JP2715587B2 - Hydrazone compounds and insecticides containing the same as active ingredients - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel hydrazone compound and an insecticide containing the same as an active ingredient.

<Problems to be Solved by Conventional Techniques and Inventions> Conventionally, various compounds have been used as insecticides. However, these compounds have problems in that a high dose is required to obtain a sufficient effect and that the insecticidal spectrum is narrow. In addition, even those which have conventionally exhibited excellent insecticidal activity have become unable to obtain a sufficient control effect due to the spread of drug-resistant insects.

Also, that certain hydrazone compounds have insecticidal activity, for example EP3913A ₁ JP, Sho 56-45452
No., published in Japanese Unexamined Patent Publication No.

However, these compounds are not necessarily sufficient in terms of insecticidal activity and insecticidal spectrum.

<Means for Solving the Problems> In view of such circumstances, the present inventors have conducted various studies in order to develop a compound having excellent insecticidal activity.
The present inventors have found that a hydrazone-based compound represented by the following formula [I] has excellent insecticidal activity, and have reached the present invention.

That is, the present invention provides a compound of the formula [I] And an insecticide containing the same as an active ingredient.

The compound of the present invention is included in the general formula described in JP-A-56-45452, but there is no specific description of the compound of the present invention in this publication, and it is clear from the test examples described below. Thus, the compounds of the present invention have extremely high insecticidal activity as compared with the related compounds described in the publication.

The pests against which the compound of the present invention is effective include, for example, Japanese moth moth, Japanese mulberry, Japanese moth moth, armyworm, lingua,
Lepidoptera such as cabbage butterflies, moths and moths, diptera such as mosquitoes, anopheles, and sea mosquitoes, houseflies and the like, reticulates such as cockroaches, brown cockroaches, brown cockroaches and the like, southern corn rootworms,
Coleoptera such as northern corn rootworm and scarab beetles, other hymenoptera, alloptera, orthoptera, etc., are also effective against pests that have developed resistance to existing insecticides.

Typical production methods of the compound of the present invention include, for example, the following methods.

Production method A Formula [II] And a compound represented by the general formula (III) [In the formula, R represents a lower alkyl group. By reacting the compound represented by the formula (I)
A method for obtaining the present compound represented by the formula:

In the production method A, a solvent is not necessarily required for production, but when a solvent is used, for example, ethers such as diethyl ether, tetrahydrofuran, and siloxane; alcohols such as ethylene glycol, glycerin, methanol, and ethanol; Acid amides such as N, N-diethylformamide and N, N-dimethylacetamide; aromatic hydrocarbons such as benzene, toluene and chlorobenzene; halogenated hydrocarbons such as methylene chloride and chloroform; acetone nitrile And the like, water or a mixed solvent thereof is used, and the compound represented by the general formula [II] is usually used per 1 mol of the compound represented by the formula [II].
The compound represented by I] is used in a proportion of 1 to 50 mol. The reaction temperature is usually from room temperature to 200 ° C, preferably from 50 to 150 ° C.
The reaction time is usually 5 minutes to 100 hours, preferably 30 minutes to 5 hours.
0 hours.

If necessary, as a reaction catalyst, for example, a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, propionic acid,
Organic acids such as methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid, and addition salts of amines such as pyridine hydrochloride and triethylamine hydrochloride are used in an amount of 0.001 to 1 mol per mol of the compound represented by the formula [II]. One mole can be used. After completion of the reaction, the desired compound of the present invention can be obtained by performing ordinary post-treatment.

Production method B Formula [IV] A compound of the formula [V] By reacting with a compound represented by the formula (I)
A method for obtaining the present compound represented by the formula:

In the production method B, a solvent is not necessarily required for production, but when a solvent is used, for example, ethers such as diethyl ether, tetrahydrofuran, dioxane, alcohols such as ethylene glycol, glycerin, methanol, ethanol, N , N-dimethylformamide, N, N-dimethylacetamide and other acid amides, sulfolane, dimethylsulfoxide and the like, benzene, toluene, aromatic hydrocarbons such as chlorobenzene, methylene chloride, halogenated hydrocarbons such as chloroform, Aliphatic hydrocarbons such as pentane, hexane and heptane, alicyclic hydrocarbons such as cyclohexane, pyridines such as pyridine and picoline, acetic acid, water and the like or a mixed solvent thereof are used, and usually represented by the formula (IV). The compound represented by the formula [V] is added to 1 mole of the compound represented by the formula: It is used in a proportion of 0.5 to 10 mol. The reaction temperature is usually −20 to 200 ° C., preferably −10 to 150 ° C., and the reaction time is generally 5 minutes to 300 hours, preferably 5 minutes to 120 hours. If necessary, as a reaction catalyst, for example, mineral acids such as hydrochloric acid, sulfuric acid and nitric acid, organic acids such as formic acid, acetic acid, propionic acid, methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid, and pyridine hydrochloride , An acid addition salt of an amine such as triethylamine hydrochloride with respect to 1 mol of the compound represented by the formula [IV]
0.001-1 mol can be used. After completion of the reaction, the desired compound of the present invention can be obtained by performing ordinary post-treatment.

Production method C formula [VI] A method for obtaining a compound of the present invention represented by the formula [I] by reacting the compound represented by the formula with dimethylamine.

Production method D formula [VII] A method for obtaining a compound of the present invention represented by the formula [I] by reacting the compound represented by the formula with dimethylamine.

In the production methods C and D, a solvent is not necessarily required for production, but when a solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene, and pyridine , Pyridines such as picoline, chloroform, carbon tetrachloride, 1,2
-Dichloroethane, 1,1,1-trichloroethane, tetrachloroethylene, halogenated hydrocarbons such as trichloroethylene, n-hexane, n-heptane, aliphatic hydrocarbons such as cyclohexane, water and the like or a mixed solvent thereof is used, Usually, dimethylamine is used in a proportion of 1 to 100 mol per 1 mol of the compound represented by the formula [VI]. Dimethylamine is used in a proportion of 1 to 100 mol per 1 mol of the compound represented by the formula [VII]. The reaction temperature is usually -20 to 200 ° C, preferably 0 to 100 ° C.
° C, and the reaction time is usually 5 minutes to 100 hours. After completion of the reaction, the desired compound of the present invention can be obtained by performing ordinary post-treatment.

The compounds represented by the formulas (II) and (IV) are known compounds and can be produced, for example, by the method described in JP-A-56-45452, and represented by the general formulas (III) and (V). The compounds shown are commercially available or can be prepared by methods analogous to those known in the art.

On the other hand, the compounds represented by the formulas (VI) and (VII) are novel compounds, and the compound represented by the formula (VI) is, for example, a compound represented by the formula (VIII) Can be produced by reacting a compound of the formula (II) with phosphorus pentachloride.The compound of the formula (VII) can be produced, for example, by reacting a compound of the formula (VIII) with phosphorus oxychloride. can do.

In these production methods, a solvent is not necessarily required, but when a solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, o-dichlorobenzene, chloroform, carbon tetrachloride, ,
Halogenated hydrocarbons such as 2-dichloroethane, 1,1,1-trichloroethane, tetrachloroethylene and trichloroethylene; aliphatic hydrocarbons such as n-hexane and n-heptane; alicyclic hydrocarbons such as cyclohexane and the like; A mixed solvent is used.

When a compound represented by the formula [VI] is produced by reacting a compound represented by the formula [VIII] with phosphorus pentachloride, usually, 1 mol of the compound represented by the formula [VIII] is used in an amount of 1 mol. It is used in a proportion of up to 5 mol. The reaction temperature is usually from temperature to 250 ° C, preferably from 100 to 180 ° C, and the reaction time is usually from 5 minutes to 100 hours.

When the compound represented by the formula [VIII] is reacted with phosphorus oxychloride to produce the compound represented by the formula [VII], the oxychloride is usually added to 1 mol of the compound represented by the formula [VIII]. Phosphorus is used in a proportion of 1 to 5 mol.
The reaction temperature is generally 0 to 250 ° C, preferably 10 to 180 ° C, and the reaction time is generally 5 minutes to 100 hours.

After completion of the reaction, the compound represented by the formula [VI] or [VII] can be obtained by performing ordinary post-treatment.

(VI) or (VII) produced by these methods
Can also be used for the reaction of Production Method C or D, respectively, without isolation and purification.

The compound represented by the formula [VIII] is a known compound and can be produced, for example, by the method described in JP-A-56-45452.

The compound of the present invention has two types of geometric isomers depending on the configuration of the double bond of the hydrazone, including both geometric isomers and a mixture of the two geometric isomers, each of which is an insecticide. It can be used as an agent.

When the compound of the present invention is used as an active ingredient of an insecticide, it may be used as it is without adding any other components, but it is usually mixed with a solid carrier, a liquid carrier, a gaseous carrier, a bait, and the like. If necessary, add surfactants and other formulation auxiliaries, oils, emulsions, wettable powders, flowables, granules, powders, aerosols, aerosols (fogging etc.),
Formulated in poison bait and used.

In these preparations, the compound of the present invention as an active ingredient,
Usually, it is contained in an amount of 0.01% to 95% by weight.

Examples of solid carriers used in the formulation include clays (kaolin clay, diatomaceous earth, synthetic hydrous silicon oxide,
Bentonite, fubasami clay, acid clay, etc.), talc, ceramics, other inorganic minerals (sericite, quartz, sulfur, activated carbon, calcium carbonate, hydrated silica, etc.),
Fine powders or granular materials such as chemical fertilizers (ammonium sulfate, phosphorous ammonium, ammonium nitrate, urea, salt ammonium, etc.) are listed.
For example, water, alcohols (methanol, ethanol, etc.), ketones (acetone, methyl ethyl ketone, etc.),
Aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, methylnaphthalene, etc.), aliphatic hydrocarbons (hexane, kerosene, light oil, etc.), alicyclic hydrocarbons (cyclohexane, etc.), esters (ethyl acetate, Butyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile, etc.), ethers (diisopropyl ether, dioxane, etc.), acid amides (N, N-dimethylformamide, N, N-dimethylacetamide, etc.), halogenated carbonized Hydrogens (dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide, soybean oil, vegetable oils such as cottonseed oil and the like are mentioned. Examples include dimethyl ether and carbon dioxide.

Examples of the surfactants used for emulsification, dispersion, wet spreading, etc. include alkyl sulfates, alkyl (aryl) sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl aryl ether phosphates, and naphthalene. Examples include anionic surfactants such as sulfonic acid formalin condensate, and nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester.

Examples of pharmaceutical auxiliaries such as fixatives and dispersants include casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, sugars, synthetic water-soluble polymers (polyvinyl alcohol) , Polyvinylpyrrolidone, polyacrylic acids and the like), and examples of the stabilizer include PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), and BHA (2-tert-butylphenol). -Butyl-
A mixture of 4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, surfactants, fatty acids or esters thereof, and the like.

As a bait bait, for example, preservatives such as cereal flour, starch, vegetable essential oil, sugar, crystalline cellulose sugar, antioxidants such as dibutylhydroxytoluene, butylhydroxyanisole, nordihydroguaiaretic acid, and dehydroacetic acid Foods, sweet food powder and other ingestion preventives, cheese flavors, onion flavors and other attractive flavors.

The preparation thus obtained is used as it is or diluted with water or the like. Also, other insecticides, nematicides,
It can also be used with or without mixing with miticides, soil pesticides, pesticides, fungicides, herbicides, plant growth regulators, synergists, fertilizers, soil conditioners.

When the compound of the present invention is used as an agricultural pesticide, the application rate is usually 5 g to 500 g per 10 ares, an emulsion,
When using wettable powders, flowables, etc. diluted with water,
The application concentration is 1 ppm to 500 ppm, and granules, powders and the like are applied as they are without dilution. When used as an insecticide for epidemics, emulsions, wettable powders, flowables, etc. are diluted with water to 1 ppm to 500 ppm and applied, and oils,
Aerosols, aerosols and poison baits are applied as they are.

All of these application rates and application concentrations depend on the type of formulation,
It depends on the situation such as application time, application place, application method, type of pest, degree of damage, etc., and can be increased or decreased without being concerned with the above range.

<Examples> Hereinafter, the present invention will be described in more detail with reference to Production Examples, Formulation Examples, and Test Examples, but the present invention is not limited thereto.

 First, formulation examples are shown.

Production Example 1 300 g (0.79 mmol) of 4-chloro-4'-trifluoromethylsulfonyloxybenzonephenonehydrazone and N,
127 g of N-dimethylacetamide dimethyl acetal (0.9
(5 mmol) was heated at 120 ° C. for 5 hours under reflux. The reaction mixture was concentrated under reduced pressure to obtain 350 g of the desired compound of the present invention as a yellow oil.

It solidified upon standing at room temperature for 2 weeks and showed a melting point of 79-81 ° C.

Production Example 2 300 mg (0.83 mmol) of 4-chloro-4'-trifluoromethylsulfonyloxybenzophenone, 233 mg (20.6 mmol) of N, N-dimethylacetamidohydrazone, 0.3 ml of acetic acid
And a mixture of 10 ml of ethanol were heated at reflux for 56 hours.
After the reaction mixture was concentrated under reduced pressure, methylene chloride 100 ml
, And washed with a 2.5N aqueous sodium hydroxide solution and then with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 320 mg of the desired compound of the present invention. Although this was a yellow oil, it solidified by standing at room temperature for 2 weeks, and the physical constants almost coincided with the values shown in Production Example 1.

Production Example 3 300 mg of 4-chloro-4'-trifluoromethylsulfonyloxybenzophenone-N, N'-acetylhydrazone
(0.71 mmol) Phosphorus pentachloride 163 mg (0.78 mmol) and p
-A mixture of 5 mg of xylene was heated at reflux under a nitrogen atmosphere for 10 hours. After the reaction was completed, the mixture was cooled to 5 to 10 ° C., and dimethylamine (50% aqueous solution)
l was added all at once.

After stirring at room temperature for 2 hours, the layers were separated. The obtained xylene solution was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained oil was recrystallized from methanol to obtain 312 mg of the present invention as yellow crystals. The melting point almost coincided with the value shown in Production Example 1.

Production Example 4 300 mg of 4-chloro-4'-trifluoromethylsulfonyloxybenzophenone-N'-acetylhydrazone
(0.71 mmol), a mixture of phosphorus oxychloride (120 mg, 0.78 mmol) and toluene (5 ml) was heated to reflux under a nitrogen atmosphere for 10 hours. After the reaction was completed, the mixture was cooled to 5 to 10 ° C., and 5 ml of dimethylamine (50% aqueous solution) was added all at once with vigorous stirring. After stirring at room temperature for 15 hours, liquid separation was performed, and the obtained toluene solution was washed with water and dried over anhydrous sodium sulfate.
By concentrating under reduced pressure, the desired compound of the present invention is obtained.
160 mg were obtained. Although this was a yellow oil, it solidified when left at room temperature for 2 weeks.
Almost coincided with the values shown in FIG.

Production Example 5 4-chloro-4'-trifluoromethylsulfonyloxybenzophenone-N '-(1-chloroethylidene)
To a stirred solution of 300 mg (0.68 mmol) of hydrazone in benzene (5 ml) was added 5 ml of dimethylamine (50% aqueous solution) in one portion at 5-10 ° C. After stirring at room temperature for 2 hours, the same post-treatment as in Preparation Example 3 was performed, and yellow crystals (mp79
8181 ° C.) to obtain 297 mg of the desired compound of the present invention.

Production Example 6 A solution of 300 mg (0.56 mmol) of 4-chloro-4'-trifluoromethylsulfonyloxybenzophenone-N '-[1- (dichlorophosphonyloxy) ethylidene] hydrazone in toluene (5 ml) was stirred vigorously. To 5
At 1010 ° C., 5 ml of dimethylamine (50% aqueous solution) was added in one portion. After stirring at room temperature for 15 hours, the same post-treatment as in Production Example 4 was performed to obtain 120 mg of the desired compound of the present invention. Although this was a yellow oil, it solidified by being located at room temperature for 2 weeks, and the physical constants almost coincided with the values shown in Production Example 1.

 Next, formulation examples are shown. Parts are parts by weight.

Formulation Example 1 An oil solution is obtained by mixing 0.2 part of the compound of the present invention, 2 parts of xylene, 2 parts of DMF, and 95.8 parts of white kerosene.

Formulation Example 2 An emulsion is obtained by thoroughly mixing 10 parts of the compound of the present invention, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 35 parts of xylene and 35 parts of DMF.

Formulation Example 3 20 parts of the compound of the present invention, 10 parts of fenitrothion, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate
Parts and 65 parts of synthetic hydrous silicon oxide are thoroughly pulverized and mixed to obtain a wettable powder.

Formulation Example 1 1 part of the compound of the present invention, 2 parts of carbaryl, 87 parts of kaolin clay and 10 parts of talc are well pulverized and mixed to obtain a powder.

Formulation Example 5 5 parts of the compound of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium ligninsulfonate, 30 parts of bentonite and 62 parts of kaolin clay are thoroughly pulverized and mixed, water is added and kneaded, and the mixture is granulated and dried. To obtain granules.

Formulation Example 6 0.05 part of the compound of the present invention, 0.2 part of tetramethrin, 0.05 part of resmethrin, 7 parts of xylene and 42.7 parts of deodorized kerosene are mixed and dissolved, filled in an aerosol container, a valve part is attached, and a propellant ( An aerosol is obtained by filling 50 parts of liquefied petroleum gas under pressure.

Formulation Example 7 20 parts of the compound of the present invention, 3 parts of a formalin condensate of sodium naphthalene sulfonate and 75 parts of water are thoroughly pulverized and mixed, and 2 parts of methylcellulose as a thickener is added and mixed to obtain a flowable agent.

Formulation Example 8 One part of the compound of the present invention was mixed with 3 parts of sesame oil, and 0.03 part of butylhydroxyanisole and 0.1 part of dehydroacetic acid were added thereto.
Parts, 10 parts of brown sugar, 30 parts of crystalline cellulose and 55.87 parts of potato starch, and after uniform mixing, 15 kg / cm ²
Pressure to form a tablet into tablets of about 4 g (diameter of about 30 mm) to obtain a bait.

Next, test examples will be described. The compounds used as comparative controls are indicated by the compound symbols in Table 1.

Test Example 1 (Insecticidal test against Kobumemeiga) 20 ml of a 20,000-fold diluted solution (5 ppm) of water of an emulsion of the test compound obtained according to Formulation Example 2 was inoculated with about 20 larvae of the 3rd to 4th instar larvae the day before. The rice was planted in plastic cups of 7 cm in diameter and 7 cm in depth.

Three days after the drug treatment, the larvae were examined for survival or death (2 replicates).

 Table 2 shows the results.

Test Example 2 (field test on Japanese moth) A 1,000-fold diluted solution (100 ppm) of an emulsion of the test compound obtained in accordance with Formulation Example 2 with water was applied to 3.9 m ² (1.3 mx 3
m) Spray 1.5 times on the perilla field, before the chemical treatment, treatment 8
The day number, 14 days, 21 days, 28 days, and 35 days later, the number of Japanese moth larvae were examined for 10 strains in each section (3 replicates). Table 3 shows the control value obtained from the number of larvae. The control value was determined from the following equation.

n: Number of surveys after application Cb: Density before application in non-application area Cai: Density of i-th application after application in non-application area Tb: Density before application in application area Tai: Density of i-type application after application in application area Test Example 3 (Food Poisoning Test against German Cockroach) Acetone solution of the test compound was dropped into 0.5 g of solid feed for mice and rats (solid feed CE-2 for rearing and breeding of CLEA Japan), and 1% drug-treated feed (poisonous feed) I got Bottom diameter 11cm,
In a polyethylene container having a height of 10.5 cm, a drug-treated bait and a non-treated bait, water, and a paper shelter were placed in small cups (3 cm in diameter). Twenty adult German cockroaches (10 males and 10 females) were released into this container, and the mortality of the three days later was examined. The results are shown in Table 4.

Test Example 4 (Insecticidal Test Against Southern Corn Root Worm) A test compound was made into an emulsion according to Formulation Example 2, and 1 ml of a water dilution (50 ppm) was laid on the bottom of a polyethylene cup having a diameter of 5.5 cm in the same size as paper. After that, 20 to 30 eggs of southern corn rootworm and one corn sprout were put therein and the lid was put. Eight days later, the larvae were examined for life and death. The effect criteria are as follows.

Mortality a: 100% b: 90% or more and less than 100% c: less than 90% The results are shown in Table 5.

<Effects of the Invention> The compounds of the present invention include, but are not limited to, Leptoptera, Diptera, Reticulida, Coleoptera,
It has an insecticidal effect against insects such as Hymenoptera, Orthoptera, Orthoptera, and is also effective against insects that have developed resistance to existing insecticides.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Kyouri Hase 4-2-1 Takashi, Takarazuka-shi, Hyogo Sumitomo Chemical Co., Ltd. (72) Inventor Sumio Nishida 3 Kasuganaka, Konohana-ku, Osaka-shi, Osaka No. 1-98, Sumitomo Chemical Co., Ltd. (56) References JP-A-56-45452 (JP, A)

Claims (2)

(57) [Claims] (1) Expression A human razone compound represented by the formula: 2. An insecticide comprising the hydrazone compound according to claim 1 as an active ingredient.