JPH1135541A - Benzophenone hydrorazone derivative and insecticide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound useful for an insecticide having high insecticidal activity and safety. SOLUTION: This compound is a benzophenone hydrazone derivative of formula I [X is a halogen; R<1> and R<2> are each H, a (substituted) 1-4C alkyl; R<3> is a (substituted) 1-6C alkyl or a 3-8C cycloalkyl; a total carbon number of the R<1> to R<3> is >=3; R<4> is H, COR<6> , etc.; R<5> is H, a (substituted) alkyl, etc.; R<6> is H, a (substituted) alkyl, etc.], or its geometrical isomer mixture, e.g. ethyl 2- 1 -(4-chlorophenyl) -1-(4 -neopentylphenyl) methylidene} -1-hydrazine carboxylate. The compound of the formula I is obtained by reacting a compound of formula II, such as (4-chlorophenyl) (4 -neopentylphenyl) methanone with a compound of formula III, such as ethyl carbazate in a diluent such as ethanol and in the presence of an acid catalyst such as pyridinium p-toluene sulfonate at about 20-150 deg.C under normal pressure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel benzophenone hydrazone derivative, a method for producing the same, and use as an insecticide.

[0002]

[Prior art and technical issues] British Crop Protectio
n Conference Pests and Diseases, 1984, Vol. 2, 405
-412, JP-A-54-122261, JP-A-56-122
No. 45452, JP-A-2-138246, JP-A-3-74356, JP-A-4-1173, JP-A-6-25134, JP-A-6-1840
7, JP-A-7-149708, JP-A-7-149708
JP-A-242618, JP-A-7-247261,
JP-A-8-41013, WO96 / 33168 and WO97 / 11050 describe that 4-substituted-4'-substituted alkylsulfonyloxybenzophenone hydrazone derivatives have insecticidal activity.

Further, Japanese Patent Publication No. 48-37028 and Japanese Patent Application Laid-Open No. 6-263686 describe benzophenones and a method for producing the same.

The present inventors have been conducting research for many years to develop excellent insecticides, and have synthesized many compounds in order to develop compounds having higher insecticidal activity and higher safety. Its insecticidal properties have been studied.

[0005]

As a result, a novel benzophenone hydrazone derivative represented by the following formula (I) having excellent insecticidal activity has been found.

[0006]

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In the formula, X represents a halogen, R ¹ and R ² each independently represent hydrogen or an optionally substituted C _1-4 alkyl, and R ³ represents an optionally substituted C _{1- 6 represents} alkyl or C _3-8 cycloalkyl, the total number of carbon atoms of R ¹ , R ² and R ³ is 3 or more, R ⁴ represents hydrogen, COR ⁶ or CO ₂ R ⁶ , R ⁵ represents hydrogen Represents an optionally substituted alkyl, COR ⁶ or CO ₂ R ⁶ , and R ⁶ represents hydrogen, an optionally substituted alkyl or an optionally substituted phenyl.

The compound of the above formula (I) has a geometric isomer, and the compound of the formula (I) of the present invention is not limited to the isolated geometric isomer, but may have any proportion of the geometric isomer. Mixtures are also included.

The compound of the above formula (I) of the present invention can be synthesized, for example, by the following production method (a) or (b). That is, production method (a) : In producing a compound of the formula (I) in which R ⁵ represents a hydrogen atom,

[0010]

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Wherein R ¹ , R ² , R ³ and X are as defined above,

[0012]

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Wherein R ⁴ has the same meaning as defined above.

Process (b) : In preparing a compound of the formula (I) wherein R ⁵ represents an optionally substituted alkyl, COR ⁶ or CO ₂ R ⁶ ,

[0015]

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Wherein R ¹ , R ² , R ³ , R ⁴ and x have the same meanings as defined above, and a compound represented by the formula: R ⁷ -hal (V) wherein R ⁷ is substituted Good alkyl, COR ⁶ or CO
₂ A method for reacting with a compound represented by the formula: R ⁶ and hal represents chlorine, bromine or iodine.

The benzophenone hydrazone derivative of the formula (I) of the present invention has a strong insecticidal action.

The benzophenone hydrazone derivatives of the formula (I) provided by the present invention surprisingly have, for example, a substantially very good insecticidal action compared to the known compounds described in the prior art mentioned above. Show.

In the present specification, when a group which may be "substituted" is substituted with a plurality of substituents, those substituents may be the same or different.

Halogen in "halogen" and "haloalkyl" represents fluorine, chlorine, bromine or iodine,
Preferable is fluorine, chlorine or bromine.

"Alkyl" can be straight or branched and includes, for example, methyl, ethyl, propyl,
Isopropyl, n-, iso-, sec- or tert-butyl, n
-, Iso-, sec-, tert- or neo-pentyl, n-, iso
-, Sec-, tert- or neo-hexyl and the like.

Examples of the substituent in "optionally substituted alkyl" include halogen, alkoxy and the like.

"Alkoxy" means alkyl-O- and includes, for example, methoxy, ethoxy, propoxy, isopropoxy, n-, iso-, sec- or tert-butoxy.

"Haloalkyl" is alkyl substituted by one or more halogens, such as trifluoromethyl, 2,2,2-trifluoroethyl and the like.

"Cycloalkyl" can be a cyclic alkyl group having 3 to 8 carbon atoms, such as cyclopentyl, cyclobutyl, cyclopentyl, cyclohexyl,
Cyclooctyl and the like.

Examples of the substituent in "phenyl which may be substituted" include, for example, halogen, alkyl, alkoxy, haloalkyl and the like.

In the compound of the formula (I), preferably, X represents fluorine, chlorine or bromine, and R ¹ is hydrogen or C
_{Represents 1-4} alkyl, R ² represents hydrogen or C _1-4 alkyl, R ³ is optionally substituted halogen C _1-4 alkyl or C
_{Represents 3-6} cycloalkyl, and the total number of carbon atoms of R ¹ , R ² and R ³ is 3 or more, and R ⁴ is hydrogen, group COR ⁶ or group CO
_{2 represents} R ⁶ , wherein R ⁵ is hydrogen, C _1-4 alkyl, C _1-4 alkoxy-
A C _1-4 alkyl group, a group COR ⁶ or a group CO ₂ R ⁶ , and R
⁶ includes a compound representing phenyl optionally substituted by hydrogen, C _1-6 alkyl, C _1-6 haloalkyl or halogen, or a mixture of geometrical isomers thereof.

In the compound of the above formula (I), it is particularly preferable that X represents chlorine or bromine, R ¹ and R ² represent hydrogen, R ³ represents C _3-4 branched alkyl, and R ⁴ represents Hydrogen, group
COR ⁶ or the group CO ₂ R ⁶ , wherein R ⁵ is hydrogen, C _1-4 alkyl, C
_{1-3 represents an} alkoxy-C _1-3 alkyl group, COR ⁶ or a group CO ₂ R ⁶ , and R ⁶ may be substituted by hydrogen, C _1-4 alkyl, C _1-4 haloalkyl or halogen A compound showing phenyl or a mixture of geometric isomers thereof can be mentioned.

Specific examples of the compound of the formula (I) of the present invention include the compounds shown in Table 1 below.

In Table 1, Pr-cyc is cyclopropyl, Bu-cyc is cyclobutyl, Pe-cyc is cyclopentyl, and He-cyc is cyclohexyl.

[0031]

[Table 1]

[0032]

[Table 2]

In the production method (a), as a raw material, for example,
When (4-chlorophenyl) (4-neopentylphenyl) methanone and ethyl carbazate are used, they are represented by the following reaction formula.

[0034]

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In the production method (b), for example,
When using ethyl 2- {1- (4-chlorophenyl) -1- (4neopentylphenyl) methylidene} -1-hydrazinecarboxylate and methyl iodide, it is represented by the following reaction formula.

[0036]

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In the above production method (a), the compound of the formula (II) used as a raw material is a known compound, for example, obtained from a known raw material by the following production method (c) or production method (d) known per se. be able to.

Production method (c) : Formula

[0039]

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In the formula, R ¹ , R ² and R ³ are as defined above.
A compound represented by the formula

[0041]

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Wherein X is as defined above, and a reaction with a compound represented by the formula (I) in the presence of a Lewis acid.

Production method (d) : Formula

[0044]

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Wherein X is the same as defined above,

[0046]

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In the formula, R ¹ , R ² and R ³ are as defined above.
A compound represented by the formula (1) in the presence of a Lewis acid.

In the production method (a), as an example of the compound of the formula (II) used as a raw material, (4-chlorophenyl)
(4-tert-butylphenyl) methanone, (4-chlorophenyl) (4-isobutylphenyl) methanone, (4-chlorophenyl) (4-neopentylphenyl) methanone, [4- (2-bromoethyl) phenyl] (4- Chlorophenyl) methanone, [4- (3-bromopropylethyl) phenyl] (4-chlorophenyl) methanone, [4-
(2-chloroethyl) phenyl] (4-chlorophenyl)
Methanone and the like can be mentioned.

In the production method (a), the compound of the formula (III) used as a raw material is a compound well known in the field of organic chemistry, and examples thereof include hydrazine hydrate, methyl carbazate, ethyl carbazate, Examples thereof include n-propyl carbazate, isopropyl carbazate, n-butyl carbazate, isobutyl carbazate, tert-butylhydrazine, acetohydrazide, and benzohydrazide.

In the production method (b), the compound of the formula (IV) used as a raw material is the compound of the present invention synthesized by the production method (a). Examples of compounds of formula (IV) include ethyl 2- {1- (4-chlorophenyl) -1- (4-neopentylphenyl) methylidene} -1-hydrazinecarboxylate, ethyl 2- {1- (4-chlorophenyl) )-
1- (4-tert-butylphenyl) methylidene} -1-hydrazinecarboxylate methyl 2- {1- (4-chlorophenyl) -1- (4-neopentylphenyl) methylidene} -1
-Hydrazinecarboxylate, methyl 2- {1- (4-chlorophenyl) -1- (4-tert-butylphenyl) methylidene} -1-hydrazinecarboxylate, and the like.

In the compound of formula (V) used as a raw material in the production method (b), R ⁷ is preferably C _1-4
Alkyl, C _1-4 alkoxy-C _1-4 alkyl, COR ⁶ or CO ₂
It indicates R ^6, wherein R ⁶ has the same meaning as the preferred definitions of R ^6, hal is preferably iodine if R ⁷ represents a C _1-4 alkyl, R ⁷ is C _1-4 alkoxy -C _{1 -4} alkyl, COR ⁶ or CO ₂
When R ⁶ is indicated, chlorine is preferred.

Compounds of formula (V) are well known in the field of organic chemistry, for example, methyl iodide,
Ethyl iodide, propyl iodide, chloromethyl methyl ether, chloromethyl ethyl ether, acetyl chloride, benzoyl chloride, methyl chlorocarbonate, ethyl chlorocarbonate, propyl chlorocarbonate, isopropyl chlorocarbonate, butyl chlorocarbonate, isobutyl chlorocarbonate, chlorocarbonate tert-butyl and the like.

The reaction of the above process (a) can be used in a suitable diluent, and examples of the diluent which can be used include aliphatic, cycloaliphatic and aromatic hydrocarbons (in some cases). Chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroin,
Benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc .; ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME ), Tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM), etc .; nitriles, for example, acetonitrile, propionitrile, acrylonitrile, etc .; alcohols, for example, methanol, ethanol, isopropanol, butanol, ethylene glycol, etc .; Ethyl acetate, amyl acetate and the like; acid amides such as dimethylformamide (DM
F), dimethylacetamide (DMA), N-methylpyrrolidone, ^1, 3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide (HMPA) and the like; sulfonic,
Sulfoxides, for example, dimethyl sulfoxide (DMS
O), sulfolane and the like.

The production method (a) can be carried out in the presence of an acid catalyst. Examples of the acid catalyst that can be used in this case include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, hydrobromic acid, etc .; Acids, for example, formic acid, acetic acid, trifluoroacetic acid, propionic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and the like; organic amine hydrochlorides, for example, pyridine hydrochloride, triethylamine hydrochloride, pyridine p-toluenesulfone Acid salts and the like can be mentioned.

The reaction of the production method (a) can be carried out within a substantially wide temperature range, but is usually carried out at about -20 to -20.
It can be carried out at a temperature of about 200C, preferably between about 20 and about 150C. The reaction is desirably carried out under normal pressure, but may be operated under pressure or under reduced pressure in some cases.

In carrying out the production method (a), for example, the compound 1 of the formula (II) is dissolved in a diluent such as ethanol.
The compound of formula (III) from 1 to 10 molar amount relative to moles acid catalyst, for example, by reacting in the presence of pyridine p- toluenesulfonate, wherein in the case where R ⁵ represents hydrogen (I) A compound can be obtained.

The above process (b) can be carried out in a suitable diluent. Examples of the diluent that can be used include:
Aliphatic, cycloaliphatic and aromatic hydrocarbons such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene and the like; ethers such as ethyl ether, methyl ethyl ether,
Isopropyl ether, butyl ether, dioxane,
Dimethoxyethane (DME), tetrahydrofuran (TH
F), diethylene glycol dimethyl ether (DGM)
Ketones, for example, acetone, methyl ethyl ketone (MEK), methyl-isopropyl ketone, methyl isobutyl ketone (MIBK), etc .; nitriles, for example, acetonitrile, propionitrile, acrylonitrile, etc .; esters, for example, ethyl acetate, acetic acid Amyl; acid amides, for example, dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide (HMPA) and the like; sulfone And sulfoxides such as dimethyl sulfoxide (DMSO) and sulfolane; and bases such as pyridine.

The production method (b) can be carried out in the presence of an acid binder. Examples of the acid binder that can be used include hydrides and hydroxides of alkali metals and alkaline earth metals as inorganic bases. , Carbonates and bicarbonates, such as, for example, sodium hydride, sodium bicarbonate, potassium bicarbonate,
Sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and the like;
Inorganic alkali metal amides, for example, lithium amide,
Sodium amide, potassium amide and the like; organic bases such as alcoholates, tertiary amines, dialkylaminoanilines and pyridines such as triethylamine, 1,1,4,4-tetramethylethylenediamine (TMED
A), N, N-dimethylaniline, N, N-diethylaniline,
Pyridine, 4-dimethylaminopyridine (DMAP), 1,4
-Diazabicyclo [2,2,2] octane (DABCO), 1,8-
Examples include diazabicyclo [5,4,0] undec-7-ene (DBU).

The production method (b) can be carried out within a substantially wide temperature range, but is usually from about -70 to about 1
It can be carried out at a temperature of 50C, preferably between about -70 and about 100C. The reaction is desirably performed under normal pressure, but may be optionally performed under elevated or reduced pressure.

In carrying out the production method (b), for example, 1 to 5 mol of the compound of the formula (V) is added to 1 mol of the compound of the formula (IV) in a diluent, for example, tetrahydrofuran. By reacting in the presence, a compound of formula (I) wherein R ⁵ represents a group other than hydrogen can be obtained.

The compounds of the formula (I) according to the invention have a strong insecticidal action. The active compound of the formula (I) of the present invention exerts an accurate control effect on harmful insects without causing phytotoxicity to cultivated plants. Therefore, they can be used as pesticides.

The compounds of the present invention can be used for controlling a wide variety of pests, harmful sucking insects, chewing insects, soil pests and other plant parasitic pests, grain storage pests, sanitary pests and the like. Can be applied for their eradication.

[0063] Examples of such pests include the following pests. As insects, Coleoptera pests, for example, Callosobruchus chi
nensis), Sitophilus zeamais, Tribolium castaneum, Epilachna vigintioctomaculata,
Black-tailed beetle (Agriotes fuscicollis),
Butterfly (Anomala rufocuprea), Colorado potato beetle (Leptinotarsa decemlineata), Diabloteica (Diabrotica spp.), Pine beetle (Monochamus alternatus), Rice weevil (Lisso)
rhoptrus oryzophilus, turtle beetle (Aulacophora fe)
moralis), Lyctus bruneus, etc .;
Lepidopteran pests, for example, Lymantria dispa
r), Pterodactyla (Malacosoma neustria), Green caterpillar (Pieris rapae), Spodoptera litur
a), armyworm (Mamestra brassicae), Nikamechu (Chilo suppressalis), Awanomeiga (Pyrausta nub)
ilalis), Aspen moth (Ephestia cautella),
Kokikumamonamaki (Adoxophyes orana), Codling moth (Carpocapsa pomonella), Kaburayaga (Agrotis fuco)
sa), honeybee (Galleria mellonella), diamondback moth (Plutella xylostella), Heliothis (Heliothis v)
irescens), Citrus leaf moth (Phyllocnistis citrel)
la) etc .; Hemiptera pests, for example, Nephotid leafhopper (Nepho
tettix cincticeps), brown planthopper (Nilaparvata l)
ugens), Pseudodococcus comstoc
ki), moss aphid (Unaspis yanonensis), peach aphid (Myzuspersicae), apple aphid (Aphis pomi), cotton aphid (Aphis gossypi
i), radish aphid (Lipaphis erysimi),
Nashigumbai (Stephanitis nashi), Green stink bug (N
ezara spp.), bed bugs (Cimex lectularius), whiteflies (Trialeurodes vaporariorum), psyllids (Psylla spp.), etc .;
ana), grasshopper (Locusta migratoria migratoriodes)
Etc .; Isopteran pests such as the termite (Deucoterme)
s speratus, House termite (Coptotermes formosanu)
s) etc .; dipteran pests such as housefly (Musca domesti)
ca), Aedes aegypti (Aedes aegypti),
ylemia platura), Culex pipiens, Culex pipiens, Anopheles sinensis, Culex tritaeniorhynchus, etc .; As mites,
For example, the spider mite (Tetranychus kanzawai), the spider mite (Tetranychus urticae), the mandarin spider mite (Pan
onychus citri, citrus mite (Aculops pelekass)
i), dust mite (Tarsonemus spp.) and the like; nematodes include, for example, sweet potato nematodes (Melo)
idogyne incognita, pine wood nematode (Bursaph)
elenchus xylophilus, rice singing nematode (Aph
elenchoides besseyi), soy cyst nematode (Het)
erodera glycines), Pratylench
us spp.) and the like.

Furthermore, in the pharmaceutical field of veterinary medicine, mention may be made of various harmful animal parasites (endo- and ecto-parasites), such as insects and helminths.

As examples of such animal parasites, the following pests can be exemplified.

As insects, for example, horse flies (Gast
rophilus spp.), fly (Stomoxys spp.), lice (Trichodectes spp.), and sand turtle (Rhodnius sp.)
p.), dog flea (Ctenocephalides canis) and the like.

The mites include, for example, Kazuki mites (Or
nithodoros spp.), ticks (Ixodes spp.), ox ticks (Boophilus spp.) and the like.

In the present specification, substances having an insecticidal action against pests including all of them may be collectively referred to as insecticides.

When used as an insecticide, the active compounds of the present invention can be formulated into usual pharmaceutical forms.
Formulations include, for example, solutions, wettable powders, emulsions, suspensions, powders, foams, pastes, tablets, granules, aerosols, active compound infiltration-natural and synthetic, microcapsules, seed coatings, Formulations with a combustion device (for example, fumigation and fume cartridges,
Can and coil), ULV [cold mist (cold m
ist), warm mist] and the like.

These preparations can be manufactured by a method known per se. For example, an active compound can be used as a developing agent,
Liquid diluent; liquefied gas diluent; solid diluent or carrier, optionally a surfactant, ie, emulsifier and / or
Alternatively, it can be produced by mixing with a dispersant and / or a foam-forming agent.

The liquid diluent or carrier generally includes aromatic hydrocarbons (eg, xylene, toluene,
Alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (eg, chlorobenzenes, ethylene chlorides, methylene chloride, etc.), aliphatic hydrocarbons [eg, cyclohexane, etc., paraffins (eg, mineral oil fractions) )], Alcohols (eg, butanol, glycol and their ethers and esters), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), strong polar solvents (eg, dimethylformamide, dimethyl sulfoxide, etc.) ) And water. When water is used as the developing agent, for example, an organic solvent can be used as an auxiliary solvent.

The liquefied gas diluent or carrier is obtained by liquefying a gaseous substance at normal temperature and normal pressure.
For example, aerosol propellants such as butane, propane, nitrogen gas, carbon dioxide, and halogenated hydrocarbons can be mentioned.

Examples of the solid diluent include soil natural minerals (eg, kaolin, clay, talc, chalk, quartz, attapull guide, montmorillonite or diatomaceous earth), soil synthetic minerals (eg, highly dispersed silicic acid, alumina, silicate) And the like).

Examples of solid carriers for granules include:
Crushed and sorted rocks (eg, calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic grains of inorganic and organic powders,
Fine particles of organic substances (eg, sawdust, coconut, corn cob, tobacco stem, etc.) can be mentioned.

Examples of the emulsifier and / or foaming agent include nonionic and anionic emulsifiers [for example, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid alcohol ether (for example, alkylaryl polyglycol ether, alkyl sulfonate, alkyl sulfonate, Sulfates,
Arylsulfonate, etc.]] and albumin hydrolysis products.

The dispersants include, for example, lignin sulfite waste liquor and methylcellulose.

Fixing agents can also be used in preparations (powder, granules, emulsions).
For example, carboxymethyl cellulose, natural and synthetic polymers (for example, gum arabic, polyvinyl alcohol, polyvinyl acetate, etc.) and the like can be mentioned.

Coloring agents can be used. Examples of the coloring agent include inorganic pigments (for example, iron oxide, titanium oxide, Prussian blue, etc.), organic dyes such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and the like. And trace elements such as iron, manganese, boron, copper, cobalt, molybdenum, zinc and salts of these metals.

The preparation generally contains the active ingredient in an amount of from 0.1 to 9%.
It can be contained in an amount of 5% by weight, preferably 0.5 to 90% by weight.

The active compounds of the formula (I) according to the invention can be used in the form of their commercially useful preparations or in the form of use prepared from their preparations, by means of other active compounds such as insecticides, baits, fungicides, It can also be present as an admixture with acaricides, nematicides, fungicides, growth regulators, herbicides and the like. Here, examples of the insecticide include organophosphorus agents, carbamate agents, carboxylates, chlorinated hydrocarbons, and insecticides produced by microorganisms.

Furthermore, the active compounds of the formula (I) of the present invention
It can also be present as a mixture with a synergist. The synergist need not be active per se, but is a compound that amplifies the action of the active compound.

The content of the active compounds of the formula (I) according to the invention in commercially useful forms can vary within wide limits and is, for example, from 0.0000001 to 100% by weight, preferably from 0.00001 to 1% by weight. Within the range.

The compound of the formula (I) of the present invention can be used for pests in a usual manner suitable for the use form. The active compounds according to the invention, when used as sanitary pests, pests on stored products, have very good stability against alkali on lime substances and residual effects on wood and soil.

Next, the present invention will be described more specifically with reference to examples, but the present invention should not be limited to these examples.

[0085]

【Example】

 Example 1

[0086]

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An ethanol solution (50 ml) of (4-chlorophenyl) (4-neopentylphenyl) methanone (2.9 g), ethyl carbazate (1.2 g) and pyridinium p-toluenesulfonate (0.1 g) was added to 6 Heated to reflux for an hour. After cooling to room temperature, the reaction mixture was poured into ice water, extracted with ethyl acetate, washed with water and dried over anhydrous magnesium sulfate. After evaporating the solvent, the crude product was subjected to silica gel column chromatography (developing solvent n-hexane: ethyl acetate =
5: 1) to give ethyl 2- {1- (4-chlorophenyl) -1- (4-neopentylphenyl) methylidene} -1-
Hydrazinecarboxylate (1.1 g) was obtained as a mixture of isomers.

Melting point: 152-157 ° C. A compound prepared in the same manner as in the above-mentioned Example 1 was prepared in the same manner as in Example 1.
Table 2 below shows the compounds prepared in the above.

[0089]

[Table 3]

Preparation of Intermediate Example 2

[0091]

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In a dichloromethane (100 ml) solution of neopentylbenzene (13 g) and ferric chloride (19.5 g), 4-chlorobenzoyl chloride (1
7.5 g) were added dropwise. Subsequently, the mixture was stirred at room temperature for 3 hours. The reaction mixture was poured into water and extracted with dichloromethane. The mixture was washed successively with 2N hydrochloric acid, 5% aqueous sodium hydroxide solution and saturated saline, and dried over anhydrous magnesium sulfate. The crude crystals after distilling off the solvent were washed with petroleum ether to obtain (4-chlorophenyl) (4-neopentylphenyl) methanone (20.9 g).

Melting point: 81-82 ° C. Biological test example Test on larvae of Spodoptera litura Preparation method of reagents: Solvent: 3 parts by weight of xylol Emulsifier: 1 part by weight of polyoxyethylene alkyl phenyl ether , Active compound 1
Parts by weight were mixed with the above amount of solvent containing the above amount of emulsifier, and the mixture was diluted with water to a predetermined concentration.

Test method: Cabbage leaves were immersed in an aqueous solution of the active compound having a predetermined concentration, and after air-drying of the chemical solution, 10 larvae of the third cutworm cutworm were released in a petri dish having a diameter of 9 cm and placed in a constant temperature room at 25 ° C. After 7 days, the number of dead insects was examined and the insecticidal rate was calculated. The test was performed in duplicate, and the insecticidal rate was the average.

Results: As test examples, Compound Nos. 1 to 6 showed an insecticidal rate of 100% at a concentration of 500 ppm.

[0096]

The novel benzophenone hydrazone derivative of the present invention has an excellent insecticidal activity as shown in the above biological test examples.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Katsuhiko Shibuya, Inventor 6-14-4 Midori, Kawachi-cho, Kawachi-gun, Tochigi Prefecture (72) Takehisa Abe 272-1 Yokokura Nitta, Oyama City, Tochigi Prefecture

Claims (4)

[Claims] 1. The formula: embedded image In the formula, X represents a halogen, R ¹ and R ² each independently represent hydrogen or an optionally substituted C _1-4 alkyl, and R ³ represents an optionally substituted C _1-6 alkyl or C _3-8 cycloalkyl, and the total number of carbon atoms of R ¹ , R ² and R ³ is 3 or more; R ⁴ represents hydrogen, COR ⁶ or CO ₂ R ⁶ ;
⁵ is hydrogen, optionally substituted alkyl, COR ⁶ or CO ₂
It indicates R ^6, and, R ⁶ is hydrogen, alkyl which may be substituted or be substituted represents an phenyl, in benzophenone hydrazone derivatives and mixture of geometric isomers represented. 2. X is fluorine, chlorine or bromine, and R ¹
_Represents hydrogen or C _1-4 alkyl, R ² represents hydrogen or C _1-4 alkyl, R ³ represents C _1-4 alkyl or C _3-6 cycloalkyl which may be halogen-substituted, and R ¹ , R ² and
The total number of carbon atoms of R ³ is 3 or more, R ⁴ represents hydrogen, group COR ⁶ or group CO ₂ R ⁶ , and R ⁵ is hydrogen, C _1-4 alkyl, C _1-4 alkoxy-C _{1- 2. The} group of claim 1 wherein the group represents a ₄ alkyl group, a group COR ⁶ or a group CO ₂ R ⁶ , and R ⁶ represents phenyl optionally substituted by hydrogen, C _1-6 alkyl, C _1-6 haloalkyl or halogen. Or a geometric isomer mixture thereof. 3. X represents chlorine or bromine, and R ¹ and R ²
Represents hydrogen, R ³ represents C _3-4 branched alkyl, R ⁴ represents hydrogen, a group COR ⁶ or a group CO ₂ R ⁶ , R ⁵ is hydrogen, C _1-4 alkyl, C _1-3 Alkoxy-C _1-3 alkyl group, COR ⁶ or group CO ₂ R ⁶
And R ⁶ represents phenyl optionally substituted by hydrogen, C _1-4 alkyl, C _1-4 haloalkyl or halogen or a mixture of geometric isomers thereof. 4. A pesticide containing the compound according to claim 1 as an active ingredient.