JPH0796481B2 - Insecticide, acaricide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention is a novel substance, which is a 2,3-disubstituted-4-hydroxyquinoline derivative as an active ingredient. Regarding acaricide.

[Conventional technology]

Conventionally, various natural components and synthetic substances having insecticidal and acaricidal activity have been researched, developed and put into practical use.
As a quinoline-based substance, 3-p-bromophenyl-1-o-hydroxystyrylbenzo [f] quinoline is known to have acaricidal activity and fungicidal activity [Ve
stsi Akad.Navuk BSSR, Ser.Khim.Navuk. (3), 76-8
(1987)].

Further, a bactericidal / insecticide containing a copper complex of 8-alkoxyquinolines as an active ingredient is also known (Japanese Patent Publication No. 54-34738). However, the insecticidal activity of these compounds is not sufficient in terms of their strength and selectivity.

[Problems to be Solved by the Invention]

Conventionally known insecticides, various substances having acaricidal activity, the activity efficacy is not sufficient due to the problem of insecticide resistance in recent years, and the development of new insecticides and acaricides having excellent activity has been demanded. .

It is an object of the present invention to provide an excellent insecticidal and acaricidal agent that meets this need.

[Means for Solving the Problems]

The present inventors have previously chemically synthesized microbial metabolites and their analogs, have a strong leukotriene D ₄ antagonism, and maintain the living body of mammals including humans, especially for the important immune system and cardiac blood flow. A novel 2,3-disubstituted-4-hydroxyquinoline derivative which is an effective substance for treating immune diseases and brain diseases and a method for producing the same are invented, and Japanese Patent Application No. 63-3192.
Filed as No. 31

The present inventors further studied the action of this substance,
The inventors have found that the insecticidal and acaricidal activities are excellent and completed the present invention.

The present invention has the general formula (I) [Wherein R ¹ represents a hydrogen atom or R ³ CO— (R ³ represents a lower alkyl group), R ² represents a hydrogen atom, a methyl group or an ethyl group, and A represents The insecticide and acaricide having one or more of 2,3-disubstituted-4-hydroxyquinoline derivatives represented by the following as an active ingredient.

The compound represented by the above formula (I) which is the active ingredient of the present invention is a 2,3-disubstituted-4-quinolone represented by the formula (II) when R ^{1 in} the formula is a hydrogen atom. Although it has a tautomeric relationship with the derivative, the present compound also falls within the scope of the present invention.

[Wherein R ² and A have the same meanings as above] The 2,3-disubstituted-4-hydroxyquinoline derivatives, which are the active ingredients of the present invention, are all novel compounds which have not been published in the literature. The typical compounds are listed below.

1.2- (trans-1-nonenyl) -3-methyl-4-
Acetoxyquinoline 2.2- (cis-1-nonenyl) -3-methyl-4-acetoxyquinoline 3.2- (trans-1-nonenyl) -3-methyl-4-
Quinolone 4.2- (cis-1-nonenyl) -3-methyl-4-quinolone 5.2- (trans-2-nonenyl) -3-methyl-4-
Acetoxyquinoline 6.2- (trans-2-nonenyl) -3-methyl-4-
Quinolone 7.2- (1-Hydroxy-2-nonynyl) -3-methyl-4-acetoxyquinoline 8.2- (1-Hydroxy-2-nonynyl) -3-methyl-4-quinolone 9.2- (trans-1-hydroxy-2 -Nonenyl)-
3-Methyl-4-acetoxyquinoline 10.2- (trans-1-hydroxy-2-nonenyl)-
3-methyl-4-quinolone and the like.

The numbers given to the names of the compounds are cited in the examples below.

2,3-disubstituted-4 represented by the above general formula (I) of the present invention
-Insecticides containing a hydroxyquinoline derivative as an active ingredient include hemiptera of aphids, planthoppers, leafhoppers, stink bugs, etc., Lepidoptera of Spodoptera litura, Kokonaga, Nikameiga etc., Coleoptera of weevils, Chrysomelidae, etc., Housefly,
Diptera, such as Culex pipiens, reticules, such as cockroaches, other orthoptera, insects such as Thrips, and spider mites, ticks,
It has a particularly remarkable activity against pests such as mite and mites.

In the insecticidal and acaricidal agent of the present invention, one or more compounds represented by the general formula (I) may be used as they are as an active ingredient, but they are generally used for the preparation of agricultural chemicals. Solid carriers, liquid carriers, gaseous carriers, surfactants, dispersants, other auxiliary agents for formulation, baits and the like are mixed by a usual method, and emulsions, liquids, wettable powders, powders, granules, oils, aerosols, Use it in a suitable dosage form such as a flowable agent or poison bait.

Examples of solid carriers include talc, bentonat,
Examples thereof include clay, kaolin, diatomaceous earth, vermiculite, white carbon, calcium carbonate, and the like. Examples of liquid carriers include alcohols such as methanol, n-hexanol, ethylene glycol, and cellosolve, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, Kerosene, aliphatic hydrocarbons such as kerosene, benzene,
Aromatic hydrocarbons such as toluene, xylene and methylnaphthalene, halogenated hydrocarbons such as dichloroethane, trichloroethylene and carbon tetrachloride, ethers such as diethyl ether, dioxane and tetrahydrofuran, esters such as ethyl acetate, acetonitrile, iso Examples thereof include nitriles such as butyronitrile, acid amides such as dimethylformamide and dimethylacetamide, vegetable oils such as soybean oil and cottonseed oil, dimethyl sulfoxide, and water. Examples of the gas carrier include LPG, CFC gas, air, nitrogen, carbon gas, dimethyl ether and the like.

Examples of surfactants and dispersants for emulsification, dispersion, spreading and the like include alkyl sulfates, alkyl (aryl) sulfonates, polyoxyalkylene alkyl (aryl) ethers, polyhydric alcohol esters,
Lignin sulfonate or the like is used.

Further, as an auxiliary agent for improving the properties of the preparation, for example, carboxymethyl cellulose, gum arabic, polyethylene glycol, calcium stearate, etc. are used.

The above carrier, surfactant, dispersant and auxiliary agent may be used alone or in combination as necessary.

Insecticide in the present invention, the content of active ingredients of acaricide,
Emulsion is usually 1 to 50% by weight, powder is usually 0.3 to 25% by weight.
% By weight, usually 1 to 90% by weight for wettable powders, usually for granules,
0.5 to 10% by weight is suitable.

These formulations are used as they are or after being diluted. Further, it can be used as a mixture with other insecticides, acaricides, fungicides, herbicides, plant growth regulators, fertilizers, soil conditioners, synergists and the like.

〔Example〕

Next, the present invention will be described in more detail with reference to examples and effects of the present invention, but the present invention is not limited to these examples.

Production Example 1 Production Example of Compounds 1 and 2 Octyltriphenylphosphonium bromide 218 mg
0.29 ml of a hexane solution of 0.48 mmol of n-butyllithium is added to a 3 ml solution of (0.48 mmol) of tetrahydrofuran, and the mixture is stirred at room temperature for 5 minutes.

After cooling this solution to −78 ° C., 1.43 g (8 mmol) of hexamethylphosphorus triamide was added and stirred for 5 minutes, and further 2-formyl-3-methyl-4-acetoxyquinoline 9
A solution of 1.6 mg (0.40 mmol) of tetrahydrofuran in 2 ml is added, and the mixture is stirred at -78 ° C for 15 minutes and at -42 ° C for 30 minutes. The reaction solution was added to 20 ml of water, extracted with ethyl acetate, washed with a saturated aqueous solution of sodium chloride, and then dried over anhydrous sodium sulfate. After distilling off the solvent under reduced pressure, the residue was purified by silica gel column chromatography [Wakogel C-200 (Wako Pure Chemical Industries, Ltd.) (solvent n-hexane: ethyl acetate = 15: 1)] to give 2- (trans-1-nonenyl). -3-methyl-4
13 mg of acetoxyquinoline (10% yield) and 15 mg of 2- (cis-1-nonenyl) -3-methyl-4-acetoxyquinoline (12% yield) are obtained.

2- (trans-1-nonenyl) -3-methyl-4-acetoxyquinoline [Compound 1] Melting point 74-75 ° C NMR (CDCl ₃ ) δ = 0.90 (t, J = 7Hz, 3H) 1.2-1.5 (m, 10H), 2.31 (s, 3H), 2.33 to 2.40 (m, 2H), 2.51 (s, 3H), 6.80 (d, J = 15.4Hz, 1H), 7.08 (dt, J = 15.4Hz, J = 7.1) Hz, 1H), 7.4 to 7.8 (m, 3H), 8.04 (d, J = 8.8Hz, 1H) 2- (cis-1-nonenyl) -3-methyl-4-acetoxyquinoline [compound 2] NMR (CDCl ₃ ) δ = 0.84 (t, J = 6Hz 3H 1.1 to 1.6 (m, 10H), 2.2 to 2.7 (m, 2H), 2.26 (s, 3H), 2.49 (s, 3H), 6.02 (dt, J = 12Hz, J = 7Hz, 1H), 6.61 (d, J = 12Hz, 1H), 7.3 ~ 8.1 (m, 4H) Example 1 Emulsion compound 1 20% by weight, N, N-dimethylformamide 20% by weight, xylene 50 10% by weight of polyoxyethylene alkylallyl ether was added to the weight% and mixed uniformly and dissolved to obtain an emulsion.

Example 2 Wettable powder 25% by weight of compound 2, 30% by weight of clay, 35% by weight of diatomaceous earth, 3% by weight of calcium lignin sulfonate, 7% by weight of polyoxyethylene alkylallyl ether were uniformly mixed and pulverized to obtain water. I got a Japanese medicine.

Example 3 Powder Dust was obtained by uniformly mixing 2% by weight of compound 1, 60% by weight of clay, 37% by weight of talc, and 1% by weight of calcium stearate.

Example 4 Granules Compound 2 5% by weight, bentonite 40% by weight, talc 53
% By weight and 2% by weight of calcium ligninsulfonate were uniformly pulverized and mixed, water was added thereto and kneaded well, and then granulated and dried to obtain granules.

Next, the tests and results showing the effects of the insecticidal and acaricidal agents of the present invention are shown.

Test Example 1 Efficacy test against peach mosquito (wingless fetus adult) A test sample prepared according to Example 1 was treated with a surfactant (0.
Cabbage leaf pieces (5 cm x 5 cm) inoculated with 10 adult female peach aphid wingless female embryos were immersed in a test solution diluted to 1000 ppm with water containing 01%) for 10 seconds. After air-drying, put it in a plastic cup with a diameter of 9 cm and leave it in a constant temperature room at 25 ° C.
The number of live and dead insects after the day was investigated and the mortality rate was calculated.

The results are shown in Table 1.

Test Example 2 Adult female mites of the spider mites (organic phosphorus drug resistance)
Efficacy test against cultivated 6-cm diameter plastic pot cultivated primary leaves of Phellinus linteus were inoculated with 10 adult females of the spider mite mite.
One day after the inoculation, the test solution prepared according to Example 1 was diluted to 1000 ppm with water containing a surfactant (0.01%), and 10 ml of the test solution was sprayed in a spray tower. After the treatment, the sample was left in a thermostatic chamber at 25 ° C., and the number of live and dead insects was investigated 2 days later to determine the mortality rate.

The results are shown in Table 2.

Test Example 3 Insecticidal test against 3rd-instar larvae of silkworm A dead sample prepared according to Example 1 was diluted with water to 400 p.
100 ml of the drug solution having a concentration of pm was prepared. Dry artificial feed for silkworms (Vita silk for silkworms produced by Kyodo Feed Co., Ltd.)
Was soaked and fully impregnated. This artificial feed is 9 cm in diameter
In a plastic cup of No. 10, 10 3rd-instar larvae of Bombyx mori were released, and the number of live and dead larvae was examined 6 days later to determine the mortality rate.

The results are shown in Table 3.

[Effects of the Invention] The present invention is an extremely useful insecticide and acaricide having a remarkable insecticidal and acaricidal effect.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Nobuto Minowa Norito Minowa 760 Shimooka-cho, Kohoku-ku, Yokohama-shi, Kanagawa Meiji Seika Co., Ltd., Pharmaceutical Research Laboratory (72) Tomoya Machinami, 760 Meiji-cho, Kohoku-ku, Yokohama-shi, Kanagawa (72) Inventor Seiji Shibahara, 760 Seiji-cho, Kohoku-ku, Yokohama-shi, Kanagawa Meiji Seika Co., Ltd.

Claims (1)

[Claims] 1. A formula [In the formula, R ¹ represents a hydrogen atom or R ³ CO— (R ³ represents a lower alkyl group), R ² represents a hydrogen atom, a methyl group or an ethyl group, and A represents An insecticidal or acaricidal agent comprising, as an active ingredient, one or more of 2,3-disubstituted-4-hydroxyquinoline derivatives represented by