HRP920507A2 - Hydrazone compounds, processes for the production thereof, intermediates useful for the production thereof and pesticidal compositions containing the same - Google Patents

Description

The field of technology

The invention is from the field of organic and photopharmaceutical chemistry.

Technical problem

The subject invention relates to hydrazone compounds, processes for their preparation, intermediates applicable for their preparation and pesticide preparations and pesticide methods.

State of the art

Hydrazone compounds are described, for example, in Japanese Examined Patent Application No. 16410/1975 and EP 3,913A, EP 26,040A, EP 254461A and EP 355 832A. However, the compounds of the present invention represented later herein by formula I are not described by these references.

Description of the solution to the technical problem with examples

The subject invention provides hydrazone compounds of formula I or their salts:

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where each of R1, R2 and R4 are independently a hydrogen atom, a halogen atom, nitro, cyano, hydroxyl, a trialkylsilyl group, an alkyl group which may be substituted, a cycloalkyl group which may be substituted, an alkoxy group which may be substituted, an alkylthio group which may be substituted, a carboxyl group which may be substituted, an aryl group which may be substituted or an aryloxy group which may be substituted, R3 is a hydrogen atom, a halogen atom, nitro, cyano, a hydroxyl group, an alkyl group which may be substituted, a cycloalkyl group which may be substituted, an alkoxy group which may be substituted, an alkylthio group which may be substituted, a carboxyl group which may be substituted, XlSO2NH-, X2CO2-, X3SO-, X4SO2-, X5SO3- or (X6Y1)2P(=Y2)Y3 and each R5 and R6 is independently a hydrogen atom, an alkyl group which may be substituted, X7CO-, X8CO-, X9SO2, a carbamoyl group which may be substituted, an alkenyl group which may be substituted, a heteroaryl group which may be substituted or R5 and R6 together form the =CR7R8 group =CR7R8 where X1, X2, X3, X4, X5, X8 and X9 are each independently a substituted alkyl group, a substituted alkoxy group, a substituted alkenyl group or an aryl group which may be substituted, X6 is an alkyl group which may be substituted, an alkenyl group which may be substituted or an aryl group which may be substituted, X7 is a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted or an aryl group which may be substituted, each Y1, Y2 and Y3 is independently an oxygen or sulfur atom, each R7 and R8 is independently a hydrogen atom, an alkyl group which may be substituted, a cycloalkyl group which may be substituted, an alkoxy group which may be substituted, an alkenyl group which may be substituted, an aryl group which may be substituted, an amino group which may be substituted or a cyclic amino group which may be substituted, provided in that the following cases (1) to (10) are excluded:

(1) the case where R3 and R4 are simultaneously hydrogen atoms,

(2) the case where at least one of R5 and R6 is an unsubstituted carbamoyl group

(3) the case where at least one of R1, R2, R3 and R4 is a nitro group,

(4) the case where R2, R4 and R5 are hydrogen atoms, R6 is an ethoxycarbonyl group and at least one of R1 and R3 is a p-methoxy group,

(5) the case where R1, R2, R4 and R5 are hydrogen atoms, R3 is a p-tertbutyl group and R6 is an ethoxycarbonyl group,

(6) the case where R1, R2 and R4 are hydrogen atoms, R3 is a p-fluorine atom, R5 is an isopropyl group, and R6 is a hydrogen atom or an acetyl group,

(7) the case where R1, R2, R4, R5 and R6 are hydrogen atoms and R3 is a p-chloro atom,

(8) the case where R7 is an unsubstituted phenyl group and R8 is a benzyl group which may be substituted,

(9) the case where R1, R2 and R3 are methyl groups, i

(10) the case where R5 is a hydrogen atom and R6 is a phenylsulfonyl group which may be substituted, and a process for obtaining them.

The present invention also provides an intermediate (II-5):

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where each of R12, R13, R14 and R15 is independently a hydrogen atom, a halogen atom or an alkyl group which can be substituted with a halogen atom, assuming that cases (1) to (4) are excluded:

(1) the case where each of R12, R13, R14 and R15 is independently a hydrogen atom or a halogen atom,

(2) the case where R12 or R13 is a p-trifluoromethyl group, and R14 or R15 is a p-trifluoromethyl group,

(3) serve where R 12 or R 13 is a halogen atom, and R 14 or R 15 is a methyl group, an ethyl group or a propyl group, and

(4) the case where R12 or R13 is a methyl group, an ethyl group, a propyl group and R14 or R15 is a halogen atom.

Further, the present invention provides a pesticide preparation comprising a pesticidally effective amount of a hydrazone compound of formula (IX) or its salt:

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where R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are as defined above, with the limitation that the case where R 3 and R 4 are hydrogen atoms at the same time is excluded, and an agricultural adjuvant, and a pesticidal process comprising applying to pests an effective amount of a hydrazone compound of formula (IX) or its salts.

Now the subject invention will be described in detail with regard to preferred embodiments.

The substituent for each alkyl group which may be substituted, alkoxy group which may be substituted, alkylthio group which may be substituted, alkenyl group which may be substituted, alkynyl group which may be substituted in the definitions, formulas I and II, may be a halogen atom, an alkoxy group which may be substituted by a halogen atom, a phenyl group which may be substituted by a halogen atom or an alkyl group which may be substituted by a halogen atom; a phenoxy group which may be substituted with a halogen atom or an allyl group which may be substituted with a halogen atom; cyano group; an alkylamino group or an alkoxycarbonyl group.

A carboxyl group that can be substituted is a carboxyl group in which the hydrogen atom can be substituted by another substituent that can be an alkyl group that can be substituted with a halogen atom or an aryl group that can be substituted with a halogen atom or an alkyl group that can be substituted with a halogen atom, the substituent for each heteroaryl group which may be substituted, aryl group which may be substituted, aryloxy group which may be substituted and cycloalkyl group which may be substituted may be a halogen atom, an alkoxy group which may be substituted with a halogen atom, an alkyl group which may be substituted , a halogen atom, a phenyl group which may be substituted by a halogen atom or an alkyl group which may be substituted by a halogen atom, a phenoxy group which may be substituted by a halogen atom or an alkyl group which may be substituted by a halogen atom, a cyano group, an alkylamino group or an alkoxycarbonyl group, and substituent for each carb an amyl group which may be substituted, an amino group which may be substituted and a cyclic amino group which may be substituted may be an alkoxy group which may be substituted with a halogen atom, an alkyl group which may be substituted with a halogen atom, a phenyl group which may be substituted with a halogen atom or an alkyl group which may be substituted with a halogen atom, a phenoxy group which may be substituted with a halogen atom or an alkyl group which may be substituted with a halogen atom, a cyano group, an alkylamino group or an alkoxycarbonyl group.

The number of these substituents is one or more. Furthermore, the number of halogen atoms, alkyl groups, alkyl groups substituted with a halogen atom and halogen atoms of alkyl groups substituted with a halogen atom for these substituents is 1 or more.

In the case where the number of these substituents or radicals is 2 or more, such plurality of substituents or radicals may be the same or different.

In the definitions of formulas I and II-5 and IX, the alkyl group or alkyl moiety can be a Cl-6 alkyl group such as a methyl, ethyl, propyl, butyl, pentyl or hexyl group,

The alkenyl group or alkenyl moiety may be a C2-6 alkenyl group such as a vinyl, propenyl, butenyl, pentenyl or hexenyl group, and

an alkynyl group or alkynyl moiety may be a C2-6 alkynyl group such as an athynyl, propynyl, butynyl, pentynyl or hexynyl group.

Such suitable groups and moieties include structural isomers of normal and branched aliphatic chains.

Further, the cycloalkyl group or cycloalkyl moiety in the definitions of formulas I and IX may be a C3-6 cycloalkyl group such as a cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl group.

In the definitions of formulas I and IX, the aryl group can be, for example, a phenyl or naphthyl group, and the heteroaryl group can be, for example, a furyl, thienyl or pyridyl group.

The cyclic amino group in the definitions of formulas I and IX can be where n is an integer from 2 to 7.

The halogen atom in the definitions of formulas I, II-5 and IX can, for example, be a fluorine, chlorine, bromine or iodine atom.

Preferred among the compounds of formula I and IX are:

(1) Each R1, R2 and R4 is independently preferably a hydrogen atom, a halogen atom, an alkyl group which may be substituted, an alkoxy group which may be substituted, an alkylthio group which may be substituted, or a carboxyl group which may be substituted, more preferably a hydrogen atom , a halogen atom, an alkyl group that can be substituted or an alkoxy group that can be substituted, most preferably a hydrogen atom, a halogen atom, an alkyl group that can be substituted by a halogen atom or an alkoxy group that can be substituted by a halogen atom.

(2) R3 is preferably a halogen atom, an alkyl group that can be substituted, an alkoxy group that can be substituted, an alkylthio group that can be substituted, a carboxyl group that can be substituted, or X5SO3- (where X5 is an alkyl group that can be substituted) , more preferably a halogen atom, an alkyl group that can be substituted or an alkoxy group that can be substituted, most preferably a halogen atom, an alkyl group that can be substituted by a halogen atom or an alkoxy group that can be substituted by a halogen atom.

(3) Each R5 and R6 is independently and preferably a halogen atom, an alkyl group which may be substituted, X7CO- (where X7 is as defined above), X8OCO- (where X8 is an alkyl group which may be substituted, an alkenyl group which may be substituted or an aryl group which may be substituted (, a substituted carbamoyl group, an alkenyl group which may be substituted, an alkynyl group which may be substituted, a heteroaryl group which may be substituted or R5 and R6 together form a =CR7R8 group (where each R7 and R8 is independently a hydrogen atom, an alkyl group which may be substituted, a cycloalkyl group which may be substituted, an alkoxy group which may be substituted, an alkenyl group which may be substituted or an amino group which may be substituted), more preferably a hydrogen atom, an alkyl group which may be substituted X7CO- (where X7 is a hydrogen atom or an alkyl group which may be substituted), X8OCO- )where X8 is an alkyl group which may be substituted), substituted carbamols group or R 5 and R 6 together form =CR 7 R 8 (where each R 7 and R 8 is independently a hydrogen atom, an alkyl group that may be substituted, a cycloalkyl group that may be substituted, an alkoxy group that may be substituted, or an amino group that may be substituted), most preferably R5 is a hydrogen atom or an alkyl group and R6 is X7CO- (where X7 is a hydrogen atom or an alkyl group) or X8OCO- (where X8 is an alkyl group), or R5 and R6 together form =CR7R8 (where R7 is a hydrogen atom or an alkyl group and R8 is an amino group which can be substituted by an alkyl group or an alkoxy group).

(4) The following compounds are the most preferred among the compounds of formulas I and IX:

/4'-chloro-2-(4-trifluoromethylphenyl)acetophenone/ N-r-/1-dimethyl-amino)ethylidene/hydrazone,

/4'-fluoro-2-(4-trifluoromethylphenyl)acetophenone/ N'-1/1-dimethyl-amino)ethylidene/hydrazone,

ethyl 3-[1-(4-chlorophenyl)-2-(4-trifluoromethylphenyl)ethylidene]-carbazate,

/4'-chloro-2-(4-tert-butylphenyl)acetophenone/ N'-/1-(dimethylamino)ethylidene/hydrazone, and

/4'-fluoro-2-(4-tert-butylphenyl)acetophenone/N'-?1-dimethylamino)-ethylidene/hydrazone.

Compounds of formulas I and IX can form salts with acidic or basic substances. Salts with acidic substances include salts of inorganic acids such as hydrochlorides and sulfates. Salts with basic substances include salts with inorganic or organic bases, such as sodium, potassium, calcium, ammonium and dimethylamine salts.

Furthermore, compounds of formulas I and IX give geometrical isomers, eg E-form and Z-form, depending on the double bond of the hydrazone. The present invention includes such isomers and mixtures of such isomers.

Compounds of formula I can be obtained, nor. by the following reaction stages 1-7.

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In the above formulas R 1 , R 2 , R 3 , R 4 , R 7 and R 8 are as defined above, and J 1 is an alkyl group.

The case where R 5 and R 6 together form =CR 7 R 8 , where R 7 and R 8 are each independently a hydrogen atom, an alkyl group which may be substituted, a cycloalkyl group which may be substituted, an alkenyl group which may be substituted, an aryl group which may be substituted.

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In the above formulas, R 1 , R 2 , R 3 and R 4 are as defined above, and each of R 9 and R 10 is independently a hydrogen atom, an alkyl group which may be substituted, a cycloalkyl group which may be substituted, an alkenyl group which may be substituted, or an aryl group which may be substituted.

In the case where R 5 and R 6 together form =CR 7 R 8 , where R 8 is an amino group which may be substituted or a cyclic amino group which may be substituted.

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In the above formulas R1, R2, R3, R4 and R7 are as defined above, each J2 and J3 is independently a hydrogen atom; an alkyl group which may be substituted by a halogen atom; an alkoxy group which may be substituted by a halogen atom; a phenyl group which may be substituted by a halogen atom or an alkyl group which may be substituted by a halogen atom; a phenoxy group which may be substituted by a halogen atom or an alkyl group which may be substituted by a halogen atom; cyano group; an alkylamino group; the alkoxycarbonyl group or J2 and J3 together form with the nitrogen atom to which the cyclic amino group is attached a group that can be substituted.

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In the above formulas R1, R2, R3, R4, R7, J2 and J3 are as defined above.

The case where R6 is X7CO-, X8OCO- or X9SO2-.

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In the above formulas, R1, R2, R3 and R4 are as defined above, R11 is a hydrogen atom, an alkyl group which may be substituted, X7CO-, X8OCO-, X9SO2- (wherein X7, X8 and X9 are as defined forward), a carbamoyl group which may be substituted, an alkenyl group which may be substituted, an alkenyl group which may be substituted, an alkynyl group which may be substituted or a heteroaryl group which may be substituted and J4 independently of R11 is X7CO-, X8OCO-, X9SO2 (where X7, X8 and X9 are as defined above).

The case where R 6 is J 5 NHCO- (which is part of a carbamoyl group which may be substituted).

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In the above formulas, R 1 , R 2 , R 3 , R 4 and R 11 are as defined above, J 5 is an alkyl group which may be substituted by a halogen atom; a phenyl group which may be substituted by a halogen atom or an alkyl group which may be substituted by a halogen atom; an alkylamino group; or an alkoxycarbonyl group.

In reaction step 7, the hydrogen atom in the J5NHCO- compounds of formula (1-7) can be alkylated by a conventional alkylation reaction.

Furthermore, compounds of formula II can be obtained, for example, by the following reaction steps 8 to 16.

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In the above formulas, R1, R2, R3 and R4 are as defined above.

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In the above formulas, R1, R2, R3 and R4 are as defined above, and Hal is a halogen atom.

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In the above formulas R1, R2, R3, R4 and Hal are as defined above.

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In the above formulas R1, R2, R3, R4 and Hal are as defined above, and Ph is a phenyl group.

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In the above formulas, R1, R2, R3, R4, Hal and Ph are as defined above.

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In the above formula, R1, R2, R3 and R4 are as defined above. Case where R3 is X2CO2- or X5SO3-.

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In the above formulas R 1 , R 2 , R 4 and Hal are as defined above, and J 6 is X 2 CO- or X 5 SO 2 (wherein X 2 and X 5 are as defined above).

The case where R3 is X1SO2NH-,

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where R1, R2, R4 and X1 are as defined above.

The case where R3 is X3SO- or X4SO2-.

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In the above formulas, R 1 , R 2 and R 4 are as defined above, X 10 is the same as X 3 or X 4 and n is 1 or 2.

Compounds of formula (I-2) can be obtained, for example, using the following reaction step 17.

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Compounds of formula VI can be obtained, for example, by the following reaction step 18.

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Compounds of formula VIII can be obtained, for example, by the following reaction step 19.

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In formula (I-8), R 1 , R 2 , R 3 , R 4 , R 7 and X 7 are as defined above.

Compounds of formula VI can be obtained by the process for obtaining compounds of formula I or compounds of formula 1-2. Compounds of formula XII and formula XIII can be obtained in the same way as the procedure for obtaining compounds of formula II. further, compounds of formula IX are outside the scope of compounds of formula I, they can also be obtained according to the above procedures.

The reactions of the above reaction steps 1, 3 and 17 are usually carried out in the presence of a solvent, and if necessary, in the presence of an acid catalyst, and the reaction temperatures are usually in the range of -20 to +200ºC, preferably from -10 to +150ºC, and reaction times are usually from 0.1 to 150 hours. The solvent may be, for example, an ether such as diethyl ether, tetrahydrofuran or dioxane; an alcohol such as ethylene glycol, glycerol, methanol or ethanol; an aprotic polar solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide or sulforane; an aromatic hydrocarbon such as benzene, toluene or chlorobenzene; a halogenated hydrocarbon such as methylene chloride or chloroform; an aliphatic hydrocarbon such as pentane, hexane or heptane; an alicyclic hydrocarbon such as cyclohexane; a pyridine such as pyridine or picoline; acetic acid; or water. These solvents can be used in combination as a mixture. The acid catalyst can be, for example, a mineral acid such as hydrochloric, sulfuric or nitric acid; an organic acid such as formic, acetic, propionic, methanesulfonic, benzenesulfonic or p-toluenesulfonic acid, an acid addition salt of an amine such as pyridine hydrochloride or triethylene hydrochloride.

The reaction of the above reaction step 2 is carried out, if necessary, in the presence of a solvent and/or an acid catalyst, wherein the reaction temperature is usually from 0 to 200ºC, preferably from 50 to 150ºC, and the reaction time is usually from 0.1 to 100 hours . The solvent can be, for example, an ether, an alcohol, an aprotic polar solvent, an aromatic hydrocarbon, a halogenated hydrocarbon and water as used in the above reaction steps 1, 3 and 17 as well as a nitrile such as acetonitrile. These solvents can be used in combination as a mixture. The acid catalyst can be, for example, the same as in reaction steps 1, 3 and 17 above.

The reactions of the above reaction stages 4 and 5 are carried out, if necessary, in the presence of a solvent, wherein the reaction temperatures are usually -20 to +200ºC, preferably from 0 to 100ºC, and the reaction periods are usually from 0.1 to 100 hours. The solvent can be, for example, an aromatic hydrocarbon, pyridine, a halogenated hydrocarbon, an aliphatic hydrocarbon or water, as used in the above reaction steps 1, 3 and 17. These solvents can be used in combination as a mixture.

The reactions of the above reaction steps 6, 7, 14 and 15 are usually carried out in the presence of a solvent, and if necessary in the presence of an acid binding agent, the reaction temperatures being usually in the range of -20 to +200ºC, preferably from 0 to 150ºC, and reaction times are usually from 0.1 to 100 hours. The solvent can be, for example, an inert organic solvent such as ether, an aprotic polar solvent, an aromatic hydrocarbon, a halogenated hydrocarbon, an aliphatic hydrocarbon, an alicyclic hydrocarbon, pyridine or water as used in the above reaction steps 1, 3 and 17 or a nitrile such as acetonitrile . These solvents can also be used as a combination, as a mixture. The acid binding agent can be, for example, a tertiary alkylamine such as triethylamine, an alkali metal carbonate such as sodium carbonate or pyridine.

The reaction of the above reaction step 8 is usually a Friedel-Crafts reaction, which is carried out in the presence of a solvent and a catalyst. The reaction temperature is usually -20 to +200ºC, preferably -10 to +100ºC and the reaction time is from 0.1 to 100 hours. The solvent can be, for example, carbon disulfide, a halogenated hydrocarbon as used in reaction steps 1, 3 and 17 above, or nitrobenzene. The catalyst can be, for example, a Lewis acid, such as aluminum chloride, lead chloride, ferrous chloride, ferric chloride, titanium tetrachloride, stannous chloride, zinc chloride or polyphosphoric acid.

The reactions of the above reaction stages 9 and 10 are usually Grignard reactions, which are carried out in the presence of a solvent. The reaction temperatures are usually in the range from -20 to +200ºC, preferably from -10 to +100ºC and the reaction time is from 0.1 to 100 hours. The solvent may be an ether as used in reaction steps 1, 3 and 17 above.

The first reaction in each of the above reaction steps 11 and 12 is usually a Wittig reaction, which is carried out in the presence of a base and a catalyst. The reaction temperature is usually from -20 to +200ºC, preferably from -10 to +150ºC, and the reaction time is from 0.1 to 100 hours. the base can be, for example, the hydroxide, carbonate or acetate of an alkali metal or alkaline earth metal or an organometallic compound such as butyllithium. The solvent can be, for example, an ether, an alcohol, an aprotic polar solvent, an aromatic hydrocarbon, a halogenated aromatic hydrocarbon, a halogenated hydrocarbon or water, as used in the above reaction steps 1, 3 and 17. These solvents can be used in combination as a mixture.

The second reaction in each of the above reaction steps 11 and 12 is usually a halogenation reaction, whereby a halogen (here preferably chlorine or bromine) is added in the presence of peroxide or under light irradiation. The reaction temperature is usually from -20 to +200ºC, preferably from -10 to +100ºC, and the reaction time is from 0.1 to 100 hours. The solvent is preferably a hydrocarbon or halogenated hydrocarbon, but other solvents can also be used as used in reaction steps 1, 3 and 17 above.

The third reaction in each of the above reaction steps 11 and 12 is usually dehalogenation which is carried out using a dehalogenating agent in the presence of a solvent. The halogenating agent can be, nor. an alkali metal or its alcoholate or hydroxide. the reaction temperature is usually from -20 to +200ºC, preferably from -10 to +150ºC and the reaction time is from 0.1 to 100 hours. The solvent can be the same as used in the first reaction.

The fourth reaction in each of the above reaction steps 11 and 12 is usually an oxidation reaction carried out using, for example, a mercury(II) salt in the presence of an acid catalyst. The reaction temperature is usually from 0.1 to 100 hours. The solvent can be acetic acid or the same solvent as in the first reaction is used. These solvents can be used in combination as a mixture. The acid catalyst can be, for example, an inorganic acid such as sulfuric or nitric acid or an organic acid such as acetic or trifluoroacetic acid.

The reaction of the previous reaction step 13 is usually an oxidation reaction that is carried out in the presence of a solvent and an oxidizing agent. The reaction temperature is usually in the range of -20 to +200ºC, preferably -10 to +150ºC, and the reaction time is from 0.1 to 100 hours. The oxidizing agent can be, for example, a chromium(VI) salt, lead tetraacetate, nitric acid or dimethylsulfoxide. As a solvent, water or acetic acid are mainly used, but other solvents such as a hydrocarbon, a halogenated aromatic hydrocarbon or an aprotic polar solvent, an aromatic hydrocarbon or a halogenated hydrocarbon can be used, as used in the previous reaction steps 1, 3 and 17. This solvents can be used in combination as a mixture.

The reaction of the above reaction step 16 is usually an oxidation reaction with, for example, H2O2, which is usually carried out in the presence of a solvent. The reaction temperature is usually in the range from -20 to +200ºC, preferably from -10 to +100ºC, and the reaction time is from 0.1 to 100 hours. The solvent may be the same as that used in the above reaction step 13. Such solvents may be used in combination as a mixture.

The reactions of the above reaction stages 18 and 19 are carried out, if necessary, in the presence of a solvent. The reaction temperature is usually from 0 to 250ºC, preferably from 10 to 180ºC, and the reaction time from 0.1 to 100 hours. The solvent can be, for example, an aromatic hydrocarbon, a halogenated hydrocarbon, an aliphatic hydrocarbon or an alicyclic hydrocarbon as used in the above reaction steps 1, 3 and 17. These solvents can be used in combination as a mixture.

Specific synthetic examples of compounds of formula I will now be described.

Synthesis example 1

Synthesis of /4'-chloro-2-(4-chlorophenyl)acetophenone/-N'-/1-dimethylamino)-ethylidenehydrazone (compound no. 1)

1) 1.33 g (5 mmol) of 4'-chloro-2-(4-chlorophenyl)acetophenone is dissolved in 25 ml of ethanol and 1.25 g (25 mmol) of hydrazine monohydrate is added. The mixture is refluxed with heating for 2 hours. At the end of the reaction, ethanol is distilled off under reduced pressure and water is added to the residue. The mixture is extracted with dichloromethane. The extract is dried over anhydrous sodium sulfate. The solvent is then distilled off to obtain 1.44 g of (4'-chloro-2-(4-chlorophenyl)acetophenone)hydrazone as a yellow oily substance.

2) 0.51 g (4.2 mmol) of N,N-dimethylacetamide dimethyl acetal is added to 1.0 g (3.6 mmol) of 4"-chloro-2-(4-chlorophenyl)acetophenone/hydrazone obtained in the above step 1) , and the mixture is heated to 120ºC for 2 hours. After the completion of the reaction, the reaction solution is purified by chromatography on a silica-gel column (developing solvent: ethyl acetate:n-hexane=1:4) to obtain 0.56g of the desired product (compound no. 1) which has a melting point of 125 to 127ºC.

Synthesis example 2

Synthesis of methyl 3-[1,2-bis(4-chlorophenyl)ethylidene/carbazate (compound no. 201)

1) 0.43 g (1.5 mmol) of /4'-chloro-2-(4-chlorophenyl)acetophenone/hydrazone obtained in synthesis example 1 (1) is dissolved in 5 ml of pyridone, while cooling with ice, 0 .2 ml (2.5 mmol) of methyl chlorocarbonate. After the addition is complete, the mixture is stirred at room temperature for 3 hours. At the end of the reaction, the mixture is placed in water and extracted with dichloromethane. The extract is dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue was purified by silica gel column chromatography (developing solvent: ethyl acetate/n-hexane=3:7) to obtain 0.37 g of the desired product (compound no. 201) having a melting point of 156 to 159ºC.

Synthesis example 3

Synthesis of /4'-chloro-(4-chlorophenyl)acetophenone/-4-(4-txifluoromethyl-phenyl) semicarbazone (compound no. 200)

1) 0.97 g (6 mmol) of p-aminobenzotrifluoride is dissolved in 10 ml of ethyl acetate and 1.1 ml (9 mmol) of trichloromethyl chloroformate is added. The mixture is refluxed with heating for 2 hours. The excess of ethyl acetate and trichloromethyl chloroformate is then distilled off under reduced pressure. The residue is dissolved in 5 ml of ethyl ether and the solution is added dropwise while cooling with ice to 20 ml of a diethyl ether solution containing 1.4 g (5 mmol) of /4'-chloro-2-/4-chlorophenyl)acetophenone/hydrazone obtained in the same way as in synthesis example 1 (1). At the end of the addition, the mixture is stirred at room temperature for 1.5 hours. At the end of the reaction, the solvent is distilled off and a small amount of water is added to the residue. The mixture is extracted with dichloromethane, and the extract is dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue is purified by chromatography on a silica gel column (developing solvent: ethyl acetate/n-hexane=1:4) to obtain 1.53 g of the desired compound (compound no. 200) having a melting point of 194 to 198ºC.

Synthesis example 4

Synthesis of /4'-chloro-2-(4-tertbutylphenyl)acetophenone/N'-/1-dimethyl-amino)ethylidene/hydra-zone (compound no. 32)

1) 0.7 g of magnesium (shavings) and 100 ml of iodine pieces are added to 5 ml of anhydrous ethyl ether. 10 ml of an anhydrous ether solution of 5.6 g of p-bromochlorobenzene is added dropwise under a stream of nitrogen at a rate just sufficient to maintain a gentle reflux. Iva solution is stirred at room temperature for 20 minutes to react, a solution of 4.8 g of p-tert-butylphenyl acetonitrile in 5 ml of anhydrous diethyl ether is added dropwise at a rate sufficient to maintain a gentle reflux. The solution is further stirred for 30 minutes for the reaction. At the end of the reaction, a mixture of log ice and 6M HCl solution is added and the reaction product is extracted with ethyl acetate. The extract is washed with water and saturated sodium chloride solution, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue is purified by chromatography on a silica gel column (developing solvent: ethyl acetate/n-hexane=1:9) to obtain 1.3 g of 4'-chloro-2-(4-tert-butylphenyl)acetophenone,

2) 1.3 g (4.5 mmol) of 4'-chloro-2-((4-tert-butylphenyl)acetophenone is dissolved in 15 ml of ethanol and 0.2 g (4.5 mmol) of hydrazine monohydrate is added. the mixture is refluxed with heating for 3 hours. At the end of the reaction, ethanol is distilled off under reduced pressure. Water is added to the residue, and the mixture is extracted with dichloromethane. The extract was dried over anhydrous sodium sulfate, and the solvent was distilled off to give 1.3 g of (4'-chloro-2-(4-tert-butylphenyl)-acetophenone/liidrazone as a yellow oily substance).

3) 1.3 g (4.3 mmol) of /4'-chloro-2-(4-tert-butylphenyl)acetophenone/-hydrazone obtained in the previous step (2) is dissolved in 15 ml of acetonitrile, and 0.6 g is added (4.7 mmol) of N,N-dimethylacetoamide dimethyl acetal. The mixture is refluxed with heating for 24 hours. After completion of the reaction, the acetonitrile is distilled off under reduced pressure and the residue is purified by silica gel column chromatography (developing solvent: ethyl acetate/n-hexane=1:8) to obtain 0.4g of the desired product (compound no. 32) which has a melting point of 100 to 101ºC.

Synthesis example 5

Synthesis of (4'-Fluoro-2-(4-1-fluoromethylphenyl)acetophenone-NV1-(dimethylamino)ethylidene/-hydrazone (compound no. 38)

1) 8.9 g (72 mmol) of 4-fluorobenzaldehyde and 32 g (72 mmol) of (4-trifluoromethylbenzyl)triphenylphosphonium chloride are dissolved in 300 ml of methylene chloride. With strong stirring of the solution at room temperature, 280 ml (0.84 mmol) are added in drops. After the dropwise addition, the mixture is stirred at room temperature for 2 hours. At the end of the reaction, the mixture is subjected to liquid separation. The organic layer is washed with water and then dried over anhydrous sodium sulfate, then the solvent is distilled off. The residue was purified by silica gel column chromatography (developing solvent/n-hexane) to obtain 12.4 g of 4-fluoro-4'-trifluoromethylstilbene.

2) 12.4 g (47 mmol) of 4-fluoro-4'-trifluorostilbene are dissolved in 80 ml of chloroform. After irradiating the solution with the light of a 160W mercury lamp, 2.4 ml (47 mmol) of bromine in 20 ml of chloroform are dropped at 40ºC. Then the mixing continues for 30 minutes. At the end of the reaction, the solvent is distilled off to obtain a yellow oily substance. Without purification, this oily substance is dissolved in 100 ml of ethanol. A solution of 12.3 g of potassium hydroxide in 45 ml of water is added dropwise while refluxing and heating. At the end of the instillation, refluxing is continued with heating for 3 hours. At the end of the reaction, ethanol is distilled off and water is added to the residue. The mixture is extracted with diethyl ether and then dried over anhydrous sodium sulfate. The solvent was then distilled off to obtain 12.2 g of 4-fluoro-4'-trifluoromethyltoluene as a yellow solid. Without purification, this yellow substance is used for the next reaction.

3) In 12.2 g (46 mmol) of 4-fluoro-4'-trifluoromethyltoluene, 60 ml of water, 60 ml of acetic acid, 40 ml of H2SO4 and 13.6 g (46 mmol) of mercury(II) sulfate are added and the mixture is stir at 90ºC for 3.5 hours. After completion of the reaction, water is added to the reaction mixture and the mixture is extracted with diethyl ether. The extract is dried over anhydrous sodium sulfate and the solvent is distilled off. The residue was purified by silica gel column chromatography (developing solvent: ethyl acetate/n-hexane=1:9) to obtain 5.1 g of 4'-fluoro-2-(4-trifluoromethylphenyl)acetophenone, which has a melting point of 87 to 89ºC.

4) 5.1 g (18.1 mmol) of 4'-fluoro-2-((4-trifluoromethylphenyl)acetophenone is dissolved in 100 ml of ethanol and 8.8 ml (181 mmol) of hydrazine monohydrate is added. The mixture is refluxed with heating for 2 hours. At the end of the reaction, ethanol is distilled off under reduced pressure and water is added to the residue. The mixture is extracted with dichloromethane. The extract was dried over anhydrous sodium sulfate and the solvent was distilled off to give /4'-fluoro-2-(4-trifluoromethylphenyl)-acetophenone/hydrazone as a yellow oil.

5) In /4'-fluoro-2-(4-trifluoromethylphenyl)acetophenone/hydrazone obtained in the previous step (4), add 3.13 g (23.5 mmol) of N',N-dimethylacetamide dimethyl acetal. The mixture is heated to 120ºC for 2 hours. After completion of the reaction, the residue is purified by chromatography on a silica gel column (developing solvent: ethyl acetate/n-hexane=1:19) in order to obtain 3.10 g of the desired product (compound no. 38) which has a melting point of 86 to 88ºC .

Synthesis example 6

Synthesis of /4'-chloro-2-(4-trifluoromethylphenyl)acetophenone/N'-/1-dimethylamino)ethylidene/hydrazone (compound no. 9)

The synthesis was carried out in the same manner as in Synthesis Example 5, except that 4-fluorobenzaldehyde was replaced by 4-chlorobenzaldehyde to give a gelled product (compound no. 9) having a melting point of 94 to 97ºC.

Synthesis example 7

Synthesis of /4'-fluoro-2-(4-tert-butylphenyl)acetophenone/N'-/1-(dimethylamino)ethylidene/hydrazone (compound no. 60)

1) A mixture of 3g (11 mmol) of 4'-fluoro-2-(4-tert-butylphenyl)acetophenone, 0.8g (11 mmol) of acetyl hydrazide, 60 ml of acetic acid and 20 ml of ethanol is refluxed with heating for 20 hours. At the end of the reaction, ethanol is distilled off under reduced pressure to concentrate the reaction product. This is purified by chromatography on a silica gel column (developing solvent: n-hexane/ethyl acetate=2:1) to obtain 1.09 g of /4'-fluoro-2-(4-tert-butylphenyl)-acetophenone/ N' -(acetyl)hydrazone which has a melting point of 132 to 134ºC.

2) A mixture of a solution of 1g of (4'-fluoro-2-(4-tert-butylphenyl)acetophenone/-N'-(acetyl)hydrazone, 0.64g of phosphorus pentachloride and 15 ml of dichloromethane is stirred at room temperature for 1 hour and it is refluxed for 2 hours for the reaction. After the completion of the reaction, the reaction solution is concentrated under reduced pressure, 10 ml of dichloromethane and 1.38 g of dimethylamine are added at room temperature for the reaction at the same temperature for 2 hours with stirring. After the completion of the reaction, the reaction product is diluted with 30 ml of dichloromethane, washed with water, dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to concentrate. It was purified by silica gel column chromatography (developing solvent: n-hexane/ethyl acetate=9:1) to give 0.33g of the desired product (compound no. 60) which has a melting point of 65-67ºC.

Typical examples of compounds of formula I will now be given in the following Tables 1 and 2.

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Table 2

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Atypical examples of compounds of formula IX which are outside the scope of compounds of formula I will now be given in Table 3.

Compounds of formula II-5 is an intermediate applicable in the preparation of compounds of formulas I and IX and is considered a new compound. Typical examples of these compounds will be given in the following table 4.

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Table 4

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In tables 1-4, Ph represents the phenyl group; t-Bu, n-Bu and s-Bu represent tertiary, normal and secondary butyl groups, iso-Pr and n-Pr represent iso and normal propyl groups, and cyclo-Pr and cyclo-hex represent cyclopropyl and cyclohexyl groups, further, numbers before substituents, eg 4-Cl for R1 in compound no. 1 indicates that C1 is located in position 4 of the benzene ring. Connection no. 221 is the geometric isomer of compound no. 215.

The compounds of formulas I and IX of the subject invention show outstanding pesticidal activities as active components for pesticides. For example, they are effective against plant parasitic worms such as the two-spotted spider mite (Tetranvchus urticea), the crimson spider mite (Tetranvchus cinnabarius) or the lemon red aphid (Panonvchus citri) or the bulbous aphid (Rhizogluphus achinopus); agricultural insect pests such as the carrot moth (Plutella xylostella), cabbage worm (Maestra brassicae), common cutworm (Spodoptera lit.), rice leaf bender (Cnaphalocrocis medinalis), Adoxopyes sp., Colorado potato beetle (Leptinotarsa decemlieta), apple butterfly (Laspevresia pomonella), seed borer (Heliothis zea), tobacco flower borer (Heliothis virescens), seed weevil (Anthonumus grandis), gypsy moth (Lymantria dispar), squash leaf beetle (Aulacophora femoralis), lice, grasshoppers, scale insects, bedbugs, whiteflies, sapsuckers, insects, antflies, black shearer (Agrotis ipsilon), shearer (Agrotis segetum) or ants; hygienic insect pests such as tropical rat worms (Ornithonvssus bacoti), cockroaches, house flies (Musca domestica) or mosquitoes (Culex pipens pallens); insecticidal pests of stored grain such as the Angoma grain moth (Sitotroga cerelella), the open seed weevil (Callosubruchus chinensis), the confused dust beetle (Triboliu confusum) or the mealybug; insect pests of household value such as fabric destroying moths (Tiea pellitonella), black carpet beetle (Anthrenus schropularidae) or subterranean termites; and other parasites of domestic animals such as bugs, lice. Furthermore, they are also effective against nematode plant parasites such as root-knot nematodes, cyst nematodes, root-damaging nematodes, rice white jumping nematode (Aphelenechoides bessevi), strawberry blossom nematode (Nothotvlenechus acris) or botwood nematode (Bursaphelenchus lignicolus). Furthermore, they are also effective against soil pests. The soil pests of this invention are gastropods such as snails or isopods such as weevils. The compounds of the present invention show particularly and outstanding pesticidal activity against Lepidoptera and Coleoptera pests among the aforementioned pests, furthermore, they are also effective against insecticidal pests such as the caroline moth and the house fly which have resistance to organophosphorus and peritroid insecticides, furthermore, the compounds of this present invention have systematic features. Therefore, their application in soil treatment ensures control not only of harmful insects, worms, nematodes, gastropods and isopods in the soil, but also of leaf pests. The compounds of the present invention are completely harmless to mammals, fish and beneficial insects and are therefore suitable for use as pesticides.

For use as active substances for pecticides, the compounds of the present invention can be formulated together with agricultural adjuvants for various forms such as powders, granules, wettable powders, water-dispersible granules, suspenzoid concentrates, emulsion concentrates, aerosols or slurries, in fact as common agricultural chemicals.

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Such formulations are usually composed of 0.1 to 90 parts by weight, preferably 0.5 to 90 parts by weight, more preferably 0.5 to 80 parts by weight of active substance and 10 to 99.9 parts by weight, preferably 10 to 99.5 parts by weight parts, preferably 20-99.5 parts by mass of agricultural adjuvant. Such formulations when actually used may be used as such or after dilution with suitable diluents such as water to a predetermined concentration.

As agricultural adjuvants can be mentioned carriers, emulsifiers, suspending agents, dispersants, extenders, penetrants, wetting agents, thickeners, anti-foaming agents, stabilizers and anti-freezing agents. They can be added as the case requires. Carriers can be divided into solid and liquid carriers, as solid carriers we can mention powders of animal or plant origin, such as starch, activated carbon, soybean, wheat or tree flour, fish meal, milk powder; mineral powders such as talc, kaolin, bentonite, calcium carbonate, zeolite, diatomaceous earth, white coal, clay or alumina; sulfur powder or anhydrous sodium sulfate, water, alcohols such as methyl alcohol or ethylene glycol can be mentioned as liquid carriers; ketones such as acetone, methyl ethyl ketone or N-methyl-2-pyrrolidone; ethers such as dioxane or tetrahydrofuran; aliphatic hydrocarbons such as kerosene; aromatic hydrocarbons such as xylene, trimethylbenzene, tetramethylbenzene, cyclohexane or solvent naphtha; halogenated hydrocarbons such as chloroform or chlorobenzene; acid amides such as dimethylformamide; ethers such as ethyl acetate or glycerin fatty acid ester; nitriles such as acertonitrile; sulfur-containing compounds such as dimethyl sulfoxide or vegetable oils such as soybean or corn oil.

Examples of pesticide formulations containing compounds of the present invention as active substances will now be described. However, compounds as active ingredients, types of agricultural adjuvants, and types of formulation are not limited to these specific examples.

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The above components are uniformly mixed to obtain a wettable powder.

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The above components are uniformly mixed to obtain a powder.

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The above components are uniformly mixed and dissolved to obtain an emulsion concentrate.

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The mixture of final components is mixed with compound no. 38 in a mass ratio of 4:1 in order to obtain a wettable powder.

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The above components are uniformly mixed and sprayed to obtain a water-based suspension concentrate.

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The above components are introduced at high speed into the mixing atomizer, and 20% of water is added, the mixture is granulated and dried to obtain water-dispersible granules.

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The above components, a suitable amount of water for granulation are mixed and granulated to obtain granules.

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The above components are uniformly mixed and dissolved to obtain an ultra-small volume formulation.

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The above components are uniformly mixed to obtain an emulsion concentrate.

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The above components are uniformly mixed and sprayed to obtain an oil-based suspension concentrate.

Furthermore, pesticides containing the compounds of the present invention as active ingredients can be used in a mixture or combination with other agricultural chemicals such as insecticides, miticides, nematocides, fungicides, antiviral agents, baits, herbicides or plant growth regulators, as the case requires. In some cases, the effectiveness will be improved by such a combination.

For example, as such insecticides, miticides and nematicides, organophosphorus compounds such as O-(4-bromo-2-chlorophenyl)O-ethyl S-propyl phosphorothioates, O-(2,2-dichlorovinyl) O,O- dimethyl phosphate, O-ethyl O-/3-methyl-4-(methylthio)phenyl/ N-isopropylphosphoramidate, O,O-dimethyl O-(nitro-m-tolyl)phosphorothioate, O-ethyl 0-(4-nitrophenyl) -phosphorothioate, O,O-dimethyl O-(3,5,6-trichloro-2-pyridyl)phosphorothioate,0,S-dimethyl N-acetylphosphoroamidothioate, O-(2,4-dichlorophenyl) O-ethyl S-propyl phosphorothioate or (RS)-S-sec-butyl O-ethyl 2-oxo, 3-thiazolidin-3-yl phosphonothioate, carbamate compounds such as 1-naphthyl N-methylcarbamate, 2-isopropoxyphenyl N-methylcarbamate, 2-methyl 2-( methylthio)propionaldehyde O-methylcarbamoyloxime, 2,3-dihydro-2,2-dimethylbenzofuran-7-yl N-methylcarbamate,dimethyl N,N-/thiobis/-(methylamino)carbonyloxy//bisetanimidiothiomate, S-methyl N-(methyl -carbamoyloxy)thioacetoimidate, N,N-dimethyl-2-methylcarbamoyloxyimino-2-(methylthio)acetamide, 2-(ethylthiomethyl)phenyl N-methylcarbamate, 2-dimethyl-amino-5,6-di methylpyridin-4-yl N,N-dimethylcarbamate or 2-sec-butylphenyl-N-methylcarbamate; nonreistoquine derivatives such as S,S'-2-dimethyl aminotrimethylene bis(thiocarbamate) or N,N-dimethyl-1,2,3-trithian-5-yl amine; organic chlorine compounds such as 2,2,2-trichloro-1,1-bis(4-chlorophenyl)ethanol or 4-chlorophenyl-2,4,5-trichlorophenyl sulfone; organic metal compounds such as bis/tris-(2-methyl-2-phenyl-propyl)tin/oxide; pyrethroid compounds such as (RS)-alpha-cyano-3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3-methylbutyrate, 3-phenoxybenzyl (lRS)-cis,trans-3-(2,2-dichlorovinyl (-2,2-dimethyl-cyclopropanecarboxylate, (RS)-alpha-cyano-3-phenoxybenzyl (lRS)-cis,trans-3-(2,2-dichlorovinyl)-2,2 -dimethylcyclopropanecarboxylate, (S)-alpha -cyano-3-phenoxybenzyl (lRS)-cis- 3 -(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate, (RS)-alpha-cyano-3-phenoxybenzyl(lRS)-cis, trans-3 - ( 2-chloro-3,3,3-trifluoroprepenyl) - 2,2-dimethylcyclopropanecarboxylate, 4-methyl - 2, 3, 5, 6-tetrafluorobenzyl - 3 - (2-chloro-3,3,3-trifluoro-l- propenyl)-2,2-dimethylcyclopropane carboxylate or 2-(4-ethoxyphenyl)-2-methylpropyl 3-phenoxybenzyl ether (generic name etofenoprox hereafter designated as simple compound No. A-l); benzoyl urea compounds such as l-(4- chlorophenyl)-3-(2,6-difluoro-benzoyl)urea, 1-/3,5-dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy-phenyl/3-(2,6-difluorobenzoyl )urea or 1-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzoyl) urea; youth hormone analogs such as isopropyl (2E,4E)-11-methoxy-3,7,11-trimethyl-2,4-dodecadienoate; pyridazinone compounds such as 2-tert-butyl-5-(4-tert-butyl-benzylthio)-4-chloro-3(2H)-pyridazinone; pyrazole compounds such as tert-butyl 4-(1,3-dimethyl-5-phenoxypyrazol-4-yl)methylene aminooxymethyl/benzoate; nitro compounds such as 1-(6-chloro-3-pyridyl-methyl)-N-nitro-imidazolidin-2-ylideneamine (generic name: imidaclopyride, later designated as compound A-2), 1-/N-(6 -chloro-3-pyridylmethyl)-N-ethylamino/-1-methylamino/-1-methylamino-2-nitroethylene (EP 302389A, designated here simply as compound A-2), 2-methylamino-2-/N-methyl- N-(6-Chloro-3-pyridylmethyl)amino/-l-nitroethylene (EP 302389A, herein referred to simply as compound A-4), l-(6-chloro-3-pyridylmethyl)-amino-l-dimethylamino- 2-nitroethylene (EP 302389A, hereafter simply designated as compound A-5), l-(6-chloro-3-pyridylmethyl)-2-(l-nitro-2-allylthioethylidene)imidazolidine (EP) 437784A, hereafter simply designated as compound A-6), l-(6-chloro-3-pyridylmethyl)-2-(1-nitro-2-ethylthioethylidene)imidazolidine (EP 437784A, here simply designated as compound A-7), l-(6- chloro-3-pyridylmethyl)-2-(l-nitro-2-beta-methylallyl-thioethylidene)imidazolidine (EP 437784A, herein simply designated as compound A-8), l-(6-ildoro-3-pyridumethyl)-3 -rmethyl-2-nitroguanidine (EP 383091A, here simply designated as compound A-(), 1-(6-chloro-3-pyridylmethyl)-3,3-dimethyl-2-nitroguanidine (EP 383091A, herein simply designated as compound A-10), 3-(6-chloro -3-pyridyl-methyl)-2-nitromethylene-thiazolidine (EP 192060A, here simply designated as compound A-11), 1-(6-chloro-3-pyridylmethyl)-2-(nitromethylene)imidazolidine (EP 163855A, here simply designated as compound A-12), 6-(6-chloro-3-pyridylmethylamino)-1,3-dimethyl-5-nitro-1,2,3,4-terahydropyrimidine (EP 366085A, herein simply designated as compound A -13) or 1-(6-chloro-3-pyridylmethyl)-5-nitro-3-methyl-6-methylamino-1,2,3,4-tetxahydropyrimidine (EP 366085A, there simply designated as compound A-14) , dinitro compounds; organic sulfur compounds; triazine compounds; hydrazine compounds and other compounds such as 2-tert-butylamino-3-isopropyl-5-phenyl-3,4,5,6-tetrahydro-2H-1,3,5-thiadiazin-4-one (common name buprofezin, here simply designated as compound A-15), trans-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2-oxothiazolidinone-3-carboxamide, N-methylbis(2,4-xylyl-iminomethyl)amine, N - ( 4-chloro-o-tolyl)-N,N-dimethylformamidine or (4-ethoxyphenyl)-(3-(4-fluoro-3-phenoxyphenyl)propyl/(dimethyl)silane (common name silafluophene, here simply referred to as compound A -16),. further, microbiological insecticides such as Bacillus thurigiesisagens or nuclear polyhedrosis virus; antibiotics such as avermectin or milbemycin; or similar can also be used in a mixture with or in combination with the pesticides of the subject invention, among these insecticides, miticides and nematicides of compounds no. A-l, A-2, A-3, A-4, A5, A-6, A-7, A-8, A-9, A-10, A-ll, A-12, A-13, A- 14, A-15 and A-16 are preferred. Compounds no. A-1, A-2, A-3, A-6, A-10 and A-16. It is particularly desirable that at least one of compounds no. 9, 32, 38, 42, 60 and 210 of the subject invention and at least one compound no. A-1, A-2, A-3, A-6, A-15 and A-16 are mixed and the mixture is applied so that the former is from 50 to 5, and the latter from 10 to 5000 g/ha, which gives an extraordinary pesticide effect against insect pests such as the carol ice moth (Plutella xylostella), the rice leaf bender (Cnaphalocrocis medinalis), Adoxophyes sp., grasshoppers and lice. As fungicides, we can mention organophosphorus compounds such as S-benzylO,O-diisopropyl phosphorothioate, O-ethyl S,S-diphenyl phosphorodithioate or aluminum hydrogen phosphonate; organic chlorine compounds such as 4,5,6,7-tetrachlorophthalide or tetrachloroisophthalonitrile; dithiocarbamate compounds such as polymeric manganese ethylenebis(dithiocarbamate), polymeric zinc ethylenebis(dithiocarbamate), manganese ethylenebis(dithiocarbamate) complex with zinc salt, dizinc bis(dimethylthiocarbamate)-ethylenebis(dithiocarbamate) or polymeric zinc propylenebis(dithiocarbamate); N-halogenothioalkyl compounds such as 3a,4,7,7a-tetrahydro-N-(trichloromethylsulfenyl)-phthalimide, 3a,4,7,7a-tetrahydro-N-(1,1,2,2-tetrachlorosulfenyl)phthalimide or N -(trichloro-methylsulfenyl)phthalimide; dicarboxy imide compounds such as 3-(3,5-dichlorophenyl)-N-isopropyl-2,4-dioxoimidazolidine-1-carboxamate (RS)-3-(3,5-dichlorophenyl)-5-methyl-5-vinyl- 1,3-oxazolidine-2-4-dione or N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide; benzimidazole compounds such as methyl 1-(butyl-carbamoyl)benzimidazol-2-yl-carbamate or dimethyl 4,4'-(o-phenylene)bis(3-thiohalophonate), azole compounds such as 1-(4-chlorophenoxy)- 3,3-dimethyl-1-(1H-1)-4-triazol-1-yl)butanone, 1-(biphenyl-4-yloxy)-3,3-dimethyl-1-(1H-1,2-triazole) -1-yl)butan-2-ol, 1-?N-(4-chloro-2-trifluoromethylphenyl)-2-propoxyacetoimidoyl/imidazole, 1-(2-(2,4-dichlorophenyl)-4-ethyl-1 ,3-dioxolan-2-ylmethyl/ -1H-1,2,4-triazole, 1-(2,4-dichlorophenyl)-4-propyl-1,3-dioxo-lan-2-ylmethyl/-1H-1 ,2,4-triazole or 1-(2-(2,4-dichlorophenyl)pentyl)-1H-1,2,4-triazole; carbinol compounds such as 2,4'-dichloro-alpha-(pyrimidin-5-yl)benzhydryl alcohol or (+-)-2,4'-difluoro-alpha-(1H,1,2,4-triazol- 1-ylmethyl)benzhydryl alcohol, benzanilide compounds such as 3'-isopropoxy-o-toluanilide or alpha,alpha,alpha-trifluoro-3'-isopropoxy-o-toluanilide; phenylamide compounds such as methyl N-(2-methoxyacetyl)-N-(2,6-xylyl)-DL-2,6-dinitro-4-alpha,alpha,alpha-trifluorotolyl)-5-trifluoromethyl-2-pyridinamine; piperazine compounds; morpholine compounds; quinine compounds; quinoxaline compounds; crotonic acid compounds; sulfenic acid compounds; urea compounds and other compounds such as 1,3-dithiolane-2-ylidenemalonate, 5-methyl-1,2,4-triazolo/3,4-b/benzothiazole, 1,2,5,6-tetrahydropyrrolo/3,3 ,1-quinolin-4-one, 6-(3,5-dichloro-4-methylphenyl)-3(2H)-pyridazinone, 3-allyloxy-1,2-benzisothiazol-1,1-dioxide or l-(4 -chlorobenzyl)-1-cyclopentyl-3-phenyl urea. Furthermore, antibiotic substances such as validamycin A can also be used in admixture with or in combination with the pesticides of the present invention.

The mixing ratio of the compounds of the present invention to another agricultural chemical is usually in the range of 1:100 to 100:1, preferably from 1:50 to 50:1. The pesticide containing the compound of the present invention as an active ingredient is applied at a concentration of the active ingredient from 1 to 100,000 ppm, preferably from 1 to 50,000 ppm, more preferably from 10 to 200,000 ppm. The concentration of the active ingredient can optionally be changed depending on the formulation, method, purpose, time and place of application and the abundance of the insecticidal pest. For example aquatic harmful insects can be controlled by applying a formulation having the aforementioned concentration at the point of origin, and therefore the concentration of the active ingredient in the water is less than the aforementioned area.

The amount of application of the active ingredient per unit area is usually from about 1 to 50,000 g, preferably from 10 to 10,000 g, more preferably from 50 to 5,000 g per hectare. However, in some special case, the amount of application may be outside the above range.

The various formulations containing the compounds of the present invention or their diluted preparations can be applied by conventional methods commonly used, such as spraying (e.g. by spraying, spraying, fogging, atomizing, dusting or granulating or dispersing in water), applying to land (e.g. mixing or drainage), surface application (e.g. coating, dusting or covering) or impregnation to obtain toxic food. Furthermore, it is possible to feed domestic animals with food containing the above active ingredient in order to control the beginning of the growth of pests, especially insect pests, with their feces. Further, the active ingredient can be applied using the so-called ultra low volume application methods. In this method, the preparation can contain 100% of the active substance.

Example of test 1

Insecticidal test against Spodoptera litur

Each formulation containing the active ingredient was dispersed in water to obtain a dispersion containing the active ingredient at a concentration of 800 ppm. Cabbage leaves are immersed in the dispersion for about 10 seconds and then air-dried. A sheet of moistened filter paper is placed in a petri dish with a diameter of 9 cm, and dried cabbage leaves are placed on the filter paper. Larvae of Spodoptera litura in the second or third stage of metamorphosis are placed on the leaves and the petri dish is covered and kept in a constant temperature room with lighting at a temperature of 26ºC. On the fifth day, dead insects are counted and mortality is calculated according to the following equation:

Mortality (%)=[image] 100

As a result of the test, mortality was 100% with each of the following compounds no. 1, 2, 4-12, 15, 17, 30-34, 36-39, 42, 43, 45, 47-49, 51, 53, 55-62, 74, 210, 202, 210-215, 221, 224, 225 and 303 and 90% with each of the following compounds 20, 65, 200 and 304.

Example of test 2

Insecticidal test against Plutella xylostella

Testing was performed in the same manner as in Example 1, except that the test insect was Plutella xylostella in the second or third stage of metamorphosis and mortality was determined in the same manner. Mortality was 100% with each of the compounds no. 1, 2, 4, 5, 7-12, 30, 32, 34, 38, 39, 41-45, 49, 60, 61, 201, 202, 210, 213 and 301.

Example of test 3

Insecticidal test against Cnaphalocrocis medinalis

Each formulation containing the active ingredient was dispersed in water to obtain a dispersion containing the active ingredient at a concentration of 800 ppm. Corn leaves are immersed in the dispersion for about 10 seconds and then air-dried. A sheet of moistened filter paper is placed in an ice cream container with a diameter of 8 cm and dry sheets are placed on the filter paper. 5 larvae of Cnaphalocrocis medinalis in the second or third stage of metamorphosis are released on the leaves and the container is covered and kept in a room with constant temperature and lighting at a temperature of 26ºC. On the fifth day, dead insects are counted and mortality is calculated in the same way as in test example 1.

Mortality was 100% with each of the compounds no. 9, 32-34, 38, 210 and 211.

Example of test 4

Insecticidal test against Adoxophyes sp.

Each formulation containing the active ingredient was dispersed in water to obtain a dispersion containing the active ingredient at a concentration of 800 ppm. A small piece of artificial food (brand: Insecta LF, product of Nippon Nosan Kogyo K.K.) is immersed in the dispersion for 60 seconds and then left to stand at room temperature for about 1 hour. A sheet of filter paper is placed in an ice cream container with a diameter of 8 cm and the treated artificial food is placed on the filter paper. Larvae Adoxophyes sp. in the second or third stage of metamorphosis, they are placed in a container. It is covered and kept in a room with constant temperature and lighting at a temperature of 26ºC. On the eighth or ninth day, the number of dead insects was counted and mortality was calculated in the same way as in test example 1.

Mortality was 100 with each of compound no. 9, 32, 38, 60 and 210.

Example of test 5

Insecticidal test against Aulacophora femoralis

Each formulation containing the active ingredient was dispersed in water to obtain a dispersion containing the active ingredient at a concentration of 800 ppm. Cucumber leaves are immersed in the dispersion for about 10 seconds and then air-dried. A sheet of moistened filter paper is placed in an ice cream container with a diameter of 8 cm and the dried leaves are placed on the filter paper. Five adult Aulacophora femoralis insects are placed on the leaves and the container is covered and kept in a room with constant temperature and sensibility at 26ºC. On the fifth day, dead insects are counted and mortality is calculated in the same way as in test example 1.

Mortality was 100% with compound no. 9.

Claims (15)

1. Hydrazone compound of formula I or its salt, characterized by: [image] wherein each R 1 , R 2 and R 4 is independently a hydrogen atom, a halogen atom, nitro, cyano, hydroxyl, trialkylsilyl, an alkyl group which may be substituted, a cycloalkyl group which may be substituted, an alkoxy group which may be substituted, an alkyl group which may be substituted, a carboxyl group which may be substituted, an aryl group which may be substituted or an aryloxy group which may be substituted, R3 is a hydrogen atom, a halogen atom, nitro, cyano, a hydroxyl group, an alkyl group which may be substituted, a cycloalkyl group which may be substituted, an alkoxy group which may be substituted, an alkylthio group which may be substituted, a carboxyl group which may be substituted, X1SO2NH-, X2CO2-, X3SO-, X4SO2-, X5SO3- or (X6Y1)2P(=Y2)Y3- and each R5 and R6 are independently a hydrogen atom, an alkyl group that can be substituted, X7CO-, X8OCO-, X9SO2-, a carbamoyl group that can be substituted, an alkenyl group that can be substituted, an alkynyl group that can b is substituted, or a heteroaryl group which may be substituted or R5 and R6 together form =CR7R8, where X1, X2, X3, X4, X5, X8 and X9 are each independently a substituted alkyl group, a substituted alkoxy group, an alkenyl group which may be substituted or an aryl group which may be substituted, X5 is an alkyl group which may be substituted, an alkenyl group which may be substituted or an aryl group which may be substituted, X7 is a hydrogen atom, an alkyl group which may be substituted, alkenyl a group which may be substituted or an aryl group which may be substituted, each Yl, Y2 and Y3 is independently an oxygen or sulfur atom and each R7 and R8 is independently a hydrogen atom, an alkyl group which may be substituted, a cycloalkyl group which may be substituted, alkoxy a group which may be substituted, an alkenyl group which may be substituted, a sryl group which may be substituted, an amino group which may be substituted or a cyclic amino group which can be substituted assuming the following cases 1) to 10) are included: 1) the case where R3 and R4 are simultaneously hydrogen atoms, 2) the case where at least one of R5 and R6 is an unsubstituted carbamoyl group, 3) the case where at least one of R1, R2, R3 and R4 is a nitro group, 4) the case where R2, R4 and R5 are hydrogen atoms, R6 is an ethoxycarbonyl group and at least one of R1 and R3 is a p-methoxy group, 5) the case where R1, R2, R4 and R5 are hydrogen atoms, R3 is a p-tert-butyl group and R6 is an ethoxycarbonyl group, 6) the case where R1, R2 and R4 are hydrogen atoms, and R6 is a hydrogen atom or an acetyl group, 7) the case where R1, R2, R4, R5 and R6 are hydrogen atoms and R3 is a p-chloro atom, 8) the case where R7 is an unsubstituted phenyl group and R8 is a benzyl group that can be substituted, 9) the case where R1, R2 and R3 are a methoxy group, R4 is a hydrogen atom, and R5 and R6 are methyl groups, and 10) the case where R5 is a hydrogen atom and R6 is a phenylsulfonyl group that can be substituted. 2. A hydrazone compound or its salt according to claim 1, characterized in that the substituent for each alkyl, alkoxy, alkylthio, alkenyl and alkynyl group that can be substituted is a halogen atom, an alkoxy group that can be substituted by a halogen, a phenyl group that can be substituted a halogen atom or an alkyl group which may be substituted by a halogen atom, a phenoxy group which may be substituted by a halogen atom or an alkyl group which may be substituted by a halogen atom, a cyano group, an alkyl amino group or an alkoxycarbonyl group; a carboxyl group that can be substituted is one where the hydrogen atom can be substituted by another substituent, such as an alkyl group that can be substituted by a halogen atom, an aryl group that can be substituted by a halogen atom, or an alkyl group that can be substituted by a halogen atom; the substituent for each heteroaryl group, aryloxy or cycloalkyl group which may be substituted is a halogen atom, an alkoxy group which may be substituted with a halogen atom, an alkyl group which may be substituted with a halogen atom, a phenyl group which may be substituted with a halogen atom or an alkyl group which may be substituted with a halogen atom, a phenoxy group which may be substituted with a halogen atom, or an alkyl group, a group which may be substituted with a halogen atom, a cyano group, an alkyl amino group, or an alkoxycarbonyl group, and the substituent for each carbamoyl, amino, and cyclic group which may be substituted is an alkoxy group which may be substituted by a halogen atom, an alkyl group which may be substituted by a halogen atom, a phenyl group which may be substituted by a halogen atom or an alkyl group which may be substituted by a halogen atom, a phenoxy group which may be substituted by a halogen atom or an alkyl group which may be substituted by halogen atom, a cyano, alkylamino or alkoxycarbonyl group. 3. A hydrazone compound and its salt according to claim 1, characterized in that each R1, R2 and R4 is independently a hydrogen atom, a halogen atom, an alkyl, alkoxy, alkylthio or a carboxyl group which can be substituted, R3 is a halogen atom or an alkyl , an alkoxy, alkylthio or carboxyl group which may be substituted or X5SO3- (wherein X5 is an alkyl group which may be substituted) and each R5 and R6 is independently a hydrogen atom, an alkyl group which may be substituted, X7CO- (where X7 is as is defined above), X8OCO- (wherein X8 is an alkyl, alkenyl or aryl group which may be substituted), a substituted carbamoyl group which may be substituted, an alkenyl group which may be substituted, an alkynyl group which may be substituted, a heteroaryl group which may be substituted, or R 5 and R 6 together form =CR 7 R 8 (wherein each R 7 and R 8 is independently a hydrogen atom, alkyl, cycloalkyl, alkoxy, alkenyl or amino group which may be substituted). 4. A hydrazone compound or its salt according to claim 1, characterized in that each R1, R2 and R4 is independently a hydrogen atom, a halogen atom, an alkyl or alkoxy group which can be substituted, R3 is a halogen atom, an alkyl or an alkoxy group which can be substituted and each R5 and R6 is independently a hydrogen atom, an alkyl group which may be substituted, X7CO- (where X7 is a hydrogen atom or an alkyl group which may be substituted, X8OCO- (where X8 is an alkyl group which may be substituted, a substituted carbamoyl group or R 5 and R 6 together form =CR 7 R 8 (where each R 7 and R 8 is independently a hydrogen atom, alkyl, cycloalkyl, alkoxy or amino group which may be substituted. 5. A hydrazoin compound or its salt according to claim 1, characterized in that each R1, R2 and R4 is independently a hydrogen atom, a halogen atom, an alkyl or alkoxy group which can be substituted by a halogen atom, R3 is a halogen atom, alkyl or alkoxy a group which may be substituted by a halogen atom, R5 is a hydrogen atom or an alkyl group, R6 is X7CO- (where X7 is a hydrogen atom or an alkyl group) or X8OCO- (where X8 is an alkyl group) or R5 and R6 together form =CR7R8 (where R7 is a hydrogen atom or an alkyl group and R8 is an amino group which can be substituted by an alkyl group or an alkoxy group). 6. The compound according to claim 1, characterized in that /4'-chloro-2-(4-trifluoromethylphenyl) acetophenone/ N'-/1-(dimethylamino)ethylidene/-hydrazone, /4'-fluoro-2-( 4-trifluoromethylphenyl)acetophenone/ N'-l-(dimethylamino)ethylidene/ hydrazone, ethyl 3-/l - (4-chlorophenyl) – 2 - (4-fluoromethylphenyl) ethylidene/carbazate, /4'-chloro – 2 - ( 4-tert-butylphenyl)acetophenone/ N'-/1-(dimethylamino)ethylidene/hydrazone or /4'-fluoro-2-(4-tert-butylphenyl)aceto-phenone/ N'-/1-(dimethylamino )ethylidene/hydrazone. 7. Procedure for obtaining the hydrazone compound of formula I or its salt: [image] where each R1, R2 and R4 is independently a halogen atom, nitro, cyano, hydroxyl or trialkylsilyl group, an alkyl, cycloalkyl, alkoxy, alkylthio, carboxyl, aryl or aryloxy group which may be substituted, R3 is a hydrogen atom, a halogen atom, nitro, cyano or hydroxyl group, alkyl, cycloalkyl, alkylthio or carboxyl group which may be substituted, X1SO2NH-, X2CO2-, X3SO-, X4SO2-, X5SO3- or (X6Y1)2P(=Y2)Y or each R5 and R6 is independently an atom hydrogen, an alkyl group which may be substituted, X7CO-, X8OCO-, X9SO2- or a carbamoyl, alkenyl, alkynyl or heteroaryl group which may be substituted, X6 is an alkyl, alkenyl or aryl group which may be substituted, X7 is a hydrogen atom, alkyl , an alkenyl or aryl group which may be substituted, each Y1, Y2 and Y3 is independently an oxygen or sulfur atom and each R7 and R8 is independently a hydrogen atom, alkyl, cycloalkyl, alkenyl, aryl, amino or cyclic amino group which may be substituted with assuming that the following cases 1) to 10) are included : 1) the case where R3 and R4 are simultaneously hydrogen atoms, 2) the case where at least one of R5 and R6 is an unsubstituted carbamoyl group, 3) the case where at least one of Rl, R4 and R5 are hydrogen atoms, R6 is an ethoxycarbonyl group and at least one of Rl and R3 is a p-methoxy group, 5) the case where R1, R2, R4 and R5 are hydrogen atoms, R3 is a p-tert-butyl group and R5 is an ethoxycarbonyl group, 6) the case where R1, R2 and R4 are hydrogen atoms, R3 is a p-fluoro atom, R5 is an isopropyl group and R6 is a hydrogen atom or an acetyl group, 7) the case where R1, R2, R4, R5 and R6 are hydrogen atoms and R3 is a p-chloro atom, 8) the case where R7 is an unsubstituted phenyl group and R8 is a benzyl group that can be substituted, 9) the case where R1, R2 and R3 are methoxy groups, R4 is a hydrogen atom and R5 and R6 are methyl groups and 10) the case where R5 is a hydrogen atom and R6 is a phenylsulfonyl group that can be substituted, indicated by the fact that it includes the reaction of the compound of formula II: [image] where R1, R2, R3 and R4 are as defined above, with a compound of formula III: [image] where R5 and R6 are as defined above. 8. Procedure for obtaining the hydrazone compound of formula (1-1) or its salt: [image] wherein each R1, R2 and R4 is independently a hydrogen atom, halogen atom, nitro, cyano, hydroxyl or trialkylsilyl group, alkyl, cycloalkyl, alkoxy, alkylthio, carboxyl, aryl or aryloxy group which may be substituted, R3 is hydrogen atom, halogen atom , nitro, cyano, hydroxyl group, alkyl, cycloalkyl, alkoxy, alkylthio or carboxyl group which may be substituted, XlSO2NH-, X2CO2-, X3SO-, X4SO2-, X5SO3- or (X6Yl)2P(=Y2)Y3- where each X1, X2, X3, X4 and X5 are independently an alkyl, alkoxy, alkenyl or aryl group which may be substituted, and Yl, Y2 and Y3 are each independently an oxygen or sulfur atom and each R7 and R8 are independently a hydrogen atom, alkyl, cycloalkyl , alkoxy, alkenyl, aryl, amino or a cyclic amino group which may be substituted provided that the following cases 1) to 3) are included: 1) the case where R3 and R4 are simultaneously hydrogen atoms, 2) the case where at least one of R1, R2, R3 and R4 is a nitro group, i 3) the case where R7 is an unsubstituted phenyl group and R8 is a benzyl group that can be substituted, indicated by the fact that it includes the reaction of the compound of formula 1-2: [image] where R1, R2, R3 and R4 are as defined above, with a compound of formula IV: [image] where R 7 and R 8 are as defined above, and J 1 is an alkyl group. 9. Procedure for obtaining the hydrazone compound of formula 1-3 or its salt: [image] where each of R1, R2 and R4 is independently a hydrogen atom, halogen atom, nitro, cyano, hydroxyl or trialkylsilyl group, alkyl, cycloalkyl, alkoxy, alkylthio, carboxyl, aryl or aryloxy group which may be substituted, R3 is hydrogen atom, halogen atom, nitro, cyano or hydroxyl group, alkyl, cycloalkyl, alkoxy, alkylthio or carboxyl group which may be substituted, XlSO2NH-, X2CO2-, X3SO-, X4SO2-, X5SO3- or (X6Y1)2P(=Y2)Y3- where each X 1 , X 2 , X 3 , X 4 and X 5 is independently an alkyl, alkoxy, alkenyl or aryl group which may be substituted, each Y 1 , Y 2 and Y 3 is independently an oxygen or sulfur atom and each R 9 and R 10 is independently a hydrogen atom, alkyl, cycloalkyl , an alkenyl or an aryl group which may be substituted provided that the following cases 1) to 3) are included: 1) the case where R3 and R4 are simultaneously hydrogen atoms, 2) the case where at least one of R1, R2, R3 and R4 is a nitro group, i 3) the case where R9 is an unsubstituted phenyl group and R10 is a benzyl group that can be substituted, indicated by the fact that it includes the reaction of the compound of formula 1-2: [image] where R1, R2, R3 and R4 are as defined above, with a compound of formula (V): [image] where R9 and R10 are as defined above. 10. Procedure for obtaining the hydrazone compound of formula 1-4 and its salt: [image] where each R1, R2 and R4 is independently a hydrogen atom, halogen atom, nitro, cyano, hydroxyl or trialkylsilyl group, alkyl, cycloalkyl, alkoxy, alkylthio, carboxyl, aryl or aryloxy group which may be substituted, R3 is hydrogen atom, halogen atom , a nitro, cyano or hydroxyl group which may be substituted, XlSO2NH-, X2CO2-, X3SO-, X4SO2-, X5SO3- or (X6Y1)2P(=Y2)Y3-, where each Xl, X2, X3, X4 and X5 independently is an alkyl, alkoxy, alkenyl or aryl group which may be substituted, X6 is an alkyl, alkenyl or aryl group which may be substituted and each Yl, Y2 and Y3 is independently an oxygen or sulfur atom, R7 is a hydrogen atom, alkyl, cycloalkyl, alkoxy . substituted with a halogen atom, cyano, alkylamino and or the alkoxycarbonyl group, or J2 and J3 form together with the nitrogen atom to which it is attached a cyclic amino group which can be substituted assuming that the following cases 1) to 2) are included: 1) the case where R3 and R4 are simultaneously hydrogen atoms, i 2) the case where at least one of R1, R2, R3 and R4 is a nitro group, indicated by the fact that it includes the reaction of the compound of formula VI: [image] where R 1 , R 2 , R 3 , R 4 and R 7 are as defined above, or of a compound of formula VIII: [image] where R 1 , R 2 , R 3 , R 4 and R 7 are as defined above with a compound of formula VII: [image] where J2 and J3 are as defined above. 11. Compound of formula II-5, indicated by [image] where each R 12 , R 13 , R 14 and R 15 is independently a hydrogen atom or an alkyl group which may be substituted by a halogen atom, provided that the following cases 1) to 4) are included: 1) the case where each R12, R13, R14 and R15 is independently a hydrogen atom or a halogen atom, 2) the case where R12 or R13 is a p-trifluoromethyl group and R14 or R15 is a p-trifluoromethyl group, 3) the case where R12 and R13 is a halogen atom and R14 or R15 is a methyl, ethyl or propyl group, and 4) the case where R12 or R13 is a methyl, ethyl or propyl group and R14 or R15 is a halogen atom. 12. Pesticidal preparation, characterized by the fact that it comprises a pesticidally effective amount of the hydrazone compound of formula IX or its salt: [image] where each R1, R2 and R4 is independently a hydrogen atom, halogen atom, nitro, cyano, hydroxyl or trialkylsilyl group, alkyl, cycloalkyl, alkoxy, alkylthio, carboxyl, aryl or aryloxy group which may be substituted, R3 is hydrogen atom, halogen atom , a nitro, cyano or hydroxyl group which may be substituted, XlSO2NH-, X2CO2-, X3SO-, X4SO2-, X5SO3- or (X6Y1)2P(=Y2)Y3- and each R5 and R6 is independently a hydrogen atom, an alkyl group which may be substituted, X7CO-, X8OCO-, X9SO2-, carbamoyl, alkenyl, alkynyl or a heteroaryl group which may be substituted, or R5 and R6 form =CR7R8, where each X1, X2, X3, X4, X5, X8 and X9 independently is an alkyl, alkoxy, alkenyl or aryl group which may be substituted, X6 is an alkyl, alkenyl or aryl group which may be substituted, X7 is a hydrogen atom, an alkyl, alkenyl or aryl group which may be substituted, each Yl, Y2 and Y3 independently is an oxygen or sulfur atom and each R7 and R8 is independently a hydrogen atom, alkyl, cycloalkyl, alkoxy, alkenyl, aryl, amino or a cyclic amino group which may be substituted, assuming that the case where R 3 and R 4 are hydrogen atoms and an agricultural adjuvant is included. 13. Pesticide preparation according to claim 12, characterized in that the compound of formula IX is a compound according to claim 3. 14. Pesticidal method, characterized by the fact that it includes the application to pests of an effective amount of the hydrazone compound of formula IX or its salt: [image] where each R1, R2 and R4 is independently a hydrogen atom, halogen atom, nitro, cyano, hydroxyl or trialkylsilyl group, alkyl, cycloalkyl, alkoxy, alkylthio, carboxyl, aryl and aryloxy group which may be substituted, R3 is hydrogen atom, halogen atom , a nitro, cyano or hydroxyl group, an alkyl, cycloalkyl, alkoxy, alkylthio or carboxyl group which may be substituted, X1SO2NH-, X2CO2-, X3SO-, X4SO2-, X5SO3- or (X6Y1)2P(=Y2)Y3- and each R5 and R6 are independently a hydrogen atom, an alkyl group which may be substituted, X7CO-, X8OCO-, X9SO2-, a carbamoyl, alkenyl, alkynyl or heteroaryl group which may be substituted, or R5 and R6 together form a =CR7R8 group, where each X1, X 2 , X 3 , X 4 , X 5 , X 8 and X 9 are independently an alkyl, alkoxy, alkenyl or aryl group which may be substituted, X 6 is an alkyl, alkoxy, alkenyl or aryl group which may be substituted, X 7 is a hydrogen atom, alkyl, alkenyl or an aryl group which may be substituted, each Yl, Y2 and Y3 is independently an oxygen or sulfur atom and each R 7 and R 8 are independently a hydrogen atom, alkyl, cycloalkyl, alkoxy, alkenyl, arylamino or a cyclic amino group which may be substituted for the assumption that the case when R 3 and R 4 are simultaneously hydrogen atoms is included. 15. Pesticide method according to claim 14, characterized in that the compound of formula IX is the compound of claim 3.