JPH111458A - Benzophenone hydrazone derivative and insecticide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound capable of manifesting adequate insecticidal activities against harmful insects without imparting damage by chemicals to cultivation plants. SOLUTION: This compound is a benzophenone hydrazone derivative of formula I X is a halogen; R<1> and R<2> are each independently H, a (substituted) alkyl, etc.; R<3> is cyano, nitro, etc.; R<4> is H, or COR<6> [R<6> is H, a (substituted) alkyl or a (substituted) phenyl], etc.; R<5> is H, a (substituted) alkyl, COR<6> , etc.}, and the geometrical isomer mixture thereof, e.g. ethyl 2- 1-(4- chlorophenyl)-1-[4-(1-methyl-1-nitroethyl)phenyl]methylidene}-1- hydrazinecarboxylate. For example, the compound of formula I in which R<5> is H is obtained by reacting a compound of formula III with a compound of formula IV. An excellent insecticide is obtained by using the compound as an active ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel benzophenone hydrazone derivative, its production method and use as an insecticide, and a novel production intermediate and its production method.

[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-56-122561
-45452, JP-A-2-138246,
JP-A-3-74356, JP-A-4-173, 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, and R ¹ and R ²
Each independently represents hydrogen or an optionally substituted alkyl, or together with the carbon atom to which they are attached, form a C _3-8 hydrocarbon cyclic group, and R ³ is R represents cyano, nitro, CO ₂ R ⁶ or CONR ⁶ R ⁷ ;
⁴ represents hydrogen, COR ⁶ or CO ₂ R ⁶ , R ⁵ represents hydrogen, optionally substituted alkyl, COR ⁶ or CO ₂ R ⁶ , and R ⁶ and R ⁷ each independently represent hydrogen,
Indicate 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 includes not only the isolated geometric isomer but also an arbitrary proportion of the geometric isomer. Body 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, the production method (a) : for 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.

[0014] Process (b): R ⁵ is alkyl optionally substituted, to produce a compound of formula (I) may exhibit COR ⁶ or CO ₂ R ^6, wherein

[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 ⁸ -hal (V) wherein R ⁸ is substituted the method also alkyl, shows a COR ⁶ or CO ₂ R ^6, and hal is reacted with chlorine, indicating bromine or iodine, a compound represented by.

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, preferably 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.

"Alkoxy" can be straight-chain or branched and includes, for example, methoxy, ethoxy, propoxy, isopropoxy, n-, iso-, sec- or tert-
-Butoxy and the like.

"Haloalkyl" can be straight-chain or branched and includes, for example, trifluoromethyl,
2,2,2-trifluoroethyl and the like.

The "hydrocarbon cyclic group" can be a saturated or unsaturated cyclic hydrocarbon group having 3 to 8 carbon atoms, and particularly, for example, cycloalkyl such as cyclopentyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl and the like. Alkyl groups are preferred.

Examples of the substituent in “optionally substituted alkyl” include, for example, halogen, alkoxy and the like. Examples of the substituent in “optionally substituted phenyl” include, for example, halogen, alkyl ,
Haloalkyl, alkoxy and the like can be mentioned.

In the compound of the formula (I), preferably, X represents fluorine, chlorine or bromine, and R ¹ and R ²
Each independently represents a C _1-4 alkyl or C _1-4 haloalkyl, or together with the carbon atom to which they are attached, forms a C _3-6 saturated hydrocarbon cyclic group;
R ³ is cyano, nitro, group CO ₂ R ⁶ or group CONR ⁶ R ⁷
R ⁴ represents hydrogen, a group COR ⁶ or a group CO ₂ R ⁶ ,
R ⁵ represents hydrogen, C _1-4 alkyl, C _1-4 alkoxy-C _1-4 alkyl group, group COR ⁶ or group CO ₂ R ⁶ , and
R ⁶ and R ⁷ each independently represent a compound or a mixture of geometric isomers thereof, which represents hydrogen, C _1-6 alkyl, C _1-6 haloalkyl or phenyl optionally substituted by halogen.

In the compound of the above formula (I), it is particularly preferable that X represents chlorine or bromine, and R ¹ and R ² each independently represent C _1-4 alkyl or C _1-4 haloalkyl, or together with the carbon atom to which they are attached, cyclopropyl, form a cyclobutyl, cyclopentyl or cyclohexyl, R ³ represents cyano, nitro, a group CO ₂ R ⁶ or a group CONR ⁶ R ^7, R ⁴ Represents hydrogen, a group COR ⁶ or a group CO ₂ R ⁶ , and R ⁵ represents hydrogen, C
_1-4 alkyl, C _1-3 alkoxy-C _1-3 alkyl group, CO
R ⁶ or a group CO ₂ R ⁶ , and R ⁶ and R ⁷ each independently represent hydrogen, C _1-4 alkyl, C _1-4 haloalkyl or phenyl optionally substituted by halogen; The compound or its geometric isomer mixture 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, Ph is a phenyl group, and Ph (4-C
l) represents a phenyl group substituted with chloro at the 4-position.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

[Table 3]

In the production method (a), as a raw material, for example,
(4-Chlorophenyl) (4- (1-methyl-1-nitroethyl)
When phenylmethanone 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- [4- (1-cyano-1-methylethyl) phenyl] methylidene} -1-hydrazinecarboxylate and methyl iodide,
It is represented by the following reaction formula.

[0036]

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In the above-mentioned production method (a), the compound of the formula (II) used as a raw material is the above-mentioned R ¹ , R ² , R ³ and x
Means the one based on the definition of Preferably, the R
Preferred definitions of ¹ , R ² , R ³ and x are as defined above.

The compound of the formula (II) includes a novel compound and can be produced, for example, by the following production methods (c) to (g).

Process (c) : R ¹ represents hydrogen and R ³
To prepare a compound of formula (II) wherein represents cyano,

[0040]

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Wherein X, R ² and hal have the same meanings as described above, and a compound represented by the formula: is cyanated with sodium cyanide or potassium cyanide.

Process (d) : R ¹ represents an optionally substituted alkyl, or R ¹ and R ² together with the carbon atom to which they are attached form a C _3-8 hydrocarbon To prepare a compound of formula (III) when forming a cyclic group,

[0043]

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Wherein X and R ² have the same meaning as defined above, and a compound represented by the formula R ⁹¹ -Hal (VIII) wherein hal has the same meaning as defined above, and R ⁹¹ may be substituted. Or a compound of the formula (VII) wherein R ² represents hydrogen
Compound of the formula hal-R ⁹² -hal (IX) expression corresponding to, hal are as defined above, and R ^92, the carbon to which R ¹ and R ² in the formula (II) they are attached A method for reacting with a compound represented by the formula ( ¹ ), which represents a group corresponding to R ¹ and R ² when forming a C _3-8 hydrocarbon cyclic group together with an atom.

Production method (e) : To produce a compound of formula (II) where R ³ represents CO ₂ R ⁶ ,

[0046]

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Wherein x, R ¹ and R ² have the same meaning as defined above, and a compound represented by the formula R ⁶ —OH (XI) wherein R ⁶ has the same meaning as defined above. How to react.

Process (f) : To prepare a compound of formula (II) where R ¹ and R ² represent hydrogen and R ³ represents nitro,

[0049]

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Wherein x and hal have the same meanings as defined above, and the compound is reacted with silver nitrite.

Process (g) : To prepare a compound of formula (II) wherein R ¹ and R ² each represent optionally substituted alkyl and R ³ represents nitro,

[0052]

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Wherein x is as defined above, and the compound represented by the formula

[0054]

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Wherein R ⁹ and R ¹⁰ are each independently
A method of reacting with a compound represented by the formula (I), which represents an optionally substituted alkyl or forms a _C3-8 hydrocarbon cyclic group together with a carbon atom to which they are bonded.

Among the compounds of the formula (II) synthesized by the above production methods (c) to (g), the novel compounds can be represented by the following formula (XV).

Formula:

[0058]

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In the formula, X represents a halogen, and R ⁹ and R
¹⁰ each independently represent an optionally substituted alkyl, or together with the carbon atom to which they are attached, form a C _3-8 hydrocarbon cyclic group, wherein R ³ is cyano,
Represents nitro, CO ₂ R ⁶ or CONR ⁶ R ⁷ and R
⁶ and R ⁷ each independently represent hydrogen, optionally substituted alkyl, or optionally substituted phenyl.

In the above production method (a), examples of the compound of the formula (II) used as a raw material include 2- (4- (4-chlorobenzoyl) phenyl) acetonitrile, 2- (4- (4- (4-
Bromobenzoyl) phenyl) acetonitrile, 2- (4-
(4-fluorobenzoyl) phenyl) acetonitrile, 2
-(4- (4-chlorobenzoyl) phenyl) -2-methylpropanenitrile, 2- (4- (4-chlorobenzoyl) phenyl) propanenitrile, (4-chlorophenyl) {4- (1-
Methyl-1-nitroethyl) phenyl) methanone, ethyl 2
-(4- (4-chlorobenzoyl) phenyl) acetate, methyl 2- [4- (4-chlorobenzoyl) phenyl] propanoate and the like can be mentioned.

The compound of the formula (VI) used as a raw material in the production method (c) is described, for example, in JP-B-46-10164.
Known compounds described in Japanese Patent Application Laid-Open Publication No. H10-209, for example, 4-chloro-4′-chloromethylbenzophenone,
4-bromomethyl-4'-chlorobenzophenone, 4-bromomethyl-4'-fluorobenzophenone, 4-bromo-4 '
-Bromomethylbenzophenone, 4- (1-bromoethyl)-
4'-chlorobenzophenone and the like can be mentioned.

The above production method (c) is described in, for example, Journal of Or
ganic Chemistry Vol.26, P.1636.

The compound of the formula (VII) used as a raw material in the production method (d) is a partially known compound and can be obtained by the production method (c). Examples of compounds of formula (VII) include 2- (4- (4-chlorobenzoyl) phenyl) acetonitrile, 2- (4- (4-chlorobenzoyl) phenyl) propanenitrile, methyl 2- {4- (4- Chlorobenzoyl) phenyl} acetate.

The compound of the formula (VIII) and the compound of the formula (IX) used as a raw material in the production method (d) are well-known compounds in the field of organic chemistry.
Methyl iodide, methyl bromide, ethyl iodide, n-propyl iodide, 1-bromo-2-chloroethane, 1,3-dibromoethane, 2-iodo-1,1,1-trifluoroethane, and the like. be able to.

The above production method (d) can be carried out according to a generally well-known alkylation reaction in the presence of a base.

This alkylation can be carried out on compounds of the formula (I) in which R ¹ and / or R ² represent hydrogen.

The compound of the formula (X) used as a raw material in the production method (e) is a partially known compound and can be obtained by the production method (c) or the production method (d). Examples of the formula (X) include 2- (4- (4-chlorobenzoyl) phenyl) acetonitrile. on the other hand,
The compound of the formula (XI) is well known in the field of organic chemistry, and examples thereof include methanol and ethanol.

The production method (e) can be carried out in the same manner as the nitrile hydrolysis method widely used in organic chemistry.

Formula (XII) used as a raw material in the production method (f) is a known compound described in, for example, Japanese Patent Publication No. 46-10164, and its example is 4-chloro-4'-. Chloromethylbenzophenone, 4-
Bromomethyl-4'-chlorobenzophenone, 4-bromomethyl-4'-fluorobenzophenone, 4-bromo-4'-bromomethylbenzophenone and the like can be mentioned.

The above production method (f) is, for example, described in Organic Synth
eses Collective .Vol.IV P.728.

The compound of the formula (XIII) used as a starting material in the production method (g) is a known compound.
Chemische Berichte vol.49, p.2251, (1916) states that 4-
Chloro-4'-nitrobenzophenone is described along with its synthesis. Examples of other compounds of formula (XIII) include 4-bromo-4'-nitrobenzophenone and 4-
Fluoro-4'-nitrobenzophenone can be mentioned.

The compound of the formula (XIV) used as a raw material in the production method (g) is a known compound.
ournal of the American Chemical Society, vol. 96,
p.2580 describes lithium 2-nitropropane and a method for producing it. Examples of other compounds of the formula (XIV) include lithium 2-nitrobutane, lithium nitrocyclohexane, and the like.

The production method (g) is described, for example, in Journal Organic C
hemistry, vol.41, P.1560, (1976).

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

The compound of the formula (IV) used as a raw material in the production method (b) is a compound of the present invention synthesized by the above-mentioned production method (a). As an example of the compound of the formula (IV), ethyl 2- { 1- (4-chlorophenyl) -1- [4- (1-
Cyano-1-methylethyl) phenyl] methylidene} -1-hydrazinecarboxylate, ethyl 2- {1- (4-chlorophenyl) -1- [4- (1-methyl-1-nitroethyl) phenyl] methylidene} -1 -Hydrazine carboxylate and the like.

In the compound of the formula (V) used as a raw material in the production method (b), R ⁸ is preferably C _1-4
Alkyl, C _1-4 alkoxy C _1-4 alkyl, COR ⁶ or CO ₂ R ⁶ , wherein R ⁶ has the same meaning as the preferable definition of R ⁶ above, and hal represents that R ⁸ is C _1-4 alkyl. Is preferred, and when R ⁸ represents C _1-4 alkoxy C _1-4 alkyl, COR ⁶ or CO ₂ R ⁶ , 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, tert-butyl chlorocarbonate and the like can be mentioned.

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; sulfone,
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; organic acids,
For example, formic acid, acetic acid, trifluoroacetic acid, propionic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and the like; organic amine salts such as pyridine hydrochloride, triethylamine hydrochloride, pyridine p-toluenesulfonic acid and the like Can be mentioned.

The reaction of process (a) can be carried out within a substantially wide temperature range, but is generally about -20
It can be carried out at a temperature of from about 200C to about 200C, preferably from about 20C to about 150C. The reaction is desirably performed under normal pressure, but may be operated under increased or 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 and the like; acid amides, for example, dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide (HMPA); Sulfones, sulfoxides, for example, dimethylsulfoxide (DMSO), sulfolane and the like; bases, for example, pyridine and the like.

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 of alkali metals and alkaline earth metals as inorganic bases.
Hydroxides, carbonates, bicarbonates, etc., for example, sodium hydride, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, etc .; Alkali metal amides such as lithium amide, sodium amide, potassium amide and the like; alcoholates, tertiary amines, dialkylaminoanilines and pyridines such as triethylamine, 1,1, and
4,4-tetramethylethylenediamine (TMEDA), N, N-
Dimethylaniline, N, N-diethylaniline, pyridine,
4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo [2,2,2] octane (DABCO), 1,8-diazabicyclo [5,4,0] undec-7-ene (DBU) and the like. Can be.

The reaction of process (b) can be carried out within a substantially wide temperature range, but is generally about -70
To about 150 ° C, preferably between about -70 to about 100 ° C. 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 (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 such as tetrahydrofuran in the presence of sodium hydride. By reacting under
When R ⁵ represents a group other than hydrogen, a compound of formula (I) 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, biting insects, soil pests and other plant parasitic pests, grain storage pests, sanitary pests and the like. , Can be applied for their eradication eradication.

As examples of such pests, the following pests can be exemplified. 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, Flycatcher beetle (Lyctus b
runeus), etc .; Lepidopteran pests, for example, Lymant
ria dispar), Pterodactyla (Malacosoma neustria),
Caterpillar (Pieris rapae), Spodoptera (Spodopte)
ra litura), armyworm (Mamestra brassicae), Japanese squirrel (Chilo suppressalis), Awanomeiga (Pyra)
usta nubilalis), Elephalia caute (Ephestia caute)
lla), kamakumamakimaki (Adoxophyes orana), codling moth (Carpocapsa pomonella), kaburayaga (Agroti)
s fucosa), honeybee (Galleria mellonella), diamondback moth (Plutella xylostella), heliotis (Helioth)
is virescens), Citrus leaf moth (Phyllocnistis ci)
trella) and the like; pests of the order Hemiptera, for example,
ephotettix cincticeps, brown planthopper (Nilaparva)
ta lugens), Pseudodococcus com
stocki) and Unaspis yanonensi
s), peach aphid (Myzuspersicae), apple aphid (Aphis pomi), cotton aphid (Aphis goss)
ypii), radish aphid (Lipaphis erysim)
i), Stephanitis nashi, Green stink bug (Nezara spp.), Bed bug (Cimex lectulariu)
s), White-eared whiteflies (Trialeurodes vaporarioru)
m), psyllium (Psylla spp.) and the like; Orthoptera pests, for example, German cockroaches (Blattela germanica), American cockroaches (Periplaneta americana), and mushrooms (Gryllotal)
pa africana), ivy (Locusta migratoria migrato)
riodes) and the like; insects of the order Isoptera, such as the termites
ucotermes speratus, house termite (Coptotermes fo)
rmosanus) and the like; dipteran pests such as housefly (Musca)
domestica), Aedes aegypti, Aedes fly (Hylemia platura), Culex pipiens (Culex pipien)
s), Anopheles sinensis, Culex tritaeniorhynchus, and the like.

The mites include, for example, Tetranychus kanzawai and Tetranychus
urticae), citrus red mite (Panonychus citri), citrus red mite (Aculops pelekassi), dust mite (Tarso)
nemus spp.).

The nematodes include, for example, sweet potato nematodes (Meloidogyneincognita), pine wood nematodes (Bursaphelenchus xylophilus), rice singing nematodes (Aphelenchoides besseyi), soybean cyst nematodes (Heterodera glycines), Negusrat enchus p. Can be mentioned.

Further, in the field of veterinary medicine, various harmful animal parasites (endo and ectoparasites) such as insects and helminths can be mentioned.

Examples of such animal parasites include the following pests.

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.

Examples of 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,
That is, it can be produced by mixing with a liquid diluent; a liquefied gas diluent; a solid diluent or carrier, and optionally a surfactant, ie, an emulsifier and / or dispersant and / or a foam former. .

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 or carrier include, for example,
Examples include soil natural minerals (eg, kaolin, clay, talc, chalk, quartz, attapull guide, montmorillonite, diatomaceous earth, etc.) and soil synthetic minerals (eg, highly dispersed silicic acid, alumina, silicates, etc.).

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 [eg, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (eg, alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates). , Arylsulfonates, etc.]], albumin hydrolysis products and the like.

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 may be used. Examples of the coloring agent include inorganic pigments (eg, 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 formulations generally comprise the active ingredient in the range of 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 concentrations of the active compounds of the formula (I) according to the invention in the commercially useful forms can vary within wide limits and are, for example, from 0.0000001 to 100% by weight, preferably from
It can be in the range of 0.00001 to 1% by weight.

The compounds of the formula (I) of the present invention can be applied to 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 is not limited to these examples.

[0111]

【Example】

 Example 1

[0112]

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(4-Chlorophenyl) (4- (1-methyl-1-
(Nitroethyl) phenyl) methanone (1.3 g), ethyl carbazate (1 g) and pyridinium p-toluenesulfonate (0.05 g) in ethanol solution (50 ml)
Was heated to reflux for 6 hours. 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 purified by silica gel column chromatography (developing solvent: n-hexane: ethyl acetate = 3: 1) to give ethyl 2- {1-
(4-Chlorophenyl) -1- [4- (1-methyl-1-nitroethyl) phenyl] methylidene} -1-hydrazinecarboxylate (1.2 g) was obtained as a mixture of isomers.

124-125 ° C. (4-chlorophenyl) (4- (1-methyl-1-nitroethyl)
2- (4- (4-chlorobenzoyl) phenyl) -2-methylpropanenitrile (1.5
g), and the reaction was carried out in the same manner using ethyl 2- {1- (4-
Chlorophenyl) -1- [4- (1-cyano-1-methylethyl)
Phenyl] methylidene} -1-hydrazide carboxylate (1.3 g) was obtained as a mixture of isomers.

Mp 154-163 ° C.

Embodiment 2

[0117]

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Ethyl 2- {1- (4-chlorophenyl) -1-
To a toluene solution (50 ml) of [4- (1-cyano-1-methylethyl) phenyl] methylidene} -1-hydrazinecarboxylate (1.1 g) was added a 30% aqueous sodium hydroxide solution (20 ml) and tetra- After adding n-butylammonium iodide (0.1 g), the mixture was heated to 70 to 80 ° C. Under vigorous stirring, a toluene solution (100 ml) of ethyl iodide (2 g) was added dropwise. After dropping,
Stir vigorously at 70-80 ° C for 2 hours. After completion of the reaction, the toluene layer was washed with water and dried over anhydrous magnesium sulfate.
After the solvent was distilled off, the resulting crude product was subjected to silica gel column chromatography (developing solvent n-hexane: ethyl acetate =
4: 1) to give ethyl 2- {1- (4-chlorophenyl) -1- [4- (1-cyano-1-methylethyl) phenyl] methylidene} -1-ethyl-1-hydrazinecarboxylate ( 0.8 g) of a mixture of isomers was obtained.

N ²⁰ _D = 1.5635 The compounds prepared in the same manner as in Example 1 or 2 are shown in Table 2 below together with the compounds prepared in Examples 1 and 2.

[0120]

[Table 4]

Preparation of Intermediate Example 3

[0122]

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Sodium cyanide (52 g) was added to 4-bromomethyl-4'-chlorobenzophenone (31 g) in a mixed solvent of dioxane (150 ml) and water (150 ml), and the mixture was refluxed for 2 hours. After returning the reaction mixture to room temperature, the organic layer was separated, and a 10% aqueous sodium hydroxide solution (100 ml ×
3), washed sequentially with water and saturated saline, and dried over anhydrous magnesium sulfate. The crude crystals after distilling off the solvent were washed with petroleum ether to obtain 2- (4- (4-chlorobenzoyl) phenyl) acetonitrile (24 g).

136-137 ° C.

Embodiment 4

[0126]

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2- (4- (4-chlorobenzoyl) phenyl)
Acetonitrile (5.1 g) in tetrahydrofuran (1
(00 ml), 60% sodium hydride (1.6 g) was added to the solution under an argon atmosphere, and the mixture was stirred at room temperature until hydrogen evolution ceased. Subsequently, a solution of methyl iodide (11.4 g) in tetrahydrofuran (20 ml) was added, and the mixture was stirred at room temperature for 16 hours. The reaction mixture was poured into ice water, extracted with ethyl acetate, washed sequentially with 2N hydrochloric acid, water and saturated saline, and dried over anhydrous magnesium sulfate. After evaporating the solvent, the crude product was purified by silica gel column chromatography (n-hexane: ethyl acetate = 5: 1) to give 2- (4- (4-chlorobenzoyl) phenyl) -2-methylpropanenitrile (1 .8
g) was obtained.

Mp 79-81 ° C.

Embodiment 5

[0130]

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2- (4- (4-Chlorobenzoyl) phenylacetonitrile (25.5 g) was refluxed with a solution of concentrated sulfuric acid (20 ml) in ethanol (20 ml) for 6 hours, cooled to room temperature, poured into ice water and diluted with dichloromethane. The crude product after the solvent was distilled off was purified by silica gel column chromatography (developing solvent n-hexane: ethyl acetate = 5: 1). Thus, ethyl 2- [4- (4-chlorobenzoyl) phenyl] acetate (10.0 g) was obtained.

(Viscous oil) ¹ H-NMR (90 MHz, CDCl ₃ solvent, σ value) 1.27 (3H, t) 3.67 (2H, s) 4.17 (2H, d) 7.1- 7.8 (8H, m) Example 6

[0133]

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An anhydrous ether of silver nitrite (4.6 g) (1
(50 ml), a solution of 4-bromo-4'-chlorobenzoyl (6.2 g) in anhydrous ether (100 ml) was added dropwise to the suspension at 0 ° C, and the mixture was stirred at 0 ° C for 20 hours. After further stirring at room temperature for 2 hours, the precipitate was separated by filtration, and the filtrate was 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:
Purification with ethyl acetate = 2: 1) (4-chlorophenyl) (4
-(Nitromethyl) phenyl) methanone (3.1 g) was obtained.

Melting point 112-114 ° C.

Embodiment 7

[0137]

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To a solution of 4-chloro-4'-nitrobenzophenone (1.7 g) in hexamethylphosphoric triamide (40 ml) was added 2-nitropropane lithium salt (3
g) was added and the mixture was stirred at room temperature for 24 hours. The reaction mixture was poured into ice water, extracted with toluene, washed with water and dried over anhydrous magnesium sulfate. After evaporating the solvent, the crude product was purified by silica gel column chromatography (developing solvent: n-hexane: ethyl acetate = 5: 1) to give (4-chlorophenyl) (4- (1-
(Methyl-1-nitroethyl) phenyl) methanone (1.3
g) was obtained.

Mp 76-79 ° C.

Biological test example: Test for larvae of Spodoptera litura Preparation method of reagents: Solvent: 3 parts by weight of xylol Emulsifier: 1 part by weight of polyoxyethylene alkylphenyl ether
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. 6 and 8 showed an insecticidal rate of 100% at a concentration of 500 ppm.

[0143]

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 (5)

[Claims] (1) Formula (1) Wherein X represents halogen, R ¹ and R ² each independently represent hydrogen or optionally substituted alkyl, or together with the carbon atom to which they are attached, form C _{3- 8} to form a hydrocarbon cyclic group, R ³ represents cyano, nitro, CO ₂ R ⁶ or CONR ⁶ R ^7, R ⁴ is hydrogen, C
OR ⁶ or CO ₂ R ⁶ , R ⁵ is hydrogen, optionally substituted alkyl, COR ⁶ or CO ₂ R ⁶ , and R ⁶ and R ⁷ are each independently hydrogen, substituted A benzophenone hydrazone derivative represented by an optionally substituted alkyl or an optionally substituted phenyl, and a geometric isomer mixture thereof. 2. X represents fluorine, chlorine or bromine;
¹ and R ² each independently represent C _1-4 alkyl or C _1-4 haloalkyl, or together with the carbon atom to which they are attached, a C _3-6 saturated hydrocarbon cyclic group Wherein R ³ is cyano, nitro, a group CO ₂ R ⁶ or a group CONR ⁶ R ⁷ and R ⁴ is hydrogen, a group COR ⁶ or a group CO
₂ R ⁶ , R ⁵ represents hydrogen, C _1-4 alkyl, C _1-4 alkoxy-C _1-4 alkyl group, group COR ⁶ or group CO ₂ R ⁶ , and R ⁶ and R ⁷ represent Each independently represents hydrogen, C
_1-6 alkyl, C _1-6 show a phenyl optionally substituted by haloalkyl or halogen, A compound according to claim 1 or a geometric isomer mixture described. 3. X represents chlorine or bromine, and R ¹ and R ² each independently represent C _1-4 alkyl or C _1-4 haloalkyl, or together with the carbon atom to which they are attached. Becomes, cyclopropyl, cyclobutyl,
Forming cyclopentyl or cyclohexyl, wherein R ³ represents cyano, nitro, a group CO ₂ R ⁶ or a group CONR ⁶ R ⁷ ;
R ⁴ represents hydrogen, group COR ⁶ or group CO ₂ R ⁶ , and R ⁵ represents 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 and R
The compound of claim 1, wherein ⁷ independently represents hydrogen, C _1-4 alkyl, C _1-4 haloalkyl or phenyl optionally substituted by halogen, or a mixture of geometric isomers thereof. 4. A pesticide containing the compound according to claim 1 as an active ingredient. 5. A compound of the formula Wherein X represents a halogen, R ⁹ and R ¹⁰ each independently represent an optionally substituted alkyl or, together with the carbon atom to which they are attached,
Forming a _3-8 hydrocarbon cyclic group, wherein R ³ is cyano, nitro, C
A benzophenone derivative represented by the formula: O ₂ R ⁶ or CONR ⁶ R ⁷ , and R ⁶ and R ⁷ each independently represent hydrogen, optionally substituted alkyl or optionally substituted phenyl .