Hydrazinecarboxyamide derivatives, a process for production thereof and uses thereof

Abstract

The present invention relates to a hydrazinecarboxamide derivative of the general formula (I) shown below: ##STR1## wherein the substituents are as defined in the specification, which has a wide insecticidal spectrum at a low dosage, a process for producing said derivative, and utilization of said derivative as an insecticide.

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to hydrazinecarboxamide derivatives, in particular, compounds having a wide insecticidal spectrum.

2. Related Art

Jap. Pat. Appln. Kokai (Laid-Open) No. 48-91223 discloses that semicarbazides are effective as insecticides. Jap. Pat. Appln. Kokai (Laid-Open) No. 54-119029 discloses that thiosemicarbazones are useful as agricultural and horticultural disease-controlling agents. Jap. Pat. Appln. Kokai (Laid-open) No. 63-93761 discloses that substituted hydrazones are effective as pest-controlling agents.

However, a compound having a wide insecticidal spectrum has not yet been disclosed.

SUMMARY OF THE INVENTION

The present inventors earnestly investigated in order to develop a novel insecticide and consequently found that a hydrazinecarboxamide derivative represented by the general formula (I) shown below has an excellent insecticidal effect at a low dosage, whereby the present invention was accomplished.

That is, the present invention relates to a hydrazinecarboxamide derivative represented by the general formula (I): ##STR2## wherein R.sup.1 is a hydrogen atom or a lower alkyl group, R.sup.2 is a hydrogen atom or a lower alkyl group, R.sup.3 is a hydrogen atom; a hydroxyl group; a lower alkyl group; a lower alkoxy group; a lower alkylcarbonyloxy group; an unsubstituted phenylcarbonyloxy group; or a substituted phenylcarbonyloxy group having on the phenyl ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, lower alkyl groups and lower haloalkyl groups, R.sup.4 is a hydrogen atom or a lower alkyl group, R.sup.3 and R.sup.4 being able to be taken together to represent an oxygen atom, A is ##STR3## (wherein X represents 1 to 5 atoms or groups which may be the same or different and are selected from the group consisting of hydrogen atom; hydroxyl group; halogen atoms; cyano group; lower alkyl groups; lower haloalkyl groups; lower alkoxy groups; lower haloalkoxy groups; lower alkoxyalkyl groups; lower alkenyloxy groups; cycloalkylcarbonyloxy groups; lower alkoxycarbonyloxy groups; lower alkoxycarbonylalkyloxy groups; lower alkylcarbonylalkyloxy groups; lower alkylsulfonyloxy groups; phenoxy group; methylenedioxy group; alkenylene groups having 3 to 4 carbon atoms so as to form a polycyclic ring together with the adjacent carbon atom of the phenyl ring; unsubstituted amino group; substituted amino groups having as the substituent(s) 1 or 2 lower alkyl groups which may be the same or different; substituted aminocarbonyloxy groups having as the substituent(s) 1 or 2 lower alkyl groups which may be the same or different; and dioxolane group, and R.sup.5 is a hydrogen atom; a lower alkylcarbonyl group; a lower haloalkylcarbonyl group; a cycloalkylcarbonyl group; a lower alkoxycarbonyl group; a lower alkoxydicarbonyl group; an unsubstituted phenylcarbonyl group; substituted phenylcarbonyl groups having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, lower alkyl groups, lower haloalkyl groups, lower alkoxy groups and lower haloalkoxy groups; or a substituted aminocarbonyl group having 1 or 2 substituents which may be the same or different and are selected from the group consisting of hydrogen atom, lower alkyl groups, unsubstituted phenyl group, and substituted phenyl groups having 1 to 5 substituents which may be the same or different and are selected from halogen atoms, lower alkyl groups, lower haloalkyl groups, lower alkoxy groups and lower haloalkoxy groups), Y represents 1 to 5 atoms or groups which may be the same or different and are selected from the group consisting of hydrogen atom; hydroxyl group; halogen atoms; cyano group; nitro group; alkyl groups; lower haloalkyl groups; lower alkoxy groups; lower haloakoxy groups; lower alkenyloxy groups; lower alkylcarbonyloxy groups; lower alkylsulfonyloxy groups; lower haloalkylsulfonyloxy groups; lower alkylthio groups; lower haloalkylthio groups; lower alkylsulfinyl groups; lower haloalkylsulfinyl groups; lower alkylsulfonyl groups; lower haloalkylsulfonyl groups; lower alkoxycarbonyl groups; unsubstituted amino group; substituted amino groups having 1 or 2 substituents selected from the group consisting of formyl group, lower alkylcarbonyl groups, lower alkylsulfonyl groups, and substituted aminocarbonyl groups having as the substituent(s) one or more lower alkyl groups which may be the same or different; unsubstituted aminocarbonyl group; substituted aminocarbonyl groups having as the substituent(s) 1 or 2 lower alkyl groups which may be the same or different; substituted aminosulfonyl groups having as the substituent(s) 1 or 2 lower alkyl groups which may be the same or different; phenyl group; or azaalkenylene groups having 2 to 3 carbon atoms so as to form a polycyclic ring together with the adjacent carbon atom of the phenyl ring, Z represents 1 to 5 atoms or groups which may be the same or different and are selected from the group consisting of hydrogen atom; halogen atoms; cyano group; nitro group; alkyl groups; lower haloalkyl groups; unsubstituted cycloalkyl groups; substituted cycloalkyl groups having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms and lower alkyl groups; lower alkoxy groups; lower haloalkoxy groups; lower alkylthio groups; lower haloalkylthio groups; lower alkylsulfinyl groups; lower haloalkylsulfinyl groups; lower alkylsulfonyl groups; lower haloalkylsulfonyl groups; lower alkylcarbonyl groups; lower alkoxycarbonyl groups; lower alkylcarbonyloxy groups; lower alkylsulfonyloxy groups; lower haloalkylsulfonyloxy groups; unsubstituted phenoxy group; substituted phenoxy groups having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, lower alkyl groups, lower haloalkyl groups, lower alkoxy groups and lower haloalkoxy groups; unsubstituted pyridyloxy group; substituted pyridyloxy groups having as the substituent(s) 1 to 4 atoms or groups which may be the same or different and are selected from the group consisting of halogen atoms, lower alkyl groups, lower haloalkyl groups, lower alkoxy groups and lower haloalkoxy groups, and W is an oxygen atom or a sulfur atom. The present invention further relates to a process for producing said derivative, and an agricultural and horticultural insecticide containing said derivative as an active ingredient.

In the definition of the substituents of the hydrazinecarboxamide derivative of the general formula (I), the term "lower" is used for expressing a number of carbon atoms of 1 to 6, and the prefix "halo" is used for expressing that a group has as its substituent(s) one or more halogen atoms which may be the same or different and are selected from the group consisting of chlorine atom, fluorine atom, bromine atom and iodine atom.

Of the hydrazinecarboxamide derivatives of the general formula (I) of the present invention, a hydrazinecarboxamide derivative of the genera formula (1') shown hereinafter has geometrical isomers, i.e., E-form and Z-form. The present invention also includes the E-form, the Z-form and mixtures comprising the E-form and Z-form in an arbitrary ratio. Each of hydrazinecarboxamide derivatives of the general formulas (I") and (I"') shown hereinafter have stereoisomers, i.e., R-form and S-form. The present invention also includes the R-form, the S-form and mixtures comprising the R-form and the S-form in an arbitrary ratio.

All of the hydrazinecarboxamide derivatives of the general formulas (I'), (I") and (I"') are included in the hydrazinecarboxamide derivatives of the general formula (I).

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

Preferable examples of the substituents of the hydrazinecarboxamide derivative of the above general formula (I) of the present invention are as follows. R.sup.1, R.sup.2, R.sup.3 and R.sup.4, which may be the same or different are preferably hydrogen atoms; hydroxyl groups; or lower alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, etc. Preferable examples of substituent(s) for X are a hydrogen atom; halogen atoms such as chlorine, fluorine, bromine, iodine, etc.; a cyano group; lower alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, etc.; lower haloalkyl groups such as dichloromethyl, difluoromethyl, trichloromethyl, trifluoromethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, etc.; lower alkoxy groups such as methoxy, ethoxy, propoxy, etc.; and lower haloalkoxy groups such as difluoromethoxy, trifluoromethoxy, difluoroethoxy, trifluoroethoxy, etc. As to the position(s) of the substituent(s) for X, at least one substituent is preferably at the 3-position.

Preferable examples of substituent(s) for Y are a hydrogen atom; halogen atoms such as chlorine, fluorine, bromine, iodine, etc.; a cyano group; a nitro group; alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, pentyl, heptyl, etc.; lower haloalkyl groups such as dichloromethyl, difluoromethyl, trichloromethyl, trifluoromethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, etc.; lower alkoxy groups such as methoxy, ethoxy, propoxy, etc.; lower haloalkoxy groups such as difluoromethoxy, trifluoromethoxy, difluoroethoxy, trifluoroethoxy, etc.; lower alkylsulfonyloxy groups such as methyl sulfonyloxy, etc.; lower haloalkylsulfonyloxy groups such as trifluoromethyl sulfonyloxy, etc.; and lower alkoxycarbonyl groups such as methoxycarbonyl, etc. As to the position(s) of the substituent(s) for Y, at least one substituent is preferably at the 4-position. A particularly preferable example of the substituent(s) for Y is a cyano group.

Preferable examples of substituent(s) for Z are a hydrogen atom; halogen atoms such as chlorine, fluorine, bromine, iodine, etc.; a cyano group; alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, pentyl, heptyl, etc.; lower haloalkyl groups such as dichloromethyl, difluoromethyl, trichloromethyl, trifluoromethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, etc.; lower alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, etc.; lower haloalkoxy groups such as dichloromethoxy, difluoromethoxy, trichloromethoxy, trifluoromethoxy, difluoroethoxy, trifluoroethoxy, tetrafluoroethoxy, etc.; lower alkylthio groups such as methylthio, ethylthio, etc.; lower haloalkylthio groups such as difluoromethylthio, trifluoromethylthio, trifluoroethylthio, tetrafluoroethylthio, etc., lower alkylsulfinyl groups such as methylsulfinyl, ethylsulfinyl, etc.; lower haloalkylsulfinyl groups such as difluoromethylsulfinyl, trifluoromethylsulfinyl, trifluoroethylsulfinyl, tetrafluoroethylsulfinyl, etc.; lower alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, etc.; and lower haloalkylsulfonyl groups such as difluoromethylsulfonyl, trifluoromethylsulfonyl, trifluoroethylsulfonyl, tetrafluoroethylsulfonyl, etc. As to the position(s) of the substituent(s) for Z, at least one substituent is preferably at the 4-position.

R.sup.5 is preferably a hydrogen atom; a lower alkylcarbonyl group such as methylcarbonyl, ethylcarbonyl or the like; a lower haloalkylcarbonyl group such as difluoromethylcarbonyl, trifluoromethylcarbonyl, tetrafluoroethylcarbonyl, or the like; or a lower alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, or the like. W is preferably an oxygen atom. However, the substituents of the hydrazinecarboxamide derivative of the general formula (I) of the present invention are not limited to the above-exemplified atoms and groups.

As to typical processes for producing the hydrazinecarboxamide derivative of the general formula (I) of the present invention, said derivative can be produced, for example, by the production processes illustrated below. ##STR4## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, X, Y, Z and W have the same meanings as those defined above.

A hydrazinecarboxamide derivative of the general formula (I') can be produced by reacting a compound of the general formula (VIII) with a compound of the general formula (VI) in the presence of an inert solvent and in the presence or absence of a catalyst.

Reaction A-1.

General formula (VIII).fwdarw.general formula (I')

As the inert solvent used in this reaction, any inert solvent may be used so long as it does not markedly inhibit the progress of the reaction. There can be exemplified alcohols such as methanol, ethanol, propanol, butanol, etc.; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, etc.; nitriles such as acetonitrile, benzonitrile, etc.; ethers such as Methyl Cellosolve, diethyl ether, diglyme, dioxane, tetrahydrofuran, etc.; carboxylic acids such as acetic acid, etc.; dimethylacetamide; dimethyl sulfoxide; and water.

These inert solvents may be used singly or as a mixture thereof.

As the catalyst used in the reaction, there can be used, for example, inorganic acids such as hydrochloric acids, sulfuric acid and the like, or organic acids such as p-toluenesulfonic acid and the like.

As to the amount of the catalyst used, it is sufficient that the catalyst is present in the reaction system in an amount of 0.001 to 10% by weight based on the weight of the compound of the general formula (VIII).

Although the reactants are used in equimolar amount because the reaction is an equimolar reaction, either of them may be used in excess.

The reaction temperature may be properly chosen in the range of room temperature to the boiling range of the inert solvent used. The reaction is carried out preferably at 70.degree. to 80.degree. C.

Although the reaction time is varied depending on the degree of reaction, the reaction temperature, and the like, it may be chosen in the range of several minutes to 48 hours.

After completion of the reaction, the desired compound is isolated from a reaction solution containing the desired compound by a conventional method such as distilling-off of the solvent, solvent extraction, etc., and if necessary, purified by recrystallization, column chromatography, etc., whereby the desired compound can be produced. ##STR5## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, X, Y, Z and W have the same meanings as those defined above, except that R.sup.1 is not a lower alkyl group.

A hydrazinecarboxamide derivative of the general formula (I') can be produced by reacting a compound of the general formula (VIII) with a hydrazine derivative of the general formula (VII) in the presence of an inert solvent and in the presence or absence of a catalyst to obtain a compound of the general formula (V), and reacting the compound (V) with a compound of the general formula (IV) in the presence of an inert solvent and in the presence or absence of a catalyst after or without isolating the compound (V).

Reaction B-1.

General formula (VIII).fwdarw.general formula (V)

As the inert solvent used in this reaction, there can be used the inert solvents exemplified for reaction A-1.

The kind and amount of the catalyst used in this reaction may be the same as in reaction A-1.

The hydrazine derivative of the general formula (VII) used in this reaction may be used in the form of either any of various salts or an aqueous solution having a suitable concentration.

As to the amount of the hydrazine derivative of the general formula (VII) used, the hydrazine derivative can be used in an amount equimolar with or larger than the amount of the compound of the general formula (VIII). Preferably, the amount is properly chosen in the range of 2 to 10 moles per mole of the compound of the general formula (VIII).

The reaction temperature may be properly chosen in the range of room temperature to the boiling range of the inert solvent used. The reaction is carried out preferably at 70.degree. to 80.degree. C.

Although the reaction time is varied depending on the degree of reaction, the reaction temperature and the like, it may be chosen in the range of several minutes to 48 hours.

After completion of the reaction, the desired compound is isolated from a reaction solution containing the desired compound by a conventional method such as distilling-off of the solvent, solvent extraction, etc., and if necessary, purified by recrystallization, column chromatography, etc., whereby the desired compound can be produced.

The compound of the general formula (V) obtained by the reaction may be subjected to the subsequent reaction either after isolation and purification by the above method, or without isolation.

Typical examples of the compound of the general formula (V) obtained by the present production process are listed in Table 1. ##STR6##

TABLE 1______________________________________ PhysicalNo. R.sup.2 R.sup.3 R.sup.4 X Y properties______________________________________V-1 H H H H H mp. 55.degree. C.V-2 H H H H 4-F pasteV-3 H H H H 4-CN mp. 91.degree. C.V-4 H H H H 4-NO.sub.2 mp. 72.degree. C.V-5 H H H 4-F 4-F pasteV-6 H OH H H H pasteV-7 CH.sub.3 H H H H pasteV-8 CH.sub.3 H H 3-Cl 4-CN pasteV-9 H OH H H 4-Cl pasteV-10 H OH H 4-N(CH.sub.3).sub.2 H pasteV-11 H OH H 3-Cl 3-Cl pasteV-12 H OH H 4-CH.sub.3 4-CH.sub.3 pasteV-13 H CH.sub.3 H H H pasteV-14 H OCH.sub.3 H H H pasteV-15 H H H 3-Cl 4-CN pasteV-16 H H H 3-F 4-CN pasteV-17 H H H 3-Br 4-CN pasteV-18 H H H 3-CF.sub.3 4-CN paste______________________________________

Table 2 shows .sup.1 -NMR data of the compounds having physical properties as paste listed in Table 1.

TABLE 2______________________________________No. .sup.1 H-NMR(CDCl.sub.3 /TMS, .delta. value, ppm.)______________________________________V-2 3.74+3.95(s, 2H), 5.13+5.33(bs, 2H), 6.37-7.76(m, 9H). (Mixture of E- and Z-forms)V-5 3.72+3.98(s, 2H), 5.10+5.37(bs, 2H), 6.85-7.69(m, 8H). (Mixture of E- and Z-forms)V-6 4.73(bs, 1H), 5.18(bs, 2H), 5.31(s, 1H), 6.71-7.58(m, 10H).V-7 2.98(s, 3H), 3.95(s, 2H), 5.00(bs, 1H), 6.90-7.81(m, 10H).V-8 3.06(s, 3H), 4.00(s, 2H), 5.08(bs, 1H), 7.22-7.69(m, 8H).V-9 4.91(bs, 1H), 5.29(bs, 2H), 5.37(bs, 1H), 6.85-7.45(m, 9H).V-10 2.96(s, 6H), 4.96(bs, 1H), 5.31(bs, 2H), 5.39(bs, 1H), 6.60-7.25(m, 9H).V-11 4.73(bs, 1H), 5.32(bs, 2H), 6.18(bs, 1H), 6.81-7.12(m, 8H).V-12 2.27(s, 3H), 2.31(s, 3H), 4.81(bs, 1H), 5.25(bs, 2H), 5.86(bs, 1H), 6.86-7.52(m, 8H).V-13 1.50(d, 3H), 3.95(q, 1H), 4.98(bs, 2H), 6.77-7.52(m, 10H).V-15 3.82+4.06(s, 2H), 5.23+5.51(bs, 2H), 6.96-7.85(m, 8H). (Mixture of E- and Z-forms)V-16 3.81+4.03(s, 2H), 5.26+5.55(bs, 2H), 6.81-7.62(m, 8H), (Mixture of E- and Z-forms)V-17 3.81+4.04(s, 2H), 5.22+5.51(bs, 2H), 7.00-7.85(m, 8H). (Mixture of E- and Z-forms)V-18 3.84+4.10(s, 2H), 5.21+5.58(bs, 2H), 7.24+7.96(m, 8H). (Mixture of E- and Z-forms)______________________________________

Reaction B-2.

General formula (V).fwdarw.general formula (I')

As the inert solvent used in this reaction, there can be used, for example, the inert solvents usable in reaction A-1 except for the alcohols, the carboxylic acids and water. There can also be used esters such as ethyl acetate and the like and pyridines.

As the catalyst used in this reaction, there can be used, for example, amines such as triethylamine and the like. The amount of the catalyst used may be properly chosen in the range of catalytic amount to a number of moles larger than that of the compound of the general formula (V).

Although the reactants are used in equimolar amount because the reaction is an equimolar reaction, either of them may be used in excess.

The reaction temperature may be properly chosen in the range of -20.degree. C. to the boiling range of the inert solvent used, and is preferably in the range of -10.degree. C. to room temperature.

Although the reaction time is varied depending on the degree of reaction, the reaction temperature and the like, it may be chosen in the range of several minutes to 48 hours.

After completion of the reaction, the same treatment as in the case of reaction B-1 is carried out, whereby the desired compound can be produced. ##STR7## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, X, Y, Z and W have the same meanings as those defined above.

A hydrazinecarboxamide derivative of the general formula (I") can be produced by reducing a hydrazinecarboxamide derivative of the general formula (I') with a reducing agent or by catalytic hydrogenation in the presence or absence of an inert solvent.

Reaction C-1.

General formula (I').fwdarw.general formula (I")

This reduction reaction can be carried out by the use of a suitable reducing agent, or it can be carried out as catalytic hydrogenation in the presence of a suitable catalyst.

As the reducing agent, there can be used, for example, metal hydrides such as LiAlH.sub.4, NaBH.sub.3 CN, LiBH.sub.3 CN, etc. and reducing agents such as NaHSO.sub.3 and the like. The amount of the reducing agent used may be chosen so that its number of moles in terms of the number of moles of hydride as reducing agent may be equal to or larger than that of the hydrazinecarboxamide derivative of the general formula (I').

As the inert solvent used in the reaction, any inert solvent may be used so long as it does not markedly inhibit the progress of the reaction. There can be exemplified alcohols such as methanol, ethanol, propanol, butanol, etc.; ethers such as diethyl ether, diglyme, dioxane, tetrahydrofuran, etc., Cellosolves such as Methyl Cellosolve, etc.; dimethylformamide; dimethylacetamide; dimethyl sulfoxide; sulfolane; and water.

These inert solvents may be used singly or as a mixture thereof.

The reaction is carried out under acidic or neutral conditions in the pH range of 1 to 7. The pH is preferably in the range of 4 to 6 and is adjusted by adding hydrogen chloride, hydrogen bromide or the like to the reaction system.

The reaction temperature may be properly chosen in the range of -20.degree. C. to the boiling range of the inert solvent used.

Although the reaction time is varied depending of the scale of reaction, the reaction temperature and the like, it is several minutes to 48 hours.

After completion of the reaction, the desired compound is isolated from a reaction solution containing the desired product by a conventional method such as distilling-off of the solvent, solvent extraction, etc., and if necessary, purified by recrystallization, column chromatography, etc., whereby the desired compound can be produced.

When catalytic hydrogenation is carried out as the reduction reaction, it is carried out according to, for example, the conventional method described in Shin Jikken Kagaku Koza, Vol. 15-11, Maruzen Co., Ltd., etc. As the solvent usable in this case, there can be exemplified alcohols such as methanol, ethanol, propanol, butanol, etc.; Cellosolves such as Methyl Cellosolve, etc.; ethers such as diethyl ether, diglyme, dioxane, tetrahydrofuran, etc.; hydrocarbons such as hexane, cyclohexane, etc.; fatty acids or esters thereof, such as acetic acid, ethyl acetate, etc.; amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.; and ureas such as dimethylimidazoline, tetramethylurea, etc.

These inert solvents may be used singly or as a mixture thereof.

As the catalyst used in the reaction, there can be used typical catalysts for catalytic hydrogenation, for example, palladium-carbon, palladium black, platinum dioxide and Raney nickel. The amount of the catalyst used may be properly chosen in the range of 0.0001 to 20% by weight based on the weight of the hydrazinecarboxamide derivative of the general formula (I').

The hydrogen pressure in the reaction can be chosen in the range of atmospheric pressure to 300 atmospheres and is preferably in the range of atmospheric pressure to 50 atmospheres.

The reaction temperature may be properly chosen in the range of room temperature to the boiling range of the inert solvent used and is preferably in the range of room temperature to 80.degree. C.

Although the reaction time is varied depending on the scale of reaction, the reaction temperature and the like, it is several minutes to 80 hours.

After completion of the reaction, a reaction solution containing the desired compound is treated in the same manner as in the case of using the reducing agent, whereby the desired compound can be produced. ##STR8## wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, X, Y and Z have the same meanings as those defined above R.sup.5', is a lower alkylcarbonyl group, a lower haloalkylcarbonyl group, a cycloalkylcarbonyl group, a lower alkoxycarbonyl group, a lower alkoxydicarbonyl group, an unsubstituted phenylcarbonyl group, or a substituted phenylcarbonyl group having 1 to 5 substituents which may be the same or different and are selected from the group consisting of a halogen atoms, lower alkyl groups, lower haloalkyl groups, lower alkoxy groups and lower haloalkoxy groups, R.sup.5" is a lower alkyl group, an unsubstituted phenyl group, or a substituted phenyl group having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, lower alkyl groups, lower haloalkyl groups, lower alkoxy groups and lower haloalkoxy groups and Hal is a halogen atom.

A hydrazinecarboxamide derivative of the general formula (I"') can be produced by reacting a hydrazinecarboxamide derivative of the general formula (I") with a halide of the general formula (III) or an isocyanate of the general formula (II) in the presence of an inert solvent and a base.

Reaction D-1.

General formula (I").fwdarw.general formula (I"')

As the inert solvent used in this reaction, any inert solvent may be used so long as it does not markedly inhibit the progress of the reaction. There can be exemplified halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, etc.; esters such as ethyl acetate, etc.; nitriles such as acetonitrile, benzonitrile, etc.; ethers such as Methyl Cellosolve, diethyl ether, diglyme, dioxane, tetrahydrofuran, etc.; sulfolane; and dimethylsulfoxide. The inert solvents may be used singly or as a mixture thereof.

As the base used in the reaction, inorganic based or organic bases can be used. As the inorganic bases, there can be exemplified hydroxides, carbonates and alcoholates of alkali metals or alkaline earth metals, for example, sodium, potassium, magnesium and calcium. As the organic bases, triethylamine and pyridine can be exemplified.

Although the reactants are used in equimolar amount because the reaction is an equimolar reaction, either of them may be used in excess.

The reaction temperature may be chosen in the range of 0.degree. C. to the boiling range of the inert solvent used.

Although the reaction time is varied depending on the scale of reaction, the reaction temperature and the like, it may be chosen in the range of several minutes to 48 hours.

After completion of the reaction, the desired compound is isolated from a reaction solution containing the desired compound by a conventional method and if necessary, purified by recrystallization, column chromatography, etc., whereby the desired compound can be produced.

Typical examples of the hydrazinecarboxamide derivative of the general formula (I) of the present invention are given below but they are not intended in any way to limit the scope of the present invention. ##STR9##

TABLE 3 - Physical No. R.sup.1 R.sup.2 R.sup.3 R.sup.4 X Y Z W properties A001 H H H H H H H O m.p. 181.degree. C. A002 H H H H H H 2-Cl O m.p. 197.degree. C. A003 H H H H H H 3-Cl O m.p. 188.degree. C. A004 H H H H H H 4-Cl O m.p. 199.degree. C. A005 H H H H H H 4-OCH.sub.3 O m.p. 144.degree. C. A006 H H H H H H 4-OCHF.sub.2 O m.p. 172.degree. C. A007 H H H H H H 4-OCF.sub.3 O m.p. 149.degree. C. A008 H H H H H 4-OH 4-Cl O m.p. 206.degree. C. A009 H H H H H 4-OH 4-CF.sub.3 O m.p. 211.degree. C. A010 H H H H H 4-OH 4-OCF.sub.3 O m.p. 192.degree. C. A011 H H H H H 2-Cl 4-Cl O m.p. 224.degree. C. A012 H H H H H 2-Cl 4-CF.sub.3 O m.p. 227.degree. C. A013 H H H H H 2-Cl 4-OCF.sub.3 O m.p. 204.degree. C. A014 H H H H H 3-Cl 4-Cl O m.p. 203.degree. C. A015 H H H H H 3-Cl 4-CF.sub.3 O m.p. 209.degree. C. A016 H H H H H 3-Cl 4-OCF.sub.3 O m.p. 191.degree. C. A017 H H H H H 4-Cl 4-Cl O m.p. 206.degree. C. A018 H H H H H 4-Cl 4-CF.sub.3 O m.p. 193.degree. C. A019 H H H H H 4-Cl 4-OC.sub.4 H.sub.7 -t O m.p. 186.degree. C. A020 H H H H H 4-Cl 4-OCF.sub.3 O m.p. 197.degree. C. A021 H H H H H 4-Cl 4-OCF.sub.2 CHF.sub.2 O m.p. 217.degree. C. A022 H H H H H 4-Cl O m.p. 209.degree. C. A023 H H H H H 2,4-Cl.sub.2 4-Cl O m.p. 202.degree. C. A024 H H H H H 2,4-Cl.sub.2 4-CF.sub.3 O m.p. 219.degree. C. A025 H H H H H 2,4-Cl.sub.2 4-OCF.sub.3 O m.p. 201.degree . C. A026 H H H H H 4-Br 4-Cl O m.p. 222.degree. C. A027 H H H H H 4-Br 4-CF.sub.3 O m.p. 202.degree. C. A028 H H H H H 4-Br 4-OCF.sub.3 O m.p. 208.degree. C. A029 H H H H H 4-F 4-Cl O m.p. 213.degre e. C. A030 H H H H H 4-F 4-CF.sub.3 O m.p. 205.degree. C. A031 H H H H H 4-F 4-OCF.sub.3 O m.p. 187.degre e. C. A032 H H H H H 3-CN 4-Cl O m.p. 192.degree. C. A033 H H H H H 3-CN 4-CF.sub.3 O m.p. 181.degree. C. A034 H H H H H 3-CN 4-OCF.sub.3 O m.p. 195.degree. C. A035 H H H H H 4-CN H O m.p. 209.degree. C. A036 H H H H H 4-CN 2-Cl O m.p. 116.degree. C. A037 H H H H H 4-CN 3-Cl O m.p. 180.degree. C. A038 H H H H H 4-CN 4-Cl O m.p. 217.degree. C. A039 H H H H H 4-CN 4-Cl S m.p. 128.degree. C. A040 H H H H H 4-CN 3,4-Cl.sub.2 O m.p. 230.degree. C. A041 H H H H H 4-CN 3,5-Cl.sub.2 O m.p. 205.degree. C. A042 H H H H H 4-CN 4-Br O m.p. 208.degree. C. A043 H H H H H 4-CN 3-F O m.p. 200.degree. C. A044 H H H H H 4-CN 4-F O m.p. 207.degree. C. A045 H H H H H 4-CN 4-CN S m.p. 195.degree . C. A046 H H H H H 4-CN 4-NO.sub.2 O m.p. 231.degree. C. A047 H H H H H 4-CN 4-CH.sub.3 O m.p. 215.degree . C. A048 H H H H H 4-CN 4-C.sub.4 H.sub.7 -t O m.p. 213.degree. C. A049 H H H H H 4-CN 3-CF.sub.3 O m.p. 193.degree. C. A050 H H H H H 4-CN 4-CF.sub.3 O m.p. 217.degree. C. A051 H H H H H 4-CN 4-OCF.sub.3 S m.p. 116.degree. C. A052 H H H H H 4-CN 4-OCH.sub.3 O m.p. 204.degree. C. A053 H H H H H 4-CN 4-OC.sub.4 H.sub.7 -t O m.p. 204.degree. C. A054 H H H H H 4-CN 4-OCHF.sub.2 O m.p. 197.degree. C. A055 H H H H H 4-CN 4-OCHF.sub.2 S Paste A056 H H H H H 4-CN 4-OCF.sub.3 O m.p. 214.degree. C. E-form A057 H H H H H 4-CN 4-OCF.sub.3 O m.p. 159.degree. C. Z-form A058 H H H H H 4-CN 4-OCH.sub.2 CF.sub.3 O m.p. 221.degree. C. A059 H H H H H 4-CN 4-OCF.sub.2 CHF.sub.2 O m.p. 193.degree. C. A060 H H H H H 4-CN ##STR10## O m.p. 206.degree. C. A061 H H H H H 4-CN ##STR11## O m.p. 182.degree. C. A062 H H H H H 4-CN ##STR12## O m.p. 215.degree. C. A063 H H H H H 4-CN ##STR13## O m.p. 167.degree. C. A064 H H H H H 4-CN ##STR14## O m.p. 216.degree. C. A065 H H H H H 4-CN ##STR15## O m.p. 228.degree. C. A066 H H H H H 4-CN ##STR16## O m.p. 140.degree. C. A067 H H H H H 4-CN 4-COOCH.sub.3 O m.p. 230.degree. C. A068 H H H H H 2-NO.sub.2 4-CF.sub.3 O m.p. 203.degree. C. A069 H H H H H 2-NO.sub.2 4-OCF.sub.3 O m.p. 195.degree . C. A070 H H H H H 4-NO.sub.2 H O m.p. 194.degree. C. A071 H H H H H 4-NO.sub.2 2-Cl O m.p. 220.degree. C. A072 H H H H H 4-NO.sub.2 3-Cl O m.p. 182.degree. C. A073 H H H H H 4-NO.sub.2 4-Cl O m.p. 222.degree. C. A074 H H H H H 4-NO.sub.2 4-Cl S m.p. 206.degree. C. A075 H H H H H 4-NO.sub.2 4-F O m.p. 206.degree. C. A076 H H H H H 4-NO.sub.2 3-CF.sub.3 O m.p. 197.degree. C. A077 H H H H H 4-NO.sub.2 4-CF.sub.3 O m.p. 205.degree. C. A078 H H H H H 4-NO.sub.2 4-OCHF.sub.2 O m.p. 209.degree. C. A079 H H H H H 4-NO.sub.2 4-OCF.sub.3 O m.p. 189.degree. C. A080 H H H H H 4-NO.sub.2 4-OCF.sub.3 S m.p. 139.degree. C. A081 H H H H H 4-NO.sub.2 4-OCF.sub.2 CHF.sub.2 O m.p. 191.degree. C. A082 H H H H H 4-NO.sub.2 4-SCF.sub.3 O m.p. 200.degree. C. A083 H H H H H 4-CH.sub.3 4-Cl O m.p. 204.degree. C. A084 H H H H H 4-CH.sub.3 4-F O m.p. 192.degree. C. A085 H H H H H 4-CH.sub.3 3-CF.sub.3 O m.p. 205.degree. C. A086 H H H H H 4-CH.sub.3 4-CF.sub.3 O m.p. 204.degree. C. A087 H H H H H 4-CH.sub.3 4-OCF.sub.3 O m.p. 186.degree. C. A088 H H H H H 4-OCH.sub.3 4-Cl O m.p. 191.degree. C. A089 H H H H H 4-OCH.sub.3 4-CF.sub.3 O m.p. 198.degree. C. A090 H H H H H 4-OCH.sub.3 4-OCF.sub.3 O m.p. 183.degree. C. A091 H H H H H 4-OCHF.sub.2 4-OCF.sub.3 O m.p. 162.degree. C. A092 H H H H H 4-OCF.sub.2 CHF.sub.2 4-OCF.sub.3 O m.p. 161.degree. C. A093 H H H H H 4-OCF.sub.2 CHF.sub.2 4-OCF.sub.2 CHF.sub.2 O m.p. 185.degree. C. A094 H H H H H 4-OCH.sub.2 CHCH.sub.2 4-OCF.sub.3 O m.p. 168.degree. C. A095 H H H H H 4-OCOCH.sub.3 4-OCF.sub.3 O m.p. 174.degree. C. A096 H H H H H 4-OSO.sub.2 CH.sub.3 4-OCF.sub.3 O m.p. 171.degree. C. A097 H H H H H 4-OSO.sub.2 CF.sub.3 4-OCF.sub.3 O m.p. 175.degree. C. A098 H H H H H 4-SCH.sub.3 4-CF.sub.3 O m.p. 189.degree. C. A099 H H H H H 4-SCH.sub.3 4-OCF.sub.3 O m.p. 171.degree. C. A100 H H H H H 4-SOCH.sub.3 3-CH.sub.3 O m.p. 195.degree. C. A101 H H H H H 4-SOCH.sub.3 4-OCF.sub.3 O m.p. 192.degree. C. A102 H H H H H 4-SO.sub.2 CH.sub.3 4-Cl O m.p. 210.degree. C. A103 H H H H H 4-SO.sub.2 CH.sub.3 4-OCF.sub.3 O m.p. 196.degree. C. A104 H H H H H 4-NH.sub.2 4-OCF.sub.3 O m.p. 148.degree. C. A105 H H H H H 4-NHCOCH.sub.3 4-OCF.sub.3 O m.p. 206.degree. C. A106 H H H H H 4-NHSO.sub.2 CH.sub.3 4-OCF.sub.3 O m.p. 210.degree. C. A107 H H H H 2-Cl H 4-Cl O m.p. 171.degree. C. A108 H H H H 2-Cl H 4-CF.sub.3 O m.p. 177.degree. C. A109 H H H H 2-Cl H 4-OCF.sub.3 O m.p. 166.degree. C. A110 H H H H 3-Cl H 4-CF.sub.3 O m.p. 226.degree. C. A111 H H H H 3-Cl H 4-OCF.sub.3 O m.p. 212.degree. C. A112 H H H H 3-Cl 4-Cl 4-CF.sub.3 O m.p. 207.degree. C. A113 H H H H 3-Cl 4-Cl 4-OCF.sub.3 O m.p. 201.degree. C. A114 H H H H 3-Cl 4-F 4-Cl O m.p. 207.degree. C. A115 H H H H 3-Cl 4-F 4-CF.sub.3 O m.p. 195.degree. C. A116 H H H H 3-Cl 4-F 4-OCF.sub.3 O m.p. 183.degree. C. A117 H H H H 3-Cl 4-CN 2,3,4,5,6-F.sub .5 O m.p. 183.degree. C. A118 H H H H 3-Cl 4-CN 4-Cl O m.p. 206.degree. C. A119 H H H H 3-Cl 4-CN 2,3-Cl.sub.2 O m.p. 218.degree. C. A120 H H H H 3-Cl 4-CN 2,4-Cl.sub.2 O m.p. 218.degree. C. A121 H H H H 3-Cl 4-CN 2,5-Cl.sub.2 O m.p. 221.degree. C. A122 H H H H 3-Cl 4-CN 2,6-Cl.sub.2 O m.p. 186.degree. C. A123 H H H H 3-Cl 4-CN 3,4-Cl.sub.2 O m.p. 233.degree. C. A124 H H H H 3-Cl 4-CN 3,5-Cl.sub.2 O m.p. 215.degree. C. A125 H H H H 3-Cl 4-CN 4-Br O m.p. 197.degree. C. A126 H H H H 3-Cl 4-CN 4-C.sub.4 H.sub.9 -t O m.p. 226.degree. C. A127 H H H H 3-Cl 4-CN 4-CF.sub.3 O m.p. 207.degree. C. A128 H H H H 3-Cl 4-CN 4-OCH.sub.3 O m.p. 189.degree. C. A129 H H H H 3-Cl 4-CN 4-OC.sub.4 H.sub.9 -t O m.p. 198.degree. C. A130 H H H H 3-Cl 4-CN 4-OCHF.sub.2 S m.p. 167.degree. C. A131 H H H H 3-Cl 4-CN 4-OCF.sub.3 O m.p. 187.degree. C. E-form A132 H H H H 3-Cl 4-CN 4-OCF.sub.3 O m.p. 148.degree. C. Z-form A133 H H H H 3-Cl 4-CN 4-OCF.sub.3 S m.p. 199.degree. C. A134 H H H H 3-Cl 4-CN 4-OCH.sub.2 CF.sub.3 O m.p. 226.degree. C. A135 H H H H 3-Cl 4-CN 4-OCF.sub.2 CHF.sub.2 O m.p. 184.degree. C. A136 H H H H 3-Cl 4-CN 3,5-Cl.sub.2 -4-OCF.sub.2 CHF.sub.2 O m.p. 207.degree. C. A137 H H H H 3-Cl 4-CN 4-OCF.sub.2 CHClF O m.p. 196.degree. C. A138 H H H H 3-Cl 4-CN 4-OCF.sub.2 CHFCF.sub.3 O m.p. 184.degree. C. A139 H H H H 3-Cl 4-CN ##STR17## O m.p. 201.degree. C. A140 H H H H 3-Cl 4-CN ##STR18## O m.p. 198.degree. C. A141 H H H H 3-Cl 4-CN ##STR19## O m.p. 216.degree. C. A142 H H H H 3-Cl 4-CN ##STR20## O m.p. 196.degree. C. A143 H H H H 3-Cl 4-CN ##STR21## O m.p. 223.degree. C. A144 H H H H 3-Cl 4-CN ##STR22## O m.p. 206.degree. C. A145 H H H H 3-Cl 4-CN ##STR23## O m.p. 145.degree. C. A146 H H H H 3-Cl 4-CN 4-SCH.sub.3 O m.p. 194.degree. C. A147 H H H H 3-Cl 4-CN 4-SCF.sub.3 O m.p. 215.degree. C. A148 H H H H 3-Cl 4-CN 4-SCHF.sub.2 O m.p. 195.degree . C. A149 H H H H 3-Cl 4-CN 4-SCF.sub.2 CHF.sub.2 O m.p. 221.degree. C. A150 H H H H 3-Cl 4-CN 4-SOCH.sub.3 O m.p. 216.degree. C. A151 H H H H 3-Cl 4-CN 4-SOCF.sub.3 O m.p. 205.degree. C. A152 H H H H 3-Cl 4-CN 4-SOCF.sub.2 CHF.sub.2 O m.p. 217.degree. C. A153 H H H H 3-Cl 4-CN 4-SO.sub.2 CH.sub.3 O m.p. 253.degree. C. A154 H H H H 3-Cl 4-CN 4-SO.sub.2 CHF.sub.2 O m.p. 212.degree. C. A155 H H H H 3-Cl 4-CN 4-SO.sub.2 CF.sub.3 O m.p. 212.degree. C. A156 H H H H 3-Cl 4-CN 4-SO.sub.2 CF.sub.2 CHF.sub.2 O m.p. 212.degree. C. A157 H H H H 3-Cl 4-CN 4-COOCH.sub.3 O m.p. 216.degree. C. A158 H H H H 4-Cl H 4-CF.sub.3 O m.p. 211.degree. C. A159 H H H H 4-Cl H 4-OCF.sub.3 O m.p. 192.degree. C. A160 H H H H 4-Cl 4-Cl 4-Cl O m.p. 210.degree. C. A161 H H H H 4-Cl 4-Cl 4-CF.sub.3 O m.p. 184.degree. C. A162 H H H H 4-Cl 4-Cl 4-OCF.sub.3 O m.p. 190.degree. C. A163 H H H H 4-Cl 4-F 4-Cl O m.p. 201.degree. C. A164 H H H H 4-Cl 4-F 4-CF.sub.3 O m.p. 195.degree. C. A165 H H H H 4-Cl 4-F 4-OCF.sub.3 O m.p. 174.degree. C. A166 H H H H 4-Cl 4-CN 4-Cl O m.p. 221.degree. C. A167 H H H H 4-Cl 4-CN 4-CF.sub.3 O m.p. 216.degree. C. A168 H H H H 4-Cl 4-CN 4-OCF.sub.3 O m.p. 182.degree. C. A169 H H H H 4-Cl 4-CN 4-OCF.sub.3 S m.p. 193.degree. C. A170 H H H H 4-Cl 4-CN 4-OCF.sub.2 CHF.sub.2 O m.p. 201.degree. C. A171 H H H H 4-Cl 4-NO.sub. 2 4-Cl O m.p. 217.degree. C. A172 H H H H 4-Cl 4-NO.sub.2 4-CF.sub.3 O m.p. 213.degree. C. A173 H H H H 4-Cl 4-NO.sub.2 4-OCF.sub. 3 O m.p. 206.degree. C. A174 H H H H 3,4-Cl.sub.2 H 4-Cl O m.p. 212.degree. C. A175 H H H H 3,4-Cl.sub.2 H 4-CF.sub. 3 O m.p. 206.degree. C. A176 H H H H 3,4-Cl.sub.2 H 4-OCF.sub.3 O m.p. 193.degree. C. A177 H H H H 3,4-Cl.sub.2 4-CN 4-Cl O m.p. 226.degree. C. A178 H H H H 3,4-Cl.sub.2 4-CN 4-CF.sub.3 O m.p. 212.degree. C. A179 H H H H 3,4-Cl.sub.2 4-CN 4-OCF.sub.3 O m.p. 193.degree. C. A180 H H H H 3,5-Cl.sub.2 H 4-Cl O m.p. 239.degree. C. A181 H H H H 3,5-Cl.sub.2 H 4-CF.sub.3 O m.p. 227.degree. C. A182 H H H H 3,5-Cl.sub.2 H 4-OCF.sub.3 O m.p. 227.degree. C. A183 H H H H 3,5-Cl.sub.2 4-CN 4-Cl O m.p. 228.degree. C. A184 H H H H 3,5-Cl.sub.2 4-CN 4-CF.sub.3 O m.p. 213.degree. C. A185 H H H H 3,5-Cl.sub.2 4-CN 4-OCF.sub.3 O m.p. 206.degree. C. A186 H H H H 3-Br H 4-Cl O m.p. 191.degree. C. A187 H H H H 3-Br H 4-CF.sub.3 O m.p. 228.degree. C. A188 H H H H 3-Br H 4-OCF.sub.3 O m.p. 209.degree. C. A189 H H H H 3-Br 4-CN 4-Cl O m.p. 205.degree. C. A190 H H H H 3-Br 4-CN 2,3-Cl.sub.2 O m.p. 223.degree. C. A191 H H H H 3-Br 4-CN 2,4-Cl.sub.2 O m.p. 233.degree. C. A192 H H H H 3-Br 4-CN 2,6-Cl.sub.2 O m.p. 194.degree. C. A193 H H H H 3-Br 4-CN 3,4-Cl.sub.2 O m.p. 220.degree. C. A194 H H H H 3-Br 4-CN 4-CF.sub.3 O m.p. 197.degree. C. A195 H H H H 3-Br 4-CN 4-OCF.sub.3 O m.p. 176.degree. C. A196 H H H H 3-Br 4-CN 4-OCF.sub.2 CHF.sub.2 O m.p. 183.degree. C. A197 H H H H 3-Br 4-CN 4-OCF.sub.2 CHClF O m.p. 186.degree. C. A198 H H H H 3-Br 4-CN 4-OCF.sub.2 CHFCF.sub.3 O m.p. 188.degree. C. A199 H H H H 3-Br 4-CN 4-SCHF.sub.2 O m.p. 218.degree. C. A200 H H H H 3-Br 4-CN 4-SCF.sub.3 O m.p. 206.degree. C. A201 H H H H 3-Br 4-CN 4-SOCHF.sub.2 O m.p. 221.degre e. C. A202 H H H H 3-Br 4-CN 4-SOCF.sub.3 O m.p. 216.degree. C. A203 H H H H 3-Br 4-CN 4-SO.sub.2 CHF.sub.2 O m.p. 193.degree. C. A204 H H H H 3-Br 4-CN 4-SO.sub.2 CF.sub.3 O m.p. 215.degree. C. A205 H H H H 4-Br 3,4-(OCH.sub.3).sub.2 4-Cl O m.p. 204.degree. C. A206 H H H H 4-Br 3,4-(OCH.sub.3).sub.2 4-CF.sub.3 O m.p. 192.degree. C. A207 H H H H 4-Br 3,4-(OCH.sub.3).sub.2 4-OCF.sub.3 O m.p. 197.degree. C. A208 H H H H 2-F H 4-Cl O m.p. 175.degree. C. A209 H H H H 2-F H 4-CF.sub. 3 O m.p. 177.degree. C. A210 H H H H 2-F H 4-OCF.sub.3 O m.p. 173.degree. C. A211 H H H H 2-F 4-CN 4-Cl O m.p. 180.degree. C. A212 H H H H 2-F 4-CN 4-CF.sub.3 O m.p. 196.degree. C. A213 H H H H 2-F 4-CN 4-OCF.sub.3 O m.p. 170.degree. C. A214 H H H H 3-F H 4-Cl O m.p. 206.degree. C. A215 H H H H 3-F H 4-CF.sub. 3 O m.p. 223.degree. C. A216 H H H H 3-F H 4-OCF.sub.3 O m.p. 200.degree. C. A217 H H H H 3-F 4-Cl 4-CF.sub.3 O m.p. 209.degree. C. A218 H H H H 3-F 4-Cl 4-OCF.sub.3 O m.p. 191.degree. C. A219 H H H H 3-F 4-CN 4-Cl O m.p. 208.degree. C. A220 H H H H 3-F 4-CN 4-CF.sub.3 O m.p. 216.degree. C. A221 H H H H 3-F 4-CN 4-OCF.sub.3 O m.p. 202.degree. C. A222 H H H H 4-F H 4-Cl O m.p. 203.degree. C. A223 H H H H 4-F H 4-OCF.sub .3 O m.p. 191.degree. C. A224 H H H H 4-F 4-CN 4-Cl O m.p. 222.degree. C. A225 H H H H 4-F 4-CN 4-CF.sub.3 O m.p. 185.degree. C. A226 H H H H 4-F 4-CN 4-OCF.sub.3 O m.p. 184.degree. C. A227 H H H H 4-F 4-F 4-CF.sub.3 O m.p. 199.degree. C. A228 H H H H 4-F 4-F 4-OCF.sub.3 O m.p. 178.degree. C. A229 H H H H 4-F 4-F 4-OCF.sub.2 CHF.sub.2 O m.p. 187.degree. C. A230 H H H H 4-F 4-CN 4-Cl O m.p. 232.degree. C. A231 H H H H 4-F 4-CN 4-CF.sub.3 O m.p. 202.degree. C. A232 H H H H 4-F 4-CN 4-OCF.sub.3 O m.p. 210.degree. C. A233 H H H H 4-F 4-NO.sub.2 4-Cl O m.p. 209.degree. C. A234 H H H H 4-F 4-NO.sub.2 4-CF.sub.3 O m.p. 220.degree. C. A235 H H H H 4-F 4-NO.sub.2 4-OCF.sub.3 O m.p. 204.degree. C. A236 H H H H 3,5-F.sub.2 H 4-Cl O m.p. 218.degree. C. A237 H H H H 3,5-F.sub.2 H 4-CF.sub.3 O m.p. 208.degree. C. A238 H H H H 3,5-F.sub.2 H 4-OCF.sub.3 O m.p. 211.degree. C. A239 H H H H 3-I 4-CN 4-Cl O m.p. 213.degree. C. A240 H H H H 3-I 4-CN 4-CF.sub.3 O m.p. 205.degree. C. A241 H H H H 3-I 4-CN 4-OCF.sub.3 O m.p. 201.degree. C. A242 H H H H 3-I 4-CN 4-OCF.sub.2 CHF.sub.2 O m.p. 196.degree. C. A243 H H H H 2-CH.sub.3 H 4-Cl O m.p. 121.degree. C. A244 H H H H 2-CH.sub. 3 H 4-CF.sub.3 O m.p. 135.degree. C. A245 H H H H 2-CH.sub.3 H 4-OCF.sub.3 O m.p. 160.degree. C. A246 H H H H 3-CH.sub.3 H 4-Cl O m.p. 185.degree. C. A247 H H H H 3-CH.sub. 3 H 4-CF.sub.3 O m.p. 193.degree. C. A248 H H H H 3-CH.sub.3 H 4-OCF.sub.3 O m.p. 198.degree. C. A249 H H H H 3-CH.sub.3 4-CN 4-Cl O m.p. 200.degree. C. A250 H H H H 3-CH.sub. 3 4-CN 4-CF.sub.3 O m.p. 194.degree. C. A251 H H H H 3-CH.sub.3 4-CN 4-OCF.sub.3 O m.p. 189.degree. C. A252 H H H H 4-CH.sub.3 H 4-Cl O m.p. 206.degree. C. A253 H H H H 4-CH.sub. 3 H 4-OCF.sub.3 O m.p. 194.degree. C. A254 H H H H 4-C.sub.4 H.sub.9 -t 3,4-(OCH.sub.3).sub.2 4-Cl O m.p. 122.degree. C. A255 H H H H 4-C.sub.4 H.sub.9 -t 3,4-(OCH.sub.3).sub.2 4-CF.sub.3 O m.p. 202.degree. C. A256 H H H H 4-C.sub.4 H.sub.9 -t 3,4-(OCH.sub.3).sub.2 4-OCF.sub.3 O m.p. 200.degree. C. A257 H H H H 3-CF.sub.3 H 4-Cl O m.p. 206.degree. C. A258 H H H H 3-CF.sub.3 H 4-CF.sub.3 O m.p. 192.degree. C. A259 H H H H 3-CF.sub.3 H 4-OCF.sub.3 O m.p. 210.degree. C. A260 H H H H 3-CF.sub.3 4-CN 4-CF.sub.3 O m.p. 188.degree. C. A261 H H H H 3-CF.sub.3 4-CN 4-OCF.sub.3 O m.p. 191.degree . C. A262 H H H H 3-CF.sub.3 4-CN 4-OCF.sub.3 S m.p. 149.degree. C. A263 H H H H 3-CF.sub.3 4-CN 4-OCF.sub.2 CHF.sub.2 O m.p. 183.degree. C. A264 H H H H 3-CF.sub.3 4-OCHF.sub.2 4-OCF.sub.3 O m.p. 149.degree. C. A265 H H H H 3-CF.sub.3 4-OSO.sub.2 CH.sub.3 4-OCF.sub.3 O m.p. 173.degree. C. A266 H H H H 3,5-(CF.sub.3).sub.2 H 4-Cl O m.p. 233.degree. C. A267 H H H H 3,5-(CF.sub.3).sub.2 H 4-CF.sub. 3 O m.p. 227.degree. C. A268 H H H H 3-CN 4-CN 4-Cl O m.p. 229.degree. C. A269 H H H H 3-CN 4-CN 4-CF.sub.3 O m.p. 224.degree. C. A270 H H H H 3-CN 4-CN 4-OCF.sub.3 O m.p. 218.degree. C. A271 H H H H 4-CN 4-CN 4-Cl O m.p. 246.degree. C. A272 H H H H 4-CN 4-CN 4-CF.sub.3 O m.p. 247.degree. C. A273 H H H H 4-CN 4-CN 4-OCF.sub.3 O m.p. 238.degree. C. A274 H H H H 3-OCH.sub.3 4-CN 4-OCF.sub.3 O m.p. 194.degree. C. A275 H H H H 4-OCH.sub.3 H 4-Cl O m.p. 201.degree. C. A276 H H H H 4-OCH.sub.3 H 4-CF.sub.3 O m.p. 217.degree. C. A277 H H H H 4-OCH.sub.3 H 4-OCF.sub.3 O m.p. 210.degree. C. A278 H H H H 3-OC.sub.3 H.sub.7-i 4-CN 4-CF.sub.3 O m.p. 177.degree. C. A279 H H H H 3-OC.sub.3 H.sub.7-i 4-CN 4-OCF.sub.3 O m.p. 180.degree. C. A280 H H H H ##STR24## 4-CN 4-Cl O m.p. 182.degree. C. A281 H H H H ##STR25## 4-CN 4-CF.sub.3 O m.p. 168.degree. C. A282 H H H H ##STR26## 4-CN 4-OCF.sub.3 O m.p. 171.degree. C. A283 H H H H 3-OCHF.sub.2 H 4-Cl O m.p. 185.degree. C. A284 H H H H 3-OCHF.sub.2 H 4-OCF.sub.3 O m.p. 182.degree. C. A285 H H H H 3-OCHF.sub.2 4-CN 4-OCF.sub.3 O m.p. 188.degree. C. A286 H H H H 4-OCHF.sub.2 H 4-Cl O m.p. 194.degree. C. A287 H H H H 4-OCHF.sub.2 H 4-CF.sub. 3 O m.p. 204.degree. C. A288 H H H H 4-OCHF.sub.2 H 4-OCF.sub.3 O m.p. 202.degree. C. A289 H H H H 4-OCHF.sub.2 H 4-OCF.sub.2 CHF.sub.2 O m.p. 213.degree. C. A290 H H H H 4-OCHF.sub.2 H 4-SCF.sub.3 O m.p. 208.degree. C. A291 H H H H 4-OCHF.sub.2 H 4-SOCF.sub.3 O m.p. 204.degree. C. A292 H H H H 4-OCF.sub.2 CHF.sub.2 4-CN 4-OCF.sub.2 CHF.sub.2 O m.p. 175.degree. C. A293 H H H H 3-OCH.sub.2 O-4 4-CN 4-Cl O m.p. 206.degree. C. A294 H H H H 3-OCH.sub.2 O-4 4-CN 4-CF.sub.3 O m.p. 182.degree. C. A295 H H H H 3-OCH.sub.2 O-4 4-CN 4-OCF.sub.3 O m.p. 180.degree. C. A296 H H H H 2-CHCHCHCH-3 4-CN 4-Cl O m.p. 211.degree. C. A297 H H H H 2-CHCHCHCH-3 4-CN 4-CF.sub.3 O m.p. 200.degree. C. A298 H H H H 2-CHCHCHCH-3 4-CN 4-OCF.sub.3 O m.p. 199.degree. C. A299 H H H H 2-CHCHCHCH-3 4-CN 4-OCF.sub.2 CHF.sub.2 O m.p. 195.degree. C. A300 CH.sub.3 H H H H H H O m.p. 113.degree. C. A301 CH.sub.3 H H H H H 4-Cl O m.p. 132.degree. C. A302 CH.sub.3 H H H H H 4-OCF.sub.3 O m.p. 108.degree. C. A303 H CH.sub.3 H H H H H O m.p. 111.degree. C. A304 H CH.sub.3 H H H H 2-Cl O m.p. 117.degree. C. A305 H CH.sub.3 H H H H 3-Cl O m.p. 108.degree. C. A306 H CH.sub.3 H H H H 4-Cl O m.p. 98.degree. C. A307 H CH.sub.3 H H H H 3,4-Cl.sub.2 O Paste A308 H CH.sub.3 H H H H 4-Br O m.p. 85.degree. C. A309 H CH.sub.3 H H H H 4-CH.sub.3 O Paste A310 H CH.sub.3 H H H H 4-CF.sub.3 O m.p. 148.degree. C. A311 H CH.sub.3 H H H H 4-OCH.sub.3 O Paste A312 H CH.sub.3 H H H H 4-OCF.sub.3 O m.p. 115.degree. C. EZ-form A313 H CH.sub.3 H H H H 4-OCF.sub.3 O m.p. 95.degree. C. E-form A314 H CH.sub.3 H H H H 4-OCF.sub.3 O m.p. 66.degree. C. Z-form A315 H CH.sub.3 H H H 4-Cl 4-Cl O m.p. 121.degree. C. A316 H CH.sub.3 H H H 4-Cl 3,4-Cl.sub.2 O Paste A317 H CH.sub.3 H H H 4-Cl 3-CF.sub.3 O Paste A318 H CH.sub.3 H H H 4-Cl 4-OCF.sub.3 O m.p. 105.degree. C. A319 H CH.sub.3 H H 3-Cl 4-CN 4-Cl O m.p. 140.degree. C. A320 H CH.sub.3 H H 3-Cl 4-CN 4-CF.sub.3 O m.p. 127.degree. C. A321 H CH.sub.3 H H 3-Cl 4-CN 4-OCF.sub.3 O m.p. 98.degree. C. A322 H CH.sub.3 H H 4-Cl H 2-Cl O Paste A323 H CH.sub.3 H H 4-Cl H 3-Cl O Paste A324 H CH.sub.3 H H 4-Cl H 4-Cl O m.p. 109.degree. C. A325 H CH.sub.3 H H 4-Cl H 4-CF.sub.3 O m.p. 119.degree. C. A326 H CH.sub.3 H H 4-Cl H 4-OCF.sub.3 O Paste A327 H CH.sub.3 H H 4-F H 4-OCF.sub.3 O Paste A328 H CH.sub.3 H H 4-CH.sub.3 H 4-Cl O Paste A329 H CH.sub.3 H H 4-CH.sub.3 H 4-OCF.sub.3 O Paste A330 H H OH H H H H O m.p. 167.degree. C. A331 H H OH H H H 4-Cl O m.p. 188.degree. C. A332 H H OH H H H 4-CF.sub.3 O m.p. 176.degree. C. A333 H H OH H H H 4-OCF.sub.3 O m.p. 170.degree. C. A334 H H OH H H 4-Cl 4-Cl O Paste A335 H H OH H H 4-Cl 4-OCF.sub.3 O m.p. 185.degree. C. E-form A336 H H OH H H 4-Cl 4-OCF.sub.3 O m.p. 95.degree. C. Z-form A337 H H OH H H 4-CN 4-Cl O Paste A338 H H OH H H 4-CN 4-OCF.sub.3 O m.p. 113.degree. C. A339 H H OH H 2-Cl 2-Cl 4-Cl O Paste A340 H H OH H 2-Cl 2-Cl 4-OCF.sub.3 O m.p. 76.degree. C. A341 H H OH H 3-Cl 3-Cl H O m.p. 142.degree. C. A342 H H OH H 3-Cl 3-Cl 4-Cl O m.p. 149.degree. C. A343 H H OH H 3-Cl 3-Cl 4-CF.sub.3 O m.p. 141.degree . C. A344 H H OH H 3-Cl 3-Cl 4-OCF.sub.3 O m.p. 146.degree. C. A345 H H OH H 4-Cl 4-Cl 3-Cl O m.p. 81.degree. C. A346 H H OH H 4-Cl 4-Cl 4-Cl O m.p. 59.degree. C. A347 H H OH H 4-Cl 4-Cl 4-CF.sub.3 O Paste A348 H H OH H 4-Cl 4-Cl 4-OCF.sub.3 O Paste A349 H H OH H 2,4-Cl.sub.2 2,4-Cl.sub.2 4-OCF.sub.3 O m.p. 72.degree. C. A350 H H OH H 2,4-Cl.sub.2 2,4-Cl.sub.2 3,4-Cl.sub.2 O m.p. 100.degree. C. A351 H H OH H 4-F 4-F 4-Cl O m.p. 88.degree. C. A352 H H OH H 4-F 4-F 4-OCF.sub.3 O m.p. 168.degree. C. A353 H H OH H 4-CH.sub.3 4-CH.sub.3 4-Cl O m.p. 180.degree. C. A354 H H OH H 4-CH.sub.3 4-CH.sub.3 4-CF.sub.3 O m.p. 184.degree. C. A355 H H OH H 4-CH.sub.3 4-CH.sub.3 4-OCF.sub.3 O m.p. 182.degree. C. A356 H H OH H 4-OCH.sub.3 4-OCH.sub.3 4-Cl O m.p. 139.degree. C. A357 H H OH H 4-OCH.sub.3 4-OCH.sub.3 4-OCF.sub.3 O m.p. 142.degree. C. A358 H H OH H 4-CH.sub.3 4-CH.sub.3 4-OCF.sub.3 S m.p. 178.degree. C. A359 H H OH H 4-N(CH.sub.3).sub.2 H 4-OCF.sub.3 O m.p. 167.degree. C. A360 H H CH.sub.3 H H H 4-Cl O m.p. 164.degree. C. A361 H H CH.sub.3 H H H 4-CF.sub.3 O m.p. 150.degree. C. A362 H H CH.sub.3 H H H 4-CF.sub.3 O m.p. 132.degree. C. A363 H H CH.sub.3 H H H 4-OCF.sub.3 S m.p. 118.degree. C. A364 H H OCH.sub.3 H H H 3-Cl O m.p. 197.degree. C. A365 H H OCH.sub.3 H H H 4-Cl O m.p. 183.degree. C. A366 H H OCH.sub.3 H H H 3-CF.sub.3 O m.p. 192.degree. C. A367 H H OCH.sub.3 H H H 4-CF.sub.3 O m.p. 185.degree. C. A368 H H OCH.sub.3 H H H 4-OCF.sub.3 O m.p. 181.degree. C. A369 H H OC.sub.3 H.sub.7-i H H H 4-Cl O m.p. 155.degree. C. A370 H H OC.sub.3 H.sub.7-i H H H 4-CF.sub.3 O m.p. 209.degree. C. A371 H H OC.sub.3 H.sub.7-i H H H 4-OCF.sub.3 O m.p. 193.degree. C. A372 H H OC.sub.4 H.sub.9-i H H H 4-Cl O m.p. 176.degree. C. A373 H H OC.sub.4 H.sub.9-i H H H 4-OCF.sub.3 O m.p. 184.degree. C. A374 H H OCOCH.sub.3 H H H 4-OCF.sub.3 O m.p. 182.degree. C. A375 H H ##STR27## H H H 4-OCF.sub.3 O m.p. 168.degree. C. A376 H H OH CH.sub.3 H H 4-Cl O m.p. 115.degree. C. A377 H H OH CH.sub.3 H H 4-OCF.sub.3 O m.p. 130.degree. C. A378 H H O H H 4-CF.sub.3 O m.p. 150.degree. C. A379 H H O H H 4-OCF.sub.3 O m.p. 132.degree. C. A380 H H H H H 2,4-F.sub.2 4-Cl O m.p. 199.degree. C. A381 H H H H H 2,4-F.sub.2 4-OCF.sub.3 O m.p. 173.degree. C. A382 H H H H H 3,4-F.sub.2 4-Cl O m.p. 203.degree. C. A383 H H H H H 3,4-F.sub.2 4-OCF.sub.3 O m.p. 189.degree. C. A384 H H H H H 3,4-F.sub.2 4-SCF.sub.3 O m.p. 207.degree. C. A385 H H H H H 3,4-F.sub.2 4-SOCF.sub.3 O m.p. 188.degree. C. A386 H H H H H 3,4-F.sub.2 4-SO.sub.2 CF.sub.3 O m.p. 194.degree. C. A387 H H H H H 3,5-F.sub.2 4-Cl O m.p. 205.degree. C. A388 H H H H H 3,5-F.sub.2 4-Br O m.p. 201.degree. C. A389 H H H H H 3,5-F.sub.2 4-OCF.sub.3 O m.p. 196.degree. C. A390 H H H H H 4-Cl 4-OC.sub.4 H.sub.9-t O m.p. 186.degree. C. A391 H H H H H 3,4-Cl.sub.2 4-Cl O m.p. 208.degree. C. A392 H H H H H 3,4-Cl.sub.2 4-CF.sub.3 O m.p. 215.degree. C. A393 H H H H H 3,4-Cl.sub.2 4-OCF.sub.3 O m.p. 186.degree. C. A394 H H H H H 3,4-Cl.sub.2 4-OCF.sub.2 CHF.sub.2 O m.p. 187.degree. C. A395 H H H H H 4-CF.sub.3 4-OCF.sub.3 O m.p. 196.degree. C. A396 H H H H H ##STR28## 4-OCF.sub.3 O m.p. 170.degree. C. A397 H H H H H 4-NHCHO 4-OCF.sub.3 O m.p. 193.degree. C. A398 H H H H H 4-NHCONHC.sub.2 H.sub.5 4-OCF.sub.3 O m.p. 209.degree. C. A399 H H H H H 4-NO.sub.2 4-SOCF.sub.3 O Glass-like amorphous substance A400 H H H H H 4-OCF.sub.3 4-OCF.sub.3 O m.p. 168.degree. C. A401 H H H H H 4-OCF.sub.3 4-OCF.sub.3 O m.p. 204.degree. C. A402 H H H H H 4-OCH.sub.2 CF.sub.3 4-OCF.sub.3 O m.p. 169.degree. C. A403 H H H H H 4-SCHF.sub.3 4-OCF.sub.3 O m.p. 166.degree. C. A404 H H H H H 4-SOCHF.sub.3 4-OCF.sub.3 O m.p. 177.degree. C. A405 H H H H 3-F 4-CN 4-SCF.sub.3 O m.p. 214.degree. C. A406 H H H H 3-F 4-CN 4-SOCF.sub.3 O m.p. 228.degree. C. A407 H H H H 3-F 4-SO.sub.2 N(CH.sub.3).sub.2 4-Cl O m.p. 234.degree. C. A408 H H H H 3-F 4-SO.sub.2 N(CH.sub.3).sub.2 4-OCF.sub.3 O m.p. 194.degree. C. A409 H H H H 3-F 4-CN 4-OCF.sub.2 Br O m.p. 186.degree. C. A410 H H H H 4-F 4-CN 4-SCF.sub.3 O m.p. 221.degree. C. A411 H H H H 4-F 4-CN 4-SOCF.sub.3 O m.p. 224.degree. C. A412 H H H H 4-F 4-CN 4-SO.sub.2 CF.sub.3 O m.p. 165.degree. C. A413 H H H H 3-Cl 4-CN 2,3,4-Cl.sub.3 O m.p. 237.degree. C. A414 H H H H 3-Cl 4-CN 2,3,4,5-Cl.sub.4 O m.p. 255.degree. C. A415 H H H H 3-Cl 4-CN 4-I O m.p. 207.degree. C. A416 H H H H 3-Cl 4-CN 4-C.sub.6 H.sub.13-n O m.p. 173.degree. C. A417 H H H H 3-Cl 4-CN 4-COCH.sub.3 O m.p. 218.degree. C. A418 H H H H 3-Cl 4-CN 3-Cl-4-OCF.sub.2 CHF.sub.3 O m.p. 211.degree. C. A419 H H H H 3-Cl 4-CN 4-OCOCH.sub.3 O m.p. 177.degree . C. A420 H H H H 3-Cl 4-CN 4-OSO.sub.2 CF.sub.3 O m.p. 199.degree. C. A421 H H H H 3-Cl 4-CN 4-SOCF.sub.3 O m.p. 157.degree. C. Z-form A422 H H H H 3-Cl 2-Cl-4-CN 4-CF.sub.3 O m.p. 199.degree. C. A423 H H H H 3-Cl 2-Cl-4-CN 4-OCF.sub.3 O m.p. 188.degree . C. A424 H H H H 3-Cl 2-Cl-4-CN 4-SCF.sub.3 O m.p. 197.degree. C. A425 H H H H 3-Cl 3-Cl-4-CN 4-OCF.sub.3 O m.p. 180.degree . C. A426 H H H H 3-Cl 2-CH.sub.3 -4-CN 4-Cl O m.p. 209.degree. C. A427 H H H H 3-Cl 2-CH.sub.3 -4-CN 4-OCF.sub.3 O m.p. 164.degree. C. A428 H H H H 3-Cl 2-CH.sub.3 -4-CN 4-SCF.sub.3 O m.p. 189.degree. C. A429 H H H H 3-Cl 2-CH.sub.3 -4-CN 4-SOCF.sub.3 O m.p. 207.degree. C. A430 H H H H 3-Cl 2-CH.sub.3 -4-CN 4-SO.sub.2 CF.sub.3 O m.p. 205.degree. C. A431 H H H H 3-Cl 3-CH.sub.3 -4-CN 4-Cl O m.p. 209.degree. C. A432 H H H H 3-Cl 3-CH.sub.3 -4-CN 4-OCF.sub.3 O m.p. 199.degree. C. A433 H H H H 3-Cl 3-CH.sub.3 -4-CN 4-SCF.sub.3 O m.p. 213.degree. C. A434 H H H H 3-Cl 3-CH.sub.3 -4-CN 4-SOCF.sub.3 O m.p. 180.degree. C. A435 H H H H 3-Cl 3-CH.sub.3 -4-CN 4-SO.sub.2 CF.sub.3 O m.p. 152.degree. C. A436 H H H H 3-Cl 3,4-(CN). sub.2 4-OCF.sub.3 O m.p. 211.degree. C. A437 H H H H 3-Cl 4-COOCH.sub.3 4-OCF.sub.3 O m.p. 160.degree. C. A438 H H H H 3-Cl 4-OH 4-OCF.sub.3 O m.p. 193.degree. C. A439 H H H H 3-Cl 4-OCHF.sub. 2 4-CF.sub.3 O m.p. 181.degree. C. A440 H H H H 3-Cl 4-OCHF.sub.2 4-OCF.sub.3 O m.p. 170.degree. C. A441 H H H H 3-Cl 4-OCHF.sub.2 4-SCF.sub.3 O m.p. 193.degree. C. A442 H H H H 3-Cl 4-OSO.sub.2 CH.sub.3 4-OCF.sub.3 O m.p. 195.degree. C. A443 H H H H 3-Cl 4-OSO.sub.2 CF.sub.3 4-OCF.sub.3 O m.p. 173.degree. C. A444 H H H H 3-Br 4-CN 2,3,4-Cl.sub.3 O m.p. 247.degree. C. A445 H H H H 3-Br 4-CN 2,3,4,5-Cl.sub.4 O m.p. 250.degree. C. A446 H H H H 3-Br 4-CN 4-C.sub.6 H.sub.13 -n O m.p. 169.degree. C. A447 H H H H 3-Br 4-CN 3-Cl-4-OCF.sub.2 CHF.sub.2 O m.p. 228.degree. C. A448 H H H H 3-CHF.sub.2 4-CN 4-OCF.sub.3 O m.p. 177.degree. C. A449 H H H H 3-CF.sub.3 4-CN 4-OCF.sub.2 Br O m.p. 172.degree. C. A450 H H H H 3-CF.sub.3 4-CN 4-SCF.sub.3 O m.p. 215.degree. C. A451 H H H H 3-CF.sub.3 4-CN 4-SOCF.sub.3 O m.p. 210.degree. C. A452 H H H H 3-CF.sub.3 4-CN 4-SO.sub.2 CF.sub.3 O m.p. 225.degree. C. A453 H H H H 4-CF.sub.3 4-CN 4-OCF.sub.3 O m.p. 211.degree. C. A454 H H H H 3-F-5-CF.sub.3 4-CN 4-OCF.sub.3 O m.p. 196.degree. C. A455 H H H H 3-CH.sub.2 OCH.sub.3 4-CN 4-CF.sub.3 O m.p. 197.degree. C. A456 H H H H 3-CH.sub.2 OCH.sub.3 4-CN 4-OCF.sub.3 O m.p. 190.degree. C. A457 H H H H ##STR29## 4-CN 4-OCF.sub.3 O m.p. 169.degree. C. A458 H H H H 3-OH 4-CN 4-OCF.sub.3 O m.p. 224.degree. C. A459 H H H H 3-OCH.sub.2 CHCH.sub.2 4-CN 4-OCF.sub.3 O m.p. 160.degree. C. A460 H H H H 3-OCHF.sub.2 4-CN 4-OCF.sub.3 O m.p. 188.degree. C. A461 H H H H 3-OCHF.sub.2 4-CN 4-SCF.sub.3 O m.p. 204.degree. C. A462 H H H H 3-OCHF.sub.2 4-CN 4-SOCF.sub.3 O m.p. 195.degree. C. A463 H H H H 3-OCHF.sub.2 4-CN 4-SO.sub.2 CF.sub.3 O m.p. 206.degree. C. A464 H H H H 3-OCF.sub.3 4-CN 4-CF.sub.3 O m.p. 159.degree. C. A465 H H H H 3-OCF.sub.3 4-CN 4-OCF.sub.3 O m.p. 171.degree. C. A466 H H H H 3-OCF.sub.3 4-CN 4-SCF.sub.3 O m.p. 202.degree. C. A467 H H H H 3-OCF.sub.3 4-CN 4-SOCF.sub.3 O m.p. 200.degree. C. A468 H H H H 3-OCH.sub.2 COCH.sub.3 4-CN 4-OCF.sub.3 O m.p. 198.degree. C. A469 H H H H 3-OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5 4-CN 4-OCF.sub.3 O m.p. 172.degree. C. A470 H H H H 3-OCOC.sub.3 H.sub.5 -c 4-CN 4-OCF.sub.3 O m.p. 200.degree. C. A471 H H H H 3-OCON(CH.sub.3).sub.2 4-CN 4-OCF.sub.3 O m.p. 197.degree. C. A472 H H H H 3-OCO.sub.2 CH.sub.3 4-CN 4-OCF.sub.3 O m.p. 197.degree. C. A473 H H H H 3-OSO.sub.2 CH.sub.3 4-CN 4-OCF.sub.3 O m.p. 180.degree. C. A474 H H H H 3-CF.sub.3 4-CN 4-SC.sub.3 F.sub.7 -n O m.p. 201.degree. C. A475 H H H H 3-CF.sub.3 4-CN ##STR30## O m.p. 248.degree. C. A476 H H H H 3-CF.sub.3 4-CN 4-SOC.sub.3 F.sub.7 -n O m.p. 207.degree. C. A477 H H H H 3-CF.sub.3 4-CN 4-SO.sub.2 C.sub.3 F.sub.7 -n O m.p. 231.degree. C. A478 H H H H 3-CF.sub.3 4-CN 4-OCF.sub.3 O m.p. 152.degree. C. Z-form A479 H H H H 3-CF.sub.3 4-CN 4-Cl O m.p. 165.degree. C. A480 H H H H 3-CF.sub.3 4-CH.sub.3 4-OCF.sub.3 O m.p. 184.degree. C. A481 H H H H 4-F 4-NO.sub.2 4-Cl S m.p. 178.degree. C. A482 H H H H 3-F 4-CN 4-CH.sub.3 S m.p. 148.degree. C. A483 H H H H H 3-CHCHCHN-4 4-OCF.sub.3 O m.p. 214.degree. C. A484 H H H H H 3-CHCHCHN-4 4-OCF.sub.3 O m.p. >214.degree. C. Hydro- chloride A485 H H H H H 3-CHCHCHN-4 4-ClF O m.p. 210.degree. C. A486 H H H H 3-CF.sub.3 4-CN ##STR31## O m.p. 221.degree. C. In the table, c denotes an alicyclic compound and m.p. denotes melting point.

Table 4 shows .sup.1 -NMR data of the compounds having physical properties as paste listed in Table 3.

TABLE 4______________________________________No. .sup.1 H-NMR(CDCl.sub.3 /TMS, .delta. value, ppm.)______________________________________A055 3.88+4.23(s, 2H), 6.52+6.54(t, 1H), 6.95+7.77(m, 13H), 8.73+8.98+9.20+9.39(s, 2H). (Mixture of E- and Z-forms)A307 2.70(s, 3H), 3,87(s, 2H), 6.90-7.60(m, 13H), 8.23(bs, 1H).A309 2.23(s, 3H), 3.17(s, 3H), 4.20(s, 2H), 6.50-7.83(m, 15H).A311 2.73+3.20(s, 3H), 3.70(s, 3H), 3.90+4.23(s, 2H), 6.60-8.00(m, 14H), 8.17(bs, 1H). (Mixture of E- and Z-forms)A316 2.60+3.20(s, 3H), 3.87+4.20(s, 2H), 6.27-8.27(m, 13H). (Mixture of E- and Z-forms)A317 2.73+3.23(s, 3H), 3.90+4.23(s, 2H), 6.73-8.13(m, 13H), 8.40(bs, 1H). (Mixture of E- and Z-forms)A322 3.23(s, 3H), 4.20(s, 2H), 6.67-8.43(m, 13H), 8.77(bs, 1H).A323 2.73+3.23(s, 3H), 3.87+4.20(s, 2H), 6.80-8.00(m, 14H). (Mixture of E- and Z-forms)A326 2.73+3.20(s, 3H), 3.87+4.20(s, 2H), 6.43-7.93(m, 13H), 8.00(bs, 1H). (Mixture of E- and Z-forms)A327 2.73(s, 3H), 3.87(s, 1H), 6.73-7.90(m, 13H), 8.30(bs, 1H).A328 2.23+2.33(s, 3H), 2.70+3.17(s, 3H), 3.87+4.17(s, 2H), 6.43-7.90(m, 13H). (Mixture of E- and Z-forms)A329 2.30(s, 2H), 3.17(s,3H), 4.17(s, 2H), 6.83-8.30(m, 14H).A334 6.29(s, 1H), 7.65-7.92(m, 13H), 9.14(bs, 1H), 10.70(bs, 1H), (DMSO-d.sub.6)A337 3.88(bs, 1H), 3.87(s, 1H), 6.91-7.55(m, 13H), 7.73(s, 1H), 8.13(bs, 1H).A339 3.72(bs, 1H), 6.08(s, 1H), 6.77-7.68(m, 12H), 8.17(bs, 1H), 10.58(bs, 1H).A347 3.75(bs, 1H), 5.60(d, 1H), 6.94-7.61(m, 12H), 8.18(s, 1H), 10.80(s, 1H).A348 3.75(bs, 1H), 5.31(d, 1H), 6.92-7.65(m, 12H), 8.13(s, 1H), 10.75(s, 1H).A399 4.31(s, 2H), 7.31-8.14(m, 13H), 8.63(s, 1H), 9.15(s, 1H).______________________________________ ##STR32## TABLE 5__________________________________________________________________________(Wherein each of R.sup.1 and R.sup.4 is a hydrogen atom.) Phys- ical pro-No. R.sup.2 R.sup.3 R.sup.5 X Y Z W perties__________________________________________________________________________B001 H H H H H 4-Cl O m.p. 211.degree. C.B002 H H H H H 4-OCF.sub.3 O m.p. 194.degree. C.B003 H H H H 4-Cl 4-OCF.sub.3 O m.p. 209.degree. C.B004 H H H H 4-Cl 4-OCF.sub.2 CHF.sub.2 O m.p. 202.degree. C.B005 H H H H 4-Cl 0 m.p. 215.degree. C.B006 H H H H 4-CN 4-OCF.sub.3 O m.p. 204.degree. C.B007 H H H H 4-NHCOCH.sub.3 4-OCF.sub.3 O m.p. 206.degree. C.B008 H H H H 4-NO.sub.2 4-OCF.sub.3 O m.p. 188.degree. C.B009 H H H H 4-OCHF.sub.2 4-OCF.sub.3 O m.p. 202.degree. C.B010 H H H 3-F 4-Cl 4-OCF.sub.3 O m.p. 203.degree. C.B011 H H H 4-F 4-Cl 4-OCF.sub.3 O m.p. 207.degree. C.B012 H H H 3-Cl 4-Cl 4-CF.sub.3 O m.p. 189.degree. C.B013 H H H 3-Cl 4-Cl 4-OCF.sub.3 O m.p. 176.degree. C.B014 H H H 3-Cl 4-CN 4-CF.sub.3 O m.p. 198.degree. C.B015 H H H 3-Cl 4-CN 4-OCF.sub.3 O m.p. 193.degree. C.B016 H H H 3-Cl 4-CN 4-OCF.sub.2 CHF.sub.3 O m.p. 164.degree. C.B017 H H H 3-Cl 4-CN 4-OC.sub.4 H.sub.9 -t O m.p. 186.degree. C.B018 H H H 3-Cl 4-CN 4-SCF.sub.3 O m.p. 177.degree. C.B019 H H H 3-Cl 4-CN 4-SOCF.sub.3 O m.p. 178.degree. C.B020 H H H 3-Cl 4-CN 4-SO.sub.2 CF.sub.3 O m.p. 170.degree. C.B021 H H H 4-Cl 4-Cl 4-CF.sub.3 O m.p. 195.degree. C.B022 H H H 4-Cl 4-Cl 4-OCF.sub.3 O m.p. 165.degree. C.B023 H H H 4-Cl 4-CN 4-OCF.sub.3 O m.p. 210.degree. C.B024 H H H 3-Br 4-CN 4-OCF.sub.3 O m.p. 187.degree. C.B025 H H H 3-CF.sub.3 4-CN 4-OCF.sub.3 O m.p. 165.degree. C.B026 H H H 3-CF.sub.3 4-CN 4-SCF.sub.3 O m.p. 164.degree. C.B027 H H H 4-OCHF.sub.2 H 4-Cl O m.p. 192.degree. C.B028 H H H 4-OCHF.sub.2 H 4-OCF.sub.3 O m.p. 217.degree. C.B029 H H H 4-OCHF.sub.2 H 4-SCF.sub.3 O m.p. 209.degree. C.B030 H H H ##STR33## 4-CN 4-OCF.sub.3 O m.p. 164.degree . C.B031 H H H H 4-Cl 4-OCF.sub.3 S m.p. 171.degree. C.B032 H H H 3-Cl 4-CN 4-OCF.sub.3 S m.p. 149.degree. C.B033 H H H 4-Cl 4-CN 4-OCF.sub.3 S m.p. 195.degree. C.B034 H H H 3-CF.sub.3 4-CN 4-OCF.sub.3 S m.p. 209.degree. C.B035 H H COCH.sub.3 3-Cl 4-CN 4-OCF.sub.3 O m.p. 178.degree. C.B036 H H ##STR34## 3-Cl 4-CN 4-OCF.sub.3 O m.p. 221.degree . C.B037 H H CONHC.sub.2 H.sub.5 3-Cl 4-CN 4-OCF.sub.3 O m.p. 201.degree. C.B038 H OH H H H 4-CF.sub.3 O m.p. 200.degree. C.B039 H OH H H H 4-OCF.sub.3 O m.p. 190.degree. C.B040 H OCH.sub.3 H H H 4-Cl O m.p. 195.degree. C.B041 H OCH.sub.3 H H H 4-OCF.sub.3 O m.p. 183.degree. C.B042 H OCH.sub.3 H H H 4-OCF.sub.3 O m.p. 186.degree. C.B043 CH.sub.3 H H 3-Cl 4-CN 4-OCF.sub.3 O m.p. 156.degree. C.B044 H H H H 4-F 4-CF.sub.3 O m.p. 211.degree. C.B045 H H H H 4-F 4-OCF.sub.3 O m.p. 209.degree. C.B046 H H H H 2,4-F.sub.2 4-Cl O m.p. 229.degree. C.B047 H H H H 2,4-F.sub.2 4-OCF.sub.3 O m.p. 212.degree. C.B048 H H H H 3,4-F.sub.2 Cl O m.p. 201.degree. C.B049 H H H H 3,4-F.sub.2 4-OCF.sub.3 O m.p. 170.degree. C.B050 H H H H 3,4-F.sub.2 4-SCF.sub.3 O m.p. 163.degree. C.B051 H H H H 3,4-F.sub.2 4-SOCF.sub.3 O m.p. 163.degree. C.B052 H H H H 3,4-F.sub.2 4-SO.sub.2 CF.sub.3 O m.p. 182.degree. C.B053 H H H H 3,5-F.sub.2 4-Cl O m.p. 185.degree. C.B054 H H H H 3,5-F.sub.2 4-Br O m.p. 194.degree. C.B055 H H H H 4-Br 4-Cl O m.p. 233.degree. C.B056 H H H H 4-Br 4-CF.sub.3 O m.p. 227.degree. C.B057 H H H H 4-Br 4-OCF.sub.3 O m.p. 201.degree. C.B058 H H H H 4-CH.sub.3 4-CF.sub.3 O m.p. 218.degree. C.B059 H H H H 4-CH.sub.3 4-OCF.sub.3 O m.p. 201.degree. C.B060 H H H H 4-CF.sub.3 4-OCF.sub.3 O m.p. 215.degree. C.B061 H H H H 3-CN 4-CF.sub.3 O m.p. 186.degree. C.B062 H H H H 3-CN 4-OCF.sub.3 O m.p. 176.degree. C.B063 H H H H 3-CN 4-OCF.sub.2 CHF.sub.2 O m.p. 153.degree. C.B064 H H H H 4-NH.sub.2 4-OCF.sub.3 O m.p. 188.degree. C.B065 H H H H 2-NO.sub.2 4-OCF.sub.3 O m.p. 197.degree. C.B066 H H H H 4-NO.sub.2 4-SCF.sub.3 O m.p. 188.degree. C.B067 H H H H 4-OCF.sub.3 4-OCF.sub.3 O m.p. 206.degree. C.B068 H H H H 4-OCF.sub.3 4-SCF.sub.3 O m.p. 181.degree. C.B069 H H H H 4-SCHF.sub.2 4-OCF.sub.3 O m.p. 195.degree. C.B070 H H H 3-F 4-CN 4-OCF.sub.3 O m.p. 189.degree. C.B071 H H COCH.sub.3 3-F 4-CN 4-OCF.sub.3 O m.p. 193.degree. C.B072 H H COC.sub.4 H.sub.9 -t 3-F 4-CN 4-OCF.sub.3 O m.p. 218.degree. C.B073 H H H 3-F 4-CN 4-OCF.sub.2 Br O m.p. 201.degree. C.B074 H H H 3-F 4-CN 4-SCF.sub.3 O m.p. 189.degree. C.B075 H H H 3-F 4-CN 4-SOCF.sub.3 O m.p. 166.degree. C.B076 H H H 3-F 4-SO.sub.2 N(CH.sub.3).sub.2 4-Cl O m.p. 216.degree. C.B077 H H H 3-F 4-SO.sub.2 N(CH.sub.3).sub.2 4-OCF.sub.3 O m.p. 214.degree. C.B078 H H H 4-F 4-F 4-OCF.sub.3 O m.p. 174.degree. C.B079 H H H 4-F 4-CN 4-OCF.sub.3 O m.p. 194.degree. C.B080 H H H 4-F 4-CN 4-SCF.sub.3 O m.p. 211.degree. C.B081 H H H 4-F 4-CN 4-SOCF.sub.3 O m.p. 198.degree. C.B082 H H H 4-F 4-CN 4-SO.sub.2 CF.sub.3 O m.p. 177.degree. C.B083 H H H 3-Cl ##STR35## 4-OCF.sub.3 O m.p. 207.degree . C.B084 H H H 3-Cl 4-CN 4-I O m.p. 218.degree. C.B085 H H COC.sub.2 H.sub.5 3-Cl 4-CN 4-OCF.sub.3 O m.p. 202.degree. C.B086 H H COC.sub.3 H.sub.7 -n 3-Cl 4-CN 4-OCF.sub.3 O m.p. 142.degree. C.B087 H H COC.sub.3 H.sub.5 c 3-Cl 4-CN 4-OCF.sub.3 O m.p. 242.degree. C.B088 H H COC.sub.4 H.sub.9 -t 3-Cl 4-CN 4-OCF.sub.3 O m.p. 132.degree. C.B089 H H COC.sub.9 H.sub.19 -n 3-Cl 4-CN 4-OCF.sub.3 O m.p. 163.degree. C.B090 H H COCH.sub.2 Cl 3-Cl 4-CN 4-OCF.sub.3 O m.p. 191.degree. C.B091 H H ##STR36## 3-Cl 4-CN 4-OCF.sub.3 O m.p. 210.degree . C.B092 H H CO.sub.2 CH.sub.3 3-Cl 4-CN 4-OCF.sub.3 O m.p. 199.degree. C.B093 H H H 3-Cl 4-CN 4-OSO.sub.2 CF.sub.3 O m.p. 207.degree. C.B094 H H H 3-Cl 2-Cl-4-CN 4-CF.sub.3 O m.p. 203.degree. C.B095 H H H 3-Cl 2-Cl-4-CN 4-OCF.sub.3 O m.p. 196.degree. C.B096 H H H 3-Cl 2-Cl-4-CN 4-SCF.sub.3 O m.p. 205.degree. C.B097 H H H 3-Cl 2-CH.sub.3 -4-CN 4-Cl O m.p. 183.degree. C.B098 H H H 3-Cl 2-CH.sub.3 -4-CN 4-OCF.sub.3 O m.p. 191.degree. C.B099 H H H 3-Cl 2-CH.sub.3 -4-CN 4-SCF.sub.3 O m.p. 192.degree. C.B100 H H H 3-Cl 2-CH.sub.3 -4-CN 4-SOCF.sub.3 O m.p. 180.degree. C.B101 H H H 3-Cl 2-CH.sub.3 -4-CN 4-SO.sub.2 CF.sub.3 O m.p. 195.degree. C.B102 H H H 3-Cl 3-CH.sub.3 -4-CN 4-Cl O m.p. 210.degree. C.B103 H H H 3-Cl 3-CH.sub.3 -4-CN 4-OCF.sub.3 O m.p. 189.degree. C.B104 H H H 3-Cl 3-CH.sub.3 -4-CN 4-SCF.sub.3 O m.p. 179.degree. C.B105 H H H 3-Cl 3-CH.sub.3 -4-CN 4-SOCF.sub.3 O m.p. 188.degree. C.B106 H H H 3-Cl 3-CH.sub.3 -4-CN 4-SO.sub.2 CF.sub.3 O m.p. 191.degree. C.B107 H H H 3-Cl 4-(CN).sub.2 4-OCF.sub.3 O m.p. 208.degree. C.B108 H H H 3-Cl 4-OCF.sub.3 4-CF.sub.3 O m.p. 184.degree. C.B109 H H H 3-Cl 4-OCHF.sub.2 4-OCF.sub.3 O m.p. 172.degree. C.B110 H H H 3-Cl 4-OCHF.sub.2 4-SCF.sub.3 O m.p. 158.degree. C.B111 H H H 3-Cl 4-OSO.sub.2 CH.sub.3 4-OCF.sub.3 O m.p. 185.degree. C.B112 H H H 3-Cl 4-OSO.sub.2 CF.sub.3 4-OCF.sub.3 O m.p. 193.degree. C.B113 H H H 3-Br 4-CN 4-C.sub.6 H.sub.13 -n O m.p. 183.degree. C.B114 H H COCH.sub.3 3-Br 4-CN 4-OCF.sub.3 O m.p. 198.degree. C.B115 H H COC.sub.2 H.sub.5 3-Br 4-CN 4-OCF.sub.3 O m.p. 200.degree. C.B116 H H COC.sub.4 H.sub.9-t 3-Br 4-CN 4-OCF.sub.3 O m.p. 230.degree. C.B117 H H H 3-CHF.sub.2 4-CN 4-OCF.sub.3 O Glass- like amor- phous sub- stanceB118 H H H 3-CF.sub.3 4-CN 4-OCF.sub.3 O m.p. 131.degree. C. - isomerB119 H H H 3-CF.sub.3 4-CN 4-OCF.sub.3 O m.p. 126.degree. C. + isomerB120 H H COCH.sub.3 3-CF.sub.3 4-CN 4-OCF.sub.3 O m.p. 191.degree. C.B121 H H COC.sub.3 H.sub.7 -i 3-CF.sub.3 4-CN 4-OCF.sub.3 O m.p. 208.degree. C.B122 H H COC.sub.4 H.sub.9 -t 3-CF.sub.3 4-CN 4-OCF.sub.3 O m.p. 183.degree. C.B123 H H ##STR37## 3-CF.sub.3 4-CN 4-OCF.sub.3 O m.p. 251.degree . C.B124 H H H 3-CF.sub.3 4-CN 4-OCF.sub.2 Br O m.p. 190.degree. C.B125 H H H 3-CF.sub.3 4-CN 4-SOCF.sub.3 O Glass- like amor- phous sub- stanceB126 H H H 3-CF.sub.3 4-CN 4-SO.sub.2 CF.sub.3 O Glass- like amor- phous sub- stanceB127 H H H 4-CF.sub.3 4-CN 4-OCF.sub.3 O m.p. 189.degree. C.B128 H H H 3-CH.sub.2 OCH.sub.3 4-CN 4-CF.sub.3 O m.p. 153.degree. C.B129 H H H 3-CH.sub.2 OCH.sub.3 4-CN 4-OCF.sub.3 O m.p. 146.degree. C.B130 H H H 3-OCH.sub.3 4-CN 4-OCF.sub.3 O m.p. 166.degree. C.B131 H H H 3-OC.sub.3 H.sub.7 -i 4-CN 4-OCF.sub.3 O m.p. 147.degree. C.B132 H H H 3-OCHF.sub.2 4-CN 4-OCF.sub.3 O m.p. 118.degree. C.B133 H H H 3-OCHF.sub.2 4-CN 4-SCF.sub.3 O m.p. 118.degree. C.B134 H H H 3-OCHF.sub.2 4-CN 4-SOCF.sub.3 O Glass- like amor- phous sub- stanceB135 H H H 3-OCF.sub.3 4-CN 4-CF.sub.3 O m.p. 178.degree. C.B136 H H H 3-OCF.sub.3 4-CN 4-OCF.sub.3 O m.p. 147.degree. C.B137 H H H 3-OCF.sub.3 4-CN 4-SCF.sub.3 O m.p. 156.degree. C.B138 H H H 3-OCF.sub.3 4-CN 4-SOCF.sub.3 O Glass- like amor- phous sub- stanceB139 H H H 3-OCH.sub.2 CO.sub.2 CH.sub.3 4-CN 4-OCF.sub.3 O Glass- like amor- phous sub- stanceB140 H H H ##STR38## 4-CN 4-OCF.sub.3 O m.p. 154.degree . C.B141 H H H 3-OCO.sub.2 CH.sub.3 4-CN 4-OCF.sub.3 O Glass- like amor- phous sub- stanceB142 H H H H 3-CN 4-OCF.sub.3 S m.p. 120.degree. C.B143 H H H 4-F 4-NO.sub.2 4-Cl S m.p. 183.degree. C.B144 H H H 3-CF.sub.3 4-CH.sub.3 4-OCF.sub.3 O m.p. 166.degree. C.B145 H H COCOOC.sub.2 H.sub.5 3-Cl 4-CN 4-OCF.sub.3 O m.p. 192.degree. C.B146 H H H H 3-CHCHCHN-4 4-OCF.sub.3 O m.p. >300.degree. C. Hydro- chlor- ide__________________________________________________________________________ Compounds B041 and B042 are diastereomers, and the Rf value of compound B041 is higher than that of compound B042. M.p. in the "physical properties" column denotes melting point.

Table 6 shows .sup.1 -NMR data of the compounds having physical properties as glass like amorphous substance listed in Table 5.

TABLE 6______________________________________No. .sup.1 H-NMR(CDCl.sub.3 /TMS, .delta. value, ppm.)______________________________________B117 3.07(dd, 1H), 3.18(dd, 1H), 4.06-4.18(m, 2H), 6.02(s, 1H), 6.62(t, 1H), 7.06-7.61(m, 12H), 7.73(s, 1H).B125 3.12(dd, 1H), 3.23(dd, 1H), 4.12-4.32(m, 2H), 6.13(bs, 1H), 7.24-7.93(m, 12H), 8.08(bs, 1H).B126 3.11(dd, 1H), 3.23(dd, 1H), 4.13-4.28(m, 2H), 5.97(s, 1H), 7.25-7.75(m, 12H), 7.90-8.00(bs, 1H).B134 3.05(dd, 1H), 3.18(dd, 1H), 4.05-4.15(m, 1H), 4.39(d, 1H), 6.46(t, 1H), 6.49(bs, 1H), 6.98-7.67(m, 12H), 8.04(s, 1H).B138 3.04(dd, 1H), 3.16(dd, 1H), 4.03-4.21(m, 2H), 6.15(s, 1H), 6.95-7.65(m, 12H), 7.80(bs, 1H).B139 3.07(dd, 1H), 3.14(dd, 1H), 3.81(s, 3H), 3.97-4.11(m, 2H), 4.62(s, 2H), 5.72(s, 1H), 6.79-7.63(m, 12H), 7.73(s, 1H).B141 3.05(dd, 1H), 3.14(dd, 1H), 3.90(s, 3H), 3.96-4.16(m, 2H), 5.84(s, 1H), 6.69-7.61(m, 12H), 7.70(s, 1H).______________________________________

As the compound of the general formula (VIII), i.e., the starting compound for producing the hydrazinecarboxamide derivative of the general formula (I) of the present invention, there may be used either commercially available one or one which is produced, for example, by the production process illustrated below. ##STR39## wherein R.sup.3, R.sup.4, X and Y have the same meanings as those defined above, and R.sup.6 is a lower alkyl group.

That is, a compound of the general formula (VIII) can be produced by condensation reaction of a benzoic acid ester of the general formula (X) with a compound of the general formula (IX) in the presence of an inert solvent and a base.

The compound of the general formula (VI) can be produced, for example, by the production process illustrated below. ##STR40## wherein R.sup.1, R.sup.2, Z and W have the same meanings as those defined above, and V is a halogen atom or a leaving group such as a lower alkoxy group or an imidazole group.

That is, a compound of the general formula (VI) can be produced by reacting a compound of the general formula (XI) with a hydrazine derivative of the general formula (VII) in the presence of an inert solvent and a base.

Typical examples of the present invention are described below but should not be construed as limiting the scope of the invention.

EXAMPLE 1

1-1.Production of benzyl phenyl ketone hydrazone (compound No. V-1) ##STR41##

In 100 ml of ethanol was dissolved 5.0 g (26 mmoles) of benzyl phenyl ketone, followed by adding thereto 20 ml of hydrazine hydrate, and the reaction was carried out with stirring at a reaction temperature of 30.degree. to 40.degree. C. for 6 hours.

After completion of the reaction, the solvent was removed by distillation under reduced pressure from the reaction solution containing the desired compound, and the residue was purified by a silica gel column chromatography (eluent, ethyl acetate: n-hexane=1:4) to obtain 3.7 g of the desired compound as crystals.

Physical properties: m.p. 55.degree. C. Yield: 69%.

1-2. Production of 2-(1,2-diphenylethylidene)-N-phenylhydrazinecarboxamide (compound No. A001) ##STR42##

In 30 ml of tetrahydrofuran was dissolved 0.50 g (2.4 mmoles) of benzyl phenyl ketone hydrazone, followed by adding thereto 0.5 ml of triethylamine and 0.28 g (2.4 mmoles) of phenyl isocyanate, and the reaction was carried out at room temperature for 3 hours.

After completion of the reaction, the reaction solution containing the desired compound was concentrated under reduced pressure, and the residue was purified by a silica gel column chromatography (eluent, chloroform) to obtain 0.47 g of the desired compound as crystals. Physical properties: m.p. 181.degree. C. Yield: 60%.

EXAMPLE 2

Production of N-(4-chlorophenyl)-2-(1,2diphenylethylidene) hydrazinecarboxamide (compound No. A004) ##STR43##

In 30 ml of tetrahydrofuran was dissolved 0.62 g (3.0 mmoles) of benzyl phenyl ketone hydrazone, followed by adding thereto a drop of triethylamine and 0.45 g (3.0 mmoles) of 4-chlorophenyl isocyanate, and the reaction was carried out at room temperature for 3 hours.

After completion of the reaction, the solvent was removed by distillation under reduced pressure from the reaction solution containing the desired compound, and the crude crystals precipitated were washed with ether to obtain 0.90 g of the desired compound as crystals.

Physical properties: m.p. 199.degree. C. Yield: 84%.

EXAMPLE 3

3-1. Production of 4-fluorobenzylphenyl ketone hydrazone (compound No. V-2) ##STR44##

In 50 ml of ethanol was dissolved 3.0 g (14 mmoles) of 4-fluorobenzylphenyl ketone, followed by adding thereto 3 ml of hydrazine hydrate and 10 mg of p-toluenesulfonic acid, and the reaction was carried out with heating under reflux for 2 hours.

After completion of the reaction, the excess hydrazine hydrate and the ethanol were distilled off under reduced pressure. Water was added to the residue and the desired compound was extracted with ether. The ether layer was washed with water and dried over anhydrous magnesium sulfate, after which the ether was removed to obtain 3.0 g of the desired compound as paste.

Physical properties: paste. Yield: 93%.

3-2. Production of N-(4-chlorophenyl)-2-[2-(4-fluorophenyl)-1-phenylethylidene]hydrazinecarboxamide (compound No. A029) ##STR45##

In 50 ml of tetrahydrofuran was dissolved 0.80 g (3.5 mmoles) of 4-fluorobenzylphenyl ketone hydrazone, followed by adding thereto 0.53 g (3.5 mmoles) of 4-chlorophenyl isocyanate, and the reaction was carried out at room temperature for 3 hours.

After completion of the reaction, the reaction solution containing the desired compound was concentrated under reduced pressure, and the residue was purified by a silica gel column chromatography (eluent, chloroform) to obtain 0.9 g of the desired compound as crystals. Physical properties: m.p. 213.degree. C. Yield: 68%.

EXAMPLE 4

4-1. Production of 4-cyanobenzylphenyl ketone hydrazone (compound No. V-3) ##STR46##

In 200 ml of ethanol was dissolved 5.0 g (24 mmoles) of 4-cyanobenzylphenyl ketone, followed by adding thereto 15 ml of hydrazine hydrate and 15 mg of p-toluenesulfonic acid, and the reaction was carried out with heating under reflux for 4 hours.

After completion of the reaction, the excess hydrazine hydrate and the ethanol were distilled off under reduced pressure. Water was added to the residue and the desired compound was extracted with ether. The ether layer was washed with water and dried over anhydrous magnesium sulfate, after which the ether was removed to obtain 4.4 g of the desired compound as crystals.

Physical properties: m.p. 91.degree. C. Yield: 83%.

4-2. Production of 2-[2-(4-cyanophenyl)-1-phenylethylidene]-N-(4-trifluoromethylphenyl)hydrazinecarboxamide (compound No. A050) ##STR47##

In 30 ml of tetrahydrofuran was dissolved 1.0 g (4.4 mmoles) of 4-cyanobenzylphenyl ketone hydrazone, followed by adding thereto 0.81 g (4.0 mmoles) of 4-trifluoromethylphenyl isocyanate, and the reaction was carried out at room temperature for 2 hours.

After completion of the reaction, the reaction solution containing the desired compound was concentrated under reduced pressure, and the residue was purified by a silica gel column chromatography (eluent, chloroform) to obtain 0.85 g of the desired compound as crystals.

Physical properties: m.p. 217.degree. C. Yield: 50%.

EXAMPLE 5

5-1. Production of 4-nitrobenzylphenyl ketone hydrazone (compound No. V-4) ##STR48##

In 300 ml of ethanol was dissolved 5.0 g (21 mmoles) of 4-nitrobenzylphenyl ketone, followed by adding thereto 10 ml of hydrazine hydrate and 20 mg of p-toluenesulfonic acid, and the reaction was carried out at 60.degree. C. for 2 hours.

After completion of the reaction, the excess hydrazine hydrate and the ethanol were distilled off under reduced pressure. Water was added to the residue and the desired compound was extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate, after which the ethyl acetate was removed to obtain 4.9 g of the desired compound as crystals.

Physical properties: m.p. 72.degree. C. Yield: 93%.

5-2. Production of 2-[2-(4-nitrophenyl)-1-phenylethylidene)-N-(4-trifluoromethoxyphenyl)hydrazinecarbothioamide (compound No. A080) ##STR49##

In 30 ml of tetrahydrofuran was dissolved 0.80 g (3.1 mmoles) of 4-nitrobenzylphenyl ketone hydrazone, followed by adding thereto 0.62 g (2.8 mmoles) of -trifluoromethoxyphenyl isothiocyanate and three drops of triethylamine, and the reaction was carried out with heating under reflux for 5 hours. After completion of the reaction, the reaction solution containing the desired compound was concentrated under reduced pressure, and the residue was purified by a silica gel column chromatography (eluent, chloroform) to obtain 0.65 g of the desired compound as crystals.

Physical properties: m.p. 139.degree. C. Yield: 49%.

EXAMPLE 6

6-1. Production of 4-fluorobenzyl-4-fluorophenyl-ketone hydrazone (compound No. V-5) ##STR50##

In 50 ml of ethanol was dissolved 4.0 g (17 mmoles) of 4-fluorobenzyl-4-fluorophenylketone, followed by adding thereto 10 ml of hydrazine hydrate and a drop of concentrated sulfuric acid, and the reaction was carried out with heating under reflux for 2 hours.

After completion of the reaction the excess hydrazine hydrate and ethanol were distilled off under reduced pressure. Water was added to the residue and the desired compound was extracted with ether. The ether layer was washed with water and dried over anhydrous magnesium sulfate, after which the ether was removed under reduced pressure to obtain 4.2 g of the desired compound as paste.

Physical properties: paste. Yield: 100%.

6.2. Production of 2-[1,2-bis(4-fluorophenyl)ethylidene]-N-(4-trifluoromethylphenyl) hydrazinecarboxamide (compound No. A227) ##STR51##

In a mixture of 15 ml of pyridine and 15 ml of tetrahydrofuran was dissolved 0.50 g (2.0 mmoles) of 4-fluorobenzyl-4-fluorophenylketone hydrazone, followed by adding thereto 0.38 g (2.0 mmoles) of 4-trifluoromethylphenyl isocyanate, and the reaction was carried out at room temperature for 4 hours.

After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was washed with an ether-n-hexane mixed solvent, whereby 0.55 g of the desired compound was obtained as crystals.

Physical properties: m.p. 199.degree. C. Yield: 63%.

EXAMPLE 7

Production of 2-(1,2-diphenylethylidene)-N-methyl-N-phenylhydrazinecarboxamide (compound No. A300) ##STR52##

In 30 ml of ethanol were dissolved 0.65 g (3.3 mmoles) of benzyl phenyl ketone and N-methyl-N-phenylhydrazinecarboxamide, followed by adding thereto a drop of concentrated sulfuric acid, and the reaction was carried out with heating under reflux for 8 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column chromatography (eluent, ethyl acetate: n-hexane=3:2) to obtain 0.26 g of the desired compound as crystals.

Physical properties: m.p. 113.degree. C. Yield: 23%.

EXAMPLE 8

Production of 2-(1,2-diphenylethylidene)-1-methyl-N-phenylhydrazinecarboxamide (compound No. A303) ##STR53##

In 50 ml of toluene was dissolved 1.0 g (5.1 mmoles) of benzyl phenyl ketone, followed by adding thereto 0.50 g (11 mmoles) of methylhydrazine and 0.20 g (1.2 mmoles) of p-toluenesulfonic acid, and the reaction was carried out with heating under reflux for 4 hours while eliminating water from the reaction system by azeotropy by means of a Dean-Stark trap.

After completion of the reaction, the solvent was distilled off under reduced pressure, and the oil thus obtained was dissolved in 20 ml of tetrahydrofuran, followed by adding thereto 0.58 g (4.9 mmoles) of phenyl isocyanate and 0.5 ml of triethylamine. The resulting mixture was allowed to stand overnight at room temperature to be subjected to reaction.

After completion of the reaction, and the residue was purified by a silica gel column chromatography (eluent, ethyl acetate: n-hexane=1:5) to obtain 0.76 g of the desired compound as crystals.

Physical properties: m.p. 111.degree. C. Yield: 46%.

EXAMPLE 9

9-1. Production of benzoin hydrazone (compound No. V-6) ##STR54##

In 50 ml of ethanol were dissolved 5.0 g (24 mmoles) of benzoin and 10 ml of hydrazine hydrate, followed by adding thereto a drop of concentrated sulfuric acid, and the reaction was carried out with heating under reflux for 2 hours.

After completion of the reaction, the excess hydrazine hydrate and ethanol were distilled off under reduced pressure. Water was added to the residue and the desired compound was extracted with ether. The ether layer was washed with water and dried over anhydrous magnesium sulfate, after which the ether was to obtain 5.1 g of the desired compound as paste.

Physical properties: paste. Yield: 96%.

9-2. Production of 2-(2-hydroxy-1,2-diphenylethylidene)-N-phenylhydrazinecarboxamide (compound No. A330) ##STR55##

In 30 ml of tetrahydrofuran was dissolved 0.80 g (3.5 mmoles) of benzoin hydrazone, followed by adding thereto 0.42 g (3.5 mmoles) of phenyl isocyanate, and the reaction was carried out at room temperature for 4 hours.

After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel colume chromatography (eluent, tetrahydrofuran: chloroform=1:10) to obtain 0.70 g of the desired compound as crystals.

Physical properties: m.p. 167.degree. C. Yield: 57%.

EXAMPLE 10

Production of 2-[2-(4-cyanophenyl)-1-phenylethyl]-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamine (compound No. B006) ##STR56##

10-1.

In a mixture of 20 ml of tetrahydrofuran and 30 ml of methanol was dissolved 0.70 g (1.6 mmoles) of 2-[2-(4-cyanophenyl)-1-phenylethylidene]-N-(4-trifluorometh oxyphenyl)hydrazinecarboxamide, and 0.20 g (3.2 mmoles) of sodium cyanoborohydride was added to the solution. A saturated solution of hydrogen chloride in methanol was added dropwise with stirring at room temperature, and the reaction was carried out at room temperature for 1 hour.

After completion of the reaction, the solvent was distilled off under reduced pressure and ethyl acetate was added to the residue. The resulting mixture was neutralized with an aqueous sodium hydrogencarbonate solution and the ethyl acetate layer was separated. The thus obtained ethyl acetate containing the desired compound was dried over anhydrous magnedium sulfate, and the solvent was removed to obtain crude crystals of the desired compound.

The crude crystals obtained were washed with ether to obtain 0.54 g of the desired compound as crystals.

Physical properties: m.p. 204.degree. C. Yield: 77%.

10-2.

In 80 ml of tetrahydrofuran was dissolved 1.0 g (2.3 mmoles) of 2-[2-(4-cyanophenyl)-1-phenylethylidene]-N-(4-trifluoromethoxyphenyl) hydrazinecarboxamide, and 0.1 g of 5% palladium carbon was added to the solution. The resulting mixture was allowed to absorb hydrogen gas at a pressure of 6 kg/cm.sup.2 under shaking at room temperature for 60 hours.

After completion of the reaction, the catalyst was filtered off and the filtrate was evaporated under reduced pressure to obtain crude crystals of the desired compound.

The crude crystals obtained were washed with an ether-n-hexane mixture to obtain 0.97 g of the desired compound as crystals.

Physical properties: m.p. 204.degree. C. Yield: 97%.

EXAMPLE 11

Production of 2-[2-(4-nitrophenyl)-1-phenylethyl]-N-(4-trifluoromethoxyphenyl) hydrazinecarboxamide (compound No. B008) ##STR57##

In a mixture of 10 ml of tetrahydrofuran and 10 ml of methanol was dissolved 0.48 g (1.0 mmole) of 2-[2-(4-nitrophenyl)-1-phenylethylidene]-N-(4-trifluorometh oxyphenyl)hydrazinecarboxamide, and 0.07 g (1 mmole) of sodium cyanoborohydride was added to the solution. Then, 5 ml of a saturated solution of hydrogen chloride in methanol was added dropwise with ice-cooling and the reaction was carried out for 30 minutes.

After completion of the reaction, the solvent was distilled off under reduced pressure and ethyl acetate was added to the residue. The resulting mixture was neutralized with an aqueous sodium hydrogencarbonate solution and the ethyl acetate layer was separated. The thus obtained ethyl acetate containing the desired compound was dried over anhydrous magnesium sulfate, and the solvent was removed to obtain crude crystals of the desired compound.

The crude crystals obtained were washed with ether-n-hexane to obtain 0.36 g of the desired compound as crystals.

Physical properties: m.p. 188.degree. C. Yield: 75%.

EXAMPLE 12

Production of 2-[1-(4-chlorophenyl)-2-(4-cyanophenyl) ethyl-N-(4-trifluoromethoxyphenyl)hydrazinecarbothioamide (compound No. B033) ##STR58##

In a mixture of 10 ml of tetrahydrofuran and 30 ml of methanol was dissolved 0.50 g (1.0 mmole) of 2-[1-(4-chlorophenyl)-2-(4-cyanophenyl)ethylidene]-N-(4-trifluoromethoxyphenyl) hydrazinecarbothioamide, and 0.19 g (3.1 mmoles) of sodium cyanoborohydride was added to the solution. Then, 5 ml of a saturated solution of hydrogen chloride in methanol was added dropwise at room temperature, and the reaction was carried out for 2 hours.

After completion of the reaction, the solvent was distilled off under reduced pressure and the ethyl acetate was added to the residue. The resulting mixture was neutralized with an aqueous sodium hydrogencarbonate solution and the ethyl acetate layer was separated. The thus obtained ethyl acetate containing the desired compound was dried over anhydrous magnesium sulfate, and the solvent was removed to obtain crude crystals of the desired compound.

The crude crystals obtained were washed with ether-n-hexane to obtain 0.27 g of the desired compound as crystals.

Physical properties: m.p. 195.degree. C. Yield: 54%.

EXAMPLE 13

Production of 2-acetyl-2-[1-(3-chlorophenyl)-2-(4-cyanophenyl) ethyl]-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide (compound No. B035) ##STR59##

In 30 ml of tetrahydrofuran was dissolved 0.70 g (1.5 mmoles) of 2-[1-(3-chlorophenyl)-2-(4-cyanophenyl)ethyl]-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide obtained in the same manner as in Example 10. To the resulting solution were added 0.35 g (4.4 mmoles) of acetyl chloride and 45 g (4.4 mmoles) of triethylamine at room temperature, and the reaction was carried out for 2 hours.

After completion of the reaction, the solvent was distilled off under reduced pressure, water was added to the residue and the desired compound was extracted with ethyl acetate. The ethyl acetate layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was removed to obtain crude crystals of the desired compound.

The crude crystals obtained were washed with ether to obtain 0.55 g of the desired compound as crystals.

Physical properties: m.p. 178.degree. C. Yield: 54%.

EXAMPLE 14

Production of 2-[2-(4-cyanophenyl)-1-(3-trifluoromethylphenyl) ethylidene]-N-(4-trifluoromethoxyphenyl)hydrazinecarboxamide (compound No. A261) ##STR60##

In 30 ml of tetrahydrofuran was dissolved 0.50 g (1.7 mmoles) of 4-cyanobenzyl-3-trifluoromethylphenylketone hydrazone, and 1 ml of pyridine was added. Then, a solution prepared by diluting 0.32 g (1.6 mmoles) of 4-trifluoromethoxyphenyl isocyanate with 5 ml of tetrahydrofuran was added dropwise with stirring at room temperature. After completion of the dropwise addition, the reaction was carried out at room temperature for another 4 hours.

After completion of the reaction, the solvent was distilled off under reduced pressure, and crude crystals obtained was washed with ether-n-hexane to obtain 0.40 g of the desired compound as crystals.

Physical properties: m.p. 191.degree. C. Yield: 40%.

Insecticides containing the hydrazinecarboxamide derivative of the general formula (I) of the present invention as an active ingredient are suitable for controlling various insect pests such as agricultural insect pests, forest insect pests, horticultural insect pests, stored grain insect pests, sanitary insect pests, nematodes, etc. They have an insecticidal effect also, for example, on LEPIDOPTERA including summer fruit torrix (Adoxophyes orana fasciata), smaller tea tortrix (Adoxophyes sp.), Manchurian fruit moth (Grapholita inopinata), oriental fruit moth (Grapholita mlesta), soybean pod border (Leguminivora glycinivorella), mulberry leafroller (Olethreutes mori), tea leafroller (Caloptilla thevivora), Caloptilia sp. (Caloptilia zachrysa), apple leafminer (Phyllonorycter ringoniella), pear barkminer (Spulerina astaurota), common white (Piers rapae crucivora), tabacco budworm (Heliothis armigera), clodling moth (Laspeyresia pomonella), diamondback moth (Plutella xylostella), apple fruit moth (Argyresthia conjugella), peach fruit moth (Carposina niponensis), rice stem borer (Chilo suppressalia), rice leafroller (Cnaphalocrocis medinails), tabacco moth (Ephestia elutella), mulberry pyralid (Glyphodes pyloalis), yellow rice borer (Scirpophaga incertulas), rice skipper (Parnara guttata), rice armyworm (Pseudaletia separata), pink borer (Sesamia inferens), common cutworm (Spodoptera litura), beet armyworm (Spodoptera exigua), etc.; HEMIPTERA including aster leafhopper (Macrosteles fascifrons), green rice leafhopper (Nephotettix cincticeps), brown rice planthopper (Nilaparvata lugens), whitebacked rice planthopper (Sogatella furcifera), citrus psylla (Diaphorina citri), grape whitefly (Aleurolobus taonabae), sweetpotato whitefly (Bemisia tabaci), greenhouse whitefly (Trialeurodes vaporariorum), turnip aphid (Lipaphis erysimi), green peach aphid (Myzus persicae), Indian wax scale (Ceroplastes ceriferus), cottony citrus scale (Pulvinaria aurantii), camphor scale (Pseudaonidia duplex), San Jose scale (Comstockaspis perniciosa), arrowhead scale (Unaspis yanonensis), etc.; COLEOPTERA including soybean beetle (Anomala rufocuprea), Japanese beetle (Popillia japonica), tobacco beetle (Lasioderma serricorne), powderpost beetle (Lyctus brunneus), twenty-eight-spotted ladybird (Epilachna vigintioctopunctata), adzuki bean weevil (Callosobruchus chinensis), vegetable weevil (Listroderes costirostris), maize weevil (Sitophilus zeamais), boll weevil (Anthonomus grandis grandis), rice water weevil (Lissorhoptrus oryzophilus), cucurbit leaf beetle (Aulacophora femoralis), rice leaf beetle (Outlema oryzae), striped flea beetle (Phyllotreta striolata), pine shoot beetle (Tomicus piniperda), Colorade potato beetle (Leptinotarsa decemilineata), Mexican bean beetle (Epilachna varivestis), corn rootworm (Diabrotica sp.), etc.: DIPTERA including melon fly (Dacus(Zeugodacus) cucurbitae), oriental fruit fly (Dacus(Bactrocera) dorsalis), rice leafminer (Agromyza oryzae), onion maggot (Delia antiqua), seedcorn maggot (Delia platura), soybean pod gall midge (Asphodylia sp.), muscid fly (Musca domestica), house mosquite (Culex piplens), etc.; and TYLENCHIDA including root-lesion nematode (Pratylenchus sp.), coffer root-lesion nematode (Pratylenchus coffeae), potato cyst nematode (Globodera rostochiensis), root-knot nematode (meloidogyne sp.), citrus nematode (Tylenchulus semipenetrans), Aphelenchus sp. (Aphelenchus avenae), chrysanthemum foliar nematode (Aphelenchoides ritzemabosi), etc. The insecticides are markedly effective particularly against insect pests belonging to LEPIDOPTERA, COLEOPTERA and the like.

The zoological names and the like are in accordance with Applied Zoology and Entomology Society of Japan, "List of Agricultural and Forest Injurious Animals and Insects", published in 1987.

The agricultural and horticultural insecticide of the present invention has a marked insecticidal effect on the above-exemplified insect pests, sanitary insect pests, and/or nematodes, which are injurious to paddy fields, fruit trees, vegetables and other crops, and flowers and ornament plants. Therefore, the desired effect of the insecticide of the present invention can be obtained by applying the insecticide to the paddy field water, stalks and leaves of fruit trees, vegetables, other crops, flowers and ornament plants, soil, etc., or to the inside of a house or ditches around a house, in which the above-exemplified sanitary insect pests injurious to men and beasts appear or are expected to appear. The application is carried out at a season at which the insect pests, sanitary insect pests or nematodes are expected to appear, before their appearance or at the time when their appearance is confirmed.

This invention however should not be limited to these embodiments.

When the hydrazinecarboxamide derivative of the general formula (I) of this invention is used as an insecticide, it is generally prepared into conveniently usable forms according to an ordinary manner for preparation of agrochemicals.

That is, the hydrazinecarboxamide derivative of the general formula (I) of this invention and, optionally, an adjuvant are blended with a suitable inert carrier in a proper proportion and prepared into a suitable preparation form such as a suspension, emulsifiable concentrate, soluble concentrate, wettable powder, granules, dust or tablet through dissolution, dispersion, suspension, mixing, impregnation, adsorption or sticking.

The inert carrier in this invention may be solid or liquid. Examples of the solid carrier are soybean flour, cereal flour, wood flour, bark flour, saw dust, powdered tobacco stalks, powdered walnut shells, bran, powdered cellulose, extraction residues of vegetables, powdered synthetic polymers or resins, clays (e.g. kaolin, bentonite, and acid clay), talcs (e.g. talc and pyrophyllite), silica powders or flakes [e.g. diatomaceous earth, silica sand, mica and white carbon, i.e. synthetic, high-dispersion silicic acid, also called finely divided hydrated silica or hydrated silicic acid, some of commercially available products contain silicate as the major component)], activated carbon, powdered sulfur, powdered pumice, calcined diatomaceous earth, ground brick, fly ash, sand, calcium carbonate powder, calcium phosphate powder and other inorganic or mineral powders, chemical fertilizers (e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and ammonium chloride), and compost. These carriers may be used alone or as a mixture thereof.

The liquid carrier is that which itself has solubility or which is without such solubility but is capable of dispersing an active ingredient with the aid of an adjuvant. The following are typical examples of the liquid carrier and can be used alone or as a mixture thereof. Water; alcohols such as methanol, ethanol, isopropanol, butanol and ethylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and cyclohexanone; ethers such as ethyl ether, dioxane, Cellosolve, dipropyl ether and tetrahydrofuran; aliphatic hydrocarbons such as kerosene and mineral oils; aromatic hydrocarbons such as benzene, toluene, xylene, solvent naphtha and alkylnaphthalene; halogenated hydrocarbons such as dichloroethane, chloroform, carbon tetrachloride and chlorobenzene; esters such as ethyl acetate, diisopropyl phthalate, dibutyl phthalate and dioctyl phthalate; amides such as dimethylformamide, diethylformamide and dimethylacetamide; nitriles such as acetonitrile; and dimethyl sulfoxide.

The following are typical examples of the adjuvant, which are used depending upon purposes and used alone or in combination in some cases, or need not to be used at all.

To emulsify, disperse, dissolve and/or wet an active ingredient, a surfactant is used. Examples of the surfactant are polyoxyethylene alkyl ethers, polyoxyethylenealkylaryl ethers, polyoxyethylene higher fatty acid esters, polyoxyethylene resinates, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkylarylsulfonates, naphthalenesulfonic acid condensation products, ligninsulfonates and higher alcohol sulfate esters.

Further, to stabilize the dispersion of an active ingredient, tackify it and/or bind it, an adjuvant may be used. Examples of such an adjuvant are casein, gelatin, starch, methylcellulose, carboxymethylcellulose, gum arabic, polyvinyl alcohol, turpentine, bran oil, bentonite and ligninsulfonates.

To improve the flowability of a solid product, an adjuvant may be used. Examples of such an adjuvant are waxes, stearates and alkyl phosphates.

Adjuvants such as naphthalenesulfonic acid condensation products and polycondensates of phosphates may be used as a peptizer for dispersible products.

Adjuvants, e.g. silicon oils may be also used as a defoaming agent.

The content of the active ingredient may be varied as required. In dusts or granules, the suitable content thereof is from 0.01 to 50% by weight. In emulsifiable concentrates, flowable wettable powders, it is also from 0.01 to 50% by weight.

An insecticide containing the hydrazinecarboxamide derivative of the general formula (I) of this invention as an active ingredient is used to control a variety of insect pests in the following manner. That is, it is applied to the insect pests or a site where appearance of growth of the insect pests is undesirable, as it is or after being properly diluted with or suspended in water or the like, in an amount effective for control of the insect pests.

The amount of the insecticide containing the hydrazinecarboxamide derivative of the general formula (I) of this invention as an active ingredient is varied depending upon various factors such as a purpose, insect pests to be controlled, a growth state of a plant, tendency of insect pests appearance, weather, environmental conditions, a preparation form, an application method, an application site and an application time. It may be properly chosen in the range of 0.1 g to 5 kg (in terms of the active ingredient) per 10 ares depending upon purposes.

The insecticide containing the hydrozinecarboxamide derivative of the general formula (I) of this invention as an active ingredient may be used in admixture with other insecticides or fungicides in order to expand both spectrum of controllable insect pest species and the period of time when effective applications are possible or to reduce the dosage.

Typical preparation examples and test examples of the present invention are described below but should not be construed as limiting the scope of the invention.

In the preparation examples, parts are all by weight.

FORMULATION EXAMPLE 1

______________________________________Each compound of the invention 50 partsXylene 40 partsMixture of polyoxyethylene 10 partsnonlyphenyl ether and calciumalkylbenzenesulfonate______________________________________

An emulsifiable concentrate was prepared by mixing uniformly the above ingredients to effect dissolution.

FORMULATION EXAMPLE 2

______________________________________Each compound of the invention 3 partsClay powder 82 partsDiatomaceous earth powder 15 parts______________________________________

A dust was prepared by mixing uniformly and grinding the above ingredients.

FORMULATION EXAMPLE 3

______________________________________Each compound of the invention 5 partsMixed powder of bentonite and 90 partsclayCalcium lignin sulfonate 5 parts______________________________________

Granules were prepared by mixing the above ingredients uniformly, and kneading the resulting mixture together with a suitable amount of water, followed by granulation and drying.

FORMULATION EXAMPLE 4

______________________________________Each compound of the invention 20 partsMixture of kaolin and synthetic, 75 partshigh-dispersion silicic acidMixture of polyoxyethylene 5 partsnonylphenyl ether and calciumalkylbenzenesulfonate______________________________________

A wettable powder was prepared by mixing uniformly and grinding the above ingredients.

TEST EXAMPLE 1

Insecticidal effect on common cutworm (Spodoptera litura)

A piece of cabbage leaf (cultivar: Shikidori) was immersed for about 30 seconds in a liquid chemical prepared by diluting a preparation containing each compound of this invention as an active ingredient to adjust the concentration to 500 ppm. After air-drying, it was placed in a plastic Petri dish having a diameter of 9 cm, and inoculated with second-instar larvae of common cutworm, after which the dish was closed and then allowed to stand in a room thermostated at 25.degree. C. Eight days after the inoculation, the dead and alive were counted. The mortality was calculated according to the following equation and judgement was passed according to the criterion shown below. The test was carried out with triplicate groups of 10 insects.

______________________________________ ##STR61##Criterion:Degree ofinsecticidal Mortalityeffect (%)______________________________________A 100B 99-90C 89-80D 79-50E Less than 49______________________________________

The results obtained are shown in Table 7.

TABLE 7______________________________________ ConcentCompound ration Judge-No. (ppm) ment______________________________________A007 500 AA016 500 CA017 500 DA018 500 AA019 500 CA020 500 AA025 500 DA027 500 AA028 500 AA033 500 AA034 500 AA038 500 AA042 500 AA049 500 CA050 500 CA051 500 AA054 500 AA055 500 AA056 500 AA057 500 AA058 500 AA059 500 AA061 500 AA062 500 AA063 500 AA065 500 AA074 500 DA076 500 AA077 500 AA078 500 AA079 500 AA080 500 AA081 500 AA082 500 AA087 500 AA089 500 AA090 500 AA091 500 AA092 500 AA093 500 AA096 500 AA097 500 AA098 500 CA099 500 AA101 500 AA105 500 AA106 500 AA109 500 AA111 500 AA112 500 CA113 500 AA114 500 AA115 500 AA116 500 AA118 500 DA120 500 DA125 500 AA127 500 AA129 500 AA130 500 AA131 500 AA132 500 AA133 500 AA134 500 DA135 500 AA137 500 AA138 500 AA140 500 AA141 500 AA142 500 AA143 500 DA146 500 AA147 500 AA149 500 AA151 500 AA152 500 AA153 500 AA155 500 AA158 500 AA161 500 AA164 500 AA165 500 AA167 500 AA168 500 AA169 500 AA170 500 AA171 500 AA172 500 AA173 500 AA178 500 AA179 500 AA182 500 DA185 500 AA189 500 AA194 500 AA195 500 AA196 500 AA197 500 AA198 500 AA199 500 AA200 500 AA201 500 AA202 500 AA203 500 AA212 500 CA213 500 AA214 500 CA216 500 AA218 500 AA219 500 AA220 500 AA221 500 AA225 500 AA226 500 AA227 500 AA228 500 AA229 500 AA230 500 CA231 500 AA232 500 AA233 500 AA234 500 AA235 500 AA239 500 AA240 500 AA241 500 AA242 500 AA248 500 AA249 500 DA250 500 AA251 500 AA254 500 DA257 500 AA258 500 CA260 500 AA261 500 AA262 500 AA263 500 AA264 500 AA265 500 AA269 500 AA274 500 AA281 500 AA285 500 AA292 500 CA310 500 AA312 500 AA313 500 AA314 500 CA318 500 DA319 500 AA320 500 AA321 500 AA325 500 CA326 500 AA342 500 DA343 500 AA344 500 AA354 500 DA362 500 AA367 500 AA378 500 AA381 500 AA383 500 AA385 500 AA386 500 AA388 500 CA389 500 AA390 500 CA393 500 AA394 500 CA395 500 AA397 500 AA398 500 CA399 500 CA400 500 AA401 500 AA402 500 AA403 500 AA404 500 AA405 500 AA406 500 AA409 500 AA410 500 AA411 500 AA412 500 AA415 500 AA418 500 AA419 500 AA420 500 AA421 500 AA422 500 AA423 500 AA424 500 AA425 500 AA426 500 CA427 500 AA428 500 AA429 500 AA430 500 DA431 500 CA432 500 AA433 500 AA434 500 CA436 500 AA437 500 AA438 500 DA439 500 AA440 500 AA441 500 AA442 500 AA443 500 AA447 500 AA448 500 AA449 500 AA450 500 AA451 500 AA452 500 AA453 500 DA454 500 AA456 500 DA460 500 AA461 500 AA462 500 AA463 500 AA464 500 AA465 500 AA466 500 DA467 500 AA473 500 DA474 500 CA476 500 AA477 500 AA478 500 AA479 500 AA480 500 DB002 500 AB003 500 AB004 500 AB006 500 AB007 500 AB008 500 AB009 500 AB010 500 AB011 500 AB012 500 AB013 500 AB014 500 AB015 500 AB016 500 AB018 500 AB019 500 AB020 500 AB021 500 AB022 500 DB023 500 AB024 500 AB025 500 AB026 500 AB027 500 DB028 500 AB030 500 AB031 500 AB032 500 AB033 500 AB034 500 AB035 500 AB036 500 AB037 500 CB043 500 AB044 500 AB045 500 AB047 500 DB048 500 AB049 500 AB050 500 AB051 500 AB052 500 AB053 500 AB054 500 CB056 500 AB057 500 AB059 500 DB060 500 AB061 500 DB062 500 AB063 500 AB066 500 AB067 500 AB068 500 AB069 500 AB070 500 AB071 500 AB072 500 AB073 500 AB074 500 AB075 500 AB079 500 AB080 500 AB081 500 AB082 500 AB084 500 DB085 500 AB086 500 AB087 500 AB088 500 AB090 500 AB091 500 AB092 500 AB093 500 AB094 500 AB095 500 AB096 500 AB097 500 CB098 500 AB099 500 AB100 500 AB101 500 AB103 500 AB104 500 AB105 500 AB106 500 DB107 500 AB108 500 AB109 500 AB110 500 AB111 500 AB112 500 AB114 500 AB115 500 AB116 500 AB117 500 AB118 500 AB119 500 AB120 500 AB121 500 AB122 500 AB124 500 AB125 500 AB126 500 AB127 500 AB130 500 AB131 500 DB132 500 AB133 500 AB134 500 AB135 500 AB136 500 AB137 500 AB138 500 AB142 500 AB145 500 A______________________________________

TEST EXAMPLE 2

Insecticidal effect on adult maize weevil (Sitophilus zeamais)

Twenty to thirty grains of the brown rice were immersed for about 30 seconds in a liquid chemical prepared by diluting a preparation containing each compound of this invention as an active ingredient to adjust the concentration to 200 ppm. After air-drying, they were placed in a glass Petri dish having a diameter of 4 cm, and inoculated with adult maize weevils, after which the dish was closed and then allowed to stand in a room thermostated at 25.degree. C. Eight days after the inoculation, the dead and alive were counted. The mortality was calculated according to the equation described in Test Example 1 and judgement was passed according to the criterion shown in Test Example 1. The test was carried out with triplicate groups of 10 insects.

The results obtained are shown in Table 8.

TABLE 8______________________________________ ConcentCompound ration Judge-No. (ppm) ment______________________________________A004 200 DA006 200 CA007 200 AA015 200 AA016 200 BA017 200 AA018 200 AA020 200 AA021 200 AA026 200 AA027 200 AA028 200 AA029 200 AA030 200 AA033 200 AA038 200 AA040 200 AA042 200 DA044 200 DA046 200 CA050 200 AA056 200 AA057 200 AA058 200 BA059 200 AA061 200 DA062 200 DA067 200 AA073 200 AA077 200 AA078 200 AA079 200 AA080 200 DA081 200 AA082 200 BA091 200 AA092 200 AA093 200 AA096 200 AA097 200 AA098 200 AA099 200 AA101 200 AA102 200 DA103 200 AA105 200 AA106 200 AA110 200 AA111 200 AA112 200 AA113 200 AA114 200 AA115 200 CA116 200 AA118 200 AA123 200 BA125 200 AA127 200 AA131 200 AA132 200 AA133 200 AA134 200 AA135 200 AA137 200 AA138 200 AA140 200 AA141 200 DA146 200 AA147 200 AA148 200 AA149 200 AA150 200 BA151 200 AA152 200 DA154 200 AA155 200 AA156 200 AA163 200 CA164 200 AA165 200 AA161 200 DA162 200 DA166 200 CA167 200 BA168 200 AA170 200 AA172 200 DA173 200 CA175 200 DA178 200 AA179 200 BA184 200 AA185 200 AA186 200 CA187 200 CA188 200 DA189 200 AA194 200 AA195 200 AA196 200 AA197 200 AA198 200 AA199 200 AA200 200 AA201 200 AA202 200 AA203 200 AA204 200 AA212 200 DA213 200 DA215 200 AA216 200 AA217 200 AA218 200 AA219 200 AA220 200 AA221 200 AA223 200 AA224 200 AA225 200 AA226 200 AA227 200 AA228 200 AA229 200 AA230 200 BA231 200 AA232 200 AA233 200 DA234 200 AA235 200 AA236 200 DA237 200 AA238 200 AA239 200 AA240 200 AA241 200 AA242 200 AA257 200 AA258 200 CA259 200 AA260 200 AA261 200 AA262 200 AA263 200 AA264 200 AA265 200 AA268 200 AA269 200 AA270 200 AA272 200 DA273 200 DA283 200 AA284 200 AA285 200 AA288 200 AA289 200 CA292 200 AA293 200 DA294 200 BA295 200 CA319 200 AA320 200 AA321 200 AA326 200 DA351 200 AA370 200 AA374 200 DA380 200 CA381 200 AA383 200 AA385 200 AA386 200 AA388 200 CA389 200 AA390 200 CA393 200 AA394 200 CA395 200 AA397 200 AA398 200 CA400 200 AA401 200 AA402 200 AA403 200 AA404 200 AA405 200 BA406 200 DA409 200 AA410 200 BA411 200 AA415 200 AA418 200 AA419 200 AA420 200 AA421 200 AA422 200 AA423 200 AA424 200 DA425 200 AA427 200 AA429 200 DA430 200 BA436 200 AA439 200 AA440 200 AA441 200 AA442 200 AA443 200 AA447 200 AA448 200 AA449 200 AA450 200 AA451 200 AA452 200 AA453 200 DA454 200 AA460 200 AA461 200 AA462 200 AA463 200 BA464 200 AA465 200 AA466 200 AA467 200 AB001 200 AB002 200 AB003 200 AB004 200 AB006 200 AB008 200 AB009 200 AB010 200 AB011 200 AB012 200 AB013 200 AB014 200 AB015 200 AB016 200 AB018 200 AB019 200 AB020 200 AB021 200 CB022 200 DB023 200 AB024 200 AB025 200 AB026 200 AB028 200 BB031 200 AB032 200 AB034 200 AB035 200 AB036 200 AB037 200 AB044 200 AB045 200 AB047 200 AB048 200 AB049 200 DB050 200 AB051 200 AB052 200 DB055 200 AB056 200 AB057 200 AB060 200 AB061 200 AB062 200 AB063 200 CB066 200 AB067 200 CB068 200 AB069 200 AB070 200 AB071 200 AB072 200 AB073 200 AB074 200 AB075 200 AB079 200 AB080 200 AB081 200 AB082 200 AB084 200 AB085 200 AB086 200 BB087 200 AB088 200 BB090 200 AB091 200 BB092 200 AB093 200 AB094 200 AB095 200 AB096 200 AB097 200 CB098 200 BB107 200 AB108 200 AB109 200 AB110 200 AB111 200 AB112 200 AB114 200 AB115 200 AB116 200 AB117 200 AB118 200 AB119 200 AB120 200 AB121 200 AB122 200 AB124 200 AB125 200 AB126 200 AB132 200 AB133 200 AB134 200 AB135 200 AB136 200 AB137 200 AB138 200 AB145 200 A______________________________________

Claims

1. A hydrazinecarboxamide derivative represented by the general formula (I): ##STR62## wherein R.sup.1 is a hydrogen atom or a C1-3 alkyl group, R.sup.2 is a hydrogen atom or a C1-3 alkyl group, R.sup.3 is a hydrogen atom; a hydroxyl group; a C1-3 alkyl group; a C1-5 alkoxy group; a C1-3 alkylcarbonyloxy group; or an unsubstituted phenylcarbonyloxy group; R.sup.4 is a hydrogen atom or a C1-3 alkyl group, R.sup.3 and R.sup.4 being able to be taken together to represent an oxygen atom, A is ##STR63## wherein X represents 1 to 5 atoms or groups which may be the same or different and are selected from the group consisting of hydrogen atom; hydroxyl group; halogen atoms; cyano group; C1-4 alkyl groups, C1-3 haloalkyl groups; C1-3 alkoxy groups, C1-3 haloalkoxy groups; C1-3 alkoxy C1-3 alkyl groups; C3-5 alkenyloxy groups; cyclo C3-6 alkylcarbonyloxy groups; C1-3 alkoxycarbonyloxy groups; C1-3 alkoxycarbonyl C1-3 alkyloxy groups; C1-3 alkylcarbonyl C1-3 alkyloxy groups; C1-3 alkylsulfonyloxy groups; phenoxy group; methylenedioxy group; alkenylene groups having 3 to 4 carbon atoms so as to form a polycyclic ring together with the adjacent carbon atom of the phenyl ring; substituted amino groups having as the substituent(s) 1 or 2 C1-3 alkyl groups which may be the same or different; substituted aminocarbonyloxy groups having as the substituent(s) 1 or 2 C1-3 alkyl groups which may be the same or different; Y represents 1 to 5 atoms or groups which may be the same or different and are selected from the group consisting of hydrogen atom; hydroxyl group; halogen atoms; cyano group; nitro group; C1-3 alkyl groups; C1-3 haloalkyl groups; C1-3 alkoxy groups; C1-3 haloalkoxy groups; C3-5 alkenyloxy groups; C1-3 alkylcarbonyloxy groups; C1-3 alkylsulfonyloxy groups; C1-3 haloalkylsulfonyloxy groups; C1-3 alkylthio groups; C1-3 haloalkylthio groups; C1-3 alkylsulfinyl groups; C1-3 haloalkylsulfinyl groups; C1-3 haloalkylsulfonyl groups; C1-3 alkoxycarbonyl groups; unsubstituted amino group; substituted amino groups having 1 or 2 substituents selected from the group consisting of formyl group, C1-3 alkylcarbonyl groups, C1-3 alkylsulfonyl groups, and substituted aminocarbonyl groups having as the substituent(s) one or more C1-3 alkyl groups which may be the same or different; unsubstituted aminocarbonyl group; substituted aminocabonyl groups having as the substituent(s) 1 or 2 C1-3 alkyl groups which may be the same or different; substituted aminosulfonyl groups having as the substituent(s) 1 or 2 C1-3 alkyl groups which may be the same or different; phenyl group; Z represents 1 to 5 atoms or groups which may be the same or different and are selected from the group consisting of halogen atoms; cyano group; nitro group; C1-6 alkyl groups; C1-3 haloalkyl groups; substituted C3-6 cycloalkyl groups having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms C1-5 alkoxy groups; C1-3 haloalkoxy groups; C1-3 alkylthio groups; C1-3 haloalkylthio groups; C1-3 alkylsulfinyl groups; C1-3 haloalkylsulfinyl groups; C1-3 alkylsulfonyl groups; C1-3 haloalkylsulfonyl groups; C1-3 alkylcarbonyl groups; C1-3 alkoxycarbonyl groups; C1-3 alkylcarbonyloxy groups; C1-3 alkylsulfonyloxy groups; C1-3 haloalkylsulfonyloxy groups; unsubstituted phenoxy group; substituted phenoxy groups having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms and C1-3 haloalkyl groups, unsubstituted pyridyloxy group; substituted pyridyloxy groups having as the substituent(s) 1 to 4 atoms or groups which may be the same or different and are selected from the group consisting of halogen atoms, and C1-3 haloalkyl groups, and W is an oxygen atom or a sulfur atom.

2. A hydrazinecarboxamide derivative according to claim 1, wherein R.sup.1 is a hydrogen atom or a C1-3 alkyl group, R.sup.2 is a hydrogen atom or a C1-3 alkyl group, R.sup.3 is a hydrogen atom or a C1-3 alkyl group, R.sup.4 is a hydrogen atom or a C1-3 alkyl group, A is ##STR64## wherein X represents 1 to 5 carbon atoms or groups which may be the same or different and are selected from the group consisting of hydrogen atom, halogen atoms, C1-4 alkyl groups and C1-3 haloalkyl groups, and R.sup.5 is a hydrogen atom), Y represents 1 to 5 carbon atoms or groups which may be the same or different and are selected from the group consisting of hydrogen atom, halogen atoms, cyano group and nitro group, Z represents 1 to 5 atoms or groups which may be the same or different and are selected from the group consisting of halogen atoms, C1-3 haloalkyl groups, C1-3 haloalkoxy groups, C1-3 alkylthio groups, C1-3 haloalkylthio groups, C1-3 alkylsulfinyl groups, C1-3 haloalkylsulfonyl groups, C1-3 haloalkylsulfinyl groups, and C1-3 alkylsulfonyl groups, and W is an oxygen atom.

3. A hydrazinecarboxamide derivative according to claim 2, wherein X is at the 3-position and Y or Z has a substituent at the 4-position.

4. An agricultural and horticultural insecticide composition comprising as an active ingredient a hydrazinecarboxamide derivative represented by the general formula (I): ##STR65## wherein R.sup.1 is a hydrogen atom or a lower alkyl group, R.sup.2 is a hydrogen atom or a lower alkyl group, R.sup.3 is a hydrogen atom; a hydroxyl group; a lower alkyl group; a lower alkoxy group; a lower alkylcarbonyloxy group; an unsubstituted phenylcarbonyloxy group; or a substituted phenylcarbonyloxy group having on the phenyl ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, lower alkyl groups and lower haloalkyl groups, R.sup.4 is a hydrogen atom or a lower alkyl group, R.sup.3 and R.sup.4 being able to be taken together to represent an oxygen atom, A is ##STR66## wherein X represents 1 to 5 atoms or groups which may be the same or different and are selected from the group consisting of hydrogen atom; hydroxyl group; halogen atoms; cyano group; lower alkyl groups; lower haloalkyl groups; lower alkoxy groups; lower haloalkoxy groups; lower alkoxyalkyl groups; lower alkenyloxy groups; cycloalkylcarbonyloxy groups; lower alkoxycarbonyloxy groups; lower alkoxycarbonylalkyloxy groups; lower alkylcarbonylalkyloxy groups; lower alkylsulfonyloxy groups; phenoxy group; methylenedioxy group; alkenylene groups having 3 to 4 carbon atoms so as to form a polycyclic ring together with the adjacent carbon atom of the phenyl ring; unsubstituted amino group; substituted amino groups having as the substituent(s) 1 or 2 lower alkyl groups which may be the same or different; substituted aminocarbonyloxy groups having as the substituent(s) 1 or 2 lower alkyl groups which may be the same or different; Y represents 1 to 5 atoms or groups which may be the same or different and are selected from the group consisting of hydrogen atom; hydroxyl group; halogen atoms; cyano group; nitro group; alkyl groups; lower haloalkyl groups; lower alkoxy groups; lower haloakoxy groups; lower alkenyloxy groups; lower alkylcarbonyloxy groups; lower alkylsulfonyloxy groups; lower haloalkylsulfonyloxy groups; lower alkylthio groups; lower haloalkylthio groups; lower alkylsulfinyl groups; lower haloalkylsulfinyl groups; lower alkylsulfonyl groups; lower haloalkylsulfonyl groups; lower alkoxycarbonyl groups; unsubstituted amino group; substituted amino groups having 1 or 2 substituents selected from the group consisting of formyl group, lower alkylcarbonyl groups, lower alkylsulfonyl groups, and substituted aminocarbonyl groups having as the substituent(s) one or more lower alkyl groups which may be the same or different; unsubstituted aminocarbonyl group; substituted aminocarbonyl groups having as the substituent(s) 1 or 2 lower alkyl groups which may be the same or different; or substituted aminosulfonyl groups having as the substituent(s) 1 or 2 lower alkyl groups which may be the same or different; phenyl group, Z represents 1 to 5 atoms or groups which may be the same or different and are selected from the group consisting of hydrogen atom; halogen atoms; cyano group; nitro group; alkyl groups; lower haloalkyl groups; unsubstituted cycloalkyl groups; substituted cycloalkyl groups having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms and lower alkyl groups; lower alkoxy groups; lower haloalkoxy groups; lower alkylthio groups; lower haloalkylthio groups; lower alkylsulfinyl groups; lower haloalkylsulfinyl groups; lower alkylsulfonyl groups; lower haloalkylsulfonyl groups; lower alkylcarbonyl groups; lower alkoxycarbonyl groups; lower alkylcarbonyloxy groups; lower alkylsulfonyloxy groups; lower haloalkylsulfonyloxy groups; unsubstituted phenoxy group; substituted phenoxy groups having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, lower alkyl groups, lower haloalkyl groups, lower alkoxy groups and lower haloalkoxy groups; unsubstituted pyridyloxy group; substituted pyridyloxy groups having as the substituent(s) 1 to 4 atoms or groups which may be the same or different and are selected from the group consisting of halogen atoms, lower alkyl groups, lower haloalkyl groups, lower alkoxy groups and lower haloalkoxy groups, and W is an oxygen atom or a sulfur atom.

5. An agricultural and horticultural insecticide composition according to claim 4, wherein R.sup.1 is a hydrogen atom or a lower alkyl group, R.sup.2 is a hydrogen atom or a lower alkyl group, R.sup.3 is a hydrogen atom or a lower alkyl group, R.sup.4 is a hydrogen atom or a lower alkyl group, A is ##STR67## wherein X represents 1 to 5 atoms or groups which may be the same or different and are selected from the group consisting of hydrogen atom, halogen atoms, lower alkyl groups and lower haloalkyl groups, Y represents 1 to 5 atoms or groups which may be the same or different and are selected from the group consisting of hydrogen atom, halogen atoms, cyano group and nitro group, Z represents 1 to 5 atoms or groups which may be the same or different and are selected from the group consisting of hydrogen atom, halogen atoms, lower haloalkyl groups, lower haloalkoxy groups, lower alkylthio groups, lower haloalkylthio groups, lower alkylsulfonyl groups, lower haloalkylsulfinyl groups, lower alkylsulfonyl groups and lower haloalkylsulfonyl groups, and W is an oxygen atom.

6. An agricultural and horticultural insecticide composition according to claim 5, wherein X is at the 3-position and Y or Z has a substituent at the 4-position.

7. A process for controlling undesirable insect pests which comprises applying an agricultural and horticultural insecticide comprising as an active ingredient a hydrazinecarboxamide derivative represented by the general formula (I): ##STR68## wherein R.sup.1 is a hydrogen atom or a lower alkyl group, R.sup.2 is a hydrogen atom or a lower alkyl group, R.sup.3 is a hydrogen atom; a hydroxyl group; a lower alkyl group; a lower alkoxy group; a lower alkylcarbonyloxy group; an unsubstituted phenylcarbonyloxy group; or a substituted phenylcarbonyloxy group having on the phenyl ring 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, lower alkyl groups and lower haloalkyl groups, R.sup.4 is a hydrogen atom or a lower alkyl group, R.sup.3 and R.sup.4 being able to be taken together to represent an oxygen atom, A is ##STR69## wherein X represents 1 to 5 atoms or groups which may be the same or different and are selected from the group consisting of hydrogen atom; hydroxyl group; halogen atoms; cyano group; lower alkyl groups; lower haloalkyl groups; lower alkoxy groups; lower haloalkoxy groups; lower alkoxyalkyl groups; lower alkenyloxy groups; cycloalkylcarbonyloxy groups; lower alkoxycarbonyloxy groups; lower alkoxycarbonylalkyloxy groups; lower alkylcarbonylalkyloxy groups; lower alkylsulfonyloxy groups; phenoxy group; methylenedioxy group; alkenylene groups having 3 to 4 carbon atoms so as to form a polycyclic ring together with the adjacent carbon atom of the phenyl ring; unsubstituted amino group; substituted amino groups having as the substituent(s) 1 or 2 lower alkyl groups which may be the same or different; substituted aminocarbonyloxy groups having as the substituent(s) 1 or 2 lower alkyl groups which may be the same or different; Y represents 1 to 5 atoms or groups which may be the same or different and are selected from the group consisting of hydrogen atom; hydroxyl group; halogen atoms; cyano group; nitro group; alkyl groups; lower haloalkyl groups; lower alkoxy groups; lower haloalkoxy groups; lower alkenyloxy groups; lower alkylcarbonyloxy groups; lower alkylsulfonyloxy groups; lower haloalkylsulfonyloxy groups; lower alkylthio groups; lower haloalkylthio groups; lower alkylsulfinyl groups; lower haloalkylsulfinyl groups; lower alkylsulfonyl groups; lower haloalkylsulfonyl groups; lower alkoxycarbonyl groups; unsubstituted amino group; substituted amino groups having 1 or 2 substituents selected from the group consisting of formyl group, lower alkylcarbonyl groups, lower alkylsulfonyl groups, and substituted aminocarbonyl groups having as the substituent(s) one or more lower alkyl groups which may be the same or different; unsubstituted aminocarbonyl group; substituted aminocarbonyl groups having as the substituent(s) 1 or 2 lower alkyl groups which may be the same or different; or substituted aminosulfonyl groups having as the substituent(s) 1 or 2 lower alkyl groups which may be the same or different; phenyl group, Z represents 1 to 5 atoms or groups which may be the same or different and are selected from the group consisting of hydrogen atom; halogen atoms; cyano group; nitro group; alkyl groups; lower haloalkyl groups; unsubstituted cycloalkyl groups; substituted cycloalkyl groups having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms and lower alkyl groups; lower alkoxy groups; lower haloalkoxy groups; lower alkylthio groups; lower haloalkylthio groups; lower alkylsulfinyl groups; lower haloalkylsulfinyl groups; lower alkylsulfonyl groups; lower haloalkylsulfonyl groups; lower alkylcarbonyl groups; lower alkoxycarbonyl groups; lower alkylcarbonyloxy groups; lower alkylsulfonyloxy groups; lower haloalkylsulfonyloxy groups; unsubstituted phenoxy group; substituted phenoxy groups having 1 to 5 substituents which may be the same or different and are selected from the group consisting of halogen atoms, lower alkyl groups, lower haloalkyl groups, lower alkoxy groups and lower haloalkoxy groups; unsubstituted pyridyloxy group; substituted pyridyloxy groups having as the substituent(s) 1 to 4 atoms or groups which may be the same or different and are selected from the group consisting of halogen atoms, lower alkyl groups, lower haloalkyl groups, lower alkoxy groups and lower haloalkoxy groups, and W is an oxygen atom or a sulfur atom) in an amount of 0.1 g to 5 kg in terms of the active ingredient per 10 ares in order to protect useful crops against undesirable insect pests.