Triazole derivatives and uses thereof

Disclosed are triazole derivatives represented by the following formula, insecticides and acaricides containing the triazole derivatives as active ingredients, and a method of controlling insect pests and mites. ##STR1## wherein R.sup.1 represents a hydrogen atom, a lower alkyl group, a halogen atom, 1-pyrrolyl group, a group represented by the formula NR.sup.2 R.sup.3 ; R.sup.5 represents a methyl or ethyl group substituted with at least one halogen atom; n represents 0, 1 or 2; Y represents a nitrogen atom or a group represented by the formula CX.sup.2 ; and X.sup.1 and X.sup.2 are the same or different and each represent a halogen atom, a nitro group or a cyano group.

BACKGROUND OF THE INVENTION 
The present invention relates to triazole derivatives and uses thereof. 
It is disclosed in JP-A-1-230562 and JP-A-2-91061 that some triazole 
derivatives can be used as active ingredients of insecticides. 
However, these compounds are not necessarily sufficient as active 
ingredients of insecticides in insecticidal efficacy. 
The present inventors have made intensive studies in an attempt to find 
compounds having excellent insecticidal efficacy and, as a result, have 
found that triazole derivatives represented by the following formula have 
an excellent insecticidal and acaricidal efficacy. Thus, the present 
invention has been accomplished. 
SUMMARY OF THE INVENTION 
That is, the present invention provides a triazole derivative represented 
by the following formula 1! (hereinafter referred to as "the present 
compound" and insecticides and acaricides containing the triazole 
derivative as an active ingredient: 
##STR2## 
{wherein R.sup.1 represents a hydrogen atom, a lower alkyl group (for 
example, a C.sub.1 -C.sub.4 alkyl group such as methyl group and ethyl 
group, a halogen atom (for example, fluorine atom, chlorine atom, bromine 
atom or the like), 1-pyrrolyl group, a group represented by the formula 
NR.sup.2 R.sup.3 where R.sup.2 and R.sup.3 are the same or different and 
each represent a hydrogen atom, an alkyl group (for example, a C.sub.1 
-C.sub.8 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, 
isobutyl, sec-butyl, tert-butyl and neopentyl group), a cycloalkyl group 
(for example, a C.sub.3 -C.sub.8 cycloalkyl group such as cyclopropyl, 
cyclobutyl, cyclopentyl and cyclohexyl group), an alkoxyalkyl group (for 
example, a (C.sub.1 -C.sub.8 alkoxy) C.sub.1 -C.sub.8 alkyl group such as 
methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, 
butoxymethyl, isobutoxymethyl, sec-butoxymethyl, 2-methoxyethyl, 
1-methoxy-2,2-dimethylpropyl, 1-ethoxy-2,2-dimethylpropyl, 
1-methoxy-1,2,2-trimethylpropyl and 1-ethoxy-1,2,2-trimethylpropyl group), 
an alkylthiocarbonyl group (for example, C.sub.2 -C.sub.5 
alkylthiocarbonyl group such as ethylthiocarbonyl, methylthiocarbonyl, 
isopropylthiocarbonyl, butylthiocarbonyl group), an alkoxycarbonylsulfenyl 
group (for example, C.sub.2 -C.sub.5 alkoxycarbonylsulfenyl group such as 
methoxycarbonylsulfenyl, ethoxycarbonylsulfenyl, 
isopropoxycarbonylsulfenyl and butoxycarbonylsulfenyl group), an alkylthio 
group (for example, C.sub.1 -C.sub.4 alkylthio group such as butylthio, 
isopropylthio, tert-butylthio, ethylthio and propylthio group), an 
alkylsulfonyl group (for example, C.sub.1 -C.sub.4 alkylsulfonyl group 
such as methanesulfonyl, ethanesulfonyl and butanesulfonyl group), a 
substituted phenyl group (for example, 
2,6-dichloro-4-trifluoromethylphenyl, 
2-chloro-4-nitro-5-trifluoromethylphenyl, 
3-chloro-6-nitro-4-trifluoromethylphenyl and 
3-chloro-2,6-dinitro-4-trifluoromethylphenyl group), an alkylthioalkyl 
group (for example, a (C.sub.1 -C.sub.8 alkylthio) C.sub.1 -C.sub.8 alkyl 
group such as methylthiomethyl, ethylthiomethyl, propylthiomethyl, 
isopropylthiomethyl, butylthiomethyl, isobutylthiomethyl, 
sec-butylthiomethyl, 2-methylthioethyl, 1-methylthio-2,2-dimethylpropyl, 
1-ethylthio-2,2-dimethylpropyl, 1-methylthio-1,2,2-trimethylpropyl and 
1-ethylthio-1,2,2-trimethylpropyl group), an alkoxycarbonyl group (for 
example, a (C.sub.1 -C.sub.8 alkoxy)-carbonyl group such as 
methoxycarbonyl and ethoxycarbonyl group), an unsubstituted or 
alkoxy-substituted alkanoyl group (for example, a C.sub.2 -C.sub.8 
alkanoyl group such as acetyl, propanoyl, butanoyl, 3-methylbutanoyl, 
2-methylpropanoyl and pentanoyl group, a C.sub.3 -C.sub.6 
alkoxy-substituted alkanoyl group such as methoxyacetyl, ethoxyacetyl, 
propoxyacetyl, isopropoxyacetyl and butoxyacetyl group) or a saturated 
heterocyclic ring (for example, 2-tetrahydropyranyl group), or the formula 
##STR3## 
wherein R.sup.2' and R.sup.3' are the same or different and each 
represent an alkyl group (for example, a C.sub.1 -C.sub.4 alkyl group such 
as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-tutyl and 
tert-butyl group), an alkoxycarbonyl group (for example, an C.sub.2 
-C.sub.5 alkoxycarbonyl group such as methoxycarbonyl, ethoxycarbonyl and 
butoxycarbonyl group), an alkoxycarbonyl-substituted alkyl group (for 
example, an C.sub.4 -C.sub.7 alkoxycarbonyl-substituted alkyl group such 
as, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl and 2-butoxycarbonyl 
ethyl group), or R.sup.2' and R.sup.3' link to each other to form an 
oxygen-containing alkylene group (for example, CH.sub.2 CH.sub.2 OCH.sub.2 
CH.sub.2) or R.sup.2 and R.sup.3 represent a nitrogen-containing saturated 
heterocyclic ring which may be substituted or a pyrrolyl group in 
combination with nitrogen atom to which they bond! or a group represented 
by the formula N.dbd.CR.sup.4 R.sup.6 where R.sup.4 represents a hydrogen 
atom, an alkyl group (for example, a C.sub.1 -C.sub.8 alkyl group such as 
methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and 
tert-butyl group) or an unsubstituted or substituted phenyl group and 
R.sup.6 represents a hydrogen atom, an alkyl group (for example, a C.sub.1 
-C.sub.8 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, 
isobutyl, sec-butyl or tert-butyl group), an alkoxy group (for example, a 
C.sub.1 -C.sub.8 alkoxy group such as methoxy and ethoxy group) or a 
dialkylamino group (for example, a C.sub.1 -C.sub.8 dialkylamino group 
such as dimethylamino or diethylamino group)!; R.sup.5 represents a methyl 
group substituted with at least one halogen atom such as fluorine, 
chlorine and bromine atom (for example, trifluoromethyl, difluoromethyl, 
chlorodifluoromethyl or bromodifluoromethyl group) or an ethyl group 
substituted with at least one halogen atom such as fluorine, chlorine and 
bromine atom (for example, 1,1,2,2-tetrafluoroethyl, 2,2,2-trifluoroethyl, 
pentafluoroethyl, 1,1-difluoroethyl or 2-bromo-1,1,2,2-tetrafluoroethyl 
group); n represents 0, 1 or 2; Y represents a nitrogen atom or a group 
represented by the formula CX.sup.2 ; and X.sup.1 and X.sup.2 are the same 
or different and each represent a halogen atom (for example, chlorine, 
bromine or fluorine atom), a nitro group or a cyano group}. The present 
invention further provides insecticide and/or acaricides containing the 
above triazole derivative as an active ingredient. 
DESCRIPTION OF THE INVENTION 
As the substituents in the case that NR.sup.2 R.sup.3 represents a 
nitrogen-containing saturated heterocyclic ring which may be 
substituented, mention may be made of, for example, an alkyl group (for 
example, a C.sub.1 -C.sub.4 alkyl group such as methyl, ethyl, propyl, 
isopropyl, butyl, isobutyl, sec-butyl and tert-butyl group), a halogen 
atom (for example, fluorine, chlorine or bromine atom), an alkoxy group 
(for example, a C.sub.1 -C.sub.4 alkoxy group such as methoxy and ethoxy 
group), a hydroxyl group, a mercapto group, an alkoxycarbonyl group (for 
example, a (C.sub.1 -C.sub.4 alkoxy)carbonyl group such as methoxycarbonyl 
and ethoxycarbonyl group), an oxo group or an acyloxy group (for example, 
a C.sub.1 -C.sub.10 acyloxy group such as acetoxy, pivaloyloxy and 
benzoyloxy group). 
As the saturated heterocyclic ring in the case that NR.sup.2 R.sup.3 
represents a nitrogen-containing saturated heterocyclic ring which may be 
substituted, mention may be made of, for example, 3-membered or 4-membered 
saturated heterocyclic rings such as aziridine ring and azetidine ring and 
5-membered or 6-membered saturated heterocyclic rings which may contain an 
oxygen atom or a sulfur atom in addition to the nitrogen atom, such as 
pyrrolidine ring, morpholine ring, thiomorpholine ring, isothiazolidine 
ring, 1,3-oxazolidine ring and 1,3-thiazolidine ring. 
As the substituents in the substituted phenyl group represented by R.sup.2, 
R.sup.3 or R.sup.4, mention may be made of, for example, a hydroxyl group, 
an alkoxy group (for example, a C.sub.1 -C.sub.4 alkoxy group such as 
methoxy and ethoxy group), an alkyl group (for example, a C.sub.1 -C.sub.4 
alkyl group such as methyl and ethyl group), a nitro group, a halogen atom 
(for example, fluorine, chlorine or bromine atom), a phenyl group, a 
phenoxy group, an alkylthio group (for example, a C.sub.1 -C.sub.4 
alkylthio group such as methylthio and ethylthio group), an amino group, a 
carboxyl group, a cyano group, an alkoxycarbonyl group (for example, a 
(C.sub.1 -C.sub.4 alkoxy)carbonyl group such as methoxycarbonyl and 
ethoxycarbonyl group), and an acyloxy group (for example, a C.sub.1 
-C.sub.10 acyloxy group such as acetoxy, pivaloyloxy and benzoyloxy 
group). 
In the present invention, R.sup.1 is preferably hydrogen atom, methyl group 
or a group represented by NR.sup.2 R.sup.3, and R.sup.2 and R.sup.3 are 
preferably hydrogen atom, an alkoxycarbonyl group or an alkanoyl group for 
R.sup.2 and hydrogen atom, alkyl group, cycloalkyl group, alkoxycarbonyl 
group, alkoxycarbonylsulfenyl group, alkoxyalkyl group or the formula 
##STR4## 
for R.sup.3. R.sup.5 is preferably a group represented by the formula 
CF.sub.2 Z where Z represents a halogen atom (for example, fluorine, 
chlorine or bromine atom), a hydrogen atom, a methyl group, a 
difluoromethyl group, a trifluoromethyl group or a bromodifluoromethyl 
group!. Y is preferably a group represented by the formula CX.sup.2. 
The process for preparation of the present compound will be explained in 
detail below. The present compound can be prepared, for example, by the 
following (process 1)-(process 10). 
(Process 1) 
(Process for the preparation of the present compound represented by the 
formula 1! where n is 0): 
The present compound where n is 0 can be prepared by reacting a disulfide 
compound represented by the formula 2!: 
##STR5## 
wherein R.sup.1, X.sup.1 and Y are as defined above! with a halide 
compound represented by the formula 3!: 
EQU Z.sup.1 --R.sup.5 3! 
wherein R.sup.5 is as defined above and Z.sup.1 represents a bromine atom 
or an iodine atom! in the presence of a reducing agent. 
Examples of the halide compound 3! are iodotrifluoromethane, 
bromotrifluoromethane, dibromodifluoromethane, bromochlorodifluoromethane, 
iodopentafluoroethane and iodotetrafluoroethane. 
Examples of the reducing agent used are hydroxymethanesulfinates formed 
with various cations (for example, alkali metal hydroxymethanesulfinates 
such as sodium hydroxymethanesulfinate) and alkali metal dithionites (for 
example, sodium dithionite). 
As for the amounts of the reactants, generally, the halide compound 3! is 
used in an amount of 2-3 mols and the reducing agent is used in an amount 
of 2-6 mols for 1 mol of the disulfide compound 2!. 
This reaction is carried out usually at a temperature in the range of about 
-20.degree. C. to 150.degree. C. for about 1-24 hours in a solvent, if 
necessary, in a pressure vessel. 
As examples of the solvent used, mention may be made of aliphatic 
hydrocarbon solvents such as hexane, heptane, ligroin and petroleum ether; 
aromatic hydrocarbon solvents such as benzene, toluene and xylene; 
halogenated hydrocarbon solvents such as dichloroethane, chlorobenzene and 
dichlorobenzene; ketone solvents such as acetone, methyl ethyl ketone, 
methyl isobutyl ketone, isophorone and cyclohexanone; ester solvents such 
as ethyl acetate and butyl acetate, solvents such as acetonitrile and 
isobutyronitrile nitrile; acid amides such as formamide, 
N,N-dimethylformamide and N,N-dimethylacetamide; sulfur compounds such as 
dimethyl sulfoxide and sulfolane; water; and mixtures thereof. 
After the completion of the reaction, the desired present compound can be 
isolated by carrying out usual after-treatments such as extraction with 
organic solvents and concentration. If necessary, the product can be 
further purified by chromatography, distillation, recrystallization or the 
like. 
(Process 2) 
(Process for the preparation of the present compound represented by the 
formula 1! where n is 0): 
The present compound where n is 0 can be prepared by reacting a mercaptan 
represented by the formula 4!: 
##STR6## 
where R.sup.1, X.sup.1 and Y are as defined above! with a halide 
represented by the formula 5!: 
EQU Z.sup.2 --R.sup.5 5! 
wherein R.sup.5 is as defined above and Z.sup.2 represents a halogen atom 
(such as chlorine, bromine or iodine atom)! or with CF.sub.2 
.dbd.CF.sub.2. 
Examples of the halide 5! are dibromodifluoromethane, 
iodotrifluoromethane, bromotrifluoromethane, bromochlorodifluoromethane, 
chlorodifluoromethane, 1-bromo-2-chlorotetrafluoroethane and 
1,2-dibromotetrafluoroethane. 
This reaction is carried out usually at a temperature of about -5.degree. 
C. to 150.degree. C. for about 1-24 hours in a solvent in the presence of 
a dehydrohalogenating agent. 
As the dehydrohalogenating agent used optionally, mention may be made of, 
for example, organic bases such as pyridine, triethylamine and 
N,N-diethylaniline, inorganic bases such as sodium hydroxide, potassium 
hydroxide, sodium carbonate, potassium carbonate, sodium 
hydrogencarbonate, calcium carbonate and sodium hydride, and alkali metal 
alkoxides such as sodium methoxide, potassium tert-butoxide and sodium 
ethoxide. 
As for the amounts of the reactants, generally, the halide 5! or CF.sub.2 
.dbd.CF.sub.2 is used in an amount of 1-5 mols and the dehydrohalogenating 
agent used optionally is used in an amount of 1-10 mols or more for 1 mol 
of the mercaptan 4!. 
As examples of the solvent, mention may be made of aliphatic hydrocarbon 
solvents such as hexane, heptane, ligroin and petroleum ether; aromatic 
hydrocarbon solvents such as benzene; halogenated hydrocarbon solvents 
such as dichloroethane, chlorobenzene and dichlorobenzene; ether solvents 
such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran and 
ethylene glycol dimethyl ether; ketone solvents such as acetone, methyl 
ethyl ketone, methyl isobutyl ketone, isophorone and cyclohexanone; ester 
solvents such as ethyl acetate and butyl acetate; nitro compound solvents 
such as nitroethane and nitrobenzene; nitrile solvents such as 
acetonitrile and isobutyronitrile; tertiary amines such as pyridine, 
triethylamine, N,N-diethylaniline, tributylamine and N-methylmorpholine; 
acid amides such as formamide, N,N-dimethylformamide and 
N,N-dimethylacetamide; sulfur compounds such as dimethyl sulfoxide and 
sulfolane; water; and mixtures thereof. 
After the completion of the reaction, the desired present compound can be 
isolated by carrying out usual after-treatments such as extraction with 
organic solvents and concentration. If necessary, the product can be 
further purified by chromatography, distillation, recrystallization or the 
like. 
(Process 3) 
(Process for the preparation of the present compound represented by the 
formula 1! where n is 1 or 2): 
The present compound where n is 1 or 2 can be prepared by oxidizing the 
present compound where n is 0. 
Examples of the oxidizing agent used are organic peroxides such as hydrogen 
peroxide and tert-butylhydroperoxide; organic peracids such as 
m-chloroperbenzoic acid and peracetic acid; metal compounds such as 
chromic anhydride; peroxosulfuric acid or salts thereof; and sulfur 
oxides. The amount of the oxidizing agent used is usually an excess amount 
of 1 mol or more per 1 mol of the present compound where n is 0 in the 
case of preparing the present compound where n is 1 and an excess amount 
of 2 mols or more per 1 mol of the present compound where n is 0 in the 
case of preparing the present compound where n is 2. 
This reaction is carried out usually at a temperature of about -5.degree. 
C. to 150.degree. C. for about 1-24 hours in a solvent. 
As examples of the solvent used, mention may be made of aliphatic 
hydrocarbon solvents such as hexane, heptane, ligroin and petroleum ether; 
aromatic hydrocarbon solvents such as benzene, toluene and xylene; 
halogenated hydrocarbon solvents such as chloroform, carbon tetrachloride, 
dichloroethane, chlorobenzene and dichlorobenzene; ether solvents such as 
diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran and ethylene 
glycol dimethyl ether; ester solvents such as ethyl acetate and butyl 
acetate; nitro compounds such as nitroethane and nitrobenzene; acid amides 
such as formamide, N,N-dimethylformamide and N,N-dimethylacetamide; sulfur 
compounds such as sulfolane; organic acids such as acetic acid; water; and 
mixtures thereof. 
After the completion of the reaction, the desired present compound can be 
isolated, if necessary, by removing excess oxidizing agent with a reducing 
agent such as aqueous sodium sulfite solution and carrying out usual 
after-treatments such as extraction with organic solvents and 
concentration. If necessary, the product can be further purified by 
chromatography, distillation, recrystallization or the like. 
(Process 4) 
Process for the preparation of the present compound represented by the 
formula 1! where R.sup.1 is NR.sup.21 R.sup.31 (in which R.sup.21 and 
R.sup.31 are the same or different and each represent an alkyl group, a 
cycloalkyl group, an alkoxyalkyl group, an alkylthioalkyl group, an 
alkoxycarbonyl group or an alkanoyl group)!: 
The said present compound can be prepared by reacting the present compound 
where R.sup.1 is an amino group with a halide derivative represented by 
the formula 6! or 7!: 
EQU R.sup.21 --Z.sup.2 6! 
and/or 
EQU R.sup.31 --Z.sup.2 7! 
wherein R.sup.21, R.sup.31 and Z.sup.2 are as defined above! usually in 
the presence of a dehydrohalogenating agent. 
As the dehydrohalogenating agent used, mention may be made of, for example, 
organic bases such as pyridine, triethylamine and N,N-diethylaniline, 
inorganic bases such as sodium hydroxide, potassium hydroxide, sodium 
carbonate, potassium carbonate, sodium hydrogencarbonate, calcium 
carbonate and sodium hydride, and alkali metal alkoxides such as sodium 
methoxide and sodium ethoxide. 
As for the amounts of the reactants, generally, the halide derivative 6! 
and/or 7! is used in an amount of 1-2 mols and the dehydrohalogenating 
agent is used in an amount of 1-4 mols for 1 mol of the present compound 
where R.sup.1 is an amino group. 
This reaction is carried out usually at a temperature of about -5.degree. 
C. to 150.degree. C. for about 1-24 hours in a solvent. 
As examples of the solvent used, mention may be made of aliphatic 
hydrocarbon solvents such as hexane, heptane, ligroin and petroleum ether; 
aromatic hydrocarbon solvents such as benzene, toluene and xylene; 
halogenated hydrocarbon solvents such as chloroform, carbon tetrachloride, 
dichloroethane, chlorobenzene and dichlorobenzene; ether solvents such as 
diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran and ethylene 
glycol dimethyl ether; ester solvents such as ethyl acetate and butyl 
acetate; nitro compounds such as nitroethane and nitrobenzene; nitrile 
solvents such as acetonitrile and isobutyronitrile; tertiary amines such 
as pyridine, triethylamine, N,N-diethylaniline, tributylamine and 
N-methylmorpholine; acid amides such as formamide, N,N-dimethylformamide 
and N,N-dimethylacetamide; sulfur compounds such as dimethyl sulfoxide and 
sulfolane; and mixtures thereof. 
After the completion of the reaction, the desired present compound can be 
isolated by carrying out usual after-treatments such as extraction with 
organic solvents and concentration. If necessary, the product can be 
further purified by chromatography, distillation, recrystallization or the 
like. 
(Process 5) 
(Process for the preparation of the present compound represented by the 
formula 1! where R.sup.1 is a halogen atom): 
The present compound where R.sup.1 is a halogen atom can be prepared by 
reacting the present compound where R.sup.1 is an amino group with a 
nitrite ester represented by the formula 8!: 
EQU R.sup.7 --ONO.sub.2 8! 
where R.sup.7 represents an alkyl group (for example, tert-butyl group or 
isoamyl group)! in the presence of a haloform (such as chloroform, 
bromoform or iodoform). 
As for the amounts of the reactants, usually, the nitrite ester 8! is used 
in an amount of 1-4 mols and the haloform is used in an amount of 1-50 
mols for 1 mol of the present compound where R.sup.1 is an amino group. 
This reaction is carried out usually at a reaction temperature of about 
-5.degree. C. to 150.degree. C. for about 1-24 hours in a solvent. 
After the completion of the reaction, the desired present compound can be 
isolated by carrying out usual after-treatments such as concentration. If 
necessary, the product can be further purified by chromatography, 
distillation, recrystallization or the like. 
(Process 6) 
Process for the preparation of the present compound represented by the 
formula 1! where R.sup.1 is NR.sup.22 R.sup.32 (in which R.sup.22 and 
R.sup.32 each represent R.sup.2 other than hydrogen atom and R.sup.3 other 
than hydrogen atom and R.sup.2 and R.sup.3 are as defined above!: 
The desired present compound can be prepared by reacting the present 
compound where R.sup.1 is a halogen atom (such as chlorine, bromine or 
iodine atom) with an amine derivative represented by the formula 9!: 
EQU HN(R.sup.22)R.sup.32 9! 
wherein R.sup.22 and R.sup.32 are as defined above!, if necessary, in the 
presence of a dehydrohalogenating agent. 
As the dehydrohalogenating agent used, mention may be made of, for example, 
organic bases such as pyridine, triethylamine and N,N-diethylaniline, 
inorganic bases such as sodium hydroxide, potassium hydroxide, sodium 
carbonate, potassium carbonate, sodium hydrogencarbonate, calcium 
carbonate and sodium hydride, and alkali metal alkoxides such as sodium 
methoxide and sodium ethoxide in addition to the amine derivatives 9! per 
se. 
As for the amounts of the reactants, usually, the amine derivative 9! is 
used in an amount of 1-2 mols and the dehydrohalogenating agent is used in 
an amount of 1-4 mols for 1 mol of the present compound where R.sup.1 is a 
halogen atom. When the amine derivative 9! per se is also allowed to act 
as the dehydrohalogenating agent, the amine derivative can be used in a 
highly excess amount. 
This reaction is carried out usually at a temperature of about -5.degree. 
C. to 150.degree. C. for about 1-24 hours in a solvent and, if necessary, 
in a pressure vessel. 
The solvent is not necessarily used. If the solvent is used, examples 
thereof are aliphatic hydrocarbon solvents such as hexane, heptane, 
ligroin and petroleum ether; aromatic hydrocarbon solvents such as 
benzene, toluene and xylene; halogenated hydrocarbon solvents such as 
chloroform, carbon tetrachloride, dichloroethane, chlorobenzene and 
dichlorobenzene; ether solvents such as diethyl ether, diisopropyl ether, 
dioxane, tetrahydrofuran and ethylene glycol dimethyl ether; ketone 
solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; 
ester solvents such as ethyl acetate and butyl acetate; nitro compounds 
such as nitroethane and nitrobenzene; nitrile solvents such as 
acetonitrile and isobutyronitrile; tertiary amines such as pyridine, 
triethylamine, N,N-diethylaniline, tributylamine and N-methylmorpholine; 
acid amides such as formamide, N,N-dimethylformamide and 
N,N-dimethylacetamide; sulfur compounds such as dimethyl sulfoxide and 
sulfolane; and mixtures thereof. 
After the completion of the reaction, the desired present compound can be 
isolated by carrying out usual after-treatments such as concentration. If 
necessary, the product can be further purified by chromatography, 
distillation, recrystallization or the like. 
(Process 7) 
Process for the preparation of the present compound represented by the 
formula 1! where R.sup.1 is N.dbd.CR.sup.9 (OR.sup.8) in which R.sup.9 
represents a hydrogen atom or an alkyl group (for example, a C.sub.1 
-C.sub.4 alkyl group such as methyl group and ethyl group) and R.sup.8 
represents an alkyl group (for example, a C.sub.1 -C.sub.4 alkyl group 
such as methyl group and ethyl group)!: 
The desired present compound can be prepared by reacting the present 
compound where R.sup.1 is an amino group with an orthoester derivative 
represented by the formula 10!: 
EQU R.sup.9 C(OR.sup.8).sub.3 10! 
wherein R.sup.9 and R.sup.8 are as defined above!, usually, in the 
presence of an acid catalyst. 
The reaction is carried out usually at a reaction temperature of about 
-5.degree. C. to 150.degree. C. for about 1-24 hours. 
The acid used optionally includes, for example, inorganic acids such as 
hydrochloric acid and sulfuric acid, organic acids such as acetic acid and 
p-toluenesulfonic acid, and Lewis acids such as boron trifluoride. 
As for the amounts of the reactants, usually, the orthoester derivative 
10! is in an amount of 1-7 mols for 1 mol of the present compound where 
R.sup.1 is an amino group. 
The solvent is not necessarily used. If the solvent is used, examples 
thereof are aliphatic hydrocarbon solvents such as hexane, heptane, 
ligroin and petroleum ether; aromatic hydrocarbon solvents such as 
benzene, toluene and xylene; halogenated hydrocarbon solvents such as 
chloroform, carbon tetrachloride, dichloroethane, chlorobenzene and 
dichlorobenzene; ether solvents such as diethyl ether, diisopropyl ether, 
dioxane, tetrahydrofuran and ethylene glycol dimethyl ether; ester 
solvents such as ethyl acetate and butyl acetate; nitro compounds such as 
nitroethane and nitrobenzene; nitrile solvents such as acetonitrile and 
isobutyronitrile; acid amides such as formamide, N,N-dimethylformamide and 
N,N-dimethylacetamide; sulfur compounds such as dimethyl sulfoxide and 
sulfolane; and mixtures thereof. 
After the completion of the reaction, the desired present compound can be 
isolated by carrying out usual after-treatments such as concentration. If 
necessary, the product can be further purified by chromatography, 
distillation, recrystallization or the like. 
(Process 8) 
Process for the preparation of the present compound represented by the 
formula 1! where R.sup.1 is NHR.sup.33 (in which R.sup.33 represents an 
alkyl group!: 
The desired present compound can be prepared by reducing the present 
compound where R.sup.1 is N.dbd.CR.sup.9 (OR.sup.8) (in which R.sup.9 and 
R.sup.8 are as defined above) with a metal hydride in the presence or 
absence of an acid catalyst or hydrogenating the compound in the presence 
of a hydrogenation catalyst. 
The reaction is carried out usually at a temperature of about -5.degree. C. 
to 150.degree. C. for about 1-24 hours and usually in a solvent and, if 
necessary, in the presence of an acid catalyst when the metal hydride is 
used. 
The acids used include, for example, inorganic acids such as hydrochloric 
acid and sulfuric acid, organic acids such as acetic acid and 
p-toluenesulfonic acid, and Lewis acids such as boron trifluoride. 
The metal hydrides when the reduction is carried out therewith include, for 
example, sodium borohydride and lithium borohydride. 
The catalysts used for carrying out the hydrogenation include, for example, 
platinum oxide and Pd/C. 
As for the amounts of the reactants, usually, the metal hydride is used in 
an amount of 1/2-10 mols for 1 mol of the present compound where R.sup.1 
is N.dbd.CR.sup.9 (OR.sup.8). 
As examples of the solvent, mention may be made of aliphatic hydrocarbon 
solvents such as hexane, heptane, ligroin and petroleum ether; aromatic 
hydrocarbon solvents such as benzene, toluene and xylene; halogenated 
hydrocarbon solvents such as dichloroethane, chlorobenzene and 
dichlorobenzene; alcohol solvents such as methanol, ethanol and isopropyl 
alcohol; ether solvents such as diethyl ether, diisopropyl ether, dioxane, 
tetrahydrofuran and ethylene glycol dimethyl ether; ester solvents such as 
ethyl acetate and butyl acetate; and mixtures thereof. 
After the completion of the reaction, the desired present compound can be 
isolated by carrying out usual after-treatments such as extraction with 
organic solvents and concentration. If necessary, the product can be 
further purified by chromatography, distillation, recrystallization or the 
like. 
(Process 9) 
Process for the preparation of (i) the present compound represented by the 
formula 1! where R.sup.1 is NR.sup.2 R.sup.3 in which R.sup.2 is a 
hydrogen atom and R.sup.3 is a 2-tetrahydropyranyl group, (ii) the present 
compound where R.sup.1 is a 1-pyrrolyl group, or (iii) the present 
compound where R.sup.1 is a group represented by N.dbd.CR.sup.4 R.sup.61 
(where R.sup.4 is as defined above and R.sup.61 represents a hydrogen 
atom, an alkyl group or a dialkylamino group)!: 
The desired present compound can be prepared by reacting the present 
compound where R.sup.1 is an amino group with (i) dihydropyran, (ii) 
2,6-dimethoxytetrahydrofuran or (iii-1) a carbonyl compound represented by 
the formula 11!: 
EQU R.sup.4 --C(.dbd.O)--R.sup.9 11! 
(wherein R.sup.4 and R.sup.9 are as defined above) or (iii-2) an acetal 
represented by the formula 12!: 
EQU (R.sup.8 O).sub.2 C(R.sup.4)R.sup.61 12! 
(wherein R.sup.4, R.sup.8 and R.sup.61 are as defined above). 
The reaction is carried out usually at a reaction temperature of about 
-5.degree. C. to 150.degree. C. for about 1-24 hours and usually in a 
solvent or without solvent, usually, in the presence of an acid in a 
catalytic amount with removing water from the reaction system by a water 
separator or the like if water is produced. 
The acids used include, for example, inorganic acids such as hydrochloric 
acid and sulfuric acid, organic acids such as acetic acid and 
p-toluenesulfonic acid, and Lewis acids such as boron trifluoride. 
As for the amounts of the reactants, usually, dihydropyran, 
2,6-dimethoxytetrahydrofuran, the carbonyl compound 11! and the acetal 
12! are used in an amount of 1-20 mols for 1 mol of the present compound 
where R1 is an amino group, respectively. 
As examples of the solvent, mention may be made of aliphatic hydrocarbon 
solvents such as hexane, heptane, ligroin and petroleum ether; aromatic 
hydrocarbon solvents such as benzene, toluene and xylene; halogenated 
hydrocarbon solvents such as chloroform, carbon tetrachloride, 
dichloroethane, chlorobenzene and dichlorobenzene; ether solvents such as 
diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran and ethylene 
glycol dimethyl ether; ester solvents such as ethyl acetate and butyl 
acetate; nitro compounds such as nitroethane and nitrobenzene; and 
mixtures thereof. 
After the completion of the reaction, the desired present compound can be 
isolated by carrying out usual after-treatments such as concentration. If 
necessary, the product can be further purified by chromatography, 
distillation, recrystallization or the like. 
(Process 10) 
Process for the preparation of the present compound represented by the 
formula 1! wherein R.sup.1 is NHR.sup.34 (in which R.sup.34 represents an 
alkoxyalkyl group or an alkylthioalkyl group)!: 
The desired present compound can be prepared by reacting the present 
compound where R.sup.1 is a group represented by N.dbd.CR.sup.4 R.sup.9 
(in which R.sup.4 and R.sup.9 are as defined above) with a compound 
represented by the formula 13!: 
EQU R.sup.7 AH 13! 
wherein A represents an oxygen atom or a sulfur atom and R.sup.7 is as 
defined above! in the presence of an acid catalyst. 
As for the amounts of the reactants, usually, the compound 13! is in an 
amount of 1-10 mols for 1 mol of the present compound where R.sup.1 is 
N.dbd.CR.sup.4 R.sup.9. 
The acids used optionally include, for example, inorganic acids such as 
hydrochloric acid and sulfuric acid, organic acids such as acetic acid and 
p-toluenesulfonic acid, and Lewis acids such as boron trifluoride. 
The reaction is carried out usually at a reaction temperature of about 
-5.degree. C.-150.degree. C. for about 1-24 hours in a solvent. 
Examples of the solvent used are aliphatic hydrocarbon solvents such as 
hexane, heptane, ligroin and petroleum ether; aromatic hydrocarbon 
solvents such as benzene, toluene and xylene; halogenated hydrocarbon 
solvents such as chloroform, carbon tetrachloride, dichloroethane, 
chlorobenzene and dichlorobenzene; ether solvents such as diethyl ether, 
diisopropyl ether, dioxane, tetrahydrofuran and ethylene glycol dimethyl 
ether; ester solvents such as ethyl acetate and butyl acetate; nitro 
compounds such as nitroethane and nitrobenzene; sulfur compounds such as 
dimethyl sulfoxide and sulfolane; and mixtures thereof. When the compound 
13! is liquid, the compound 13! per se may be used as the solvent. 
After the completion of the reaction, the desired present compound can be 
isolated by carrying out usual after-treatments such as concentration. If 
necessary, the product can be further purified by chromatography, 
distillation, recrystallization or the like. 
The disulfide compound 2! and the mercaptan 4! which are intermediates in 
the preparation of the present compound can be prepared, for example, in 
accordance with the following scheme. 
##STR7## 
wherein A represents a halogen atom (fluorine atom, chlorine atom or the 
like) and X.sup.1, Y and R.sup.1 are as defined above!. 
The reaction of the step 1 is carried out usually at a reaction temperature 
of about -5.degree. C.-150.degree. C. for about 1-24 hours in a solvent in 
the presence of a base. 
As the bases used, mention may be made of, for example, organic bases such 
as pyridine, triethylamine and N,N-diethylaniline, inorganic bases such as 
sodium hydroxide, potassium hydroxide, sodium carbonate, potassium 
carbonate, sodium hydrogencarbonate, calcium carbonate and sodium hydride, 
and alkali metal alkoxides such as sodium methoxide and sodium ethoxide. 
As for the amounts of the reactants, usually, the compound represented by 
the formula I! is used in an amount of 2-4 mols and the base is used in 
an amount of 2-4 mols for 1 mol of the disulfide represented by the 
formula II!. 
Examples of the solvent used are aliphatic hydrocarbon solvents such as 
hexane, heptane, ligroin and petroleum ether; aromatic hydrocarbon 
solvents such as benzene, toluene and xylene; halogenated hydrocarbon 
solvents such as chloroform, carbon tetrachloride, dichloroethane, 
chlorobenzene and dichlorobenzene; ether solvents such as diethyl ether, 
diisopropyl ether, dioxane, tetrahydrofuran and ethylene glycol dimethyl 
ether; ketone solvents such as acetone, methyl ethyl ketone, methyl 
isobutyl ketone, isophorone and cyclohexanone; ester solvents such as 
ethyl acetate and butyl acetate; nitro compounds such as nitroethane and 
nitrobenzene; nitrile solvents such as acetonitrile and isobutyronitrile; 
tertiary amines such as pyridine, triethylamine, N,N-diethylaniline, 
tributylamine and N-methylmorpholine; acid amides such as formamide, 
N,N-dimethylformamide and N,N-dimethylacetamide; sulfur compounds such as 
dimethyl sulfoxide and sulfolane; and mixtures thereof. 
After the completion of the reaction, the desired disulfide compound 2! 
can be isolated by carrying out usual after-treatments such as extraction 
with organic solvents and concentration. If necessary, the product can be 
further purified by chromatography, distillation, recrystallization or the 
like. 
The compounds represented by the formula I! can be prepared by the 
processes described, for example, in U.S. Pat. Nos. 3,888,932 and 
3,928,416, European Patent Laid-Open Application Nos.23,100 and 34,402, 
West German Patent Laid-Open Application Nos.2,606,393 and 3,545,570, U.S. 
Pat. No. 4,181,041, J. Org. Chem., 25, 1710 (1960), British Patent 
Laid-Open Application Nos.2,002,368 and 1,121,211, JP-A-59-20,269 and U.S. 
Pat. No. 5,109,004 and processes similar to these processes. 
The disulfides represented by the formula II! are prepared, for example, 
by the process described in JP-A-3-153676 or process similar to this 
process. 
The reaction of the step 2 is carried out usually at a reaction temperature 
of about -5.degree. C.-150.degree. C. for about 1-24 hours in a solvent. 
As the reducing agents used, mention may be made of, for example, metals in 
the presence of acids such as zinc in the presence of acid and tin in the 
presence of acid; metal hydrides such as lithium aluminum hydride and 
sodium borohydride; sodium sulfide, potassium sulfide and 
triphenylphosphine. 
The amount of the reducing agent is usually 1-10 mols for 1 mol of the 
disulfide compound 2!. 
Examples of the solvent used are aliphatic hydrocarbon solvents such as 
hexane, heptane, ligroin and petroleum ether; aromatic hydrocarbon 
solvents such as benzene, toluene and xylene; ether solvents such as 
diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran and ethylene 
glycol dimethyl ether; water; and mixtures thereof. 
After the completion of the reaction, the desired mercaptan 3! can be 
isolated by carrying out usual after-treatments such as extraction with 
organic solvents and concentration. If necessary, the product can be 
further purified by chromatography, distillation, recrystallization or the 
like. 
Examples of the present compounds are as shown in the following table. (The 
compounds are shown by the definitions of the substituents in the formula 
1!. In the table, Ph denotes phenyl group, Va denotes 
4-hydroxy-3-methoxyphenyl group, and tBu or t-Bu denotes tert-butyl 
group.) 
TABLE 1 
______________________________________ 
X.sup.1 
Y R.sup.1 R.sup.5 
n 
______________________________________ 
Cl CCl H CF.sub.3 
0 
Cl CCl CH.sub.3 CF.sub.3 
0 
Cl CCl NH.sub.2 CF.sub.3 
0 
Cl CCl H CF.sub.3 
1 
Cl CCl CH.sub.3 CF.sub.3 
1 
Cl CCl NH.sub.2 CF.sub.3 
1 
Cl CCl NH.sub.2 CF.sub.3 
2 
Cl CCl H CF.sub.2 Br 
0 
Cl CCl CH.sub.3 CF.sub.2 Br 
0 
Cl CCl NH.sub.2 CF.sub.2 Br 
0 
Cl CCl H CF.sub.2 Br 
1 
Cl CCl CH.sub.3 CF.sub.2 Br 
1 
Cl CCl NH.sub.2 CF.sub.2 Br 
1 
Cl CCl NH.sub.2 CF.sub.2 Br 
2 
Cl CCl H CF.sub.2 H 
0 
Cl CCl CH.sub.3 CF.sub.2 H 
0 
Cl CCl NH.sub.2 CF.sub.2 H 
0 
Cl CCl H CF.sub.2 H 
1 
Cl CCl CH.sub.3 CF.sub.2 H 
1 
Cl CCl NH.sub.2 CF.sub.2 H 
1 
Cl CCl NH.sub.2 CF.sub.2 H 
2 
Cl CCl H CF.sub.2 Cl 
0 
Cl CCl CH.sub.3 CF.sub.2 Cl 
0 
Cl CCl NH.sub.2 CF.sub.2 Cl 
0 
Cl CCl H CF.sub.2 Cl 
1 
Cl CCl CH.sub.3 CF.sub.2 Cl 
1 
Cl CCl NH.sub.2 CF.sub.2 Cl 
1 
Cl CCl NH.sub.2 CF.sub.2 Cl 
2 
NO.sub.2 
CCl H CF.sub.3 
0 
NO.sub.2 
CCl CH.sub.3 CF.sub.3 
0 
NO.sub.2 
CCl NH.sub.2 CF.sub.3 
0 
NO.sub.2 
CCl H CF.sub.3 
1 
NO.sub.2 
CCl CH.sub.3 CF.sub.3 
1 
NO.sub.2 
CCl NH.sub.2 CF.sub.3 
1 
NO.sub.2 
CCl NH.sub.2 CF.sub.3 
2 
NO.sub.2 
CCl H CF.sub.2 Br 
0 
NO.sub.2 
CCl CH.sub.3 CF.sub.2 Br 
0 
NO.sub.2 
CCl NH.sub.2 CF.sub.2 Br 
0 
NO.sub.2 
CCl H CF.sub.2 Br 
1 
NO.sub.2 
CCl CH.sub.3 CF.sub.2 Br 
1 
NO.sub.2 
CCl NH.sub.2 CF.sub.2 Br 
1 
NO.sub.2 
CCl NH.sub.2 CF.sub.2 Br 
2 
NO.sub.2 
CCl H CF.sub.2 H 
0 
NO.sub.2 
CCl CH.sub.3 CF.sub.2 H 
0 
NO.sub.2 
CCl NH.sub.2 CF.sub.2 H 
0 
NO.sub.2 
CCl H CF.sub.2 H 
1 
NO.sub.2 
CCl CH.sub.3 CF.sub.2 H 
1 
NO.sub.2 
CCl NH.sub.2 CF.sub.2 H 
1 
NO.sub.2 
CCl NH.sub.2 CF.sub.2 H 
2 
NO.sub.2 
CCl H CF.sub.2 Cl 
0 
NO.sub.2 
CCl CH.sub.3 CF.sub.2 Cl 
0 
NO.sub.2 
CCl NH.sub.2 CF.sub.2 Cl 
0 
NO.sub.2 
CCl H CF.sub.2 Cl 
1 
NO.sub.2 
CCl CH.sub.3 CF.sub.2 Cl 
1 
NO.sub.2 
CCl NH.sub.2 CF.sub.2 Cl 
1 
NO.sub.2 
CCl NH.sub.2 CF.sub.2 Cl 
2 
CN CCl H CF.sub.3 
0 
CN CCl CH.sub.3 CF.sub.3 
0 
CN CCl CH.sub.3 CF.sub.2 Cl 
1 
CN CCl H CF.sub.3 
1 
CN CCl CH.sub.3 CF.sub.3 
1 
CN CCl H CF.sub.2 Br 
0 
CN CCl CH.sub.3 CF.sub.2 Br 
0 
CN CCl H CF.sub.2 Br 
1 
CN CCl CH.sub.3 CF.sub.2 Br 
1 
CN CCl H CF.sub.2 H 
0 
CN CCl CH.sub.3 CF.sub.2 H 
0 
CN CCl H CF.sub.2 H 
1 
CN CCl CH.sub.3 CF.sub.2 H 
1 
CN CCl H CF.sub.2 Cl 
0 
CN CCl CH.sub.3 CF.sub.2 Cl 
0 
CN CCl H CF.sub.2 Cl 
1 
Cl N H CF.sub.3 
0 
Cl N CH.sub.3 CF.sub.3 
0 
Cl N NH.sub.2 CF.sub.3 
0 
Cl N H CF.sub.3 
1 
Cl N CH.sub.3 CF.sub.3 
1 
Cl N NH.sub.2 CF.sub.3 
1 
Cl N NH.sub.2 CF.sub.3 
2 
Cl N H CF.sub.2 Br 
0 
Cl N CH.sub.3 CF.sub.2 Br 
0 
Cl N NH.sub.2 CF.sub.2 Br 
0 
Cl N H CF.sub.2 Br 
1 
Cl N CH.sub.3 CF.sub.2 Br 
1 
Cl N NH.sub.2 CF.sub.2 Br 
1 
Cl N NH.sub.2 CF.sub.2 Br 
2 
Cl N H CF.sub.2 H 
0 
Cl N CH.sub.3 CF.sub.2 H 
0 
Cl N NH.sub.2 CF.sub.2 H 
0 
Cl N H CF.sub.2 H 
1 
Cl N CH.sub.3 CF.sub.2 H 
1 
Cl N NH.sub.2 CF.sub.2 H 
1 
Cl N NH.sub.2 CF.sub.2 H 
2 
Cl N H CF.sub.2 Cl 
0 
Cl N CH.sub.3 CF.sub.2 Cl 
0 
Cl N NH.sub.2 CF.sub.2 Cl 
0 
Cl N H CF.sub.2 Cl 
1 
Cl N CH.sub.3 CF.sub.2 Cl 
1 
Cl N NH.sub.2 CF.sub.2 Cl 
1 
Cl N NH.sub.2 CF.sub.2 Cl 
2 
Cl CCl NCHPh CF.sub.3 
0 
Cl CCl NCHPh CF.sub.3 
1 
Cl CCl NCHPh CF.sub.3 
2 
Cl CCl NCHPh CF.sub.2 Br 
0 
Cl CCl NCHPh CF.sub.2 Br 
1 
Cl CCl NCHPh CF.sub.2 Br 
2 
Cl CCl NCHPh CF.sub.2 H 
0 
Cl CCl NCHPh CF.sub.2 H 
1 
Cl CCl NCHPh CF.sub.2 H 
2 
Cl CCl NCHPh CF.sub.2 Cl 
0 
Cl CCl NCHPh CF.sub.2 Cl 
1 
Cl CCl NCHPh CF.sub.2 Cl 
2 
Cl CCl NCHVa CF.sub.3 
0 
Cl CCl NCHVa CF.sub.3 
1 
Cl CCl NCHVa CF.sub.3 
2 
Cl CCl NCHVa CF.sub.2 Br 
0 
Cl CCl NCHVa CF.sub.2 Br 
1 
Cl CCl NCHVa CF.sub.2 Br 
2 
Cl CCl NCHVa CF.sub.2 H 
0 
Cl CCl NCHVa CF.sub.2 H 
1 
Cl CCl NCHVa CF.sub.2 H 
2 
Cl CCl NCHVa CF.sub.2 Cl 
0 
Cl CCl NCHVa CF.sub.2 Cl 
1 
Cl CCl NCHVa CF.sub.2 Cl 
2 
Cl CCl NHC.sub.2 H.sub.5 CF.sub.3 
0 
Cl CCl NHC.sub.2 H.sub.5 CF.sub.3 
1 
Cl CCl NHC.sub.2 H.sub.5 CF.sub.3 
2 
Cl CCl NHC.sub.2 H.sub.5 CF.sub.2 Br 
0 
Cl CCl NHC.sub.2 H.sub.5 CF.sub.2 Br 
1 
Cl CCl NHC.sub.2 H.sub.5 CF.sub.2 Br 
2 
Cl CCl NHC.sub.2 H.sub.5 CF.sub.2 H 
0 
Cl CCl NHC.sub.2 H.sub.5 CF.sub.2 H 
1 
Cl CCl NHC.sub.2 H.sub.5 CF.sub.2 H 
2 
Cl CCl NHC.sub.2 H.sub.5 CF.sub.2 Cl 
0 
Cl CCl NHC.sub.2 H.sub.5 CF.sub.2 Cl 
1 
Cl CCl NHC.sub.2 H.sub.5 CF.sub.2 Cl 
2 
Cl CCl N(C.sub.2 H.sub.5).sub.2 
CF.sub.3 
0 
Cl CCl N(C.sub.2 H.sub.5).sub.2 
CF.sub.3 
1 
Cl CCl N(C.sub.2 H.sub.5).sub.2 
CF.sub.3 
2 
Cl CCl N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 Br 
0 
Cl CCl N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 Br 
1 
Cl CCl N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 Br 
2 
Cl CCl N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 H 
0 
Cl CCl N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 H 
1 
Cl CCl N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 H 
2 
Cl CCl N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 Cl 
0 
Cl CCl N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 Cl 
1 
Cl CCl N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 Cl 
2 
NO.sub.2 
CCl NCHPh CF.sub.3 
0 
NO.sub.2 
CCl NCHPh CF.sub.3 
1 
NO.sub.2 
CCl NCHPh CF.sub.3 
2 
NO.sub.2 
CCl NCHPh CF.sub.2 Br 
0 
NO.sub.2 
CCl NCHPh CF.sub.2 Br 
1 
NO.sub.2 
CCl NCHPh CF.sub.2 Br 
2 
NO.sub.2 
CCl NCHPh CF.sub.2 H 
0 
NO.sub.2 
CCl NCHPh CF.sub.2 H 
1 
NO.sub.2 
CCl NCHPh CF.sub.2 H 
2 
NO.sub.2 
CCl NCHPh CF.sub.2 Cl 
0 
NO.sub.2 
CCl NCHPh CF.sub.2 Cl 
1 
NO.sub.2 
CCl NCHPh CF.sub.2 Cl 
2 
NO.sub.2 
CCl NCHVa CF.sub.3 
0 
NO.sub.2 
CCl NCHVa CF.sub.3 
1 
NO.sub.2 
CCl NCHVa CF.sub.3 
2 
NO.sub.2 
CCl NCHVa CF.sub.2 Br 
0 
NO.sub.2 
CCl NCHVa CF.sub.2 Br 
1 
NO.sub.2 
CCl NCHVa CF.sub.2 Br 
2 
NO.sub.2 
CCl NCHVa CF.sub.2 H 
0 
NO.sub.2 
CCl NCHVa CF.sub.2 H 
1 
NO.sub.2 
CCl NCHVa CF.sub.2 H 
2 
NO.sub.2 
CCl NCHVa CF.sub.2 Cl 
0 
NO.sub.2 
CCl NCHVa CF.sub.2 Cl 
1 
NO.sub.2 
CCl NCHVa CF.sub.2 Cl 
2 
NO.sub.2 
CCl NHC.sub.2 H.sub.5 CF.sub.3 
0 
NO.sub.2 
CCl NHC.sub.2 H.sub.5 CF.sub.3 
1 
NO.sub.2 
CCl NHC.sub.2 H.sub.5 CF.sub.3 
2 
NO.sub.2 
CCl NHC.sub.2 H.sub.5 CF.sub.2 Br 
0 
NO.sub.2 
CCl NHC.sub.2 H.sub.5 CF.sub.2 Br 
1 
NO.sub.2 
CCl NHC.sub.2 H.sub.5 CF.sub.2 Br 
2 
NO.sub.2 
CCl NHC.sub.2 H.sub.5 CF.sub.2 H 
0 
NO.sub.2 
CCl NHC.sub.2 H.sub.5 CF.sub.2 H 
1 
NO.sub.2 
CCl NHC.sub.2 H.sub.5 CF.sub.2 H 
2 
NO.sub.2 
CCl NHC.sub.2 H.sub.5 CF.sub.2 Cl 
0 
NO.sub.2 
CCl NHC.sub.2 H.sub.5 CF.sub.2 Cl 
1 
NO.sub.2 
CCl NHC.sub.2 H.sub.5 CF.sub.2 Cl 
2 
NO.sub.2 
CCl N(C.sub.2 H.sub.5).sub.2 
CF.sub.3 
0 
NO.sub.2 
CCl N(C.sub.2 H.sub.5).sub.2 
CF.sub.3 
1 
NO.sub.2 
CCl N(C.sub.2 H.sub.5).sub.2 
CF.sub.3 
2 
NO.sub.2 
CCl N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 Br 
0 
NO.sub.2 
CCl N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 Br 
1 
NO.sub.2 
CCl N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 Br 
2 
NO.sub.2 
CCl N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 H 
0 
NO.sub.2 
CCl N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 H 
1 
NO.sub.2 
CCl N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 H 
2 
NO.sub.2 
CCl N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 Cl 
0 
NO.sub.2 
CCl N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 Cl 
1 
NO.sub.2 
CCl N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 Cl 
2 
Cl N NCHPh CF.sub.3 
0 
Cl N NCHPh CF.sub.3 
1 
Cl N NCHPh CF.sub.3 
2 
Cl N NCHPh CF.sub.2 Br 
0 
Cl N NCHPh CF.sub.2 Br 
1 
Cl N NCHPh CF.sub.2 Br 
2 
Cl N NCHPh CF.sub.2 H 
0 
Cl N NCHPh CF.sub.2 H 
1 
Cl N NCHPh CF.sub.2 H 
2 
Cl N NCHPh CF.sub.2 Cl 
0 
Cl N NCHPh CF.sub.2 Cl 
1 
Cl N NCHPh CF.sub.2 Cl 
2 
Cl N NCHVa CF.sub.3 
0 
Cl N NCHVa CF.sub.3 
1 
Cl N NCHVa CF.sub.3 
2 
Cl N NCHVa CF.sub.2 Br 
0 
Cl N NCHVa CF.sub.2 Br 
1 
Cl N NCHVa CF.sub.2 Br 
2 
Cl N NCHVa CF.sub.2 H 
0 
Cl N N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 Cl 
1 
Cl N N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 Cl 
2 
Cl N NCHVa CF.sub.2 H 
1 
Cl N NCHVa CF.sub.2 H 
2 
Cl N NCHVa CF.sub.2 Cl 
0 
Cl N NCHVa CF.sub.2 Cl 
1 
Cl N NCHVa CF.sub.2 Cl 
2 
Cl N NHC.sub.2 H.sub.5 CF.sub.3 
0 
Cl N NHC.sub.2 H.sub.5 CF.sub.3 
1 
Cl N NHC.sub.2 H.sub.5 CF.sub.3 
2 
Cl N NHC.sub.2 H.sub.5 CF.sub.2 Br 
0 
Cl N NHC.sub.2 H.sub.5 CF.sub.2 Br 
1 
Cl N NHC.sub.2 H.sub.5 CF.sub.2 Br 
2 
Cl N NHC.sub.2 H.sub.5 CF.sub.2 H 
0 
Cl N NHC.sub.2 H.sub.5 CF.sub.2 H 
1 
Cl N NHC.sub.2 H.sub.5 CF.sub.2 H 
2 
Cl N NHC.sub.2 H.sub.5 CF.sub.2 Cl 
0 
Cl N NHC.sub.2 H.sub.5 CF.sub.2 Cl 
1 
Cl N NHC.sub.2 H.sub.5 CF.sub.2 Cl 
2 
Cl N N(C.sub.2 H.sub.5).sub.2 
CF.sub.3 
0 
Cl N N(C.sub.2 H.sub.5).sub.2 
CF.sub.3 
1 
Cl N N(C.sub.2 H.sub.5).sub.2 
CF.sub.3 
2 
Cl N N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 Br 
0 
Cl N N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 Br 
1 
Cl N N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 Br 
2 
Cl N N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 H 
0 
Cl N N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 H 
1 
Cl N N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 H 
2 
Cl N N(C.sub.2 H.sub.5).sub.2 
CF.sub.2 Cl 
0 
Cl CCl NHCH.sub.3 CF.sub.3 
0 
Cl CCl NH(CH.sub.2).sub.2 CH.sub.3 
CF.sub.3 
0 
Cl CCl NH(CH.sub.2).sub.3 CH.sub.3 
CF.sub.3 
0 
Cl CCl NHCH(CH.sub.3).sub.2 CF.sub.3 
0 
Cl CCl NHCH(CH.sub.3)CH.sub.2 CH.sub.3 
CF.sub.3 
0 
Cl CCl NHCH.sub.2 CH(CH.sub.3).sub.2 
CF.sub.3 
0 
Cl CCl NHC(CH.sub.3).sub.3 CF.sub.3 
0 
Cl CCl NHCH.sub.2 C(CH.sub.3).sub.3 
CF.sub.3 
0 
Cl CCl N(CH.sub.3)CH.sub.2 CH.sub.3 
CF.sub.2 
0 
Cl CCl N(CH.sub.2).sub.2 CF.sub.3 
0 
Cl CCl 
##STR8## CF.sub.3 
0 
Cl CCl 
##STR9## CF.sub.3 
0 
Cl CCl 
##STR10## CF.sub.3 
0 
Cl CCl 
##STR11## CF.sub.3 
0 
Cl CCl 
##STR12## CF.sub.3 
0 
Cl CCl 
##STR13## CF.sub.3 
0 
Cl CCl 
##STR14## CF.sub.3 
0 
Cl CCl 
##STR15## CF.sub.3 
0 
Cl CCl 
##STR16## CF.sub.3 
0 
Cl CCl 
##STR17## CF.sub.3 
0 
Cl CCl NH(CH.sub.2).sub.2 OCH.sub.3 
CF.sub.3 
0 
Cl CCl NHCH(OCH.sub.3)C(CH.sub.3).sub.3 
CF.sub.3 
0 
Cl CCl NHCH(OCH.sub.2 CH.sub.3)C(CH.sub.3).sub.3 
CF.sub.3 
0 
Cl CCl NHCH.sub.2 OCH.sub.3 CF.sub.3 
0 
Cl CCl NHCH.sub.2 OCH.sub.2 CH.sub.3 
CF.sub.3 
0 
Cl CCl NHCH.sub.2 OCH(CH.sub.3).sub.2 
CF.sub.3 
0 
Cl CCl NHCH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.3 
CF.sub.3 
0 
Cl CCl NHCH.sub.2 O(CH.sub.2).sub.3 CH.sub.3 
CF.sub.3 
0 
Cl CCl NHCH.sub.2 OCH(CH.sub.3)CH.sub.2 CH.sub.3 
CF.sub.3 
0 
Cl CCl NHCH.sub.2 OCH.sub.2 CH(CH.sub.3).sub.2 
CF.sub.3 
0 
Cl CCl NHCOCH.sub.3 CF.sub.3 
0 
Cl CCl NHCOCH.sub.2 CH.sub.3 CF.sub.3 
0 
Cl CCl NHCO(CH.sub.2).sub.2 CH.sub.3 
CF.sub.3 
0 
Cl CCl NHCO(CH.sub.2).sub.3 CH.sub.3 
CF.sub.3 
0 
Cl CCl NHCOCH(CH.sub.3).sub.2 
CF.sub.3 
0 
Cl CCl NHCOCH.sub.2 CH(CH.sub.3).sub.3 
CF.sub.3 
0 
Cl CCl NH(COCH.sub.3).sub.2 CF.sub.3 
0 
Cl CCl NH(COCH.sub.2 CH.sub.3).sub.2 
CF.sub.3 
0 
Cl CCl NH(COCH.sub.2 CH.sub.2 CH.sub.2).sub.2 
CF.sub.3 
0 
Cl CCl NH(COCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3).sub.2 
CF.sub.3 
0 
Cl CCl NHCH(OCH.sub.3)C(CH.sub.3).sub.3 
CF.sub.3 
1 
Cl CCl NHCH(OCH.sub.3)C(CH.sub.3).sub.3 
CF.sub.3 
2 
Cl CCl NH(CH.sub.2).sub.2 CH.sub.3 
CF.sub.3 
1 
Cl CCl NH(CH.sub.2).sub.2 CH.sub.3 
CF.sub.3 
2 
Cl CCl NHCH(OCH.sub.3)C(CH.sub.3).sub.3 
CF.sub.2 CH.sub.3 
0 
Cl CCl NHCH(OCH.sub.3)C(CH.sub.3).sub.3 
CF.sub.2 CH.sub.3 
1 
Cl CCl NHCH(OCH.sub.3)C(CH.sub.3).sub.3 
CF.sub.2 CH.sub.3 
2 
Cl CCl NHCH(OCH.sub.3)C(CH.sub.3).sub.3 
CF.sub.2 Br 
0 
Cl CCl NHCH(OCH.sub.3)C(CH.sub.3).sub.3 
CF.sub.2 Br 
1 
Cl CCl NHCH(OCH.sub.3)C(CH.sub.3).sub.3 
CF.sub.2 Br 
2 
Cl CCl NHCH(OCH.sub.3)C(CH.sub.3).sub.3 
CF.sub.2 CF.sub.2 H 
0 
Cl CCl NHCH(OCH.sub.3)C(CH.sub.3).sub.2 
CF.sub.2 CF.sub.2 H 
1 
Cl CCl NHCH(OCH.sub.3)C(CH.sub.3).sub.3 
CF.sub.2 CF.sub.2 H 
2 
Cl CCl NHCH(OCH.sub.3)C(CH.sub.3).sub.3 
CF.sub.2 CF.sub.2 Br 
0 
Cl CCl NHCH(OCH.sub.3)C(CH.sub.3).sub.3 
CF.sub.2 CF.sub.2 Br 
1 
Cl CCl NHCH(OCH.sub.2)C(CH.sub.2).sub.2 
CF.sub.2 CF.sub.2 Br 
2 
Cl CCl NHCH(OCH.sub.3)C(CH.sub.3).sub.3 
CF.sub.2 H 
0 
Cl CCl NHCH(OCH.sub.3)C(CH.sub.3).sub.3 
CF.sub.2 H 
1 
Cl CCl NHCH(OCH.sub.3)C(CH.sub.3).sub.3 
CF.sub.2 H 
2 
Cl CCl NHCH(OCH.sub.3)C(CH.sub.3).sub.3 
CH.sub.2 CF.sub.3 
0 
Cl CCl NHCH(OCH.sub.3)C(CH.sub.2).sub.3 
CH.sub.2 CF.sub.3 
1 
Cl CCl NHCH(OCH.sub.3)C(CH.sub.3).sub.3 
CH.sub.2 CF.sub.3 
2 
F CCl NHCH(OCH.sub.3)C(CH.sub.3).sub.3 
CF.sub.3 
0 
F CCl NHCH(OCH.sub.3)C(CH.sub.3).sub.3 
CF.sub.3 
1 
F CCl NHCH(OCH.sub.3)C(CH.sub.3).sub.3 
CF.sub.3 
2 
Cl CCl HNC(CH.sub.3).sub.3 CF.sub.2 CH.sub.3 
0 
Cl CCl HNC(CH.sub.3).sub.3 CF.sub.2 CH.sub.3 
1 
Cl CCl HNC(CH.sub.3).sub.3 CF.sub.2 CH.sub.3 
2 
Cl CCl HNC(CH.sub.3).sub.3 CF.sub.2 Br 
0 
Cl CCl HNC(CH.sub.3).sub.3 CF.sub.2 Br 
1 
Cl CCl HNC(CH.sub.3).sub.3 CF.sub.2 Br 
2 
Cl CCl HNC(CH.sub.3).sub.3 CF.sub.2 CF.sub.2 H 
0 
Cl CCl HNC(CH.sub.3).sub.3 CF.sub.2 CF.sub.2 H 
1 
Cl CCl HNC(CH.sub.3).sub.3 CF.sub.2 CF.sub.2 H 
2 
Cl CCl HNC(CH.sub.3).sub.3 CF.sub.2 CF.sub.2 Br 
0 
Cl CCl HNC(CH.sub.3).sub.3 CF.sub.2 CF.sub.2 Br 
1 
Cl CCl HNC(CH.sub.3).sub.3 CF.sub.2 CF.sub.2 Br 
2 
Cl CCl HNC(CH.sub.3).sub.3 CF.sub.2 H 
0 
Cl CCl HNC(CH.sub.3).sub.3 CF.sub.2 H 
1 
Cl CCl HNC(CH.sub.3).sub.3 CF.sub.2 H 
2 
Cl CCl HNC(CH.sub.3).sub.3 CH.sub.2 CF.sub.3 
0 
Cl CCl HNC(CH.sub.3).sub.3 CH.sub.2 CF.sub.3 
1 
Cl CCl HNC(CH.sub.3).sub.3 CH.sub.2 CF.sub.3 
2 
F CCl HNC(CH.sub.3).sub.3 CF.sub.3 
0 
F CCl HNC(CH.sub.3).sub.3 CF.sub.3 
1 
F CCl HNC(CH.sub.3).sub.3 CF.sub.3 
2 
Cl CCl Br CF.sub.3 
0 
Cl CCl Br CF.sub.3 
1 
Cl CCl Br CF.sub.3 
2 
Cl CCl Cl CF.sub.3 
0 
Cl CCl Cl CF.sub.3 
1 
Cl CCl Cl CF.sub.3 
2 
Cl CCl NHCCH.sub.3 (OCH.sub.3).sup.t Bu 
CF.sub.3 
0 
Cl CCl NHCCH.sub.3 (OCH.sub.3).sup.t Bu 
CF.sub.3 
1 
Cl CCl NHCCH.sub.3 (OCH.sub.3).sup.t Bu 
CF.sub.3 
2 
Cl CCl NHCCH.sub.3 (OCH.sub.2 CH.sub.3).sup.t Bu 
CF.sub.3 
0 
Cl CCl NHCCH.sub.3 (OCH.sub.2 CH.sub.3).sup.t Bu 
CF.sub.3 
1 
Cl CCl NHCCH.sub.3 (OCH.sub.2 CH.sub.3).sup.t Bu 
CF.sub.3 
2 
Cl CCl NHCH(OCH.sub.2 CH.sub.3)C(CH.sub.3).sub.3 
CF.sub.3 
1 
Cl CCl NHCH(OCH.sub.2 CH.sub.3)C(CH.sub.3).sub.3 
CF.sub.3 
2 
Cl CCl NHCH(OCH.sub.2 CH.sub.3)C(CH.sub.3).sub.3 
CF.sub.2 Br 
0 
Cl CCl NHCH(OCH.sub.2 CH.sub.3)C(CH.sub.3).sub.3 
CF.sub.2 Br 
1 
Cl CCl NHCH(OCH.sub.2 CH.sub.3)C(CH.sub.3).sub.3 
CF.sub.2 Br 
2 
Cl CCl NHCH(OCH.sub.2 CH.sub.3)C(CH.sub.3).sub.2 
CF.sub.2 CF.sub.2 H 
0 
Cl CCl NHCH(OCH.sub.2 CH.sub.3)C(CH.sub.3).sub.2 
CF.sub.2 CF.sub.2 H 
1 
Cl CCl NHCH(OCH.sub.2 CH.sub.3)C(CH.sub.3).sub.3 
CF.sub.2 CF.sub.2 H 
2 
Cl CCl NHCH(OCH.sub.2 CH.sub.3)C(CH.sub.3).sub.3 
CF.sub.2 H 
0 
Cl CCl NHCH(OCH.sub.2 CH.sub.3)C(CH.sub.3).sub.3 
CF.sub.2 H 
1 
Cl CCl NHCH(OCH.sub.2 CH.sub.3)C(CH.sub.3).sub.3 
CF.sub.2 H 
2 
Cl CCl NHCCH.sub.3 (OCH.sub.2 CH.sub.3).sup.t Bu 
CF.sub.2 Br 
0 
Cl CCl NHCCH.sub.3 (OCH.sub.2 CH.sub.3).sup.t Bu 
CF.sub.2 Br 
1 
Cl CCl NHCCH.sub.3 (OCH.sub.2 CH.sub.3).sup.t Bu 
CF.sub.2 Br 
2 
Cl CCl NHCCH.sub.3 (OCH.sub.2 CH.sub.3).sup.t Bu 
CF.sub.2 H 
0 
Cl CCl NHCCH.sub.3 (OCH.sub.2 CH.sub.3).sup.t Bu 
CF.sub.2 H 
1 
Cl CCl NHCCH.sub.3 (OCH.sub.2 CH.sub.3).sup.t Bu 
CF.sub.2 H 
2 
Cl CCl NC(OCH.sub.2 CH.sub.3)CH.sub.3 
CF.sub.3 
0 
Cl CCl NC(OCH.sub.2 CH.sub.3)CH.sub.2 CH.sub.3 
CF.sub.3 
0 
Cl CCl NC(CH.sub.3)N(CH.sub.3).sub.2 
CF.sub.3 
0 
Cl CCl NCHC(CH.sub.3).sub.3 CF.sub.3 
0 
Cl CCl NCCH.sub.3 C(CH.sub.2).sub.3 
CF.sub.3 
0 
Cl CCl 
##STR18## CF.sub.3 
0 
Cl CCl 
##STR19## CF.sub.3 
0 
Cl CCl 
##STR20## CF.sub.3 
0 
Cl CCl 
##STR21## CF.sub.3 
0 
Cl CCl NC(OCH.sub.2 CH.sub.3)CH.sub.2 CH.sub.2 CH.sub.3 
CF.sub.3 
0 
Cl CCl 
##STR22## CF.sub.3 
0 
Cl CCl 
##STR23## CF.sub.3 
0 
Cl CCl 
##STR24## CF.sub.3 
0 
Cl CCl 
##STR25## CF.sub.3 
0 
Cl CCl 
##STR26## CF.sub.3 
0 
Cl CCl 
##STR27## CF.sub.3 
0 
Cl CCl 
##STR28## CF.sub.3 
0 
Cl CCl NHCH(SCH.sub.2 CH.sub.3)C(CH.sub.3).sub.3 
CF.sub.3 
0 
Cl CCl N(CO.sub.2 CH.sub.2 CH.sub.3).sub.2 
CF.sub.3 
0 
Cl CCl NH.sub.2 CF.sub.2 CF.sub.2 H 
0 
Cl CCl 
##STR29## CF.sub.3 
0 
Cl CCl N(CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3).sub.2 
CF.sub.3 
0 
Cl CCl 
##STR30## CF.sub.3 
0 
Cl CCl NHCOCH.sub.2 OCH.sub.3 
CF.sub.3 
0 
Cl CCl NHS(CH.sub.2).sub.3 CH.sub.3 
CF.sub.3 
0 
Cl CCl N(CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3).sub.2 
CF.sub.3 
0 
Cl CCl NCO.sub.2 CH(CH.sub.3).sub.2 !.sub.2 
CF.sub.3 
0 
Cl CCl NHCO.sub.2 CH(CH.sub.3).sub.2 
CF.sub.3 
0 
Cl CCl NHCOCH.sub.2 t-Bu CF.sub.3 
0 
Cl CCl NHSCH(CH.sub.3).sub.2 CF.sub.3 
0 
Cl CCl NHSNCH(CH.sub.3).sub.2 !CH.sub.2 CH.sub.2 CO.sub.2 CH.sub.2 
CH.sub.3 CF.sub.3 
0 
Cl CCl N(SO.sub.2 CH.sub.3).sub.2 
CF.sub.3 
0 
Cl CCl 
##STR31## CF.sub.3 
0 
Cl CCl 
##STR32## CF.sub.3 
0 
Cl CCl NHCH.sub.2 SCH.sub.3 CF.sub.3 
0 
Cl CCl 
##STR33## CF.sub.3 
0 
Cl CCl NHSN(CH.sub.3)CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 
CF.sub.3 
0 
Cl CCl NHSN(CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3).sub.2 
CF.sub.3 
0 
Cl CCl 
##STR34## CF.sub.3 
0 
Cl CCl 
##STR35## CF.sub.3 
0 
Cl CCl NHSCO.sub.2 CH.sub.3 CF.sub.3 
0 
Cl CCl N(COSCH.sub.2 CH.sub.3).sub.2 
CF.sub.3 
0 
______________________________________ 
The present compounds can be used as agricultural insecticides and 
acaricides and epidemic preventing insecticides and acaricides. 
Examples of insect and other pests (noxious insects and mites) on which the 
present compounds exhibit controlling effects are as follows: 
Insects of Hemiptera order: 
Planthoppers such as small brown planthopper, brown rice planthopper and 
whitebacked rice planthopper, leafhoppers such as green rice leafhopper, 
aphids, stink bugs, whiteflies, Coccidae, lace bugs, jumping plantlices, 
etc. 
Insects of Lepidoptera order: 
Pyralid moths such as rice stem borer, rice leafroller and armyworms such 
as common cutworm, rice armyworm and cabbage armyworm, sulfur butterflies 
such as common cabbage worm, leafroller months such as summer fruit 
tortrix, Carposinidae, lyonetiid moths, oriental tussock moths, , insects 
of Agrotis spp. such as turnip moth and dark sword grass moth, insects of 
Heliothis spp, diamondback moth, casemaking clothes moth, webbing clothes 
moth, etc. 
Insects of Diptera order: 
Culices such as Culex pipiens pallens and Culex tritaniorhynchus, striped 
mosquitoes such as tropical striped mosquito and one-striped mosquito, 
Anopheles mosquitoes such as chinese anopheles mosquito, midges, house 
flies such as allies and large houseflies, black flies, flesh flies, 
anthomyiid flies such as seedcorn maggot, small house fly and onion 
maggot, fruit flies, vinegar flies, moth flies, horseflies, gnats, biting 
flies, etc. 
Insects of Coleoptera order: 
Corn root worms such as western corn root worm and southern corn root worm, 
scarabs such as cupreous chafer and soybeen beetle, weevils such as maize 
weevil, ricewater weevil and adzuki been weevil, darkling beetles such as 
yellow mealworm and red flour beetle, leaf beetles such as striped flea 
beetle and cucurbit leaf beetle, deathwatch and drugstore beetles, insects 
of Epilachna spp. such as twenty-eight-spotted ladybird, powder post 
beetles, false powderspot beetles, longicorn beetles, Paederus idae Lewis, 
etc. 
Insects of Dictyoptera order: 
Cockroaches such as German cockroach, oriental cockroach (Blatta 
orientalis), American cockroach, brown cockroach, 
Insects of Thysanoptera order: 
, flower thrips, etc. 
Insects of Hymenoptera order: 
Ants, hornets, bethylid wasps, sawflies such as cabbage sawfly, etc. 
Insects of Orthoptera order: 
Mole crickets, grasshoppers, etc. 
Insects of Aphaniptera order: 
Human flea, etc. 
Insects of Anoplura order: 
Lice, phthiridae, etc. 
Insects of Isoptera order: 
Reticulitermes speratus Kolbe, Formosan subterranean termite, etc. 
House dust mites: 
Dermatophagoides spp. such as Dermatophagoides farinae and Dermatophagoides 
pteronyssinus; Acaridae such as Tyrophagus putrescentiae and Aleuroglyphus 
ovatus; Glycyphagus spp. such as Glycyphagus privatus, Glycyphagus 
domesticus and Glycyphagus destructor; Cheyetidae such as Cheyletus 
malaccensis and Cheyletus fortis; Tarsonemidae; Haplochthoninus simplex; 
etc. 
Spider mites: 
Carmine spider mite, two-spotted spider mite, Kanzawa spider mite, citrus 
red mite, European red mite, etc. 
Furthermore, the present compounds are also effective on insect pests which 
have increased resistance to the conventional insecticides and acaricides. 
When the present compound is used as an active ingredient of insecticides 
and acaricides, it may be used without adding any other components, but, 
usually, it is mixed with solid carriers, liquid carriers, gaseous 
carriers, baits or the like or substrates such as porous ceramics sheets 
and nonwoven fabrics are impregnated with the compound. If necessary, with 
addition of surface active agents and other auxiliaries for formulation, 
the compound is used in the formulations of oil solution, emulsifiable 
concentrate, wettable powder, flowable, granule, dust, aerosol, fogging 
agent, smoking agent, poison bait, acaricidal sheet, and the like. 
These formulations contain usually 0.01-95% by weight of the present 
compound as an active ingredient. 
The solid carriers used for formulation include, for example, fine powders 
or granules of clays (such as kaolin clay, diatomaceous earth, synthetic 
silicon oxide, bentonite, Fubasamiclay and acid clay), talcs, ceramics, 
other inorganic minerals (such as sericite, quartz, sulfur, active carbon, 
calcium carbonate and hydrated silica), and chemical fertilizers (such as 
ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and ammonium 
chloride). The liquid carriers include, for example, water, alcohols (such 
as methanol and ethanol), ketones (such as acetone and methyl ethyl 
ketone), aromatic hydrocarbons (such as benzene, toluene, xylene, 
ethylbenzene and methylnaphthalene), aliphatic hydrocarbons (hexane, 
cyclohexane, kerosene and light oil), esters (such as ethyl acetate and 
butyl acetate), nitrites (such as acetonitrile and isobutyronitrile), 
ethers (such as dusopropyl ether and dioxane), acid amides (such as 
N,N-dimethylformamide and N,N-dimethylacetamide), halogenated hydrocarbons 
(such as dichloromethane, trichloroethane and carbon tetrachloride), 
dimethyl sulfoxide, and vegetable oils such as soybean oil and cottonseed 
oil. The gaseous carriers, namely, propellants include, for example, Freon 
gas, butane gas, LPG (liquefied petroleum gas), dimethyl ether and carbon 
dioxide. 
The surface active agents include, for example, alkylsulfate esters, 
alkylsulofonate salts, alkylarylsulfonate salts, alkylaryl ethers and 
polyoxyethylene compounds thereof, polyethylene glycol ethers, polyhydric 
alcohol esters and sugar alcohol derivatives. 
The auxiliaries for formulation such as adhesive agents and dispersing 
agents include, for example, casein, gelatin, polysaccharides (such as 
starch powder, gum arabic, cellulose derivatives and alginic acid), lignin 
derivatives, bentonite, sugars, synthetic water-soluble polymers (such as 
polyvinyl alcohol, polyvinyl pyrrolidone and polyacrylic acids). 
Stabilizers include, for example, PAP (acid isopropyl phosphate), BHT 
(2,6-di-tert-butyl-4-methylphenol), BHA (mixture of 
2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable 
oils, mineral oils, surface active agents and fatty acids or esters 
thereof. 
The substrates for poisen baits include, for example, bait components such 
as grain powder, vegetable oil, sugar and crystalline cellulose, 
antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic acid, 
preservatives such as dehydroacetic acid, erroneous eating inhibitors such 
as Guinea pepper powder, and attractant flavor such as cheese flavor and 
onion flavor. 
The thus obtained formulations are used as such or diluted with water. 
Furthermore, these formulations may be used alone or in admixture with 
other insecticides, nematicides, acaricides, fungicides, herbicides, plant 
growth regulating agents, synergists, fertilizers, soil improvers, animal 
feeds and the like. 
Examples of the insecticides, nematicides and acaricides are as follows: 
Organic phosphorous compounds such as fenitrothion O,O-dimethyl 
O-(3-methyl-4-nitrophenyl)phosphorothioate!, fention O,O-dimethyl 
O-(3-methyl-4-(methylthio)phenyl)phosphorothioate!, diazinon 
O,O-diethyl-O-2-isopropyl-6-methylpyrimidine-4-ylphosphorothioate, 
chlorpyrifos O,O-diethyl-O-3,5,6-trichloro-2-pyridylphosphorothioate!, 
acephate O,S-dimethylacetylphosphoramidothioate!, methidathion 
S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3-ylmethyl 
O,O-dimethylphosphorodithioate!, disulfoton O,O-diethyl 
S-2-ethylthioethylphosphorodithioate!, DDVP 
2,2-dichlorovinyldimethylphosphate!, sulprofos O-ethyl 
O-4-(methylthio)phenyl S-propylphosphorodithioate!, cyanophos 
O-4-cyanophenyl O,O-dimethylphosphorothioate!, dioxabenzofos 
2-methoxy-4H-1,3,2-benzodioxaphosphorine-2-sulfide!, dimethoate 
O,O-dimethyl-S-(N-methylcarbamoylmethyl)dithiophosphate!, phenthoate 
ethyl 2-dimethoxyphosphinothioylthio(phenyl)acetate!, malathion 
diethyl(dimethoxyphosphinothioylthio)succinate!, trichlorfon dimethyl 
2,2,2-trichloro-1-hydroxyethylphosphonate!, azinphosmethyl 
S-3,4-dihydro-4-oxo-1,2,3-benzotriazin-3-ylmethyl 
O,O-dimethylphosphoroditioate!, monocrotophos 
dimethyl(E)-1-methyl-2-(methylcarbamoyl)vinylphosphate!, and ethion 
O,O,O',O'-tetraethyl S,S'-methylenebis(phosphorodithioate)!. 
Carbamate compounds such as BPMC (2-sec-butylphenylmethylcarbamate), 
benfuracarb ethyl 
N-2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl(methyl)aminothio!-N- 
isopropyl-.beta.-araninate!, propoxur 2-isopropoxyphenyl 
N-methylcarbamate!, carbosulfan 
2,3-dihydro-2,2-dimethyl-7-benzob!furanyl N-dibutylaminothio-N-methylcar 
bamate!, carbaryl 1-naphthyl-N-methylcarbamate!, methomyl 
S-methyl-N-(methylcarbamoyl)oxy!thioacetoimidate!, ethiofencarb 
2-(ethylthiomethyl)phenylmethylcarbamate!, aldicarb 
2-methyl-2-(methylthio)propionaldehyde O-methylcarbamoyloxime!, oxamyl 
N,N-dimethyl-2-methylcarbamoyloxyimino-2-(methylthio)acetamide!, and 
fenothiocarb S-(4-phenoxybutyl)-N,N-dimethylthiocarbamate!. 
Pyrethroid compounds such as ethofenprox 
2-(4-ethoxyphenyl)-2-methylpropyl-3-phenoxybenzyl ether!, fenvalerate 
(RS)-.alpha.-cyano-3-phenoxybenzyl 
(RS)-2-(4-chlorophenyl)-3-methylbutyrate!, esfenvalerate 
(S)-.alpha.-cyano-3-phenoxybenzyl 
(S)-2-(4-chlorophenyl)-3-methylbutyrate!, fenpropathrin 
(RS)-.alpha.-cyano-3-phenoxybenzyl 
2,2,3,3-tetramethylcyclopropanecarboxylate!, cypermethrin 
(RS)-.alpha.-cyano-3-phenoxybenzyl (1RS)-cis, 
trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate!, 
permethrin 3-phenoxybenzyl (1RS)-cis, 
trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate!, 
cyhalothrin (RS)-.alpha.-cyano-3-phenoxybenzyl 
(Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopro 
panecarboxylate!, deltamethrin (S)-.alpha.-cyano-3-phenoxybenzyl 
(1R)-cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate!, 
cycloprothrin (RS)-.alpha.-cyano-3-phenoxybenzyl 
(RS)-2,2-dichloro-1-(4-ethoxyphenyl)cyclopropanecarboxylate!, fluvalinate 
(.alpha.-cyano-3-phenoxybenzyl 
N-(2-chloro-.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)-D-valinate), 
bifenthrin (2-methylbiphenyl-3-ylmethyl) 
(Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopro 
panecarboxylate, 2-methyl-2-(4-bromodifluoromethoxyphenyl)propyl 
(3-phenoxybenzyl) ether, tralomethrin (S)-.alpha.-cyano-3-phenoxybenzyl 
(1R-cis)3{(1'RS) 
(1',2',2',2'-tetrabromoethyl)}-2,2-dimethylcyclopropanecarboxylate!, 
silafluofen 4-ethoxyphenyl 
{3-(4-fluoro-3-phenoxyphenyl)propyl}dimethylsilane!, d-fenothrin 
3-phenoxybenzyl (1R)-cis, trans)-chrysanthemate!, cyphenothrin 
(RS)-.alpha.-cyano-3-phenoxybenzyl (1R-cis, trans)-chrysanthemate!, 
d-resmethrin 5-benzyl-3-furylmethyl (1R-cis, trans)-chrysanthemate!, 
acrinathrin (S)-.alpha.-cyano-3-phenoxybenzyl (1R-cis 
(Z))-(2,2-dimethyl-3-{oxo-3-(1,1,1,3,3,3-hexafluoropropyloxy)propenyl}cycl 
opropanecarboxylate!, cyfluthrin 
(RS)-.alpha.-cyano-4-fluoro-3-phenoxybenzyl 
3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate!, tefluthrin 
2,3,5,6-tetrafluoro-4-methylbenzyl (1RS-cis 
(Z))-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarbo 
xylate!, transfluthrin 2,3,5,6-tetrafluorobenzyl 
(1R-trans)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate!, 
tetramethrin 3,4,5,6-tetrahydrophthalimidomethyl (1RS)-cis, 
trans-chrysanthemate!, allethrin 
(RS)-3-allyl-2-methyl-4-oxocyclopent-2-enyl (1RS)-cis, 
trans-chrysanthemate!, prallethrin 
(S)-2-methyl-4-oxo-3-(2-propynyl)cyclopent-2-enyl (1R)-cis, 
trans-chrysanthemate!, empenthrin (RS)-1-ethynyl-2-methyl-2-pentenyl 
(1R)-cis, trans-chrysanthemate!, imiprothrin 
2,5-dioxo-3-(prop-2-ynyl)imidazolidin-1-ylmethyl (1R)-cis, 
trans-2,2-dimethyl-3-(2-methyl-1-propenyl)-cyclopropanecarboxylate!, 
d-flamethrin 5-(2-propynyl)-furfuryl (1R)-cis, trans-chrysanthemate!, and 
5-(2-propynyl)furfuryl 2,2,3,3-tetramethylcyclopropanecarboxylate. 
Thiadiazine derivatives such as buprofezin 
(2-tert-butylimino-3-isopropyl-5-phenyl-1,3,5-thiadiazin-4-one), 
nitroimidazolidine derivatives such as imidacloprid 
(1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylidenamine), 
neristoxin derivatives such as cartap (S,S'-(2-dimethylaminotrimethylene) 
bis(thiocarbamate), thiocyclam N,N-dimethyl-1,2,3-trithian-5-ylamine! and 
bensultap S,S'-2-dimethylaminotrimethylene di(benzenethiosulfonate)!, 
N-cyanoamidine derivatives such as 
N-cyano-N'-methyl-N'-(6-chloro-3-pyridylmethyl)acetamidine, chlorinated 
hydrocarbon compounds such as endosulfan 
6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzod 
ioxathiepine oxide!, .gamma.-BHC 1,2,3,4,5,6-hexachlorocyclohexane! and 
1,1-bis(chlorophenyl)-2,2,2-trichloroethanol, benzoylphenylurea compounds 
such as chlorfluazuron 
1-(3,5-dichloro-4-(3-chloro-5-trifluoromethylpyridin-2-yloxy)phenyl)-3-(2 
,6-difluorobenzoyl)urea!, teflubenzuron 
1-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzoyl)urea! and 
flufenoxuron 
1-(4-(2-chloro-4-trifluoromethylphenoxy)-2-fluorophenyl!-3-(2,6-difluorob 
enzoyl)urea!, formamidine derivatives such as amitraz 
N,N'(methylimino)dimethylidine! di-2,4-xylidine! and chlordimeform 
N'-(4-chloro-2-methylphenyl)-N,N-dimethylmethanimidamide!, thiourea 
derivatives such as diaphentiuron 
N-(2,6-diisopropyl-4-phenoxyphenyl)-N'-tert-butylcarbodiimide!, 
N-arylheterocyclic compounds methoxadiazon 
5-methoxy-3-(2-methoxyphenyl)-1,3,4-oxadiazol-2-(3H)-one!, bromopropylate 
isopropyl 4,4'-dibromobenzylate!, tetradifon 4-chlorophenyl 
2,4,5-trichlorophenylsulfone!, quinomethionate 
S,S-6-methylquinoxaline-2,3-diyldithiocarbonate!, propargite 
2-(4-tert-butylphenoxy)cyclohexyl prop-2-yl sulfite!, fenbutain-oxide 
bistris(2-methyl-2-phenylpropyl)thiene!xodie!, hexythiazox 
(4RS,5RS)-5-(4-chlorophenyl)-N-chlorohexyl-4-methyl-2-oxo-1,3-thiazolidin 
e-3-carboxamide!, chlofentezin 3,6-bis(2-chlorophenyl)-1,2,4,5-tetrazine!, 
pyridaben 
2-tert-butyl-5-(4-tert-butylbenzylthio)-4-chloropyridazin-3(2H)-one!, 
fenpyroximate tert-butyl 
(E)-4-(1,3-dimethyl-5-phenoxypyrazol-4-yl)methylenaminoxymethyl!benzoate! 
, debfenpyrado 
N-4-tert-butylbenzyl)-4-chloro-3-ethyl-1-methyl-5-pyrazolecarboxamide!, 
polynactins complex tetranactin, dinactin, trinactin!, pirimidiphen 
5-chloro-N-2-{4-(2-ethoxyethyl)-2,3-dimethylphenoxy}ethyl!-6-ethylpyrimi 
din-4-amine, milmectin, abamectin, ibamectin, and azadilactin AZAD!. 
The present compounds in an effective amount are applied to the places, for 
example, crops where insects and mites and insects or mites inhabit or 
will inhabit. 
When the present compounds are used as agricultural insecticides or 
acaricides, the amount of the compounds applied is usually 0.1-100 g per 
10 ares. In the case of emulsifiable concentrate, wettable powder, 
flowable, or the like which is diluted with water, the application 
concentration is usually 1-10000 ppm, and granule or dust is applied as it 
is without dilution. When the present compounds are used as epidemic 
preventing insecticides or acaricides, emulsifiable concentrate, wettable 
powder and flowable are usually diluted to 0.1-500 ppm with water and oil 
solution, aerosol, poison bait, fogging agent and acaricidal sheet are 
used as they are. 
The application amount and application concentration vary depending on the 
kind of formulations, the application time, the application place, the 
application method, the kind of insect pests, the state of damage, etc., 
and can be increased or decreased irrespective of the above-mentioned 
ranges. 
The present invention will be explained in more detail by the following 
nonlimiting preparation examples, formulation examples and test examples. 
First, the preparation examples of the present compounds are shown below.

PREATION EXAMPLE 1 
Preparation example of the present compound (1)! 
3,5-Dichloro-4-fluorobenzotrifluoride (0.93 g, 4 mmols) and 60% oily sodium 
hydride (0.16 g, 4 mmols) were added in succession to a suspension of 
3,3'-di(5-amino-1,2,4-triazolyl) disulfide (0.46 g, 2 mmols) in 
N,N-dimethylforamide (8 ml) under ice cooling. The mixture was stirred at 
room temperature for 12 hours and, then, transferred to a pressure vessel. 
The content was cooled to lower than -20.degree. C. and thereto were added 
iodotrifluoromethane (0.78 g, 4 mmols), sodium hydroxymethanesulfinate 
dihydrate (0.92 g, 5 mmols) and water (0.4 ml). After the vessel was 
closed, the content was further stirred at room temperature for 12 hours. 
The reaction mixture was poured into water and extracted with ethyl 
acetate. The organic layer was washed with saturated aqueous sodium 
chloride solution and dried over anhydrous magnesium sulfate. The residue 
obtained by concentration under reduced pressure was subjected to silica 
gel column chromatography (elution solvent; n-hexane:ethyl acetate =3:1) 
to obtain a mixture of 
5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-trifluoromethylsulfenyl 
-1,2, 4-triazole and 
5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-(2,6-dichloro-4-trifluo 
romethylphenylsulfenyl-1,2,4-triazole. The mixture was further subjected to 
recycling preparative HPLC (high performance liquid chromatography; LC-908 
manufactured by Japan Analytical Industry Co., Ltd.; elution solvent: 
chloroform) to obtain first 
5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-(2,6-dichloro-4-trifluo 
romethylphenylsulfenyl-1,2,4-triazole which was a by-product. 
.sup.1 H-NMR (250 MHz, CDCl.sub.3 /TMS): .delta. (ppm)=7.77 (s,2H), 7.68 
(s,2H), 4.68 (brs,2H). 
Furthermore, elution with chloroform was carried out to obtain 0.26 g of 
5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-trifluoromethylsulfenyl 
-1,2,4-triazole which is the desired present compound. 
m.p. 166.degree. C. .sup.1 H-NMR (250 MHz, CDCl.sub.3 /TMS): .delta. 
(ppm)=7.80 (s,2H), 5.38 (s,2H). 
PREATION EXAMPLE 2 
Preparation example of the present compound (2)! 
In a pressure vessel were charged 
3,3'-di1-(2,6-dichloro-4-trifluoromethylphenyl)-1,2,4-triazolyl! 
disulfide (1.66 g, 2.65 mmols) prepared in the Referential Preparation 
Example 1 given hereinafter, iodotrifluoromethane (1.04 g, 5.3 mmols), 
sodium hydroxymethanesulfinate dihydrate (1.02 g, 6.63 mmols), 
N,N-dimethylforamide (11 ml) and water (0.55 ml) at lower than -20.degree. 
C. After the vessel was closed, the content was stirred at room 
temperature for 12 hours. The reaction mixture was poured into water and 
extracted with ethyl acetate. The organic layer was washed with saturated 
aqueous sodium chloride solution and dried over anhydrous magnesium 
sulfate. The residue obtained by concentration under reduced pressure was 
subjected to silica gel column chromatography to obtain 1.30 g of 
1-(2,6-dichloro-4-trifluoromethylphenyl)-3-trifluoromethylphenylsulfenyl-1 
,2,4-triazole. 
m.p. 51.degree. C. .sup.1 H-NMR (250 MHz, CDCl.sub.3 /TMS): .delta. 
(ppm)=8.36 (s,1H), 7.80 (s,2H). 
PREATION EXAMPLE 3 
Preparation example of the present compound (3)! 
The present compound (1) (100 mg, 0.25 mmol) was dissolved in chloroform (2 
ml), and 70% m-chloroperbenzoic acid (62 mg, 0.25 mmol) was added to the 
resulting solution at room temperature. After stirring at room temperature 
for 12 hours, the content was diluted with ethyl acetate and washed with 
saturated aqueous sodium bicarbonate solution, 10% aqueous sodium sulfite 
solution and saturated aqueous sodium bicarbonate solution in succession. 
The organic layer was dried over anhydrous magnesium sulfate and, then, 
concentrated. The resulting residue was subjected to silica gel column 
chromatography to obtain 13 mg of 
5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-trifluoromethylsulfonyl 
-1,2,4-triazole. 
m.p. 174.degree.-176.degree. C. .sup.1 H-NMR (250 MHz, CDCl.sub.3 /TMS): 
.delta. (ppm)=7.83 (s,2H), 6.20 (s,2H). 
PREATION EXAMPLE 4 
Preparation example of the present compound (8)! 
A mixture of the present compound (1) (110 mg, 0.3 mmol), vanillin (46 mg, 
0.3 mmol), p-toluenesulfonic acid monohydrate (5 mg) and toluene (25 ml) 
was heated at reflux with removing water by Dean-Stark apparatus for 6 
hours. After cooling, the mixture was concentrated under reduced pressure 
and the obtained residue was subjected to silica gel column chromatography 
to obtain 84 mg of 
1-(2,6-dichloro-4-trifluoromethylphenyl)-5-N-(4-hydroxy-3-methoxybenzylid 
ene)!amino-3-trifluoromethylsulfenyl-1,2,4-triazole. 
Property: Resinous 
.sup.1 H-NMR (250 MHz, CDCl.sub.3 /TMS): .delta. (ppm)=9.23 (s,1H), 7.80 
(s,2H), 7.43 (dd, J=9, 3Hz, 1H), 7.36 (d, J=3Hz, 1H), 6.98 (d, J=9Hz, 1H), 
6.35 (brs, 1H), 3.90 (s,3H). 
PREATION EXAMPLE 5 
Preparation example of the present compound (9)! 
A mixture of the present compound (1) (0.40 g, 1 mmol), 
trimethylacetaldehyde (0.43 g, 5 mmols), p-toluenesulfonic acid 
monohydrate (17 mg) and toluene (10 ml) was heated at reflux with removing 
water by Dean-Stark apparatus for 3 hours. After cooling, the mixture was 
concentrated under reduced pressure, and methanol (10 ml) was added 
thereto. This mixture was stirred at room temperature for 12 hours and 
concentrated under reduced pressure. The obtained residue was subjected to 
silica gel chromatography to give 0.19 g of 
1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(2,2-dimethyl-1-methoxypropyl)a 
mino-3-trifluoromethyl sulfenyl-1,2,4-triazole. 
n.sub.D.sup.24.8 1.4880 .sup.1 H-NMR (250 MHz, CDCl.sub.3 /TMS): .delta. 
(ppm)=7.81 (s,1H), 4.93 (d; J=10Hz, 1H), 4.09 (d; J=10Hz, 1H), 3.39 (s, 
3H), 0.94 (s, 9H). 
PREATION EXAMPLE 6 
Preparation example of the present compound (10)! 
A mixture of the present compound (1) (0.31 g, 0.79 mmol), triethyl 
orthopropionate (0.83 g, 4.7 mmols) and p-toluenesulfonic acid monohydrate 
(13 mg) was heated at 80.degree. C. for 3 hours. After cooling, the 
mixture was concentrated and the residue was subjected to silica gel 
chromatography to give 0.36 g of 
1-(2,6-dichloro-4-trifluoromethylphenyl)-5-(1-ethoxypropylidene)amino-3-tr 
ifluoromethylsulfenyl-1,2,4-triazole. 
n.sub.D.sup.23.9 1.4973 .sup.1 H-NMR (250 MHz, CDCl.sub.3 /TMS): .delta. 
(ppm)=7.73 (s,2H), 4.01 (q; J=7.5Hz, 2H), 2.81 (q; J=7.5Hz, 2H), 1.19 (t, 
7.5Hz, 3H), 1.16 (t; J=7.5Hz, 3H). 
PREATION EXAMPLE 7 
Preparation example of the present compound (11)! 
The present compound (10) (0.26 g, 0.55 mmol) obtained in Preparation 
Example 6 was dissolved in 99.5% ethanol (10 ml) and thereto was added, 
little by little, sodium borohydride (0.10 g, 2.6 mmols) at room 
temperature with stirring. The mixture was stirred at room temperature for 
4 hours and, then, concentrated. The residue was extracted with ethyl 
acetate and washed with water. The organic layer was dried over anhydrous 
magnesium sulfate and, then, concentrated under reduced pressure to give 
an oily product. This was subjected to silica gel chromatography to give 
0.23 g of 
1-(2,6-dichloro-4-trifluoromethylphenyl)-5-propylamino-3-trifluoromethylsu 
lfenyl-1,2,4-triazole. 
m.p. 84.1.degree. C. .sup.1 H-NMR (250 MHz, CDCl.sub.3 /TMS): .delta. 
(ppm)=7.78 (s,2H), 4.00 (brt; J=7.0Hz, 1H), 3.42 (dt; J=7.0Hz, J=7.0Hz, 
2H), 1.63 (tq,; J=7.0Hz, J=7.0Hz, 2H), 0.94 (t; J=7.0Hz, 3H). 
PREATION EXAMPLE 8 
Preparation example of the present compound (12)! 
The present compound (1) (1.19 g, 3 mmols) was dissolved in bromoform (10 
ml), and thereto was added dropwise tert-butyl nitrite (0.93 g, 9 mmols) 
at 80.degree. C. After stirring at 80.degree. C. for 1 hour, the mixture 
was concentrated under reduced pressure. The obtained residue was 
subjected to silica gel chromatography to give 0.90 g of 
1-(2,6-dichloro-4-trifluoromethylphenyl)-5-bromo-3-trifluoromethylsulfenyl 
-1,2,4-triazole. 
n.sub.D.sup.28.8 1.5224 .sup.1 H-NMR (300 MHz, CDCl.sub.3 /TMS): .delta. 
(ppm)=7.81 (s,2H). 
PREATION EXAMPLE 9 
Preparation example of the present compound (13)! 
The present compound (12) (0.30 g, 0.63 mmol) obtained in Preparation 
Example 8 and diethylamine (5 ml) were charged in a pressure vessel, and 
the mixture was continuously heated at 80.degree. C. for 12 hours with 
stirring. After cooling, the content was concentrated, and the residue was 
subjected to silica gel chromatography to give 0.19 g of 
1-(2,6-dichloro-4-trifluoromethylphenyl)-5-diethylamino-3-trifluoromethyls 
ulfenyl-1,2,4-triazole. 
m.p. 74.2.degree. C. .sup.1 H-NMR (250 MHz; CDCl.sub.3 /TMS): .delta. 
(ppm)=7.75 (s,2H), 3.23 (q; J=7.0 Hz, 4H), 1.04 (t; J=7.0Hz, 6H). 
PREATION EXAMPLE 10 
Preparation example of the present compound (14)! 
Acetyl chloride (87 mg, 1.1 mmol) was added dropwise to a mixture of the 
present compound (1) (0.40 g, 1 mmol), triethylamine (0.11 g, 1.1 mmol) 
and toluene (20 ml) at room temperature. After stirring at room 
temperature for 6 hours, the mixture was poured into water and extracted 
with ethyl acetate. The organic layer was dried over anhydrous magnesium 
sulfate and concentrated under reduced pressure. The residue was subjected 
to silica gel chromatography to give 0.35 g of 
1-(2,6-dichloro-4-trifluoromethyl-phenyl)-5-acetylamino-3-trifluoromethyls 
ulfenyl-1,2,4-triazole. 
m.p. 154.2.degree. C. .sup.1 H-NMR (250 MHz; CDCl.sub.3 /TMS): .delta. 
(ppm)=9.95 (br,s,1H), 7.76 (s,2H), 2.24 (s, 3H). 
PREATION EXAMPLE 11 
Preparation example of the present compound (15)! 
Sixty percent oily sodium hydride (40 mg, 1 mmol) was added to a solution 
of 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-mercapto-1,2,4-triazole 0.31 
g, 1 mmol) in N,N-dimethylformamide (10 ml) at room temperature in a 
nitrogen atmosphere. After stirring at room temperature for 15 minutes, 
the atmosphere in the reaction vessel (20 ml volume) was replaced with 
tetrafluoroethylene gas, and the mixture was heated at 80.degree. C. for 1 
hour. The mixture was poured into water and extracted with ethyl acetate. 
The organic layer was dried over anhydrous magnesium sulfate and 
concentrated under reduced pressure. The obtained oily product was 
subjected to silica gel chromatography to give 0.21 g of 
1-(2,6-dichloro-4-trifluoromethylphenyl)-3-(1,1,2,2-tetrafluoroethyl)-1,2, 
4-triazole. 
n.sub.D.sup.25.8 1.4952 .sup.1 H-NMR (250 MHz; CDCl.sub.3 /TMS): .delta. 
(ppm)=8.35 (s,1H), 7.80 (s,2H), 6.23 (tt; J=54Hz, J=4.3Hz, 1H). 
PREATION EXAMPLE 12 
Preparation example of the present compound (47)! 
Sodium hydroxide (3.3 g) was added to a mixture of 
1-(2,6-dichloro-4-trifluoromethylphenyl)-3-mercapto-1,2,4-triazole (0.32 
g, 1 mmol), 1,4-dioxane (13 ml) and water (13 ml) at one time with blowing 
thereinto chlorodifluoromethane gas. The temperature rose to 
60.degree.-70.degree. C. After the rise of temperature stopped, the 
mixture was cooled to room temperature and poured into water. Ethyl 
acetate was added and the organic layer was separated and washed with 
saturated aqueous sodium chloride solution. The organic layer was dried 
over anhydrous magnesium sulfate and concentrated under reduced pressure. 
The obtained residue was subjected to silica gel chromatography to give 
0.29 g of 
1-(2,6-dichloro-4-trifluoromethylphenyl)-3-difluoromethylsulfenyl-1,2,4-tr 
iazole. 
n.sub.D.sup.23.8 1.5203 .sup.1 H-NMR (250 MHz; CDCl.sub.3 /TMS): .delta. 
(ppm)=8.28 (s,1H), 7.79 (s,2H), 7.50 (t; J=56Hz, 1H). 
PREATION EXAMPLE 13 
Preparation example of the present compound (39)! 
The procedure of Preparation Example 1 was repeated except that 0.98 g of 
iodopentafluoroethane was used in place of 0.78 g of iodotrifluoromethane, 
thereby to obtain 1.04 g of 
5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-pentafluoroethylsulfeny 
l-1,2,4-triazole. 
m.p. 133.9.degree. C. .sup.1 H-NMR (250 MHz; CDCl.sub.3 /TMS): .delta. 
(ppm)=7.80 (s,2H), 5.89 (br. s,2H). 
PREATION EXAMPLE 14 
Preparation example of the present compound (6)! 
The procedure of Preparation Example 1 was repeated except that 0.40 g of 
3,3'-di(1,2,4-triazolyl) disulfide was used in place of 0.46 g of 
3,3'-di(5-amino-1,2,4-triazolyl) disulfide and 0.86 g of 
2,3-dichloro-5-trifluoromethylpyridine was used in place of 0.93 g of 
3,5-dichloro-4-fluorobenzotrifluoride (the recycling HPLC was not needed), 
thereby to obtain 0.86 g of 
1-(3-chloro-5-trifluoromethylpyridin-2-yl)-3-trifluoromethylsulfenyl-1,2,4 
-triazole. 
m.p. 40.degree. C. .sup.1 H-NMR (250 MHz; CDCl.sub.3 /TMS): .delta. 
(ppm)=8.98 (s,1H), 8.74 (d; J=2.2Hz, 1H), 8.24 (d; J=2.2Hz, 1H). 
PREATION EXAMPLE 15 
Preparation example of the present compound (48)! 
A mixture of the present compound (47) (0.14 g, 0.38 mmol), 80% 
m-chloroperbenzoic acid (82 mg, 0.38 mmol) and chloroform (5 ml) was 
stirred for 12 hours at room temperature. The reaction mixture was washed 
in succession with 10% aqueous sodium sulfite solution, saturated aqueous 
sodium bicarbonate solution and saturated aqueous sodium chloride 
solution. The organic layer was dried over anhydrous magnesium sulfate and 
concentrated under reduced pressure. The obtained residue was subjected to 
silica gel chromatography to give 0.12 g of 
1-(2,6-dichloro-4-trifluoromethylphenyl)-3-difluoromethylsulfinyl-1,2,4-tr 
iazole. 
m.p. 129.5.degree. C. .sup.1 H-NMR (250 MHz; CDCl.sub.3 /TMS): .delta. 
(ppm)=8.49 (s,1H), 7.83 (s,2H), 6.84 (t; J=55Hz, 1H). 
Examples of the present compounds are shown in Table 2 together with 
properties thereof. 
TABLE 2 
__________________________________________________________________________ 
Compound Physical 
No. X.sup.1 
Y R.sup.1 R.sup.5 
n properties 
__________________________________________________________________________ 
(1) Cl CCl 
NH.sub.2 CF.sub.3 
0 m.p. 166.degree. C. 
(2) Cl CCl 
H CF.sub.3 
0 m.p. 51.degree. C. 
(3) Cl CCl 
NH.sub.2 CF.sub.3 
2 m.p. 174.about.176.degree. C. 
(4) Cl CCl 
CH.sub.3 CF.sub.3 
0 n.sub.D.sup.21. 3 1.4951 
(5) Cl N CH.sub.3 CF.sub.3 
0 n.sub.D.sup.21.3 1.4884 
(6) Cl N H CF.sub.3 
0 m.p. 40.degree. C. 
(7) Cl CCl 
H CF.sub.3 
2 m.p. 69.8.degree. C. 
(8) Cl CCl 
*1) CF.sub.3 
0 Resinous 
(9) Cl CCl 
NHCH(OCH.sub.3)t-Bu 
CF.sub.3 
0 n.sub.D.sup.24.8 1.4880 
(10) Cl CCl 
##STR36## CF.sub.3 
0 n.sub.D.sup.29.9 1.4973 
(11) Cl CCl 
NHCH.sub.2 CH.sub.2 CH.sub.3 
CF.sub.3 
0 m.p. 84.1.degree. C. 
(12) Cl CCl 
Br CF.sub.3 
0 n.sub.D.sup.28.8 1.5224 
(13) Cl CCl 
N(CH.sub.2 CH.sub.3).sub.2 
CF.sub.3 
0 m.p. 74.2.degree. C. 
(14) Cl CCl 
NHCOCH.sub.3 CF.sub.3 
0 m.p. 154.2.degree. C. 
(15) Cl CCl 
H CF.sub.2 CF.sub.2 H 
0 n.sub.D.sup.25.8 1.4952 
(16) NO.sub.2 
CCl 
H CF.sub.3 
0 m.p. 48.2.degree. C. 
(17) Cl CCl 
NH.sub.2 CH.sub.2 CF.sub.3 
0 m.p. 108.0.degree. C. 
(18) F CCl 
NH.sub.2 CF.sub.3 
0 m.p. 168.0.degree. C. 
(19) Cl CCl 
N(CH.sub.2 CH.sub.3)COCH.sub.3 
CF.sub.3 
0 n.sub.D.sup.25.3 1.5017 
(20) Cl CCl 
N(COCH.sub.2 CH.sub.3).sub.2 
CF.sub.3 
0 m.p. 75.7.degree. C. 
(21) Cl CCl 
##STR37## CF.sub.3 
0 oil 
__________________________________________________________________________ 
.sup.1 HMR(250MH.sub.z, CDCl.sub.3 /TMS: .delta.(ppm) = 7.73(s, 2H), 
4.01(q:J=7.1Hz, 2H) 
2.40(s, 3H), 1.17(t:J=7.1Hz, 3H) 
__________________________________________________________________________ 
(22) Cl CCl 
##STR38## CF.sub.3 
0 n.sub.D.sup.24.3 1.5339 
(23) Cl CCl 
NHCH.sub.2 CH.sub.3 
CF.sub.3 
0 m.p. 129.4.degree. C. 
(24) Cl CCl 
NHCH.sub.3 CF.sub.3 
0 m.p. 119.8.degree. C. 
(25) Cl CCl 
NCCH.sub.3 N(CH.sub.3).sub.2 
CF.sub.3 
0 Resinous 
(26) Cl CCl 
##STR39## CF.sub.3 
0 m.p. 102.0.degree. C. 
(27) Cl CCl 
N(CH.sub.3)CH.sub.2 CH.sub.3 
CF.sub.3 
0 n.sub.D.sup.25.2 1.5034 
(28) Cl CCl 
NHCH(CH.sub.3)CH.sub.2 CH.sub.3 
CF.sub.3 
0 Resinous 
(29) Cl CCl 
##STR40## CF.sub.3 
0 m.p. 88.8.degree. C. 
(30) Cl CCl 
##STR41## CF.sub.3 
0 n.sub.D.sup.26.6 1.5098 
(31) Cl CCl 
NH(CH.sub.2).sub.3 CH.sub.3 
CF.sub.3 
0 Resinous 
(32) Cl CCl 
NHCH(CH.sub.3).sub.2 
CF.sub.3 
0 m.p. 87.2.degree. C. 
(33) Cl CCl 
NHCH.sub.2 CH(CH.sub.3).sub.2 
CF.sub.3 
0 Resinous 
(34) F CCl 
NHCH(OCH.sub.3)t-Bu 
CF.sub.3 
0 n.sub.D.sup.26.4 1.4613 
(35) Cl CCl 
H CF.sub.2 CF.sub.3 
0 m.p. 50.1.degree. C. 
(36) Cl CCl 
##STR42## CF.sub.3 
0 m.p. 130.1.degree. C. 
(37) Cl CCl 
NHCH.sub.2 C(CH.sub.3).sub.2 
CF.sub.3 
0 n.sub.D.sup.24.6 1.4941 
(38) Cl CCl 
NH(CH.sub.2).sub.3 OCH.sub.3 
CF.sub.3 
0 m.p. 129.3.degree. C. 
(39) Cl CCl 
NH.sub.2 CF.sub.2 CF.sub.3 
0 m.p. 133.9.degree. C. 
(40) Cl CCl 
NHC(CH.sub.3).sub.3 
CF.sub.3 
0 oil 
__________________________________________________________________________ 
.sup.1 H-NMR(300MHz, CDCl.sub.3 /TMS): .delta.(ppm) = 7.77(s, CF.sub.3 
2H), 1.44(s, 9H) 
__________________________________________________________________________ 
(41) Cl CCl 
##STR43## CF.sub.3 
0 n.sub.D.sup.24.7 1.5081 
(42) Cl CCl 
##STR44## CF.sub.3 
0 Resinous 
(43) Cl CCl 
NHCH(OC.sub.2 H.sub.5)C(CH.sub.3).sub.3 
CF.sub.3 
0 n.sub.D.sup.23.6 1.4913 
(44) Cl CCl 
NHCH(SCH.sub.2 CH.sub.3)t-Bu 
CF.sub.3 
0 m.p. 77.5.degree. C. 
(45) Cl CCl 
N(CO.sub.2 CH.sub.2 CH.sub.3).sub.2 
CF.sub.3 
0 n.sub.D.sup.24.7 1.4877 
(46) Cl CCl 
NHCH.sub.2 OCH.sub.3 
CF.sub.3 
0 n.sub.D.sup.23.2 1.5123 
(47) Cl CCl 
H CF.sub.2 H 
0 n.sub.D.sup.23.8 1.5203 
__________________________________________________________________________ 
Compound Physical 
No. X.sup.1 
Y R.sup.3 R.sup.5 
n properties 
__________________________________________________________________________ 
(48) Cl CCl 
H CF.sub.2 H 
1 m.p. 129.5.degree. C. 
(49) Cl CCl 
NH.sub.2 CF.sub.2 H 
0 m.p. 135.4.degree. C. 
(50) Cl CCl 
NCHN(CH.sub.3).sub.2 
CF.sub.2 H 
0 m.p. 108.4.degree. C. 
(51) Cl CCl 
NH.sub.2 CF.sub.2 H 
1 m.p. 204.4.degree. C. 
(52) Cl CCl 
NH.sub.2 CF.sub.2 CF.sub.2 H 
0 m.p. 142.3.degree. C. 
(53) Cl CCl 
H CF.sub.2 Br 
0 m.p. 53.1.degree. C. 
(54) Cl CCl 
NH.sub.2 CF.sub.2 Br 
0 m.p. 216.4.degree. C. 
(55) Cl CCl 
##STR45## CF.sub.3 
0 m.p. 138.1.degree. C. 
(56) Cl CCl 
N(CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 CH.sub.3).sub.2 
CF.sub.3 
0 n.sub.D.sup.21.7 1.4790 
(57) Cl CCl 
##STR46## CF.sub.3 
0 n.sub.D.sup.24.0 1.5530 
(58) Cl CCl 
NHCH.sub.2 OCH.sub.2 CH.sub.3 
CF.sub.3 
0 n.sub.D.sup.23.7 1.5150 
(59) Cl CCl 
NHCOCH.sub.2 OCH.sub.3 
CF.sub.3 
0 resinous 
(60) Cl CCl 
NHS(CH.sub.2).sub.3 CH.sub.3 
CF.sub.3 
0 m.p. 73.2.degree. C. 
(61) Cl CCl 
N(CO.sub.2 CH.sub.2 CH.sub.2 CH.sub.3).sub.2 
CF.sub.3 
0 n.sub.D.sup.24.6 1.4812 
(62) Cl CCl 
NCO.sub.2 CH(CH.sub.3).sub.2 !.sub.2 
CF.sub.3 
0 n.sub.D.sup.24.8 1.4748 
(63) Cl CCl 
NCO.sub.2 CH(CH.sub.3).sub.2 
CF.sub.3 
0 n.sub.D.sup.24.9 1.4898 
(64) Cl CCl 
NHCOCH.sub.2 C(CH.sub.3).sub.3 
CF.sub.3 
0 m.p. 166.2.degree. C. 
(65) Cl CCl 
##STR47## CF.sub.3 
0 n.sub.D.sup.24.1 1.5405 
(66) Cl CCl 
NHSCH(CH.sub.3).sub.2 
CF.sub.3 
0 m.p. 94.3.degree. C. 
(67) Cl CCl 
NHSNCH(CH.sub.3).sub.2 !CH.sub.2 
CF.sub.3 
0 m.p. 96.3.degree. C. 
CH.sub.2 CO.sub.2 CH.sub.2 CH.sub.3 
(68) Cl CCl 
N(SO.sub.2 CH.sub.3).sub.2 
CF.sub.3 
0 m.p. 134.0.degree. C. 
(69) Cl CCl 
##STR48## CF.sub.3 
0 m.p. 117.6.degree. C. 
(70) Cl CCl 
##STR49## CF.sub.3 
0 m.p. 137.7.degree. C. 
(71) Cl CCl 
NHCH.sub.2 SCH.sub.3 
CF.sub.3 
0 m.p. 85.4.degree. C. 
(72) Cl CCl 
##STR50## CF.sub.3 
0 m.p. 96.4.degree. C. 
(73) Cl CCl 
NHSN(CH.sub.3)CO.sub.2 CH.sub.2 CH.sub.3 
CF.sub.3 
0 m.p. 119.6.degree. C. 
(74) Cl CCl 
NHSN(CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3).sub.2 
CF.sub.3 
0 n.sub.D.sup.21.3 1.5010 
(75) Cl CCl 
NHSCO.sub.2 CH.sub.3 
CF.sub.3 
0 m.p. 136.5.degree. C. 
(76) Cl CCl 
N(COSCH.sub.2 CH.sub.3).sub.2 
CF.sub.3 
0 n.sub.D.sup.21.3 1.5260 
__________________________________________________________________________ 
*1) 4Hydroxy-3-methoxybenzylideneaminis group 
Preparation examples of disulfide compounds 2! which are intermediates in 
preparing the present compounds are shown below. 
Referential Preparation Example 1 
Sixty percent oily sodium hydride (0.44 g, 11 mmols) was added to a mixture 
of 3,3'-di(1,2,4-triazolyl) disulfide (1.11 g, 5.55 mmols), 
3,5-dichloro-4-fluorobenzotrifluoride (2.59 g, 11.1 mmols) and 
N,N-dimethylformamide (25 ml) at one time at 0.degree. C. After stirring 
for 1 hour under at 0.degree. C., the mixture was further stirred for 12 
hours at room temperature. The reaction mixture was poured into water and 
extracted with ethyl acetate. The organic layer was washed with saturated 
aqueous sodium chloride solution, dried over anhydrous magnesium sulfate 
and concentrated under reduced pressure. The obtained residue was 
subjected to silica gel chromatography to give 3.13 g of 
3,3'-di1-(2,6-dichloro-4-trifluoromethylphenyl)-1,2,4-triazolyl! 
disulfide as a crystal. 
.sup.1 H-NMR (250 MHz; CDCl.sub.3 /TMS): .delta. (ppm)=8.27 (s,2H), 7.75 
(s,4H). 
Other examples of the disulfide compounds represented by the-formula 2! 
which are intermediates in preparing the present compounds are shown below 
together with .sup.1 H-NMR data. 
3,3'-Di1-(2,6-dichloro-4-trifluoromethylphenyl)-5-methyl-1,2,4-triazolyl! 
disulfide 
.sup.1 H-NMR (250 MHz; CDCl.sub.3 /TMS): .delta. (ppm)=7.75 (s,4H), 2.32 
(s,6H). 
3,3'-Di1-(3-chloro-5-trifluoromethyl-2-pyridyl)-1,2,4-triazolyl! disulfide 
.sup.1 H-NMR (250 MHz; CDCl.sub.3 /TMS): .delta. (ppm)=8.76 (d, J=2Hz, 2H), 
8.20 (d, J=2Hz, 2H), 2.53 (s,6H). 
3,3'-Di1-(2,6-dichloro-4-trifluoromethylphenyl)-5-amino-1,2,4-triazolyl! 
disulfide 
.sup.1 H-NMR (250 MHz; CDCl.sub.3 /TMS): .delta. (ppm)=7.68 (s,4H), 5.72 
(br. s,4H). 
Formulation examples are shown below, where parts are by weight and the 
present compounds used are indicated by the numbers given in Table 2. 
Formulation Example 1 Emulsifiable concentrate 
Ten parts of each of the present compounds (1)-(76) was dissolved in 35 
parts of xylene and 35 parts of dimethylformamide. To the solution were 
added 14 parts of polyoxyethylenestyrylphenyl ether and 6 parts of calcium 
dodecylbenzenesulfonate, followed by thorough stirring and mixing to 
obtain a 10% emulsifiable concentrate of each compound. 
Formulation Example 2 Wettable powder 
Twenty parts of each of the present compounds (1)-(76) was added to a 
mixture comprising 4 parts of sodium laurylsulfate, 2 parts of calcium 
lignin sulfonate, 20 parts of synthetic hydrous silicon oxide fine powder 
and 54 parts of diatomaceous earth, followed by stirring and mixing by a 
juice mixer to obtain a 20% wettable powder of each compound. 
Formulation Example 3 Granule 
Five parts of synthetic hydrous silicon oxide fine powder, 5 parts of 
sodium dodecylbenzenesulfonate, 30 parts of bentonite and 55 parts of clay 
were added to each of the present compounds (1)-(76), followed by thorough 
stirring and mixing. A suitable amount of water was added to the resulting 
mixture. This was further stirred, granulated by a granulator and air 
dried to obtain a 5% granule of each compound. 
Formulation Example 4 Dust 
One part of each of the present compounds (1)-(76) was dissolved in a 
suitable amount of acetone. To the solution were added 5 parts of 
synthetic hydrous silicon oxide fine powder, 0.3 part of PAP and 93.7 
parts of clay, followed by stirring and mixing by a juice mixer. Acetone 
was removed by evaporation to obtain a 1% dust of each compound. 
Formulation Example 5 Flowable 
Twenty parts of each of the present compounds (1)-(76) and 1.5 part of 
sorbitan trioleate were mixed with 28.5 parts of an aqueous solution 
containing 2 parts of polyvinyl alcohol. The mixture was finely ground by 
a sand grinder (3 .mu. or less in particle diameter) and, then, thereto 
were added 0.05 part of xanthane gum and 40 parts of an aqueous solution 
containing 0.1 part of aluminum magnesium silicate and further added 10 
parts of propylene glycol, followed by stirring and mixing to obtain a 20% 
flowable agent of each compound. 
Formulation Example 6 Oil solution 
0.1 Part of each of the present compounds (1)-(76) was dissolved in 5 parts 
of xylene and 5 parts of trichloroethane, and the solution was mixed with 
89.9 parts of deodorized kerosene to obtain a 0.1% oil solution of each 
compound. 
Formulation Example 7 Oily aerosol 
0.1 Part of each of the present compounds (1)-(76), 0.2 part of 
tetramethrin, 0.1 part of d-fenothrin, 10 parts of trichloroethane and 
59.6 parts of deodorized kerosene were mixed to dissolve the ingredients, 
and the solution was charged in an aerosol container, to which a valve 
part was fitted. Then, 30 parts of a propellant (liquefied petroleum gas) 
was charged under pressure through the valve part to obtain an oily 
aerosol of each compound. 
Formulation Example 8 Aqueous aerosol 
0.2 Part of each of the present compounds (1)-(76), 0.2 part of 
d-allethrin, 0.2 part of d-fenothrin, 5 parts of xylene, 3.4 parts of 
deodorized kerosene and 1 part of an emulsifier (ATMOS 300 manufactured by 
Atlas Chemical Co., Ltd.) were mixed to dissolve the ingredients. The 
solution and 50 parts of pure water were charged in an aerosol container, 
to which a valve part was fitted. Then, 40 parts of a propellant 
(liquefied petroleum gas) was charged under pressure through the valve 
part to obtain an aqueous aerosol of each compound. 
Formulation Example 9 Mosquito coil 
0.3 Gram of d-allethrin was added to 0.3 g of each of the present compounds 
(1)-(76) and the mixture was dissolved in 20 ml of acetone. The solution 
was uniformly stirred and mixed with 99.4 g of a carrier for mosquito coil 
(a mixture of camphor powder:lees powder:wood meal at 4:3:3). Thereto was 
added 120 ml of water and the mixture was well kneaded, followed by 
shaping and drying to obtain a mosquito coil of each compound. 
Formulation Example 10 Electric mosquito-repellent mat 
Acetone was added to 0.4 g of each of the present compounds (1)-(76), 0.4 g 
of d-allethrin and 0.4 g of pipenyl butoxide to dissolve the ingredients 
to prepare a solution in an amount of 10 ml in total. A substrate for 
electric mat (fibrils of a mixture of cotton linter and pulp which were 
hardened into a sheet) of 2.5 cm.times.1.5 cm.times.0.3 cm thick was 
uniformly impregnated with the above solution to obtain an electric 
mosquito-repellent mat containing each compound. 
Formulation Example 11 Heat smoking agent 
100 mg of each of the present compounds (1)-(76) was dissolved in a 
suitable amount of acetone. A porous ceramic sheet of 4.0 cm.times.4.0 
cm.times.1.2 cm thick was impregnated with the resulting solution to 
obtain a heat smoking agent containing each compound. 
Formulation Example 12 Poison bait 
10 mg of each of the present compounds (l)-(76) was dissolved in 0.5 ml of 
acetone. The solution was uniformly mixed with 5 g of a solid feed powder 
for animals (solid feed powder for breeding: CE-2 manufactured by Japan 
Kurea Co., Ltd.). Then, acetone was removed by air drying to obtain a 0.5% 
poison bait of each compound. 
Formulation Example 13 Mite-repellent sheet 
Each of the present compounds (l)-(76) was diluted with acetone and was 
dripped onto a nonwoven fabric so that the fabric was impregnated with 1 
g/m.sup.2 of the compound. Acetone was removed by air drying to obtain a 
mite-repellent sheet. 
Formulation Example 14 Mite-repellent sheet 
Each of the present compounds (1)-(76) was diluted with acetone and dripped 
onto a filter paper so that the filter paper was impregnated with 1 
g/m.sup.2 of the compound. Acetone was removed by air drying to obtain a 
mite-repellent sheet. 
The following test examples show that the present compounds are useful as 
active ingredients of insecticides and acaricides. The present compounds 
used are indicated by the numbers given in Table 2 and the compounds used 
for comparison are shown by the numbers given in Table 3. 
TABLE 3 
______________________________________ 
Chemical 
structure 
formula Notes 
______________________________________ 
(A) 
##STR51## Compound 8 de- scribed in JP-A-2-91061 
(B) 
##STR52## Compound 175 de- scribed in JP-A-1-230562 
(C) 
##STR53## Compound 40 de- scribed in JP-A-2-91061 
(D) 
##STR54## imidacloprid 
______________________________________ 
TEST EXAMPLE 1 
Acetone solution (1 .mu.l) containing 0.2 .mu.g of each test compound was 
applied to the lower side of thorax of female adult German cockroach 
(Blattella germanica), to which a feed (solid feed for breeding of rats 
manufactured by Oriental Yeast Co., Ltd.) and water were given. After 7 
days from the application of the test compound, the number of dead insects 
was checked and a mortality was obtained. (Replication of three times for 
one group consisting of 10 insects). The results are shown in Table 4. 
TABLE 4 
______________________________________ 
Compound Mortality Compound Mortality 
No. (%) No. (%) 
______________________________________ 
(1) 100 (43) 100 
(2) 100 (44) 100 
(3) 100 (45) 100 
(7) 100 (46) 100 
(9) 100 (47) 100 
(10) 100 (48) 100 
(11) 100 (49) 100 
(13) 100 (51) 100 
(14) 100 (52) 100 
(18) 100 (53) 100 
(19) 100 (54) 100 
(20) 100 (56) 100 
(21) 100 (58) 100 
(22) 100 (59) 100 
(23) 100 (60) 100 
(24) 100 (61) 100 
(31) 100 (62) 100 
(32) 100 (63) 100 
(34) 100 (66) 100 
(36) 100 (67) 100 
(39) 100 (A) 3.3 
(41) 100 (B) 3.3 
(B) 23 
______________________________________ 
TEST EXAMPLE 2 
The bottom of a polyethylene cup of 5.5 cm in diameter was covered with a 
filter paper of the same size, and 0.7 ml of a 1:200 dilution (500 ppm) 
with water of the emulsifiable concentrate of each test compound obtained 
in accordance with Formulation Example 1 was dripped onto the above filter 
paper and 30 mg of sucrose as feed was uniformly placed in the cup. Ten 
female adult house flies (Musca domestica) were put in the cup and the cup 
was covered. After 24 hours, the number of the dead insects was checked 
and a mortality was obtained. The results are shown in Table 5. 
TABLE 5 
______________________________________ 
Compound Mortality Compound Mortality 
No. (%) No. (%) 
______________________________________ 
(1) 100 (32) 100 
(2) 100 (33) 100 
(4) 100 (34) 100 
(5) 100 (35) 100 
(6) 100 (36) 100 
(7) 100 (37) 100 
(8) 100 (38) 100 
(10) 100 (39) 100 
(11) 100 (41) 100 
(12) 100 (42) 100 
(13) 100 (43) 100 
(14) 100 (44) 100 
(15) 100 (45) 90 
(16) 100 (46) 100 
(17) 100 (47) 100 
(18) 100 (48) 100 
(20) 100 (49) 100 
(22) 100 (51) 100 
(24) 100 (52) 100 
(26) 100 (55) 100 
(27) 100 (61) 100 
(28) 100 (62) 100 
(29) 100 (69) 100 
(30) 100 (A) 0 
(31) 100 (B) 50 
(C) 10 
______________________________________ 
TEST EXAMPLE 3 
Rice seeds (var.: Nipponbare) were sown in the sandy loam filled in a 
plastic cup of 90 ml. After raising for 20 days in a greenhouse, the 
seedlings were sprayed with 40 ml (for one seedling) of a dilution (a 
given concentration) with water of emulsifiable concentrate of each test 
compound obtained in accordance with Formulation Example 1. After air 
drying the sprayed solution, the seedlings were transferred to a plastic 
case, in which twenty larvae of first instar of brown rice planthopper 
(Nilaparvata lugens) were put, and the case was covered and kept in a 
greenhouse at 27.degree. C. for 6 days. Thereafter, the mortality was 
checked and the control effect was judged by the following criteria. The 
results are shown in Table 6. 
______________________________________ 
Control effect Mortality 
______________________________________ 
4 100 
3 90-99 
2 60-89 
1 30-59 
0 0-29 
______________________________________ 
TABLE 6 
______________________________________ 
Concen- Concen- 
Test tration Control Test tration Control 
compound 
(ppm) effect compound 
(ppm) effect 
______________________________________ 
(1) 12.5 4 (34) 12.5 4 
(2) 12.5 4 (35) 12.5 4 
(4) 12.5 4 (36) 12.5 4 
(10) 12.5 4 (37) 12.5 4 
(7) 12.5 4 (38) 12.5 4 
(11) 12.5 4 (41) 12.5 4 
(13) 12.5 4 (42) 12.5 4 
(14) 12.5 4 (43) 12.5 4 
(15) 12.5 4 (46) 12.5 4 
(18) 12.5 4 (47) 12.5 4 
(20) 12.5 4 (48) 12.5 4 
(22) 12.5 4 (49) 12.5 4 
(24) 12.5 4 (51) 12.5 4 
(26) 12.5 4 (52) 12.5 4 
(27) 12.5 4 (56) 12.5 3 
(28) 12.5 4 (61) 12.5 4 
(29) 12.5 3 (62) 12.5 4 
(30) 12.5 4 (A) 12.5 2 
(31) 12.5 4 (B) 12.5 2 
(32) 12.5 4 (C) 12.5 1 
(33) 12.5 4 
______________________________________ 
TEST EXAMPLE 4 
The bottom of a polyethylene cup of 5.5 cm in diameter was covered with a 
filter paper of the same size, and 1 ml of a dilution (50 ppm) with water 
of the emulsifiable concentrate of each test compound obtained in 
accordance with Formulation Example 1 was dripped onto the filter paper. 
After the diluted emulsifiable concentrate spread all over the surface of 
the filter paper, one grain of maize seed having a root of about 2 cm was 
placed thereon, and about thirty eggs of southern corn rootworm 
(Diabrotica undecimpunctata howardi) were placed about 3 cm apart from the 
seed. They were kept at 28.degree. C. for 8 days and, then, the control 
effect was evaluated in accordance with the criteria given in Test Example 
3. The results are shown in Table 7. 
TABLE 7 
______________________________________ 
Test Control Test Control 
compound effect compound effect 
______________________________________ 
(1) 4 (32) 4 
(2) 4 (33) 4 
(4) 4 (34) 4 
(5) 4 (35) 4 
(6) 4 (36) 4 
(7) 4 (37) A 
(8) 4 (38) 4 
(9) 4 (39) 4 
(10) 4 (41) 4 
(11) 4 (42) 4 
(12) 4 (43) 4 
(13) 3 (44) 4 
(14) 4 (45) 4 
(15) 4 (46) 4 
(16) 4 (47) 4 
(17) 3 (48) 4 
(18) 4 (50) 4 
(20) 4 (51) 3 
(22) 4 (52) 4 
(24) 4 (55) 4 
(26) 4 (56) 4 
(27) 4 (61) 4 
(28) 4 (62) 4 
(29) 4 (69) 4 
(30) 4 (A) 0 
(31) 4 (B) 0 
(C) 0 
______________________________________ 
TEST EXAMPLE 5 
An acetone solution of the test compound was added to a mite feed medium at 
a given concentration, followed by uniformly mixing them. Thereto was 
further added an equal amount of a mite feed medium and they were further 
uniformly mixed. The number of mites in the medium after mixing was about 
300-500/1 g. The medium was stored for 4 weeks at a constant temperature 
(25.degree. C.) and a constant humidity (75%RH for Tyrophagus 
putrescentiae and 65%RH for Dermatophagoides farinae). Thereafter, the 
number of surviving mites in a given amount of the medium was counted and 
a multiplication inhibiting rate was obtained by the following formula. 
##EQU1## 
As a result, the compound (2) at a concentration of 300 ppm (final 
concentration) showed a multiplication inhibiting rate of 100% for 
Tyrophagus putrescentiae and Dermatophagoides farinae. 
The compounds (6), (11), (15), (23), (24), (27), (32), (34), (39), (41), 
(47) at a same concentration showed more than 80% multiplication 
inhibiting rate for Dermatophagoides farinae. 
TEST EXAMPLE 6 
Rice seedlings (2.5 leaf stage) planted in a nursery box were applied with 
a test compound formulated in accordance with the formulation example 3, 
or the compound (D) of commercial granule formulation sold as Admire.RTM. 
2G in Japan. On the next day of treatment, rice seedlings were 
transplanted into a paddy field with the plot size of 6 by 7 meter for 
each treatment. One hundred twenty adult Nilaparvata lugens were released 
onto a rice plant of each treatment plot after 23, 30 and 64 days of 
treatment. At the designated days after treatment, number of live insects 
(N. lugens) on the rice plant on which N. lugens were released and four 
surrounding plants were counted. The results are shown in Table 8. 
TABLE 8 
______________________________________ 
Number of live insects/2 reps 
(10 plants) 
Test +57 +71 +91 +105 
Compound 
Rate days after treatment 
______________________________________ 
(1) 1 g 3 17 16 84 
ai/box* 
(D) 2 g 1 63 25 167 
ai/box 
untreated 
-- 35 81 193 848 
______________________________________ 
*nursery box 
TEST EXAMPLE 7 
Rice seeds were sprayed with a test compound or the compound (D) formulated 
in accordance with the formulation example 1. The treated seeds were then 
planted in nursery boxes. The rice seedlings at 2.5 leaf stage were 
transplanted into a paddy field with the plot size of 6 by 7 meter for 
each treatment after 34 days of treatment. At the designated days after 
the transplanting, number of adult Lissorhoptrus oryzophilus which 
naturally occurred in field was counted on 50 rice plants from each plot. 
The results are shown in Table 9. 
TABLE 9 
______________________________________ 
Number of live adults/3 reps 
(150 plants) 
Test +6 +13 +20 
Compound 
Rate days after transplanted 
______________________________________ 
(1) 100 g ai/ .sup. 
11 10 6 
100 kg Seed 
(D) 100 g ai/ .sup. 
26 14 27 
100 kg Seed 
untreated 
-- 18 26 43 
______________________________________