and R ⁴ represents a hydrogen atom, a halogen atom or a lower alkoxy group). They discovered that it has insecticidal activity and completed the present invention. Conventional heterocyclic ether urea compounds include:
JP-A-54-106475 describes that substituted ether-based urea compounds can be used as insecticides. Further, JP-A-55-98153 describes naphthyl ether-based urea compounds and the insecticidal action of these compounds. However, the compound of the present invention, that is, the heterocyclic ether urea compound having a quinoline or quinoxaline core represented by the above general formula, is a new compound discovered for the first time by the present inventors, which has not been described in any literature. The compound of the present invention can generally be synthesized by the method shown in the reaction formula below. (In the formula, A, X ¹ , X ² , R ¹ , R ² , R ³ and R ⁴ have the above meanings.) That is, benzoyl isocyanate represented by the general formula and the aniline derivative represented by the general formula are preferably used. is obtained by condensing the reactants in the presence of an inert solvent. As the reaction solvent, for example, benzene, toluene, acetonitrile, pyridine, etc. can be used. Although the reaction temperature and reaction time can vary widely depending on the starting materials, it is generally preferred that the reaction temperature is -20°C to 100°C and the reaction time is 0.5 hour to 24 hours. The compounds of the present invention thus obtained can be used to protect against various agricultural and horticultural pests that cause damage to paddy rice, vegetables, fruit trees, cotton, other crops, flowers, etc., including sanitary pests.
It is an extremely useful compound as a control agent for forest pests, husk pests, etc. Accordingly, the present invention provides insect killing agents for use in applying effective amounts of compounds of the present invention to insect habitats. Insect habitat means any place where insects live, such as soil, air, water, food, plants, fertilizers, inert objects, storage materials such as shells. Examples of insect pests to which the compound of the present invention can be applied are listed below, but of course the pests are not limited to these. Sanitary pests House flies, mosquitoes, cockroaches Agricultural and horticultural pests [Water rice] Japanese rice moth, rice plant beetle, rice weevil, rice leafminer fly, rice leafminer fly, Japanese brown planthopper, white-legged planthopper, brown planthopper, black leafhopper [Yanagi] armyworm, Japanese armyworm, Japanese armyworm, Kona Ga, Nijiyuyahoshi Lady beetles, green peach aphids [Fruit trees] Leaf beetles, goldenrod moth, peach beetle, peach beetle moth, blackberry aphid, mulberry scale aphid The activity of the compound of the present invention as an insecticide is to inhibit the metamorphosis mechanism of insects, thereby killing the insects. It is thought that it will cause In order to exert this effect, it is thought that it is necessary for insects to ingest it. Although death of some insects is delayed until the insect enters the stage of metamorphosis, the actual effect of this activity is insect control and eradication. Insecticides comprising the compounds of the present invention are effective against young and old larvae, and are expressed directly or through systemic transfer. To apply the insecticide of the present invention, the active ingredients are generally
It is preferably carried out at a concentration of 0.1 to 10,000 ppm, preferably 0.5 to 2,000 ppm. In the case of aquatic harmful insects, it is possible to control them by spraying a chemical solution in the concentration range mentioned above to the place where they occur, so concentration ranges other than the above range in water are also effective. When applying the compound of the present invention as an insecticide, it is generally carried out using a suitable carrier, such as a solid carrier such as clay, talc, or bentonite, or water, alcohols (methanol, ethanol, etc.), ketones, ethers, aliphatic It can be used in combination with liquid carriers such as hydrocarbons, aromatic hydrocarbons (benzene, toluene, xylene, etc.), organic bases, acid amides (dimethylformamide, etc.), esters, nitriles, etc. Emulsifier if desired;
Adding dispersants, suspending agents, spreading agents, penetrating agents, stabilizers, etc., emulsions, oils, wettable powders, powders, granules, tablets, pastes, flowables, aerosols, smoking agents, mosquito coils. It can be put to practical use in any dosage form, such as electric mosquito repellent. Note that, if necessary, it may be mixed with or simultaneously applied with other insecticides, various fungicides, herbicides, planting seasoning agents, fertilizers, etc. during formulation or spraying. The compound of the present invention also contains piperonyl butoxide, octachlorodipropyl ether, N
- The insecticidal efficacy can be further enhanced by adding a synergist such as octylbicycloheptenedicarboximide. In addition, the stability of the compounds of the present invention can be improved by adding phenolic or amine compounds such as 2,6-di-tertiary-butyl-4-methylphenol and 2,6-di-tertiary-butylphenol as antioxidants. It is also possible to increase the sex. Next, the present invention will be further explained with reference to Examples, Formulation Examples, and Test Examples, but the present invention is not limited thereto. Example 1 Formula: Synthesis of N-(2,6-dichlorobenzoyl)-N'-[4-(2-quinolyloxy)phenyl]urea (compound No. 24) 4-(2-quinolyloxy)aniline 1.2 g
1.0 g (4.6 x 10 ^-3 mol) of 2,6-dichlorobenzoyl isocyanate was added dropwise to a solution of 2,6-dichlorobenzoyl isocyanate (5.0 x 10 ^-3 mol) in 40 ml of acetonitrile under stirring at 0°C. After reacting overnight at room temperature, the obtained crystals were collected, washed with acetonitrile, and dried to obtain 1.5 g of the target compound (Compound No. 30) as white crystals with a melting point of 234 to 235.5°C. Example 2 Formula: Synthesis of N-(2,6-dimethoxybenzoyl)-N'-[3-chloro-4-(6-fluoro-2-quinoxalyloxy)phenyl]urea (compound No. 30) 3-chlor -4-(6-fluoro-2-quinoxalyloxy)aniline 0.87g (3.0×10 ^-3 mol)
in 30 ml of acetonitrile, add 2,6-
Dimethoxybenzoyl isocyanate 0.6g (2.9
x10 ^-3 mol) was added dropwise at 0° C. with stirring. After reacting overnight at room temperature, the resulting crystals were collected, washed with acetonitrile, and dried to give a melting point of 227-229°C.
Target compound (compound No. 38) as white crystals 1.0
I got g. Example 3 Formula: N-(2-chlorobenzoyl)-
Synthesis of N′-[4-(6-chloro-2-quinoxalyloxy)phenyl]urea (compound No. 8) 4-(6-chloro-2-quinoxalyloxy)
0.7 g (3.9 x 10 ^-3 mol) of 2-chlorobenzoyl isocyanate was added dropwise to a solution of 1.1 g (4.0 x 10 ^-3 mol) of aniline dissolved in 40 ml of acetonitrile at 0° C. with stirring. After reacting overnight at room temperature,
The generated crystals were collected, washed with acetonitrile, and dried to obtain 1.1 g of the target compound (Compound No. 8) as white crystals with a melting point of 238 to 240°C. The compounds shown in Tables 1 and 2 below were synthesized in the same manner as in the above examples.

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[Table] Next, examples of formulations in which the compounds of the present invention are used as insecticides are shown. In the examples, "parts" represent "parts by weight." Formulation Example 1 Emulsion Compound of the present invention 5 parts Xylene 80 parts Solpol 2680 (trade name, Toho Chemical) 15 parts The above components are mixed uniformly to form an emulsion. The obtained emulsion is diluted 50 times with water to 25 to 50 ml per ¹ m2.
or diluted 1000 to 2000 times per 10a
Spray 100-150. Formulation Example 2 Oil Agent Compound of the present invention 0.1 part Piperonyl butoxide 0.9 part White kerosene 99.0 parts The above components are mixed uniformly to prepare an oil agent. Apply the obtained oil to grooves and puddles at a rate of 25 to 50 ml ^per square meter. Formulation example 3 Wettable powder Compound of the present invention 10 parts Zeekrite (Zeeklite mining trade name)
75 parts Carplex (trade name of Shionogi & Co., Ltd.) 10 parts Solpol 8048 (trade name of Toho Chemical Co., Ltd.) 3 parts Lunox 1000 (trade name of Toho Chemical Co., Ltd.) 2 parts The above ingredients are uniformly mixed and ground to make a wettable powder.
When using, mix the obtained hydrating agent with water for 500~
Dilute 2000 times and spray 50 to 500 per 10a. Formulation Example 4 Powder Compound of the present invention 0.4 parts Piperonyl butoxide 1.6 parts Talc 98 parts The above components are mixed uniformly to prepare a powder. The resulting powder is spread at a rate of 15g per ^m2 or 3-4 kg per 10a. Formulation example 5 Granules Compound of the present invention 5 parts Bentonite 95 parts After uniformly mixing and pulverizing the above ingredients, adding a small amount of water and stirring thoroughly, granulation was performed using an extrusion granulator, and this was dried. Take the form of granules. The obtained granules are directly sprayed in an amount of 3 to 4 kg per 10 acres. Next, the compound according to the present invention exhibits excellent insecticidal action by the following formula: Commercial product represented by (difluorobenzuuron)
This will be explained by giving a test example in comparison with the following. Test Example 1 Insecticidal test against Spodoptera larvae After a cabbage leaf was immersed in a chemical solution containing an active ingredient compound dispersed in water and adjusted to a predetermined concentration for about 10 seconds, it was taken out and air-dried. This leaf piece has a diameter of 9
The leaves were placed on damp paper on a Petri dish of 1.2 cm in size, and 2nd instar Spodoptera larvae were released onto the leaf pieces, then the leaves were covered and stored in a constant temperature room with lighting at 25°C. On the 7th day after release, the larvae were determined to be alive or dead, and the mortality rate was calculated using the following formula to obtain the results shown in Table 2 below. Mortality rate = number of dead insects / number of released insects x 100

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[Table] Test Example 2 Insecticidal test against diamondback moth larvae As in Test Example 1 above, place damp paper in a Petri dish with a diameter of 9 cm, place a piece of cabbage treated with a chemical solution on the paper, and after air-drying the leaf piece, kill the 2nd instar moth. Diamondback moth larvae were released onto leaf pieces. The insect mortality rate was determined on the 7th day after the insects were released in the same manner as in Test Example 1, and the results shown in Table 4 below were obtained.

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Claims (1)

[Claims] Primary formula: (In the formula, A represents CH or a nitrogen atom, X ¹ represents a hydrogen atom, a halogen atom, or a trifluoromethyl group, X ² represents a hydrogen atom or a halogen atom, and R ¹ and R ² are each independently a hydrogen atom or a halogen atom, R ³ represents a halogen atom or a lower alkoxy group, and R ⁴ represents a hydrogen atom, a halogen atom or a lower alkoxy group). Quadratic formula: (In the formula, R ³ represents a halogen atom or a lower alkoxy group, and R ⁴ represents a hydrogen atom, a halogen atom or a lower alkoxy group.) Benzoyl isocyanate represented by the following formula: (In the formula, A represents CH or a nitrogen atom, X ¹ represents a hydrogen atom, a halogen atom, or a trifluoromethyl group, X ² represents a hydrogen atom or a halogen atom, and R ¹ and R ² are each independently (representing a hydrogen atom or a halogen atom) with the following formula: (In the formula, A, X ¹ , X ² , R ¹ , R ² , R ³ and R ⁴ have the above-mentioned meanings.) A method for producing a heterocyclic ether urea compound represented by the following. Cubic formula: (In the formula, A represents CH or a nitrogen atom, X ¹ represents a hydrogen atom, a halogen atom, or a trifluoromethyl group, X ² represents a hydrogen atom or a halogen atom, and R ¹ and R ² are each independently (represents a hydrogen atom or a halogen atom, R ³ represents a halogen atom or a lower alkoxy group, and R ⁴ represents a hydrogen atom, a halogen atom or a lower alkoxy group) as an active ingredient. An insecticide characterized by containing.