Title of Invention

A 3-TRIAZOLYLPHENYL SULFIDE DERIVATIVE

Abstract To provide novel 3-triazolylphenyl sulfide derivatives having excellent soil treatment activity as insecticides, miticides or nematicides for agricultural and horticultural plants. 3-Triazolylphenyl sulfide derivatives represented by the formula [1]: wherein R is a cyclopropylmethyl group or a trifluoroethyl group, B2 is a hydrogen atom, a halogen atom or a methyl group, B4 is a halogen atom, a cyano group, a nitro group or a C1-C6 alkyl group, and each of A1 and A3 is a hydrogen atom, a halogen atom, a C1-C6 alkyl group which may be substituted or an amino group which may be substituted.
Full Text TECHNICAL FIELD
The present invention relates to novel 3-
triazolylphenyl sulfide derivatives and insecticides,
miticides and nematicides for agricultural and
horticultural containing them as an active ingredient.
BACKGROUND ART
As known insecticides, miticides and nematicides, 3-
triazolylphenyl sulfide derivatives as disclosed in
Patent Document 1 have already been known. It is
disclosed that the group of compounds as disclosed in the
document have high effects against mites when directly
sprayed over plants. However, the document does not
disclose a soil treatment. The group of compounds as
disclosed in the document have insufficient migration in
the soil and infiltration into plants by a soil treatment.
Accordingly, no sufficient effects may be obtained in
some cases, due to non uniform spraying with chemicals,
transpiration, photolysis, outflow of the chemicals by
rain, etc.
At- present, very few miticides having practical soil

treatment activity have been known. Chemicals applicable
to a soil treatment are advantageous to farmers in view
of higher safety, more saving of labor, etc. Accordingly,
development of miticides having soil treatment activity
has been required.
Patent document 1: JP-A-2000-198768
DISCLOSURE OF THE INVENTION
PROBLEMS THAT THE INVENTION IS TO SOLVE
Under these circumstances, an object of the present
invention is to solve the above problems of conventional
insecticides, miticides and nematicides, and to provide
insecticides, miticides and nematicides excellent in
safety, pesticidal effects, residual effectiveness, etc.
MEANS OF SOLVING THE PROBLEMS
The present inventors have synthesized various 3-
triazolylphenyl sulfide derivatives and studied their
physiological activities to develop insectides, miticides
and nematicides having the above preferred
characteristics. As a result, they have found that the
following novel 3-triazolylphenyl sulfide derivatives of
the present invention (hereinafter sometimes referred to
as compounds of the present invention) exhibit
outstanding effects on various farm and garden pests,
especially mites represented by two-spotted spider mite,
Kanzawa spider mite and citrus red mite, pest

lepidopterans represented by diamondbackmoth, Asiatic
rice borer and beat armyworm, pest hemipterans
represented by brown rice planthopper, green rice
leafhopper and cotton aphid, pest coleoptera represented
by adzuki bean weevil and nematodes represented by
southern root-knot nematode, and have soil treatment
activity with which safe and labor-saving application
becomes possible. The present invention has been
accomplished on the basis of these discoveries.
That is, the present invention provides the
following.
(1) 3-Triazolylphenyl sulfide derivative represented by
the formula [I]:

wherein R is a cyclopropylmethyl group or a
trifluoroethyl group;
n is an integer of from 0 to 1;
A1 and A3 are selected from groups of Group I and Group
II, provided that at least one of them is selected from
groups of Group II;
B2 is a hydrogen atom, a halogen atom or a methyl group;
and
B4 is a halogen atom, a cyano group, a nitro group or a
C1-C6 alkyl group (which may be mono- or poly-substituted

by halogen atoms);
provided that when A3 is NH2, B2 is a halogen atom or a
methyl group:
(Group I)
a hydrogen atom, a halogen atom, a C1-C6 alkyl group
(which may be mono- or poly-substituted by halogen atoms,
hydroxyl groups, cyano groups, C2-C7 alkoxycarbonyl groups
or C1-C6 alkoxy groups) , a C3.C8 cycloalkyl group (which
may be mono- or poly-substituted by alkyl groups, halogen
atoms, cyano groups or C1-C6 alkoxy groups) , a C2-C6
alkenyl group (which may be mono- or poly-substituted by
halogen atoms or cyano groups), a C2-C6 alkynyl group
(which may be mono- or poly-substituted by halogen atoms
or cyano groups), a C1-C6 alkoxy group (which may be mono-
or poly-substituted by halogen atoms, cyano groups, C2-C5
alkoxycarbonyl groups or C1-C3 alkoxy groups) , a C1-C6
alkylthio group (which may be mono- or poly-substituted
by halogen atoms, C1-C3 alkoxy groups, C3-C8 cycloalkyl
groups which may be substituted by halogen atoms, or
cyano groups), a C1-C6 alkylsulfinyl group (which may be
mono- or poly-substituted by halogen atoms, C1-C3 alkoxy
groups, C3-C8 cycloalkyl groups which may be substituted
by halogen atoms, or cyano groups), a C1-C6 alkylsulfonyl
group (which may be mono- or poly-substituted by halogen
atoms, C1-C3 alkoxy groups or C3-C6 cycloalkyl groups which
may be substituted by halogen atoms), a C2-C6 alkynylthio
group (which may be mono- or poly-substituted by halogen

atoms, C1-C3 alkoxy groups or cyano groups), a C2-C6
alkynylsulfinyl group (which may be mono- or poly-
substituted by halogen atoms, C1-C3 alkoxy groups or cyano
groups) , a C1-C7 acyl group and a C2-C5 haloalkylcarbonyl
group;
(Group II)
a nitro group, a cyano group, a -N=CR1R2 group, a
-N=C(NR2'R3' )NR2R3 group, a -N(SO2R2)R3 group, a -N(OR3)R3'
group, a -C(=O)OR2 group, a -C(=Q)NR2R3 group, a -SO2NR2R3
group, a -NR2R3 group, a -N(COR2)R3 group and a -N(COOR2)R3
group;
wherein R1 is a hydrogen atom, a C1-C6 alkyl group (which
may be mono- or poly-substituted by halogen atoms,
hydroxyl groups, cyano groups, C2-C7 alkoxycarbonyl groups
or C1-C6 alkoxy groups) , a C3-C6 alkenyl group (which may
be mono- or poly-substituted by halogen atoms or cyano
groups), a C3-C6 alkynyl group (which may be mono- or
poly-substituted by halogen atoms or cyano groups), a
C3-C6 cycloalkyl group (which may be mono- or poly-
substituted by halogen atoms, hydroxyl groups, cyano
groups, C2-C7 alkoxycarbonyl groups or C1-C6 alkoxy groups),
an arylalkyl group (which may be mono- or poly-
substituted by halogen atoms, cyano groups, C1-C6 alkyl
groups, C1-C6 haloalkyl groups, C2-C7 alkoxycarbonyl groups
or C1-C6 alkoxy groups), a heteroarylalkyl group (which
may be mono- or poly-substituted by halogen atoms, cyano
groups, C1-C6 alkyl groups, C1-C6 haloalkyl groups, C2-C7

alkoxycarbonyl groups or C1-C6 alkoxy groups), an aryl
group (which may be mono- or poly-substituted by halogen
atoms, cyano groups, C1-C6 alkyl groups, C1-C6 haloalkyl
groups, C2-C7 alkoxycarbonyl groups, C1-C6 alkoxy groups or
hydroxyl groups), a heteroaryl group (which may be mono-
or poly-substituted by halogen atoms, cyano groups, C1-C6
alkyl groups, C1-C6 haloalkyl groups, C2-C7 alkoxycarbonyl
groups or C1-C6 alkoxy groups) , a C1-C6 alkoxy group, a
C1-C6 alkylthio group, an amino group, a C1-C6
monoalkylamino group or a C2-C12 dialkylamino group;
each of R2 and R2' is a hydrogen atom, a C1-C6 alkyl group
(which may be mono- or poly-substituted by halogen atoms,
hydroxyl groups, cyano groups, C2-C7 alkoxycarbonyl groups
or C1-C6 alkoxy groups) , a C3-C6 alkenyl group (which may
be mono- or poly-substituted by halogen atoms or cyano
groups), a C3-C6 alkynyl group (which may be mono- or
poly-substituted by halogen atoms or cyano groups), a
C3-C6 cycloalkyl group (which may be mono- or poly-
substituted by halogen atoms, hydroxyl groups, cyano
groups, C2-C7 alkoxycarbonyl groups or C1-C6 alkoxy groups) ,
an amino group, a C1-C6 monoalkylamino group, a C2-C12
dialkylamino group, an arylalkyl group (which may be
mono- or poly-substituted by halogen atoms, cyano groups,
C1-C6 alkyl groups, C1-C6 haloalkyl groups, C2-C7
alkoxycarbonyl groups or C1-C6 alkoxy groups) , a
heteroarylalkyl group (which may be mono- or poly-
substituted by halogen atoms, cyano groups, C1-C6 alkyl

groups, C1-C6 haloalkyl groups, C2-C7 alkoxycarbonyl groups
or C1-C6 alkoxy groups), an aryl group (which may be mono-
or poly-substituted by halogen atoms, cyano groups, C1-C6
alkyl groups, C1-C6 haloalkyl groups, C2-C7 alkoxycarbonyl
groups or C1-C6 alkoxy groups) or a heteroaryl group
(which may be mono- or poly-substituted by halogen atoms,
cyano groups, C1-C6 alkyl groups, C1-C6 haloalkyl groups,
C2-C7 alkoxycarbonyl groups or C1-C6 alkoxy groups) ,
each of R3 and R3' is a hydrogen atom, a C1-C6 alkyl group
(which may be mono- or poly-substituted by halogen atoms,
hydroxyl groups, cyano groups, C2-C7 alkoxycarbonyl groups
or C1-C6 alkoxy groups) , a C3-C6 alkenyl group (which may
be mono- or poly-substituted by halogen atoms or cyano
groups), a C3-C6 alkynyl group (which may be mono- or
poly-substituted by halogen atoms or cyano groups) or a
C3-C6 cycloalkyl group (which may be mono- or poly-
substituted by halogen atoms, hydroxyl groups, cyano
groups, C2-C7 alkoxycarbonyl groups or C1-C6 alkoxy
groups); and
Q is an oxygen atom or a sulfur atom;
provided that R2 and R2 in the -N=CR1R2 group may form a 5
to 6-membered ring together with the carbon atom to which
they are bonded,
R2 and R3, or R2' and R3', in the -N=C (NRV R3' ) NR2R3 group
may form a 5 to 6-membered ring together with the
nitrogen atom to which they are bonded, and
R2 and R3 in the -NR2R3 group may form a 5 to 6-membered

ring together with the nitrogen atom to which they are
bonded.
(2) The 3-triazolylphenyl sulfide derivative according
to the above (1), wherein R is a trifluoroethyl group;
n is an integer of from 0 to 1;
A1 is a C1-C6 alkyl group (which may be mono- or poly-
substituted by halogen atoms or cyano groups) , a C1-C6
alkylthio group (which may be mono- or poly-substituted
by halogen atoms) or a C1-C6 alkylsulfinyl group (which
may be mono- or poly-substituted by halogen atoms or C1-C3
alkoxy groups);
A3 is the group -NR2R3 or the group -N(COR2)R3;
each of R2 and R3 which are independent of each other, is
a hydrogen atom, a C1-C6 alkylamino group, a C1-C6 alkyl
group (which may be mono- or poly-substituted by halogen
atoms or cyano groups) or a C3-C6 alkynyl group (which may
be mono- or poly-substituted by halogen atoms or cyano
groups) , provided that R2 and R3 are not simultaneously
hydrogen atoms;
B2 is a hydrogen atom, a halogen atom or a methyl group;
and
B4 is a cyano group or a C1-C6 alkyl group (which may be
mono- or poly-substituted by halogen atoms).
(3) The 3-triazolylphenyl sulfide derivative according
to the above (1), wherein R is a trifluoroethyl group;
n is an integer of from 0 to 1;
A1 is a C1-C6 alkyl group (which may be mono- or poly-

substituted by halogen atoms or cyano groups), a C1-C6
alkylthio group (which may be mono- or poly-substituted
by halogen atoms) or a C1-C6 alkylsulfinyl group (which
may be mono- or poly-substituted by halogen atoms or C1-C3
alkoxy groups);
A3 is an amino group;
B2 is a halogen atom or a methyl group; and
B4 is a cyano group or a C1-C6 alkyl group (which may be
mono- or poly-substituted by halogen atoms).
(4) The 3-triazolylphenyl sulfide derivative according
to the above (2), wherein A1 is an isopropyl group, a t-
butyl group, a difluoromethyl group, a trifluoromethyl
group, a trifluoromethylthio group, a 2,2,2-
trifluoroethylthio group, a 1,1,2,2-tetrafluoroethylthio
group, a pentafluoroethylthio group, a
trifluoromethylsulfinyl group, a 2,2,2-
trifluoroethylsulfinyl group or a
pentafluoroethylsulfinyl group; and
A3 is a methylamino group, an ethylamino group, a
propylamino group, a cyanomethylamino group, a
propargylamino group, an acetylamino group, a
propionylamino group, a trifluoroacetylamino group or a
difluoroacetylamino group.
(5) The 3-triazolylphenyl sulfide derivative according
to the above (3), wherein A1 is an isopropyl group, a t-
butyl group, a difluoromethyl group, a trifluoromethyl
group, a trifluoromethylthio group, a 2,2,2-

trifluoroethylthio group, a 1,1,2, 2-tetrafluoroethylthio
group, a pentafluoroethylthio group, a
trifluoromethylsulfinyl group, a 2,2,2-
trifluoroethylsulfinyl group or a
pentafluoroethylsulfinyl group; and
A3 is an amino group.
(6) The 3-triazolylphenyl sulfide derivative according
to the above (2), wherein A1 is a trifluoromethyl group,
a trifluoromethylthio group or a 2,2,2-
trifluoroethylsulfinyl group; and
A3 is a methylamino group or a trifluoroacetylamino group.
(7) The 3-triazolylphenyl sulfide derivative according
to the above (2), wherein A1 is a trifluoromethyl group,
a trifluoromethylthio group or a 2,2,2-
trifluoroethylsulfinyl group; and
A3 is an amino group.
(8) An aniline derivative represented by the formula [I-
a] which is an intermediate for production of the 3-
triazolylphenyl sulfide derivative as defined in any one
of the above (1) to (7):

wherein B2 is a halogen atom or a methyl group, and B4 is
a C1-C6 alkyl group.
(9) The aniline derivative according to the above (8),

wherein B4 is a methyl group.
10. An insecticide, miticide or nematicide for
agricultural and horticultural containing the 3-
triazolylphenyl sulfide derivative as defined in any one
of the above (1) to (7) as an active ingredient.
EFFECTS OF THE INVENTION
The compounds of the present invention exhibit
excellent pesticidal effects against a wide range of
pests including pest hemiptera, pest lepidoptera, pest
coleoptera, pest diptera, pest hymenoptera, pest
orthoptera, pest isoptera, pest thysanoptera, mites and
plant-parastic nematodes, and they are also capable of
controlling pests which have acquired resistance to
conventional pesticides.
Particularly, the compounds of the present invention
exhibit outstanding effects on various pests, especially
on farm and garden pests including mites represented by
two-spotted spider mite, Kanzawa spider mite and citrus
red mite, pest lepidopterans represented by
diamondbackmoth, Asiatic rice borer and beat armyworm,
pest hemipterans represented by brown rice planthopper,
green rice leafhopper and cotton aphid, pest coleoptera
represented by adzuki bean weevil and nematodes
represented by southern root-knot nematode, and they are
excellent in systemic action. Accordingly, they can be
used for a safe and labor-saving application by a soil

treatment.
BEST MODE FOR CARRYING OUT THE INVENTION
The symbols and the terms used in this specification
will be defined below.
The halogen atom represents a fluorine atom, a
chlorine atom, a bromine atom or a iodine atom.
The expression C1-C6, etc. represents that the
subsequent substituent has from 1 to 6 carbon atoms in
this case.
The C1-C6 alkyl group means, unless otherwise
specified, a linear or branched alkyl group having from 1
to 6 carbon atoms, such as a methyl, ethyl, n-propyl, i-
propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, 1-
methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl,
1,1-dimethylpropyl, 1,2-dimethylpropyl, neopentyl, n-
hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-
methylpentyl, 1-ethylbutyl, 2-ethylbutyl, 1,1-
dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-
dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl,
1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-l-
methylpropyl or l-ethyl-2-methylpropyl group.
The C3-C6 cycloalkyl group means, unless otherwise
specified, a cycloalkyl group having from 3 to 6 carbon
atoms, such as a cyclopropyl, cyclobutyl, cyclopentyl or
cyclohexyl group.
The C2-C6 alkenyl group means, unless otherwise

specified, a linear or branched alkenyl group having from
2 to 6 carbon atoms, such as a vinyl, 1-propenyl, i-
propenyl, 2-propenyl, 1-butenyl, 1-methyl-1-propenyl, 2-
butenyl, 1-methyl-2-propenyl, 3-butenyl, 2-methyl-l-
propenyl, 2-methyl-2-propenyl, 1,3-butadienyl, 1-pentenyl,
1-ethyl-2-propenyl, 2-pentenyl, 1-methyl-1-butenyl, 3-
pentenyl, 1-methyl-2-butenyl, 4-pentenyl, 1-methyl-3-
butenyl, 3-methyl-1-butenyl, 1,2-dimethyl-2-propenyl,
1,1-dimethyl-2-propenyl, 2-methyl-2-butenyl, 3-methyl-2-
butenyl, 1,2-dimethyl-1-propenyl, 2-methyl-3-butenyl, 3-
methyl-3-butenyl, 1,3-pentadienyl, 1-vinyl-2-propenyl, 1-
hexenyl, 1-propyl-2-propenyl, 2-hexenyl, 1-methyl-l-
pentenyl, 1-ethyl-2-butenyl, 3-hexenyl, 4-hexenyl, 5-
hexenyl, 1-methyl-4-pentenyl, 1-ethyl-3-butenyl, 1-(i-
butyl)vinyl, l-ethyl-l-methyl-2-propenyl, l-ethyl-2-
methyl-2-propenyl, 1-(i-propyl)-2-propenyl, 2-methyl-2-
pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1,3-
dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 3-methyl-4-
pentenyl, 4-methyl-4-pentenyl, 1,2-dimethyl-3-butenyl,
1,3-dimethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1,5-
hexadienyl, 1-vinyl-3-butenyl or 2,4-hexadienyl group.
The C3-C6 alkynyl group means, unless otherwise
specified, a linear or branched alkynyl group having from
2 to 6 carbon atoms, such as an ethynyl, 1-propynyl, 2-
propynyl, 1-butynyl, 1-methyl-2-propynyl, 2-butynyl, 3-
butynyl, 1-pentynyl, 1-ethyl-2-propynyl, 2-pentynyl, 3-
pentynyl, 1-methyl-2-butynyl, 4-pentynyl, 1-methyl-3-

butynyl, 2-methyl-3-butynyl, 1-hexynyl, 1-(n-propyl)-2-
propynyl, 2-hexynyl, 1-ethyl-2-butynyl, 3-hexynyl, 1-
methyl-2-pentynyl, 1-methyl-3-pentynyl, 4-methyl-1-
pentynyl, 3-methyl-1-pentynyl, 5-hexynyl, l-ethyl-3-
butynyl, 1-ethyl-1-methyl-2-propynyl, 1-(i-propyl)-2 -
propynyl, 1,1-dimethyl-2-butynyl or 2,2-dimethyl-3-
butynyl group.
The C1-C6 haloalkyl group means, unless otherwise
specified, a C1-Ci linear or branched alkyl group
substituted by from 1 to 9 identical or different halogen
atoms, such as a fluoromethyl, chloromethyl, bromomethyl,
difluoromethyl, dichloromethyl, trifluoromethyl,
trichloromethyl, chlorodifluoromethyl,
bromodifluoromethyl, 2-fluoroethyl, 1-chloroethyl, 2-
chloroethyl, 1-bromoethyl, 2-bromoethyl, 2,2-
difluoroethyl, 1,2-dichloroethyl, 2,2-dichloroethyl,
2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, 1,1,2,2-
tetrafluoroethyl, pentafluoroethyl, 2-bromo-2-chloroethyl,
2-chloro-l,1,2,2-tetrafluoroethyl, 1-chloro-l,2,2,2-
tetrafluoroethyl, 1-chloropropyl, 2-chloropropyl, 3-
chloropropyl, 2-bromopropyl, 3-bromopropyl, 2-bromo-l-
methylethyl, 3-iodopropyl, 2,3-dichloropropyl, 2,3-
dibromopropyl, 3,3,3-trifluoropropyl, 3,3,3-
trichloropropyl, 3-bromo-3,3-difluoropropyl, 3,3-
dichloro-3-fluoropropyl, 2,2,3,3-tetrafluoropropyl, 1-
bromo-3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl,
2,2,2-trifluoro-1-trifluoromethylethyl, heptafluoropropyl,

1,2,2,2-tetrafluoro-1-trifluoromethylethyl, 2,3-dichloro-
1,1,2,3,3-pentafluoropropyl, 2-chlorobutyl, 3-chlorobutyl,
4-chlorobutyl, 2-chloro-l,1-dimethylethyl, 4-bromobutyl,
3-bromo-2-methylpropyl, 2-bromo-1,1-dimethylethyl, 2,2-
dichloro-1,1-dimethylethyl, 2-chloro-l-chloromethyl-2-
methylethyl, 4,4,4-trifluorobutyl, 3,3,3-trifluoro-1-
methylpropyl, 3,3,3-trifluoro-2-methylpropyl, 2,3,4-
trichlorobutyl, 2,2,2-trichloro-l,1-dimethylethyl, 4-
chloro-4,4-difluorobutyl, 4,4-dichloro-4-fluorobutyl, 4-
bromo-4,4 -di fluorobutyl, 2,4-dibromo-4,4 -di fluorobutyl,
3,4-dichloro-3,4,4-trifluorobutyl, 3,3-dichloro-4,4,4-
trifluorobutyl, 4-bromo-3,3,4,4-tetrafluorobutyl, 4-
bromo-3-chloro~3,4,4-trifluorobutyl, 2,2,3,3,4,4-
hexafluorobutyl, 2,2,3,4,4,4-hexafluorobutyl, 2,2,2-
trifluoro-1-methyl-l-trifluoromethylethyl, 3,3,3-
trifluoro-2-trifluoromethylpropyl, 2,2,3,3,4,4,4-
heptafluorobutyl, 2,3,3,3 -tetrafluoro-2-
trifluoromethylpropyl, 1,1,2,2,3,3,4,4-octafluorobutyl,
nonafluorobutyl or 4-chloro-l,1,2,2,3,3,4,4-
octafluorobutyl group.
The C1-C6 alkoxy group means an (alkyl)-0- group
wherein the alkyl moiety is as defined above, such as a
methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy,
t-butoxy, pentyloxy, i-pentyloxy or hexyloxy group.
The C1-C6 alkoxy C1-C6 alkyl group means an alkyl
group having from 1 to 6 carbon atoms substituted by an
alkoxy having from 1 to 6 carbon atoms wherein the alkyl

moiety and the alkoxy moiety are as defined above, such
as a methoxymethyl, ethoxymethyl, i-propoxymethyl, n-
butoxymethyl, i-butoxymethyl, pentyloxymethyl,
methoxyethyl, n-butoxyethyl or i-butoxyethyl group.
The C1-C6 alkylthio group means an (alkyl)-S- group
having from 1 to 6 carbon atoms wherein the alkyl moiety
is as defined above, such as methylthio, ethylthio, n-
propylthio or isopropylthio.
The C1-C6 alkylsulfinyl group means an (alkyl)-SO-
group having from 1 to 6 carbon atoms wherein the alkyl
moiety is as defined above, such as methylsulfinyl,
ethylsulfinyl, n-propylsulfinyl or i-propylsulfinyl.
The C1-C6 alkylsulfonyl group means an (alkyl)-SO2-
group having from 1 to 6 carbon atoms wherein the alkyl
moiety is as defined above, such as methylsulfonyl,
ethylsulfonyl, n-propylsulfonyl or isopropylsulfonyl.
The C1-C7 acyl group means a formyl group or an
(alkyl)-C(=O)- group having from 1 to 6 carbon atoms
wherein the alkyl moiety is as defined above, such as
acetyl or propionyl.
The C2-C7 alkoxycarbonyl group means an (alkyl)-0-
C(=O)- group having from 1 to 6 carbon atoms wherein the
alkyl moiety is as defined above, such as methoxycarbonyl,
ethoxycarbonyl, n-propoxycarbonyl or isopropoxycarbonyl.
The C1-C4 haloalkylcarbonyl group means a
(haloalkyl)-C(=O)- group having from 1 to 4 carbon atoms
wherein the haloalkyl moiety is as defined above, such as

chloroacetyl, trifluoroacetyl, pentafluoropropionyl or
difluoromethylthio.
The C1-C6 monoalkylamino group means an amino group
mono-substituted by an alkyl group wherein the alkyl
moiety is as defined above, such as methylamino,
ethylamino or n-propylamino.
The C2-C12 dialkylamino group means an amino group
di-substituted by alkyl groups wherein the alkyl moieties
are as defined above, such as dimethylamino, diethylamino
or N-ethyl-N-methylamino.
The aryl group means an aromatic hydrocarbon group,
such as phenyl or naphthyl.
The arylalkyl group means an (aryl)-(alkyl) group
wherein the aryl and alkyl moieties are as defined above,
such as benzyl, phenethyl or naphthylmethyl.
The heteroaryl group means an aromatic heterocyclic
group, such as thienyl, pyridyl or benzothiazolyl.
The heteroarylalkyl group means a (heteroaryl)-
(alkyl) group wherein the heteroaryl and alkyl moieties
are as defined above, such as thienylmethyl or
pyridylmethyl.
Preferred compounds of the above formula [I] are
compounds wherein R is a 2,2,2-trifluoroethyl group, and
n is 0 or 1.
More preferred compounds are compounds wherein R is
a 2,2,2-trifluoroethyl group, B2 is a halogen atom, B4 is
an alkyl group or a haloalkyl group, and n is 0 or 1.

Now, specific examples of the compounds of the
present invention represented by the formula [I] will be
given in Tables 1 to 6. However, the compounds of the
present invention are not limited to these compounds.
Further, these compounds include compounds having an
optical isomer. The compound numbers will be referred to
in the subsequent description.
The symbols in the Tables in this specification
denote the following respective corresponding groups.
Me: methyl, Et: ethyl,
Pr: n-propyl, Pr-i: isopropyl,
Pr-c: cyclopropyl, Bu: n-butyl,
Bu-i: isobutyl, Bu-s: sec-butyl,
Bu-t: tert-butyl, Bu-c: cyclobutyl,
Pen: n-pentyl, Pen-i: isopentyl,
Pen-c: cyclopentyl, Hex-c: cyclohexyl,
Ph: phenyl, Py: pyridyl.
For example, Ph-4-Cl means 4-chlorophenyl, and 3-Py-
6-C1 means 6-chloro-3-pyridyl.













The compounds of the present invention represented
by the formula [I] can be produced in accordance with the
following production processes. However, their
production is not restricted to these processes.

A compound of the present invention of the formula
[I-1] can be produced by a process exemplified by the
following scheme:

wherein L2 is a halogen atom, an alkylsulfonyloxy group,
a phenylsulfonyloxy group or SO2M, M is an alkali metal
or an alkaline earth metal, the alkali metal is
preferably sodium or potassium, and A1, A3, B2, B4 and R
are as defined above.
That is, a 3-triazolylphenyl sulfide derivative of
the formula [I-1] which is a compound of the present
invention can be produced by reacting a compound of the
formula [II] with a compound of the formula [III] in a
solvent in the presence of a base or in the presence of a
radical initiator.
The amount of the compound of the formula [III] to
be used may suitably be selected from a range of from 1
to 5 mols per 1 mol of the compound of the formula [I],

and it is preferably from 1.2 to 2.0 mols.
The solvent to be used in this reaction may, for
example, be an ether such as diethyl ether,
tetrahydrofuran or dioxane, an aromatic hydrocarbon such
as benzene, toluene, xylene or chlorobenzene, a
halogenated hydrocarbon such as dichloromethane,
chloroform or dichloroethane, an aprotic polar solvent
such as acetonitrile, N,N-dimethylformamide, N,N-
dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl
sulfoxide or sulfolane, an alcohol such as methanol,
ethanol or isopropyl alcohol, a nitrile such as
acetonitrile or propionitrile, an ester such as ethyl
acetate or ethyl propionate, an aliphatic hydrocarbon
such as pentane, hexane, cyclohexane or heptane, a
pyridine such as pyridine or picoline, or water, or a
solvent mixture thereof.
The base to be used in this reaction may, for
example, be an inorganic base such as a hydroxide of an
alkali metal such as sodium hydroxide or potassium
hydroxide, a hydroxide of an alkaline earth metal such as
calcium hydroxide or magnesium hydroxide, a carbonate of
an alkali metal such as sodium carbonate or potassium
carbonate, or an alkali metal bicarbonate such as sodium
hydrogen carbonate or potassium hydrogen carbonate, a
metal hydride such as sodium hydride or potassium hydride,
a metal salt of an alcohol such as sodium methoxide,
sodium ethoxide or potassium tert-butoxide, or an organic

base such as triethylamine, N,N-dimethylaniline, pyridine,
4-N,N-dimethylaminopyridine or 1,8-diazabicyclo[5.4.0]-7-
undecene.
The amount of the base to be used may suitably be
selected from a range of from 0 to 5 mols per 1 mol of
the compound of the formula [II], and it is preferably
from 0 to 1.2 mols.
The radical initiator to be used in this reaction
may, for example, be sulfurous acid, a sulfite salt or a
sulfite adduct such as Rongalit (sodium formaldehyde
sulfoxylate) . The base and the radical initiator may be
used together.
In a case where the radical initiator is used, its
amount may suitably be selected from a range of from 0.01
to 5 mols per 1 mol of the compound [II], and it is
preferably from 0.05 to 1.2 mols.
The reaction temperature may be optionally selected
from a range of from -3 0°C to the reflux temperature of
the reaction system, and it is preferably within a range
of from 0°C to 150°C. The reaction time varies depending
upon the reaction temperature, the reaction substrate,
the reaction amount, etc., and it is usually from 10
minutes to 2 0 hours.

A compound of the present invention of the formula
[I-1] can be produced also by using a compound of the
formula [IV], which is the oxidative dimer of a compound

of the formula [II] used in Production Process 1, as the
starting material:

wherein L2 is a halogen atom or a sulfinate salt, and Alr
A3, B2, B4 and R are as defined above.
That is, an aimed 3-triazolylphenyl sulfide
derivative of the formula [I-1] can be produced by-
reacting a compound of the formula [IV] with a compound
of the formula [V] in a solvent in the presence of a
radical initiator.
The amount of the compound of the formula [V] to be
used in this reaction may suitably be selected from a
range of from 1 to 5 mols per 1 mol of the compound of
the formula [IV], and it is preferably from 1.2 to 2.0
mols .
The solvent to be used in this reaction may, for
example, be an ether such as diethyl ether,
tetrahydrofuran or dioxane, an aromatic hydrocarbon such
as benzene, toluene, xylene or chlorobenzene, an aprotic
polar solvent such as N,N-dimethylformamide, N,N-
dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl
sulfoxide or sulfolane, a nitrile such as acetonitrile or

propionitrile, an ester such as ethyl acetate or ethyl
propionate, an aliphatic hydrocarbon such as pentane,
hexane, cyclohexane or heptane, a pyridine such as
pyridine or picoline, or water, or a solvent mixture
thereof.
The radical initiator may, for example, be sulfurous
acid, a sulfite salt or a sulfite adduct such as Rongalit
(sodium formaldehyde sulfoxylate).
In a case where the radical initiator is used, its
amount may suitably be selected from a range of from 0.01
to 5 mols per 1 mol of the compound [II], and it is
preferably from 0.05 to 1.2 mols.
The reaction temperature may be optionally selected
from a range of from -3 0°C to the reflux temperature of
the reaction system, and it is preferably within a range
of from 0°C to 15 0°C. The reaction time varies depending
upon the reaction temperature, the reaction substrate,
the reaction amount, etc., and it is usually from 10
minutes to 2 0 hours.

A compound of the formula [I-2] which is a compound
of the present invention can be produced by a process
exemplified by the following scheme:


wherein B5 is an electron-withdrawing group, Ai, A3, B2
and R are as defined above, L3 is a leaving group such as
a halogen atom, an alkylsulfonyloxy group or a
phenylsulfonyloxy group, and the electron-withdrawing
group is a cyano group, a nitro group or the like.
That is, a compound of the present invention of the
formula [I-2] can be produced by reacting a compound of
the formula [VI] with a compound of the formula [VII] in
a solvent in the presence of a base.
The amount of the compound of the formula [VII] may
suitably be selected from a range of from 1 to 5 mols per
1 mol of the compound of the formula [VI], and it is
preferably from 1.0 to 1.2 mols.
The solvent to be used in this reaction is not
limited so long as it does not inhibit the reaction, and
it may, for example, be an aromatic hydrocarbon such as
benzene, toluene or xylene, an ether such as diethyl
ether, tetrahydrofuran, 1,2-dimethoxyethane or dioxane, a
ketone such as acetone or methyl ethyl ketone, a nitrile
such as acetonitrile or propionitrile, an aprotic polar
solvent such as dimethyl sulfoxide, N,N-dimethylformamide
or N,N-dimethylacetamide, an aliphatic hydrocarbon such
as pentane, hexane, cyclohexane or heptane or a pyridine
such as pyridine or picoline, or a solvent mixture
thereof.
The base to be used in this reaction may, for
example, be an inorganic base such as a hydroxide of an

alkali metal such as sodium hydroxide or potassium
hydroxide, a hydroxide of an alkaline earth metal such as
calcium hydroxide or magnesium hydroxide, a carbonate of
an alkali metal such as sodium carbonate or potassium
carbonate, or an alkali metal bicarbonate such as sodium
hydrogencarbonate or potassium hydrogencarbonate, a metal
hydride such as sodium hydride or potassium hydride, a
metal salt of an alcohol such as sodium methoxide, sodium
ethoxide or potassium tert-butoxide, or an organic base
such as triethylamine, N,N-dimethylaniline, pyridine, 4-
N,N-dimethylaminopyridine or 1,8-diazabicyclo[5.4.0]-7-
undecene.
The amount of the base to be used may suitably be
selected from a range of from 1 to 5 mols per 1 mol of
the compound of the formula [II], and it is preferably
from 1.1 to 1.2 mols.
The reaction temperature may be optionally selected
from a range of from -70°C to the reflux temperature of
the reaction system, and it is preferably within a range
of from -20°C to 150°C. The reaction time varies
depending upon the reaction temperature, the reaction
substrate, the reaction amount, etc., and it is usually
from 10 minutes to 2 0 hours.

A compound of the formula [I-2] which is a compound
of the present invention can be produced also by the
following substitution reaction:


wherein Ai, A3, B2, B5 and R are as defined above, and L4
is a halogen atom, an alkylsulfonyloxy group, a
phenylsulfonyloxy group, an alkylsulfonyl group, a
phenylsulfonyl group or a nitro group.
That is, a 3-triazolylphenyl sulfide derivative of
the formula [I-2] which is a compound of the present
invention can be produced by reacting a compound of the
formula [IX] with a compound of the formula [X] in a
solvent in the presence of a base or copper(I) oxide.
The solvent to be used in this reaction may, for
example, be an ether such as diethyl ether,
tetrahydrofuran or dioxane, an aromatic hydrocarbon such
as benzene, toluene, xylene or chlorobenzene, an aprotic
polar solvent such as N,N-dimethylformamide, N,N-
dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl
sulfoxide or sulfolane, an alcohol such as methanol,
ethanol or methyl cellosolve, an aliphatic hydrocarbon
such as pentane, hexane, cyclohexane or heptane, a
pyridine such as pyridine or picoline, or water, or a
solvent mixture thereof.
The base to be used in this reaction may, for

example, be an inorganic base such as a hydroxide of an
alkali metal such as sodium hydroxide or potassium
hydroxide, a hydroxide of an alkaline earth metal such as
calcium hydroxide or magnesium hydroxide, a carbonate of
an alkali metal such as sodium carbonate or potassium
carbonate, or a bicarbonate of an alkali metal such as
sodium hydrogencarbonate or potassium hydrogencarbonate,
a metal hydride such as sodium hydride or potassium
hydride, a metal salt of an alcohol such as sodium
methoxide, sodium ethoxide or potassium tert-butoxide, or
an organic base such as triethylamine, N,N-
dimethylaniline, pyridine, 4-N,N-dimethylaminopyridine or
1, 8-diazabicyclo[5.4.0]-7-undecene.
The amount of the base or copper(I) oxide to be used
may suitably be selected from a range of from 1 to 5 mols
per 1 mol of the compound of the formula [IX], and it is
preferably from 1.0 to 1.2 mols.
The reaction temperature may be optionally selected
from a range of from -70°C to the reflux temperature of
the reaction system, and it is preferably within a range
of from 0°C to 150°C. The reaction time varies depending
upon the reaction temperature, the reaction substrate,
the reaction amount, etc., and it is usually from 10
minutes to 2 0 hours.

A compound of the formula [I] which is a compound of
the present invention can be produced by a process

exemplified by the following scheme:

wherein A1 A3, B2, B4, R and n are as defined above.
That is, a compound of the present invention
represented by the formula [I] can be produced by
reacting a compound of the formula [VI], a compound of
the formula [VIII] and an anhydrous copper salt in a
solvent in the presence of an organic base.
The amount of the compound of the formula [VIII] to
be used may suitably be selected from a range of from 1
to 5 mols per 1 mol of the compound of the formula [VI],
and it is preferably from 1.0 to 2.0 mols.
The solvent to be used in this reaction is not
limited so long as it does not inhibit the reaction, and
it may, for example, be a halogenated alkane such as
chloroform or dichloromethane, an aromatic hydrocarbon
such as benzene, toluene or xylene, an ether such as
diethyl ether, tetrahydrofuran, 1,2-dimethoxyethane or
dioxane, a ketone such as acetone or methyl ethyl ketone,
a nitrile such as acetonitrile or propionitrile, an
aprotic polar solvent such as N,N-dimethylformamide or
N,N-dimethylacetamide, an aliphatic hydrocarbon such as
pentane, hexane, cyclohexane or heptane, or a pyridine

such as pyridine or picoline, or a solvent mixture
thereof.
The anhydrous copper salt to be used in this
reaction may, for example, be anhydrous copper acetate.
The amount of the anhydrous copper salt to be used may
suitably be selected from a range of from 1 to 5 mols per
1 mol of the compound of the formula [VI], and it is
preferably from 1.2 to 2.2 mols.
The organic base to be used in this reaction may,
for example, be triethylamine, N,N-dimethylaniline,
pyridine, 4-N,N-dimethylaminopyridine or 1,8-
diazabicyclo[5.4.0]-7-undecene.
The amount of the organic base to be used may
suitably be selected from a range of from 1 to 5 mols per
1 mol of the compound of the formula [VI], and it is
preferably from 1.2 to 4.4 mols.
The reaction temperature may be optionally selected
from a range of from 0°C to the reflux temperature of the
reaction system, and it is preferably within a range of
from 10°C to 30°C.
The reaction time varies depending upon the reaction
temperature, the reaction substrate, the reaction amount,
etc., and it is usually from 8 to 48 hours.

A compound of the formula [I-1] which is a compound
of the present invention can be produced also by a
process exemplified by the following scheme:


wherein Alr A3, B2, B4, R and M are as defined above.
That is, an aimed 3-triazolylphenyl sulfide
derivative of the formula [I-1] can be produced by
converting a compound of the formula [XI] into a
diazonium salt in a solvent by means of a conventional
method (a method by using a mineral acid (such as
hydrochloric acid or sulfuric acid) and a nitrite salt or
an alkyl nitrite) and reacting the diazonium salt with a
mercaptan salt of the formula [XII] or a disulfide of the
formula [XIII].
The amount of the compound of the formula [XII] or
the compound of the formula [XIII] to be used in this
reaction may suitably be selected from a range of from 1
to 5 mols per 1 mol of the compound of the formula [XI],
and it is preferably from 1.0 to 2.0 mols.
The solvent to be used in this reaction may, for
example, be an ether such as diethyl ether,
tetrahydrofuran or dioxane, an aromatic hydrocarbon such
as benzene, toluene, xylene or chlorobenzene, a
halogenated hydrocarbon such as dichloromethane,
chloroform or dichloroethane, an aprotic polar solvent
such as acetonitrile, N,N-dimethylformamide, N,N-

dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl
sulfoxide or sulfolane, an alcohol such as methanol,
ethanol or isopropyl alcohol, a nitrile such as
acetonitrile or propionitrile, an ester such as ethyl
acetate or ethyl propionate, an aliphatic hydrocarbon
such as pentane, hexane, cyclohexane or heptane, a
pyridine such as pyridine or picoline, or water, or a
solvent mixture thereof.
The reaction temperature may be optionally selected
from a range of from -3 0°C to the reflux temperature of
the reaction system, and it is preferably within a range
of from -10°C to 100°C.
The reaction time varies depending upon the reaction
temperature, the reaction substrate, the reaction amount,
etc., and it is usually from 10 minutes to 20 hours.

A compound of the formula [I] which is a compound of
the present invention can be produced also by a process
exemplified by the following scheme:


wherein L3, A1 A3, B2, B4, R and n are as defined above,
Y1 is an alkoxy group or an alkylthio group, L5 is a
leaving group such as a halogen atom, an acyloxy group,
an alkylsulfonyloxy group or a phenylsulfonyloxy group,
and R1' is an alkyl group.
[Step 1]
That is, a compound of the present invention of the
formula [I] can be produced by reacting a compound of the
formula [XIV] with a compound of the formula [XV-1] or
[XV-2] in a solvent in the presence of a base.
The amount of the compound of the formula [XV-1] or
[XV-2] to be used in this reaction is within a range of
from 1 mol to large excess per 1 mol of the compound of
the formula [XIV], and it is preferably from 1.2 to 2.0
mols.

The solvent to be used in this reaction may, for
example, be an ether such as diethyl ether,
tetrahydrofuran or dioxane, an aromatic hydrocarbon such
as benzene, toluene, xylene or chlorobenzene, a
halogenated hydrocarbon such as dichloromethane,
chloroform or dichloroethane, an aprotic polar solvent
such as acetonitrile, N,N-dimethylformamide, N,N-
dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl
sulfoxide or sulfolane, an alcohol such as methanol,
ethanol or isopropyl alcohol, a nitrile such as
acetonitrile or propionitrile, an ester such as ethyl
acetate or ethyl propionate, an aliphatic hydrocarbon
such as pentane, hexane, cyclohexane or heptane, a
pyridine such as pyridine or picoline, or water, or a
solvent mixture thereof.
The base to be used in this reaction may, for
example, be an inorganic base such as a hydroxide of an
alkali metal such as sodium hydroxide or potassium
hydroxide, a hydroxide of an alkaline earth metal such as
calcium hydroxide or magnesium hydroxide, a carbonate of
an alkali metal such'as sodium carbonate or potassium
carbonate, or a bicarbonate of an alkali metal such as
sodium hydrogencarbonate or potassium hydrogencarbonate,
a metal hydride such as sodium hydride or potassium
hydride, a metal salt of an alcohol such as sodium
methoxide, sodium ethoxide or potassium tert-butoxide, or
an organic base such as triethylamine, N,N-

dimethylaniline, pyridine, 4-N,N-dimethylaminopyridine or
1, 8-diazabicyclo[5.4.0]-7-undecene.
The amount of the base to be used may suitably be
selected from a range of from 2 to 5 mols per 1 mol of
the compound of the formula [XIV], and it is preferably
from 2.2 to 3.0 mols.
The reaction temperature may be optionally selected
from a range of from 0°C to the reflux temperature of the
reaction system, and it is preferably within a range of
from 10°C to 150°C. The reaction time varies depending
upon the reaction temperature, the reaction substrate,
the reaction amount, etc., and it is usually from 3 to 12
hours.
As another process, an aimed 3-triazolylphenyl
sulfide derivative of the formula [I] can be produced by
reacting a compound of the formula [XIV] with aqueous
ammonia to produce a compound of the formula [XIV-1]
(Step 2-1), and reacting this compound with a compound of
the formula [XV-3] or [XV-4] in a solvent in the presence
of a base or in the presence of an acid catalyst (Step 2-
2) .
(Step 2-1)
The amount of aqueous ammonia to be used in this
step may suitably be selected from a range of from 1 to
10 mols per 1 mol of the compound of the formula [XIV],
and it is preferably from 2.0 to 5.0 mols.
The solvent to be used in this step may, for example,

be an ether such as diethyl ether, tetrahydrofuran or
dioxane, an aromatic hydrocarbon such as benzene, toluene,
xylene or chlorobenzene, a halogenated hydrocarbon such
as dichloromethane, chloroform or dichloroethane, an
aprotic polar solvent such as acetonitrile, N,N-
dimethylformamide, N,N-dimethylacetamide, N-methyl-2-
pyrrolidone, dimethyl sulfoxide or sulfolane, an alcohol
such as methanol, ethanol or isopropyl alcohol, a nitrile
such as acetonitrile or propionitrile, an ester such as
ethyl acetate or ethyl propionate, an aliphatic
hydrocarbon such as pentane, hexane, cyclohexane or
heptane, a pyridine such as pyridine or picoline, or
water, or a solvent mixture thereof.
The reaction temperature may be optionally selected
from a range of from -3 0°C to the reflux temperature of
the reaction system, and it is preferably within a range
of from -10°C to 100°C.
The reaction time varies depending upon the reaction
temperature, the reaction substrate, the reaction amount,
etc., and it is usually from 10 minutes to 20 hours.
(Step 2-2)
Further, the amount of the compound of the formula
[XV-3] or the compound of the formula [XV-4] to be used
in this step is within a range of from 1 mol to large
excess per 1 mol of the compound of the formula [XIV-1],
and it is preferably from 1.0 to 2.0 mols.
The acid catalyst to be used in this step may, for

example, be a sulfonic acid such as methanesulfonic acid
or p-toluenesulfonic acid, an inorganic acid such as
hydrochloric acid or sulfuric acid, or a carboxylic acid
such as acetic acid or trifluoroacetic acid.
The amount of the acid catalyst to be used may
suitably be selected from a range of from 0.01 mol to
large excess per 1 mol of the compound of the formula
[XIV-1], and it is preferably from 0.05 to 1.0 mols.
The solvent to be used in this step may be the same
solvent as defined for the above Step 1.
The base to be used in this reaction may, for
example, be an inorganic base such as a hydroxide of an
alkali metal such as sodium hydroxide or potassium
hydroxide, a hydroxide of an alkaline earth metal such as
calcium hydroxide or magnesium hydroxide, a carbonate of
an alkali metal such as sodium carbonate or potassium
carbonate, or a bicarbonate of an alkali metal such as
sodium hydrogencarbonate or potassium hydrogencarbonate,
a metal hydride such as sodium hydride or potassium
hydride, a metal salt of an alcohol such as sodium
methoxide, sodium ethoxide or potassium tert-butoxide, or
an organic base such as triethylamine, N,N-
dimethylaniline, pyridine, 4-N,N-dimethylaminopyridine or
1,8-diazabicyclo[5.4.0]-7-undecene.
The amount of the base to be used may suitably be
selected from a range of from 1 mol to large excess per 1
mol of the compound of the formula [XIV-1], and it is

preferably from 1.0 to 1.5 mols.
The reaction temperature may be optionally selected
from a range of from -3 0°C to the reflux temperature of
the reaction system, and it is preferably within a range
of from -10°C to 100°C.
The reaction time varies depending upon the reaction
temperature, the reaction substrate, the reaction amount,
etc., and it is usually from 10 minutes to 20 hours.


wherein Y2 is a halogen atom, an alkoxy group or an
alkylthio group which may be substituted by halogen, and
Ri', Ai, A3, B2, B4, R and n are as defined above.
(Step 3)
A compound of the present invention of the formula
[I] can be produced by reacting a compound of the formula
[XVII-1] derived from a compound of the formula [XVI-1]
and an acid halide, an acid anhydride or the like, with a

compound of the formula [XVIII].
The amount of the compound of the formula [XVII-1]
may suitably be selected from a range of from 1.0 to 5.0
mols per 1 mol of the compound of the formula [XVIII],
and it is preferably from 1.0 to 1.5 mols.
The solvent to be used in this step may, for example,
be an ether such as diethyl ether, tetrahydrofuran or
dioxane, an aromatic hydrocarbon such as benzene, toluene,
xylene or chlorobenzene, an aprotic polar solvent such as
acetonitrile, N,N-dimethylformamide, N,N-
dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl
sulfoxide or sulfolane, an alcohol such as methanol,
ethanol or isopropyl alcohol, a halogenated hydrocarbon
such as methylene chloride, chloroform or dichloroethane,
an aliphatic hydrocarbon such as pentane, hexane,
cyclohexane or heptane, a ketone such as acetone, methyl
ethyl ketone or cyclohexanone, or water.
The reaction temperature may be optionally selected
from a range of from -3 0°C to the reflux temperature of
the reaction system, and it is preferably within a range
of from -10°C to 100°C. The reaction time varies
depending upon the reaction temperature, the reaction
substrate, the reaction amount, etc., and it is usually
from 10 minutes to 20 hours.
(Step 4)
Further, an aimed 3-triazilylphenyl sulfide
derivative of the formula [I-3] can be produced by

reacting a compound of the formula [XVII-2] derived from
a compound of the formula [XVI-2] and carbon disulfide,
an alkyl halide or the like, with a compound of the
formula [XVIII].
The amount of the compound of the formula [XVII-2]
may suitably be selected from a range of from 1.0 to 10
mols per 1 mol of the compound of the formula [XVIII],
and it is preferably from 1.0 to 1.5 mols.
The solvent to be used in this step may be the same
solvent as defined for the above Step 3.
The reaction temperature may be optionally selected
from a range of from -3 0°C to the reflux temperature of
the reaction system, and it is preferably within a range
of from -10°C to 100°C.
The reaction time varies depending upon the reaction
temperature, the reaction substrate, the reaction amount,
etc., and it is usually from 10 minutes to 20 hours.


wherein Y3 is a hydrogen atom or a halogen atom, and L3,
Ai, A3, B2, B4 and R are as defined above.
A compound of the present invention of the formula
[I-1] can be produced by reacting a compound of the

formula [XIX] with a metal or an organic metal compound,
followed by reaction with a compound of the formula [XX]
or [XIII].
The amount of the compound of the formula [XX] or
[XIII] to be used may suitably be selected from a range
of from 1 to 5 mols per 1 mol of the compound of the
formula [XIX], and it is preferably from 1.0 to 2.0 mols.
The solvent to be used in this reaction may, for
example, be an ether such as diethyl ether,
tetrahydrofuran or dioxane, an aromatic hydrocarbon such
as benzene, toluene, xylene or chlorobenzene, an
aliphatic hydrocarbon such as pentane, hexane,
cyclohexane or heptane, or a pyridine such as pyridine or
picoline, or a solvent mixture thereof.
The metal to be used in this reaction may, for
example, be an alkali metal such as lithium or an
alkaline earth metal such as magnesium, and its amount to
be used may suitably be selected from a range of from 1
to 3 mols per 1 mol of the compound of the formula [XIX],
and it is preferably from 1.0 to 1.1 mols.
The organic metal compound to be used in this
reaction may, for example, be an alkyllithium such as n-
butyllithium, and its amount to be used may suitably be
selected from a range of from 1 to 3 mols per 1 mol of
the compound of the formula [XIX], and it is preferably
from 1.0 to 1.1 mols.
The reaction temperature may be optionally selected

from a range of from -90°C to the reflux temperature of
the reaction system, and it is preferably within a range
of from -78°C to 70°C.
The reaction time varies depending upon the reaction
temperature, the reaction substrate, the reaction amount,
etc., and it is usually from 10 minutes to 20 hours.


wherein Ai, A3, B2, B4 and R are as defined above.
A compound of the present invention of the formula
[I-4] can be produced by reacting a compound of the
formula [I-1] with an oxidizing agent in the presence or
absence of a catalyst.
The oxidizing agent may, for example, be hydrogen
peroxide, m-chloroperbenzoic acid, sodium periodate,
OXONE (tradename, manufactured by E.I. du Pont;
containing potassium hydrogenperoxosulfate), N-
chlorosuccinimide, N-bromosuccinimide, tert-butyl
hypochlorite or sodium hypochlorite.
The amount of the oxidizing agent to be used may
suitably be selected from a range of from 1 to 6 mols per
1 mol of the compound of the formula [I-1], and it is

preferably from 1.0 to 1.2 mols.
The catalyst to be used in this reaction may, for
example, be sodium tungstate.
The amount of the catalyst to be used may suitably
be selected from a range of from 0 to 1 mol per 1 mol of
the compound of the formula [I-1] , and it is preferably
from 0.01 to 0.1 mol.
The solvent to be used in this reaction may, for
example, be an ether such as diethyl ether,
tetrahydrofuran or dioxane, an aromatic hydrocarbon such
as benzene, toluene, xylene or chlorobenzene, an aprotic
polar solvent such as acetonitrile, N,N-dimethylformamide,
N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl
sulfoxide or sulfolane, an alcohol such as methanol,
ethanol or isopropyl alcohol, a halogenated hydrocarbon
such as methylene chloride, chloroform or dichloroethane,
an aliphatic hydrocarbon such as pentane, hexane,
cyclohexane or heptane, ketone such as acetone, methyl
ethyl ketone or cyclohexanone, acetic acid, or water, or
a solvent mixture thereof.
The reaction temperature may be optionally selected
from a range of from -3 0°C to the reflux temperature of
the reaction system, and it is preferably within a range
of from -10°C to 100°C.
The reaction time varies depending upon the reaction
temperature, the reaction substrate, the reaction amount,
etc., and it is usually from 10 minutes to 20 hours.


A compound of the present invention of the formula
[I] can be produced from a 3-triazolylphenyl sulfide
derivative by converting a functional group by a
generally known method:

wherein Ax, A3, B2, B4, n and R are as defined above, and
L6 is a hydrogen atom, a halogen atom, a methylthio group,
a methylsulfinyl group, a methylsulfonyl group, a p-
toluenesulfonyl group or the like.
(Step A)
A compound of the present invention of the formula
[I] can be produced by reacting a compound of the present
invention of the formula [I-3] with an electrophilic
reagent in the presence or absence of a solvent, in the
presence or absence of a base, in the presence or absence

of an acid and in the presence or absence of a
dehydration condensation agent.
The electrophile to be used in this step may, for
example, be a halogenated alkane, a halogenated alkene, a
halogenated alkyne, a phenylalkyl halide, a heterocyclic
alkyl halide, an acyl halide, an acid anhydride, benzoic
acid, a benzoyl halide, a heterocyclic carboxylic acid, a
heterocyclic carboxylic halide, an aliphatic carboxylic
halide, an isocyanate, an alcohol, an aromatic halide, a
heterocyclic halide, a sulfonyl halide or a sulfonic
anhydride, or a ketone or a thioketone.
The halogenated alkane to be used in this step may,
for example, be methyl iodide, ethyl iodide or propyl
iodide.
The halogenated alkene to be used in this step may,
for example, be allyl bromide or 1,1,3-trichloropropene.
The halogenated alkyne to be used in this step may,
for example, be propargyl bromide or 4-chloro-2-butyne.
The phenylalkyl halide to be used in this step may,
for example, be benzyl bromide, 4-methoxybenzyl chloride
or 4-chlorobenzyl bromide.
The heterocyclic alkyl halide to be used in this
step may, for example, be 2-chloro-5-chloromethylpyridine.
The acyl halide to be used in this step may, for
example, be acetyl chloride, propionyl chloride,
difluoroacetyl chloride, trifluoroacetyl chloride, methyl
chloroformate, ethyl chloroformate or N,N-

dimethylcarbamoyl chloride.
The acid anhydride to be used in this step may, for
example, be acetic anhydride, trifluoroacetic anhydride
or chlorodifluoroacetic anhydride.
The isocyanate to be used in this step may, for
example, be methyl isocayanate, ethyl isocyanate or
chlorosulfonyl isocyanate.
The aromatic halide to be used in this step may, for
example, be 3,5-dichloro-4-fluorobenzotrifluoride.
The heterocyclic halide to be used in this step may,
for example, be 2,3-dichloro-5-trifluoromethylpyridine.
The sulfonyl halide to be used in this step may, for
example, be trifluoromethanesulfonyl fluoride,
trifluoromethanesulfonyl chloride or
difluoromethanesulfonyl chloride.
The sulfonic anhydride to be used in this step may,
for example, be trifluoromethanesulfonic anhydride.
The ketone to be used in this step may, for example,
be acetone or 4-hydroxy-3-methoxybenzaldehyde.
The benzoyl halide to be used in this step may, for
example, be benzoyl chloride.
The heterocyclic carboxylic acid to be used in this
step may, for example, be 3-pyridine carboxylic acid or
thiophene carboxylic acid.
The heterocyclic carboxylic halide to be used in
this step may, for example, be 3-pyridinecarboxylic
chloride or thiophenecarboxylic chloride.

The aliphatic carboxylic halide to be used in this
step may, for example, be acetyl chloride or propionyl
chloride.
The alcohol to be used in this step may, for example,
be methanol, ethanol or benzyl alcohol.
The amount of the electrophile to be used may
suitably be selected from a range of from 1 to 100 mols
per 1 mol of the compound of the formula [I-3], and it is
preferably from 1 to 10 mols, more preferably from 1 to 3
mols.
In a case where a base is used in this step, the
base to be used may, for example, be an inorganic base
such as a hydroxide of an alkali metal such as sodium
hydroxide or potassium hydroxide, a hydroxide of an
alkaline earth metal such as calcium hydroxide or
magnesium hydroxide, a carbonate of an alkali metal such
as sodium carbonate or potassium carbonate, or a
bicarbonate of an alkali metal such as sodium
hydrogencarbonate or potassium hydrogencarbonate, a metal
hydride such as sodium hydride or potassium hydride, a
metal salt of an alcohol such as sodium methoxide, sodium
ethoxide or potassium tert-butoxide, or an organic base
such as triethylamine, N,N-dimethylaniline, pyridine, 4-
N,N-dimethylaminopyridine or 1,8-diazabicyclo[5.4.0]-7-
undecene.
In a case where a base is used, the amount of the
base to be used may suitably be selected within a range

of from 0.01 to 3 mols per 1 mol of the compound of the
formula [I-3], and it is preferably from 0.1 to 2 mols,
more preferably from 0.1 to 1.2 mols.
In a case where an acid is used in this step, the
acid to be used is a Lewis acid, such as a sulfonic acid
such as methanesulfonic acid or p-toluenesulfonic acid,
an inorganic acid such as hydrochloric acid, hydrobromic
acid or sulfuric acid, or a carboxylic acid such as
acetic acid or trifluoroacetic acid.
In a case where an acid is used, the amount of the
acid to be used may suitably be selected from a range of
from 0.001 to 5 mols per 1 mol of the compound of the
formula [I-3], and it is preferably from 0.01 to 2 mols,
more preferably from 0.03 to 1.0 mols.
The solvent to be used in this step may, for example,
be an ether such as diethyl ether, tetrahydrofuran or
dioxane, an aromatic hydrocarbon such as benzene, toluene,
xylene or chlorobenzene, an aprotic polar solvent such as
acetonitrile, N,N-dimethylformamide, N,N-
dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl
sulfoxide or sulfolane, an alcohol such as methanol,
ethanol or isopropyl alcohol, a halogenated hydrocarbon
such as methylene chloride, chloroform or dichloroethane,
an aliphatic hydrocarbon such as pentane, hexane,
cyclohexane or heptane, or a ketone such as acetone,
methyl ethyl ketone or cyclohexanone, or a solvent
mixture thereof.

In a case where a dehydration condensation agent is
used in this step, the dehydration condensation agent to
be used may be a carbodiimide such as
dicyclohexylcarbodiimide.
In a case where a dehydration condensation agent is
used, the amount of the dehydration condensation agent to
be used may suitably be selected from a range of from 1
to 3 mols per 1 mol of the compound of the formula [I-3],
and it is preferably from 1.0 to 1.2 mols.
The reaction temperature may be optionally selected
from a range of from -2 0°C to the reflux temperature of
the reaction system, and it is preferably within a range
of from 0°C to 80°C.
The reaction time varies depending upon the reaction
temperature, the reaction substrate, the reaction amount,
etc., and it is usually from 15 minutes to 24 hours.
(Step B)
A compound of the present invention of the formula
[I] can be produced by reacting a compound of the formula
[I-5] with a compound of the formula [I-7] in the
presence or absence of a base in the presence of a
solvent.
In a case where a base is used in this process, the
base to be used in this reaction may, for example, be an
inorganic base such as a hydroxide of an alkali metal
such as sodium hydroxide or potassium hydroxide, a
hydroxide of an alkaline earth metal such as calcium

hydroxide or magnesium hydroxide, a carbonate of an
alkali metal such as sodium carbonate or potassium
carbonate, or a bicarbonate of an alkali metal such as
sodium hydrogencarbonate or potassium hydrogencarbonate,
a metal hydride such as sodium hydride or potassium
hydride, a metal salt of an alcohol such as sodium
methoxide, sodium ethoxide or potassium tert-butoxide, or
an organic base such as triethylamine, N,N-
dimethylaniline, pyridine, 4-N,N-dimethylaminopyridine or
1,8-diazabicyclo[5.4.0]-7-undecene.
In a case where a base is used, the amount of the
base to be used may suitably be selected from a range of
from 1 to 10 mols per 1 mol of the compound of the
formula [I-5], and it is preferably from 1 to 3 mols,
more preferably from 1.0 to 1.2 mols.
The solvent to be used in this step may, for example,
be an ether such as diethyl ether, tetrahydrofuran or
dioxane, an aromatic hydrocarbon such as benzene, toluene,
xylene or chlorobenzene, an aprotic polar solvent such as
acetonitrile, N,N-dimethylformamide, N,N-
dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl
sulfoxide or sulfolane, an alcohol such as methanol,
ethanol or isopropyl alcohol, a halogenated hydrocarbon
such as methylene chloride, chloroform or dichloroethane,
an aliphatic hydrocarbon such as pentane, hexane,
cyclohexane or heptane, or a ketone such as acetone,
methyl ethyl ketone or cyclohexanone, or water, and a

solvent mixture thereof may also be used.
The reaction temperature may be optionally selected
from a range of from -2 0°C to the reflux temperature of
the reaction system, and it is preferably within a range
of from -10°C to 150°C.
The reaction time varies depending upon the reaction
temperature, the reaction substrate, the reaction amount,
etc., and it is usually from 15 minutes to 12 hours.
(Step C)
A compound of the present invention represented by
the formula [I] can be produced by reacting a compound of
the formula [I-6] with an amine, a carboxylic acid or an
alcohol in the presence or absence of a solvent.
The amine to be used in this step may, for example,
be methylamine, ethylamine, dimethylamine, propylamine,
isopropylamine, hydrazine or methylhydrazine.
The carboxylic acid to be used in this step may, for
example, be acetic acid, propionic acid, methoxyacetic
acid or benzoic acid.
The alcohol to be used in this step may, for example,
be methanol, ethanol, propanol, allyl alcohol, propargyl
alcohol or cyclopropanol.
As the amount of the amine, carboxylic acid or
alcohol to be used, from 1 mol to 100 mols, preferably
from 1 mol to 3 0 mols, more preferably from 1 mol to 3
mols, of the amine, carboxylic acid or alcohol is used
per 1 mol of the compound represented by the formula [I-

6] .
The solvent to be used in this reaction may, for
example, be an ether such as diethyl ether,
tetrahydrofuran or dioxane, an aromatic hydrocarbon such
as benzene, toluene, xylene or chlorobenzene, an aprotic
polar solvent such as acetonitrile, N,N-dimethylformamide,
N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl
sulfoxide or sulfolane, an alcohol such as methanol,
ethanol or isopropyl alcohol, a halogenated hydrocarbon
such as methylene chloride, chloroform or dichloroethane,
an aliphatic hydrocarbon such as pentane, hexane,
cyclohexane or heptane, or a ketone such as acetone,
methyl ethyl ketone or cyclohexanone, or a solvent
mixture thereof.
The reaction temperature may be optionally selected
from a range of from -2 0°C to the reflux temperature of
the reaction system, and it is preferably within a range
of from -10°C to 150°C.
The reaction time varies depending upon the reaction
temperature, the reaction substrate, the reaction amount,
etc., and it is usually from 30 minutes to 24 hours.
Now, synthesis of intermediates for production of
the compounds of the present invention will be described
in detail below.

Synthesis of production intermediates [II] and [IV]
Compounds of the formulae [II] and [IV] can be

synthesized as follows. Needless to say, they are -
interconvertible through oxidation-reduction reaction.
Especially, the compound of the formula [II] can be
easily oxidized by atmospheric oxygen into a compound of
the formula [IV] in some cases:

wherein R2' is a methyl group or a trifluoromethyl group,
and Y2, Ai, A3, B2 and B4 are as defined above.
(Step 5)
That is, an aimed compound represented by the

formula [II] or [IV] can be produced as follows. A
compound of the formula [XXI] is oxidized by an oxidizing
agent into a methyl sulfoxide, followed by the Puramerer
rearrangement reaction with acetic anhydride or
trifluoroacetic anhydride into an acyloxymethyl sulfide
represented by the formula [XXII], and then the resulting
compound is hydrolyzed.
The oxidizing agent may, for example, be hydrogen
peroxide, m-chloroperbenzoic acid, sodium periodate,
OXONE (tradename, manufactured by E.I. du Pont;
containing potassium hydrogenperoxosulfate), N-
chlorosuccinimide, N-bromosuccinimide, tert-butyl
hypochlorite or sodium hypochlorite.
The amount of the oxidizing agent to be used may
suitably be selected from a range of from 1 to 3 mols per
1 mol of the compound of the formula [XXI], and it is
preferably from 1.0 to 1.2 mols.
As the amount of acetic anhydride or trifluoroacetic
anhydride to be used, it can be used as a reaction
solvent in an amount of 1 mol or more per 1 mol of the
compound of the formula [XXI], and its amount is
preferably from 1.0 to 3.0 mols.
The reaction temperature of each reaction may be
optionally selected from a range of from -10°C to the
reflux temperature of the reaction system, and it is
preferably within a range of from 0°C to 50°C.
The reaction time varies depending upon the reaction

temperature, the reaction substrate, the reaction amount,
etc., and it is usually from 5 minutes to 12 hours.
(Step 6)
A compound represented by the formula [II] can be
produced by treating a compound of the formula [XIX] with
a metal or an organo metallic compound in a solvent and
then reacting sulfur therewith.
The solvent to be used in this step may, for example,
be an ether such as diethyl ether, tetrahydrofuran or
dioxane, an aromatic hydrocarbon such as benzene, toluene,
xylene or chlorobenzene, an aliphatic hydrocarbon such as
pentane, hexane, cyclohexane or heptane, or a pyridine
such as pyridine or picoline, or a solvent mixture
thereof.
The metal to be used in this step may, for example,
be lithium or magnesium.
The amount of the metal to be used may suitably be
selected from a range of from 1 to 3 mols per 1 mol of
the compound of the formula [XIX], and it is preferably
from 1.0 to 1.2 mols.
The organo metallic compound to be used in this step
may, for example, be n-butyllithium.
The amount of the organo metallic compound to be
used may optionally be selected from a range of from 1 to
3 mols per 1 mol of the compound of the formula [XIX],
and it is preferably from 1.0 to 1.2 mols.
The amount of sulfur to be used may suitably be

selected from a range of from 1 to 5 mols per 1 mol of
the compound of the formula [XIX], and it is preferably
from 1.0 to 2.0 mols.
The reaction temperature of each reaction may
optionally be selected from a range of from -60°C to the
reflux temperature of the reaction system, and it is
preferably within a range of from -60°C to room
temperature.
The reaction time varies depending upon the reaction
temperature, the reaction substrate, the reaction amount,
etc., and it is usually from 30 minutes to 12 hours.
(Step 7)
A compound represented by the formula [II] can be
produced as follows. A compound represented by the
formula [XI] is converted into a diazonium salt in the
same manner as in the above Production Process 6. Then,
the diazonium salt is reacted with a xanthate or a
thiocyanate, followed by alkali hydrolysis.
The amount of the xanthate or the thiocyanate to be
used may suitably be selected from a range of from 1 to 3
mols per 1 mol of the compound of the formula [XI], and
it is preferably from 1.0 to 1.5 mols.
The reaction temperature of each reaction may
optionally be selected from a range of from -70°C to the
reflux temperature of the reaction system, and it is
preferably from -20°C to 100°C.
The reaction time varies depending upon the reaction

temperature, the reaction substrate, the reaction amount,
etc., and it is usually from 10 minutes to 20 hours.
(Step 8)
A synthetic intermediate represented by the formula
[II] can be produced by treating a compound of the
formula [XXIII] with chlorosulfonic acid into a sulfonyl
chloride of the formula [XXIV], and reducing it with
lithium aluminum hydride, with zinc and an acid, with tin
and an acid or with red phosphorus and iodine.
The amount of chlorosulfonic acid to be used in this
step may suitably be selected from a range of from 2 to 5
mols per 1 mol of the compound of the formula [XXIII],
and it is preferably from 2.2 to 3.0 mols.
The acid may, for example, be hydrochloric acid or
sulfuric acid.
The amount of chlorosulfonic acid to be used may
suitably be selected from a range of from 2 to 10 mols
per 1 mol of the compound of the formula [XXIII], and it
is preferably from 2.2 to 3.5 mols.
The amount of lithium aluminum hydride, zinc and an
acid, tin and an acid, or red phosphorus and iodine, may
suitably be selected from a range of from 1 to 5 mols per
1 mol of the compound of the formula [XXIII], and it is
preferably from 1.5 to 2.0 mols.
(Step 9)
A compound represented by the formula [IV] can be
produced by reacting a compound of the formula [XXIII]

with disulfur dichloride in the presence or absence of a
catalyst. Further, a compound represented by the formula
[II] can be produced by reducing the compound represented
by the formula [IV] by a conventional method.
The amount of disulfur dichloride to be used may
suitably be selected from a range of from 1 to 5 mols per
1 mol of the compound of the formula [XXIII], and it is
preferably from 1.1 to 1.5 mols.
The catalyst to be used in this step may, for
example, be a Lewis acid catalyst such as aluminum
chloride, tin(II) chloride or tin(IV) chloride.
The amount of the catalyst to be used may suitably
be selected from a range of from 1 to 5 mols per 1 mol of
the compound of the formula [XXIII], and it is preferably
from 1.1 to 2.0 mols.
The solvent to be used in this step may, for example,
be a halogenated hydrocarbon such as methylene chloride,
chloroform or dichloroethane, or an aromatic hydrocarbon
such as chlorobenzene or dichlorobenzene.
The reaction temperature may optionally be selected
from a range of from -3 0°C to the reflux temperature of
the reaction, and it is preferably within a range of from
-10°C to 100°C.
The reaction time varies depending upon the reaction
temperature, the reaction substrate and the reaction
amount, and it is usually from 1 to 20 hours,
intermediate Production Process 2>

Further, a synthetic intermediate of the formula
[II-l] can be produced by substitution reaction from a
compound of the formula [IX] wherein B5 is an electron-
withdrawing group:

wherein L4, Ax, A3, B2 and B5 are as defined above.
That is, an aimed 3-triazolylphenylthiol derivative
represented by the formula [II-l] can be produced by
reacting a compound of the formula [IX] with a compound
of the formula [XXV] in a solvent in the presence of a
base, followed by neutralization with a mineral acid or
the like.
The amount of the compound of the formula [XXV] to
be used may suitably be selected from a range of from 1
to 3 mols per 1 mol of the compound of the formula [IX],
and it is preferably from 1.0 to 1.5 mols.
The solvent to be used in this step may, for example,
be an ether such as diethyl ether, tetrahydrofuran or
dioxane, an aromatic hydrocarbon such as benzene, toluene,
xylene or chlorobenzene, an aprotic polar solvent such as
N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-
pyrrolidone, dimethyl sulfoxide or sulfolane, an alcohol
such as methanol, ethanol or isopropyl alcohol, a

halogenated hydrocarbon such as methylene chloride,
chloroform or dichloroethane, an aliphatic hydrocarbon
such as pentane, hexane, cyclohexane or heptane, a ketone
such as acetone, methyl ethyl ketone or cyclohexanone, or
water.
The base to be used in this step may, for example,
be an inorganic base such as a hydroxide of an alkali
metal such as sodium hydroxide or potassium hydroxide, a
hydroxide of an alkaline earth metal such as calcium
hydroxide or magnesium hydroxide, a carbonate of an
alkali metal such as sodium carbonate or potassium
carbonate, or a bicarbonate of an alkali metal such as
sodium hydrogencarbonate or potassium hydrogencarbonate,
a metal hydride such as sodium hydride or potassium
hydride, a metal salt of an alcohol such as sodium
methoxide, sodium ethoxide or potassium tert-butoxide, or
an organic base such as triethylamine, N,N-
dimethylaniline, pyridine, 4-N,N-dimethylaminopyridine or
1,8-diazabicyclo[5.4.0]-7-undecene.
The amount of the base to be used may suitably be
selected from a range of from 1 to 5 mols per 1 mol of
the compound of the formula [IX], and it is preferably
from 1.0 to 1.2 mols.
The mineral acid may, for example, be hydrochloric
acid or sulfuric acid.
The amount of the mineral acid to be used may
suitably be selected from a range of from 1 to 5 mols per

1 mol of the compound of the formula [IX], and it is
preferably from 1.0 to 2.0 mols.
The reaction temperature may be optionally selected
from a range of from -3 0°C to the reflux temperature of
the reaction system, and it is preferably within a range
of from -20°C to 100°C. The reaction time varies
depending upon the reaction temperature, the reaction
substrate, the reaction amount, etc., and it is usually
from 10 minutes to 20 hours.

Synthesis of production intermediate [VI]


wherein A1 A3, R', Y1 L3 and L5 are as defined above.
(Step 10)
A synthetic intermediate represented by the formula
[VI] can be produced, in the same manner as in Production
Process 8, by converting a compound of the formula [XVI]
into a compound of the formula [XVII], and reacting
hydrazine hydrate [XXVI] of the formula [XXVI] therewith.
The amount of hydrazine hydrate [XXVI] to be used
may suitably be selected from a range of from 1 to 5 mols
per 1 mol of the compound of the formula [XVII], and it
is preferably from 1.0 to 2.0 mols.
(Step 11)
Further, a synthetic intermediate represented by the
formula [VI] can be produced, in the same manner as in
Production Process 7, by reacting a compound of the
formula [XXVII] with a compound of the formula [XV-1] or
[XV-2].
The amount of the compound represented by the
formula [XV-1] or [XV-2] to be used is from 1 mol to
large excess per 1 mol of the compound of the formula
[XXVII], and it is preferably from 1.0 to 2.0 mols.
The reaction temperature may be optionally selected
from a range of from -70°C to the reflux temperature of
the reaction system, and it is preferably within a range
of from -20°C to 100°C.
The reaction time varies depending upon the reaction
temperature, the reaction substrate, the reaction amount,

etc., and it is usually from 10 minutes to 20 hours.
(Step 12)
A synthetic intermediate represented by the formula
[VI] can be produced by reacting a compound represented
by the formula [XXVII] with aqueous ammonia to produce an
amidrazone represented by the formula [XXVII-2], and
reacting this reaction product with a compound
represented by the formula [XV-3] or [XV-4].
The amount of aqueous ammonia to be used may
suitably be selected from a range of from 1 to 10 mols
per 1 mol of the compound represented by the formula
[XXVII], and it is preferably from 2.0 to 5.0 mols.
The amount of the compound represented by the
formula [XV-3] or [XV-4] is from 1 mol to large excess
per 1 mol of the compound represented by the formula
[XXVII-2], and it is preferably from 1.0 to 2.0 mols.
The reaction temperature may be optionally selected
from a range of from -70°C to the reflux temperature of
the reaction system, and it is preferably within a range
of from -20°C to 100°C. The reaction time varies
depending upon the reaction temperature, the reaction
substrate, the reaction amount, etc., and it is usually
from 10 minutes to 20 hours.

Synthesis of production intermediate [XIV]


wherein L3, L5 A1 B2, B4, R and n are as defined above.
(Step 13)
An aimed compound represented by the formula [XIV]
can be produced by reacting a phenylhydrazine derivative
represented by the formula [XVIII] with a compound
represented by the formula [XXVIII] in a solvent in the
presence of a base for acylation to produce a compound
represented by the formula [XXIX] and then treating the
compound represented by the formula [XXIX] with a
halogenating agent.
The amount of the compound of the formula [XXVIII]

to be used may suitably be selected from a range of from
1 to 5 mols per 1 mol of the compound of the formula
[XVIII], and it is preferably from 1.0 to 1.1 mols.
The solvent to be used in this step may, for example,
be an ether such as diethyl ether, tetrahydrofuran or
dioxane, an aromatic hydrocarbon such as benzene, toluene,
xylene or chlorobenzene, a halogenated hydrocarbon such
as dichloromethane, chloroform or dichloroethane, an
aprotic polar solvent such as N,N-dimethylformamide, N,N-
dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl
sulfoxide or sulfolane, an alcohol such as methanol,
ethanol or isopropyl alcohol, a nitrile such as
acetonitrile or propionitrile, an ester such as ethyl
acetate or ethyl propionate, an aliphatic hydrocarbon
such as pentane, hexane, cyclohexane or heptane, a
pyridine such as pyridine or picoline, or water, or a
solvent mixture thereof.
The base to be used in this step may, for example,
be an inorganic base such as a hydroxide of an alkali
metal such as sodium hydroxide or potassium hydroxide, a
hydroxide of an alkaline earth metal such as calcium
hydroxide or magnesium hydroxide, a carbonate of an
alkali metal such as sodium carbonate or potassium
carbonate, or a bicarbonate of an alkali metal such as
sodium hydrogencarbonate or potassium hydrogencarbonate,
a metal hydride such as sodium hydride or potassium
hydride, a metal salt of an alcohol such as sodium

methoxide, sodium ethoxide or potassium tert-butoxide, or
an organic base such as triethylamine, N,N-
dimethylaniline, pyridine, 4-N,N-dimethylaminopyridine or
1, 8-diazabicyclo [5.4.0] -7-undecene.
The amount of the base to be used is from 1 mol to
large excess per 1 mol of the compound of the formula
[XVIII], and it is preferably from 1.0 to 1.2 mols.
The halogenating agent may, for example, be
phosphorus trichloride, phosphorus tribromide, thionyl
chloride, phosphorus oxychloride, phosphorus
pentachloride, triphenylphosphine/carbon tetrachloride or
triphenylphosphine/carbon tetrabromide.
The amount of the halogenating agent to be used is
from 1 mol to large excess per 1 mol of the compound of
the formula [XXIX], and it is preferably from 1.0 to 1.5
mols .
The reaction temperature may be optionally selected
from a range of from -70°C to the reflux temperature of
the reaction system, and it is preferably within a range
of from -20°C to 150°C.
The reaction time varies depending upon the reaction
temperature, the reaction substrate, the reaction amount,
etc., and it is usually from 10 minutes to 20 hours.
(Step 14)
Otherwise, an aimed compound represented by the
formula [XIV] can be produced by reacting a
phenylhydrazine derivative represented by the formula

[XVIII] with an aldehyde compound represented by the
formula [XXX] in a solvent in the presence or absence of
an acid catalyst to form a phenylhydrazone derivative
represented by the formula [XXXI], and treating it with a
halogenating agent.
The amount of the compound of the formula [XXX] to
be used may suitably be selected from a range of from 1
to 5 mols per 1 mol of the compound of the formula
[XVIII], and it is preferably from 1.0 to 1.2 mols.
The solvent to be used in this step is not limited
so long as it does not inhibit the reaction and it may,
for example, be ah aromatic hydrocarbon such as benzene,
toluene or xylene, an ether such as diethyl ether,
tetrahydrofuran, 1,2-dimethoxyethane or dioxane, a ketone
such as acetone or methyl ethyl ketone, a nitrile such as
acetonitrile or propionitrile, an aprotic polar solvent
such as dimethyl sulfoxide, N,N-dimethylformamide or N,N-
dimethylacetamide, an aliphatic hydrocarbon such as
pentane, hexane, cyclohexane or heptane, or a pyridine
such as pyridine or picoline, or a solvent mixture
thereof.
The acid catalyst to be used in this step may, for
example, be a Lewis acid such as a sulfonic acid such as
p-toluenesulfonic acid, or titanium tetrachloride.
In a case where an acid catalyst is used, its amount
to be used may suitably be selected from a range of from
1 to 5 mols per 1 mol of the compound of the formula

[XVIII], and it is preferably from 1.0 to 1.2 mols.
The halogenating agent to be used in this step may,
for example, be chlorine, N-chlorosuccinimide, N-
bromosuccinimide or tert-butyl hypochlorite.
The amount of the halogenating agent to be used may
suitably be selected from a range of from 1 to 5 mols per
1 mol of the compound of the formula [XXXI], and it is
preferably from 1.0 to 1.1 mols.
The reaction temperature may be optionally selected
from a range of from -70°C to the reflux temperature of
the reaction system, and it is preferably within a range
of from -20°C to 150°C. The reaction time varies
depending upon the reaction temperature, the reaction
substrate, the reaction amount, etc., and it is usually
from 10 minutes to 20 hours.
The phenylhydrazine of the formula [XVIII] can be
synthesized from the corresponding aniline in accordance
with a conventional method such as a method as disclosed
in Comprehensive Organic Functional Group Transformations,
vol. 2, p. 769.


wherein B2, B4 and R are as defined above, and Ac is an
acetyl group.
A 3-thioaniline derivative represented by the
formula [XXXVI] can be produced by converting an
acetanilide represented by the formula [XXXII] into a
disulfide represented by the formula [XXXIV] or a thiol
represented by the formula [XXXV] in the same manner as
in Intermediate Production Process 1, followed by a
process as disclosed in the above Production Process 1 or
2.
A phenylhydrazine represented by the formula [XVIII-
1] can be produced by reacting a compound presented by

the formula [XXXVI] with a nitrite in the presence of a
mineral acid to form a diazonium salt, and reducing it
with zinc powder, a sulfite, tin chloride or the like.
The mineral acid may, for example, be hydrochloric
acid or sulfuric acid.
The amount of the mineral acid to be used may
suitably be selected from a range of from 2 to 10 mols
per 1 mol of the compound [XXXVI], and it is preferably
from 3 to 5 mols.
The amount of the nitrite to be used may suitably be
selected from a range of from 1.0 to 5.0 mols per 1 mol
of the compound [XXXVI], and it is preferably from 1.0 to
1.2 mols.
The reaction temperature of each reaction may be
selected from a range of from -20°C to 50°C, and it is
preferably from -5°C to 20°C.
The reaction time varies depending upon the reaction
temperature, the reaction substrate, the reaction amount,
etc., and it is usually from 30 minutes to 5 hours.
A compound of the formula [I-5] can be produced by
the following process:


wherein A1 A3, B2, B4, n and R are as defined above, L7
is a halogen atom, and W is a methylthio group or a p-
tolylthio group.
A compound of the formula [I-5a] can be produced by
diazotizing a compound of the formula [I-3] by a
conventional method, followed by reaction with copper(I)
chloride or copper(I) bromide.
The amount of copper(I) chloride or copper(I)

bromide to be used is from 1 to 5 mols per 1 mol of the
compound of the formula [I-3], preferably from 1 to 2
mols.
The solvent to be used may, for example, be a
carboxylic acid such as acetic acid, a mineral acid such
as hydrochloric acid, hydrobromic acid or sulfuric acid,
or water, or a solvent mixture thereof.
The reaction temperature may be optionally selected
from a range of from -7 0°C to the reflux temperature of
the reaction system, and it is preferably within a range
of from -20°C to 100°C. The reaction time varies
depending upon the reaction temperature, the reaction
substrate, the reaction amount, etc., and it is usually
from 10 minutes to 20 hours.
A compound of the formula [I-5a] can be produced
also by a reaction in the coexistence of a nitrite ester
such as t-butyl nitrite or isoamyl nitrite with
copper(II) chloride or copper(II) bromide in a solvent.
The amount of the nitrite ester to be used is from 1
to 5 mols per 1 mol of the compound of the formula [I-3],
preferably from 1 to 2 mols.
The amount of copper(II) chloride or copper(II)
bromide to be used is from 1 to 5 mols per 1 mol of the
compound of the formula [I-3], preferably from 1 to 2
mols.
The amount of copper(II) chloride or copper(II)
bromide to be used is from 1 to 5 mols per 1 mol of the

compound of the formula [I-3], preferably from 1 to 2
mols.
The solvent to be used may, for example, be an ether
such as diethyl ether, tetrahydrofuran or dioxane, a
nitrile such as acetonitrile, or an aprotic polar solvent
such as N,N-dimethylformamide, N,N-dimethylacetamide, N-
methyl-2-pyrrolidone, dimethyl sulfoxide or sulfolane, or
a solvent mixture thereof.
The reaction temperature may be optionally selected
from a range of from -70°C to the reflux temperature of
the reaction system, and it is preferably within a range
of from -20°C to 100°C. The reaction time varies
depending upon the reaction temperature, the reaction
substrate, the reaction amount, etc., and it is usually
from 10 minutes to 20 hours.
A compound of the formula [I-5b] can be produced by
reacting a compound of the formula [I-5a] with methyl
mercaptan or 4-methylbenzenethiol in the presence of a
base in a solvent.
The base to be used in this reaction may, for
example, be an inorganic base such as a hydroxide of an
alkali metal such as sodium hydroxide or potassium
hydroxide, a hydroxide of an alkaline earth metal such as
calcium hydroxide or magnesium hydroxide, a carbonate of
an alkali metal such as sodium carbonate or potassium
carbonate, or a bicarbonate of an alkali metal such as
sodium hydrogencarbonate or potassium hydrogencarbonate,

a metal hydride such as sodium hydride or potassium
hydride, a metal salt of an alcohol such as sodium
methoxide, sodium ethoxide or potassium tert-butoxide, or
an organic base such as triethylamine, N,N-
dimethylaniline, pyridine, 4-N,N-dimethylaminopyridine or
1,8-diazabicyclo[5.4.0]-7-undecene.
The solvent to be used in this step may, for example,
be an ether such as diethyl ether, tetrahydrofuran or
dioxane, an aromatic hydrocarbon such as benzene, toluene,
xylene or chlorobenzene, an aprotic polar solvent such as
N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-
pyrrolidone, dimethyl sulfoxide or sulfolane, an alcohol
such as methanol, ethanol or isopropyl alcohol, a
halogenated hydrocarbon such as methylene chloride,
chloroform or dichloroethane, an aliphatic hydrocarbon
such as pentane, hexane, cyclohexane or heptane, a ketone
such as acetone, methyl ethyl ketone or cyclohexanone, or
water.
A compound of the formula [I-5c] or [I-5d] can be
produced by reacting a compound of the formula [I-5b]
with an oxidizing agent such as hydrogen peroxide, m-
chloroperbenzoic acid, sodium periodate, OXONE (tradename,
manufactured by E.I. du Pont, containing potassium
hydrogenperoxosulfate), N-chlorosuccinimide, N-
bromosuccinimide, tert-butyl hypochlorite or sodium
hypochlorite.
The amount of the oxidizing agent to be used is, in

a case of producing the compound [I-5c], from 0.5 to 1.5
mols, preferably from 0.8 to 1.2 mols, per 1 mol of the
compound of the formula [I-5b] . Further, in a case of
producing the compound [I-5d], it is from 2 to 10 mols,
preferably from 2 mols to A mols, per 1 mol of the
compound of the formula [I-5b].
The solvent to be used, the reaction temperature and
the reaction time are as defined for the above Production
Process 10.
Further, a compound of the formula [I-5d] can be
produced also by reacting a compound represented by the
formula [I-5a] with a methanesulfinic acid salt or a p-
toluenesulfinic acid salt.
The amount of the methanesulfinic acid salt or the
p-toluenesulfinic acid salt to be used is from 1 to 10
mols, 'preferably from 1 to 5 mols, more preferably from 1
to 3 mols, per 1 mol of the compound of the formula [I-
5a] .
The solvent to be used may, for example, be a
nitrile such as acetonitrile, or an aprotic polar solvent
such as dimethyl sulfoxide, N,N-dimethylformamide or N,N-
dimethylacetamide.
The reaction temperature may be optionally selected
from a range of from -0°C to the reflux temperature of
the reaction system, and it is preferably within a range
of from 10°C to 100°C.
The reaction time varies depending upon the reaction

temperature, the reaction substrate, the reaction amount,
etc., and it is usually from 1 to 24 hours.
A compound of the formula [I-5e] can be produced by
reacting a compound of the formula [I-3] with a nitrite
ester such as t-butyl nitrite or isoamyl nitrite.
The amount of the nitrite ester to be used is from 1
to 5 mols per 1 mol of the compound of the formula [I-3],
and it is preferably from 1 to 2 mols.
The solvent to be used may, for example, be an ether
such as diethyl ether, tetrahydrofuran or dioxane, a
nitrile such as acetonitrile, or an aprotic polar solvent
such as N,N-dimethylformamide, N,N-dimethylacetamide, N-
methyl-2-pyrrolidone, dimethyl sulfoxide or sulfolane, or
a solvent mixture thereof.
The reaction temperature may be optionally selected
from a range of from -70°C to the reflux temperature of
the reaction system, and it is preferably within a range
of from -20°C to 100°C. The reaction time varies
depending upon the reaction temperature, the reaction
substrate, the reaction amount, etc., and it is usually
from 10 minutes to 20 hours.


wherein A1; A3, B2, B4, n and R are as defined above.
A compound represented by the formula [I-6] can be
produced by a known process by reacting a compound
represented by the formula [I-3] with oxalyl chloride or
phosgene in the presence of a solvent.
The amount of oxalyl chloride or phosgene to be used
may suitably be selected from a range of from 1 mol to
the same amount as the amount of the reaction solvent per
1 mol of the compound represented by the formula [I-3],
and it is preferably from 1.1 to 3 mols.
The solvent to be used may, for example, be an ether
such as diethyl ether, tetrahydrofuran or dioxane, an
aromatic hydrocarbon such as benzene, toluene, xylene or
chlorobenzene, a halogenated hydrocarbon such as
dichloromethane, chloroform or dichloroethane, an
aliphatic hydrocarbon such as pentane, hexane,
cyclohexane or heptane, or a solvent mixture thereof.
When a compound of the present invention is used as
the active ingredient of a pesticide, it may be used by
itself. However, it can be formulated into various
formulations such as an emulsifiable concentrate, a
suspension, a dust, a granule, a tablet, a wettable
powder, a water-soluble concentrate, a solution, a
flowable suspension, a water dispersible granule, an
aerosol, a paste, an oil formulation, a concentrated
emulsion in water and a smoking agent in combination with
various carriers, surfactants and other adjuvants which

are commonly used for formulation as agricultural
adjuvants. They are blended usually in such proportions
that the active ingredient is from 0.1 to 90 wt% and the
agricultural adjuvants are from 10 to 99.9 wt%.
The carriers to be used for such formulation may be
classified into solid carriers and liquid carriers. The
solid carriers include, for example, animal and plant
powders such as starch, activated carbon, soybean powder,
wheat flour, wood flour, fish flour and powdered milk,
and mineral powders such as talc, kaolin, bentonite,
calcium carbonate, zeolite, diatomaceous earth, white
carbon, clay, alumina, ammonium sulfate and urea. The
liquid carriers include, for example, water; alcohols
such as isopropyl alcohol and ethylene glycol; ketones
such as cyclohexanone and methyl ethyl ketone; ethers
such as dioxane and tetrahydrofuran; aliphatic
hydrocarbons such as kerosene and light oil; aromatic
hydrocarbons such as xylene, trimethylbenzene,
tetramethylbenzen, methylnaphthalene and solvent naphtha;
halogenated hydrocarbons such as chlorobenzene; acid
amides such as dimethylacetamide; esters such as glycerin
esters of fatty acids; nitriles such as acetonitrile; and
sulfur-containing compounds such as dimethyl sulfoxide.
The surfactants include, for example, metal salts of
alkylbenzenesulfonic acids, metal salts of
dinaphthylmethanedisulfonic acids, salts of alcohol
sulfates, alkylarylsulfonates, lignin sulfonates,

polyoxyethylene glycol ethers, polyoxyethylene alkyl aryl
ethers, and polyoxyethylene sorbitan monoalkylates.
The other adjuvants include, for example, adhesive
agents and thickeners such as carboxymethylcellulose, gum
arabic, sodium arginate, guar gum, tragacanth gum, and
polyvinyl alcohol, antifoaming agents such as metal soap,
physical property improvers such as fatty acids, alkyl
phosphate salts, silicone and paraffin and coloring
agents.
When these formulations are practically used, they
may be used directly or after diluted with a diluent such
as water to a predetermined concentration. Various
formulations containing the compounds of the present
invention, whether diluted or not, may be applied by
conventional methods, i.e., application methods (such as
spraying, misting, atomizing, dusting, granule
application, paddy water application and seeding box
application), soil treatment (such as mixing or
drenching), surface application (such as painting,
dressing and covering), dipping, poison bait or smoking.
Further, the above active ingredients may be incorporated
into livestock feeds so as to prevent infestation or
growth of pest, especially pest insects after they are
voided in excrement. Otherwise, they can also be applied
in low volume at high concentration, when the active
ingredient may be contained up to 100%. The proportion
of the active ingredient is suitably selected if

necessary, and it is properly from 0.1 to 20% (by weight)
in the case of a dust or a granule, and from 1 to 30% (by
weight) in the case of an emulsifiable concentrate or a
wettable powder.
The pesticides of the present invention are applied,
when they are diluted with a diluent, usually at an
active ingredient concentration of from 0.1 to 5,000 ppm.
When they are used directly, the dose per unit area is
from 0.1 to 5,000 g per 1 ha in terms of the compound
that serves as the active ingredient. However, the dose
is not limited to such specific range.
The compounds of the present invention are
sufficiently effective when used alone. However, they
may be used, if necessary, in combination or in admixture
with fertilizers or other agrochemicals such as
insecticides, miticides, nematicides, fungicides,
antivirus agents, attractants, herbicides and plant
growth regulants, and such combined use can sometimes
produce improved effects.
Typical examples of the insecticides, fungicides,
miticides and the like which may be used in combination
with the compounds of the present invention, will be
given below.
Organophosphorus compounds and carbamate
insecticides: fenthion, fenitrothion, diazinon,
chlorpyriphos, oxydeprofos, vamidothion, phenthoate
(fentoat), dimethoate, formothion, malathion,

trichlorphon, thiometon, phosmet, dichlorvos, acephate,
EPBP, methyl-parathion, oxydimeton-methyl, ethion,
dioxabenzofos, cyanophos (cyanofos), isoxathion,
pyridafenthion, phosalone, metidation, sulprophos
(sulprofos), chlorfenvinphos, tetrachlorvinphos,
dimethylvinphos, propaphos, isofenphos, disulfoton,
profenofos, pyraclofos, monocrotophos, azinphos-methyl,
aldicarb, methomyl, thiodicarb, carbofuran, carbosulfan,
benfuracarb, furathiocarb, propoxur, fenobcarb, metolcarb,
isoprocarb, carbaryl (carbaril), pirimicarb, ethiofencarb,
dichlophenthion, pirimiphos-methyl, quinalphos,
chlorpyriphos-methyl, prothiophos, naled, EPN, XMC,
bendiocarb, oxamyl, alanycarb, chlorethoxyfos, etc.
Pyrethroid insecticides: permethrin, cypermethrin,
deltamethrin, fenvalerate, fenpropathrin, piretrine,
allethrin, tetramethrin, resmethrin, dimethrin,
proparthrin, phenothrin, prothrin, fluvalinate,
cyfluthrin, cyhalothrin, flucythrinate, etofenprox,
cycloprothrin, tralomethrin, silafluofen, tefluthrin,
bifenthrin, acrinathrin, etc.
Acylurea type and other insecticides: diflubenzuron,
chlorfluazuron, hexaflumuron, triflumuron, teflubenzuron,
flufenoksuron, flucycloxuron, buprofezin, pyriproxyfen,
lufenuron, cyromazine, methoprene, endosulphan,
diafenthiuron, imidacloprid, acetamiprid, nitenpyram,
clothianidin, dinotefuran, thiamethoxam, thiacloprid,
pymetrozine, fipronil, pyridalyl, nicotin-sulfate,

rotenone, metaldehyde, machine oil, microbial pesticides
such as BT and entomopathogenic viruses, fenoxycarb,
cartap, thiocyclam, bensultap, tebufenozide,
chlorphenapyr, emamectin-benzoate, acetaprid, nitenpyram,
sodium oleate, rapeseed oil, etc.
Nematicides: phenamiphos, fosthiazate, ethoprophos,
methyl isothiocyanate, 1,3-dichloropropene, DCIP, etc.
Miticides-. chlororbenzilate, phenisobromolate,
dicofol, amitraz, propargit, benzomate, hexythiazox,
fenbutatin oxide, polynactin, quinomethionate,
chlorfenson, tetradifon, avermectin, milbemectin,
clofentezine, pyridaben, fenpyroximate, tebufenpyrad,
pyrimidifen, fenothiocarb, dienochlor, etoxazole,
bifenazate, acequinocyl, halfenprox, spirodiclofen, etc.
Fungicides: thiophanate-methyl, benomil, carbendazol,
thiabendazol, folpet, thiuram, diram, zineb, maneb,
polycarbamate, iprobenfos, edifenphos, fthalide,
probenazole, isoprothiolane, chlorothalonil, captan,
polyoxin, blasticidin-S, kasugamycin, streptomycin,
validamycin, tricyclazole, pyroquilone, phenazine oxide,
mepronil, flutolanil, pencycuron, iprodione, hymexazol,
metalaxyl, triflumizole, triforine, triadimefone,
bitertanol, fenarimol, propikonazol, cymoxanil,
prochloraze, pefurazoate, hexaconazole, myclobutanil,
diclomezine, tecloftalam, propineb, dithianon, phosethyl,
vinclozolin, procymidone, oxadixyl, guazatine,
propamocarb--hydrochloride, fluazinam, oxolinic acid.

hydroxyisoxazole, mepanipyrim.
The compounds of the present invention exhibit
excellent pesticidal activities against pests such as
pest hemiptera, pest lepidoptera, pest coleoptera, pest
diptera, pest hymenoptera, pest orthoptera, pest isoptera,
pest thysanoptera, mites and plant-parastic nematodes.
The following pest insects may be mentioned as such pests.
Pest hemiptera: bugs (HETEROPTERA) such as bean bug
(Riptortus clavatus), southern green stink bug (Nezara
viridula), lygus bugs (Lygus sp.), hairy chinch bug
(Blissus leucopterus) and pear lace bug (Stephanitis
nashi); leafhoppers (Deltocephalinae) such as green rice
leafhopper (Nephotettix cincticeps) and leafhoppers
(Empoasca sp., Erythroneura sp., Circulifer sp.);
delphacid planthoppers such as brown rice planthopper
(Nilaparvata lugens), white-backed planthopper (Sogatella
furcifera) and small brown planthopper (Laodelphax
striatellus); jumping plantlice such as Psyllids (Psylla
sp.); whiteflies such as silverleaf whitefly (Bemisia
tabaci) and greenhouse whitefly (Trialeurodes
vaporariorum); aphides such as grapeleaf louse (Viteus
vitifolii), green peach aphid (Myzus persicae), green
apple aphid (Aphis pomi), cotton aphid (Aphis gossypii),
Aphis fabae, turnip aphid (Rhopalosiphum psedobrassicas),
glasshouse-potato aphid (Aulacorthum solani) and greenbug
(Schizaphis graminum); mealy bugs or scales such as
Comstock mealybug (Pseudococcus comstocki), red wax scale

(Ceroplastes rubens), San Jose scale (Cornstockaspis
perniciosa) and arrowhead scale (Unaspis yanonensis) and
assassin bugs (Rhodinius sp.) •
Pest lepidoptera: tortricids such as oriental tea
tortrix (Horaona magnanima), summer fruit tortrix
(Adoxophyes orana) , tortricids (Sparganothis pilleriana),
oriental fruit moth (Grapholitha molesta), soybean pod
borer (Leguminivora glycinivorella), codling moth
(Laspeyresia pomonella), Eucosma sp. and Lobesia botrana;
Cochylidae such as grape cochylid (Eupoecillia
ambiguella); bagworm moths such as Bambalina sp.; tineids
such as European grain moth (Nemapogon granellus) and
casemaking clothes moth (Tinea translucens); lyonetid
moths such as Lyonetia prunifoliella; leafblotch miners
such as apple leafminer (Phyllonorycter rigoniella);
Phyllocnistidae such as citrus leafminer (Phyllocnistis
citrella) ; yponomeutids such as diamondback moth
(Plutella xylostella) and Prays citri; clearwing moths
such as grape clearwing moth (Paranthrene regalis) and
Synanthedon sp.; gelechiid moths such as pink bollworm
(Pectinophora gossypiella), potato tuberworm (Phthorimaea
operculella) and Stomopteryx sp.; Carposinidae such as
peach fruit moth (Carposina niponensis); slug
caterpillarmoths such as oriental moth (Monema
flavescens); pyralid moths such as Asiatic rice borer
(Chilo suppressalis), rice leafroller (Cnaphalocrocis
medinalis), Ostrinia nubilalis, oriental corn borer

(Ostrinia furnacalis), cabbage webworm (Hellula undalis),
greater wax moth (Galleria mellonella), Elasmopalpus
lignosellus and Loxostege sticticalis; whites such as
common cabbageworm (Pieris rapae); geometrid moths such
as mugwort looper (Ascotis selenaria); tent caterpillar
moths such as tent caterpillar (Malacosoma neustria);
sphinx moths such as Manduca sexta; tussock moths such as
tea tussock moth (Euproctis pseudoconspersa) and gypsy
moth (Lymantria dispar); tiger moths such as fall webworm
(Hyphantria cunea); and owlet moths such as tobacco
budworm (Heliothis virescens), bollworm (Helicoverpa zea),
beet armyworm (Spodoptera exigua), cotton bollworm
(Helicoverpa armigera), common cutworm (Spodoptera
litura), cabbage armyworm (Mamestra brassicae), black
cutworm (Agrotis ipsiron), rice armyworm (Pseudaletia
separata) and cabbage looper (Trichoplusia ni).
Pest coleoptera: chafers such as cupreous chafer
(Anomala cuprea), Japanese beetle (Popillia japonica),
soybean beetle (Anomala rufocuprea) and Eutheola
rugiceps; click beetles such as wireworm (Agriotes sp.)
and Conodeus sp.; ladybirds such as twenty-eight-spotted
ladybird (Epilachna vigintioctopunctata) and Mexican bean
beetle (Epilachna varivestis); darkling beetles such as
red flour beetle (Tribolium castaneum); longicorn beetles
such as white-spotted longicorn beetle (Anoplophora
malasiaca) and pine sawyer (Monochamus alternatus); seed
beetles such as bean weevil (Acanthoscelides obtectus)

and adzuki bean weevil (Callosobruchus chinensis); leaf
beetles such as Colorado potato beetle (Leptinotarsa
decemlineata), corn rootworm (Diabrotica sp.), rice leaf
beetle (Oulema oryzae), beet flea beetle (Chaetocnema
concinna), Phaedon cochlearias, Oulema melanopus and
Dicladispa armigera; Apionidae such as Apion godtnani;
weevils such as rice water weevil (Lissorhoptrus
oryzophilus) and cotton boll weevil (Anthonomus grandis);
Rhynchophoridae such as maize weevil (Sitophilus
zeamais); bark beetles; dermestid beetles; and drugstore
beetles.
Pet diptera: rice crane fly (Tipra ano), rice midge
(Tanytarsus oryzae), gall midge (Orseolia oryzae), medfly
(Ceratitis capitata), rice leafminer (Hydrellia griseola),
cherry drosophila (Drosophila suzukii), frit fly
(Oscinella frit), rice stem maggot (Chiorops oryzae),
French bean miner (Ophiomyia phaseoli), legume leafminer
(Liriomyza trifolii), spinach leafminer (Pegomya
hyoscyami), seedcorn maggot (Hylemia platura), sorghum
fly (Atherigona soccata), muscid fly (Musca domestica),
horse bot-flies (Gastrophilus sp.), stable flies
(Stomoxys sp.), yellow fever mosquito (Aedes aegypti),
nrothern house mosquito (Culex pipiens), malaria mosquito
(Anopheles sinensis) and Culex tritaeniorhynchus.
Pest hymenoptera: stem sawflies (Cephus sp.);
eurytomids (Harmolita sp.); cabbage sawflies (Athalia
sp.), hornets (Vespa sp.) and fire ants.

Pest orthoptera: German cockroach (Blatella
germanica); American cockroach (Periplaneta americana);
African mole cricket (Gryllotalpa africana); Asiatic
locust (Locusta migratoria migratoriod.es) ; and Melanoplus
sanguinipes.
Pest isoptera: termites (Reticulitermes speratus)
and Formosan subterranean termite (Coptotermes
formosanus).
Pest thysanopetra: yellow tea thrips (Scirtothrips
dorsalis); melon thrips (Thrips palmi); greenhouse thrips
(Heliothrips haemorrholidalis) ; western flower thrips
(Frankliniella occidentalis) and rice aculeated thrips
(Haplothrips aculeatus).
Mites: two-spotted spider mite (Tetranychus
urticae); Kanzawa spider mite (Tetranychus kanzawai);
citrus red mite (Panonychus citri) ; European red mite
(Panonychus ulmi), yellow spider mite (Eotetranychus
carpini); Texas citrus mite (Eotetranychus banksi);
citrus rust mite (Phyllocoptruta oleivora); broad mite
(Polyphagotarsonemus latus); false spider mites
(Brevipalpus sp.); bulb mite (Rhizoglyphus robini) and
mold mite (Tyrophagus putrescentiae).
Plant-parasitic nematodes: root-knot nematode
(Meloidogyne sp.) ,- root-lesion nematode (Pratylenchus
sp.); soybean cyst nematode (Heterodera glycines); golden
nematode (Globodera rostochiensis); banana burrowing
nematode (Radopholus similis); strawberry bud nematode

(Aphelenchoid.es fragariae) ; rice white-tip nematode
(Aphelenchoides besseyi) and pine wood nematode
(Bursaphelenchus xylophilus).
Other pests, unfavorable animals, insanitary insects,
and parasites: gastropods (Gastropoda) such as apple
snails (Pomacea canaliculata), slugs (Incilaria sp.) and
giant African snail (Achatina fulica); isopods (Isopoda)
such as pillbug (Armadillidium sp.), sow bug and
centipede; booklice such as Liposcelis sp.; silverfish
such as Ctenolepisma sp.; fleas such as Pulex sp. and
Ctenocephalides sp.; bird lice such as Trichodectes sp.;
bed bugs such as Cimex sp.; aminal-parasitic mites such
as Boophilus microplus and Haemaphysalis longicornis and
Epidermoptidae.
Further, the compounds of the present invention are
effective also against pest insects which show resistance
to organophosphorus compounds, carbamate compounds,
synthetic pyrethroid compounds, acylurea compounds or
conventional insecticides.
EXAMPLES
Now, preparation, formulations and use of the
compounds of the present invention will be described in
further detail with reference to Examples. Preparations
of synthetic intermediates of the compounds of the
present invention will also be described.
EXAMPLE 1

Preparation of [5-(5-amino-3-trifluoromethyl-1,2,4-
triazolyl)-4-chloro-2-methylphenyl]2,2,2-trifluoroethyl
sulfide (Compound No. 7 of the present invention)
(1) Synthesis of 5-acetylthio-2-chloro-4-
methylacetanilide
55 g of 2-chloro-4-methylacetanilide was added to
100 ml of chlorosulfonic acid at from 5 to 10°C. 65 g of
60% fuming sulfuric acid was added to the mixed liquid at
from 10 to 15°C, and the resulting mixture was stirred at
room temperature for 1 hour and further stirred at 90°C
for 18 hours. After the resulting reaction mixture was
cooled to room temperature, it was poured into ice water,
toluene was added, the insolubles were filtered off, and
the resulting organic layer was washed with water and
dried over anhydrous magnesium sulfate. The solvent was
distilled off under reduced pressure, and a mixture of
the obtained residue, 31 g of red phosphorus, 1 g of
iodine and 200 ml of acetic acid was refluxed with
heating for 1 hour, and the obtained reaction liquid was
cooled to room temperature. After the insolubles were
filtered off, the liquid was concentrated under reduced
pressure, water was added, and extraction with ethyl
acetate was carried out. The organic layer was washed
with water and dried over anhydrous magnesium sulfate,
the solvent was distilled off under reduced pressure, and
the residue was purified by silica gel column
chromatography to obtain 14 g of 5-acetylthio-2-chloro-4-

methylacetanilide.
(2) Synthesis of 2-chloro~4-methyl-5-mercaptoaniline
14 g of 5-acetylthio-2-chloro-4-methylacetanilide
was dissolved in 150 ml of ethanol, and 22 g of a 50%
aqueous sodium hydroxide solution was added, followed by
reflux with heating for 4 hours. The obtained reaction
mixture was concentrated under reduced pressure, water
was added, and the mixture was neutralized with diluted
hydrochloric acid and then extracted with ethyl acetate.
The organic layer was washed with water and dried over
anhydrous magnesium sulfate, and the solvent was
distilled off under reduced pressure to obtain 9.4 g of
2-chloro-4-methyl-5-mercaptoaniline.
(3) Synthesis of 2-chloro-4-methyl-5-(2,2,2-
trifluoroethylthio)aniline
A mixture of 9.4 g of 2-chloro-4-methyl-5-
mercaptoaniline, 20 g of 2,2,2-trifluoroethyl iodide, 13
g of potassium carbonate and 200 ml of N,N-
dimethylformamide was stirred at room temperature for 16
hours. The reaction mixture was concentrated under
reduced pressure, water was added, and the mixture was
extracted with toluene. The organic layer was washed
with water and dried over anhydrous magnesium sulfate,
and the solvent was distilled off under reduced pressure
to obtain 13.5 g of 2-chloro-4-methyl-5-(2,2,2-
trifluoroethylthio)aniline.
hi-NMR data (CDC13/TMS 5(ppm) value): 2.32(3H,s),

3.33(2H,q), 3.96(2H,s), 6.94(lH,s), 7.11(lH,s)
(4) Synthesis of 2-chloro-4-methyl-5-(2,2,2-
trifluoroethylthio)phenylhydrazine
13.5 g of 2-chloro-4-methyl-5-(2,2,2-
trif luoroethylthio) aniline was added dropwise to 30 ml of
concentrated hydrochloric acid at room temperature, and
to this mixture, an aqueous solution containing 3.8 g of
sodium nitrite was added dropwise at from 0 to 5°C, and
the mixture was stirred as it was for 1 hour to prepare a
diazonium salt. 36 g of tin chloride dihydrate was
dissolved in 250 ml of 6N hydrochloric acid, and to this
mixed solution, the above aqueous diazonium salt solution
was added dropwise at from 0 to 5°C, and the solution was
further stirred at room temperature for 2 hours. Toluene
was added, the solution was neutralized with an aqueous
sodium hydroxide solution, the insolubles were filtered
off, and the organic layer was washed with water and
dried over anhydrous magnesium sulfate. The solvent was
distilled off under reduced pressure to obtain 12.1 g of
2-chloro-4-methyl-5-(2,2,2-
trifluoroethylthio)phenylhydrazine.
(5) Synthesis of trifluoroacetaldehyde {2-chloro-4-
methyl-5-(2,2,2-trifluoroethylthio)phenyl}hydrazone
A mixture of 4.1 g of 2-chloro-4-methyl-5-(2,2,2-
trifluoroethylthio)phenylhydrazine, 2.3 g of
trifluoroacetaldehyde ethyl hemiacetal, 0.1 g of p-
toluenesulfonic acid monohydrate and 50 ml of ethanol was

refluxed with heating for 6 hours. The obtained reaction
mixture was concentrated under reduced pressure, water
was added, and the mixture was extracted with toluene.
The organic layer was washed with water and dried over
anhydrous magnesium sulfate, and the solvent was
distilled off under reduced pressure to obtain 3.6 g of
trifluoroacetaldehyde {2-chloro-4-methyl-5-(2,2,2-
trifluoroethylthio)phenyl}hydrazone.
(6) Synthesis of N-{2-chloro-4-methyl-5-(2,2,2-
trifluoroethylthio)phenyl}trifluoroacetohydrazonoyl
bromide
3.6 g (10.3 mmol) of trifluoroacetaldehyde {2-
chloro-4-methyl-5-(2,2,2-
trifluoroethylthio)phenyl}hydrazone was dissolved in 30
ml of N,N-dimethylformamide, and 2.0 g of N-
bromosuccinimide was added at room temperature, followed
by stirring at room temperature for 2 hours. The
resulting reaction mixture was poured into water and
extracted with toluene, and the organic layer was washed
with water and dried over anhydrous magnesium sulfate.
The solvent was distilled off under reduced pressure to
obtain 4.1 g of N-{2-chloro-4-methyl-5-(2,2,2-
trifluoroethylthio)phenyl}trifluoroacetohydrazonoyl
bromide.
(7) Synthesis of [5-(5-amino-3-trifluoromethyl-1,2,4-
triazolyl)-4-chloro-2-methylphenyl]2,2,2-trifluoroethyl
sulfide

3.5 g of triethylamine was added at room temperature
to a mixture of 4.1 g of N-{2-chloro-4-methyl-5-(2,2,2-
trifluoroethylthio)phenyl}trifluoroacetohydrazonoyl
bromide, 4.4 g of S-methylisothiourea hydroiodate and 100
ml of tetrahydrofuran, and the mixture was stirred at
50°C for 3 hours. The reaction mixture was concentrated
under reduced pressure, and xylene was added to the
obtained residue, followed by reflux with heating for 2
hours. The reaction mixture was cooled to room
temperature and then washed with water, and the organic
layer was dried over anhydrous magnesium sulfate. The
solvent was distilled off under reduced pressure, and the
obtained crude crystals were recrystallized from ethanol
to obtain 2.0 g of [5-(5-amino-3-trifluoromethyl-1,2,4-
triazolyl)-4-chloro-2-methylphenyl]2,2,2-trifluoroethyl
sulfide as pale gray crystals (melting point 193 to
194°C).
EXAMPLE 2
Preparation of [5-(5-amino-3-trifluoromethyl-1,2,4-
triazolyl)-4-chloro-2-methylphenyl]2,2,2-trifluoroethyl
sulfoxide (Compound No. 8 of the present invention)
1.3 g of [5-(5-amino-3-trifluoromethyl-1,2,4-
triazolyl)-4-chloro-2-methylphenyl]2,2,2-trifluoroethyl
sulfide was dissolved in 80 ml of ethyl acetate, and 0.9
g (purity 75%) of m-chloroperbenzoic acid was added under
cooling with ice. The mixture was stirred under cooling
with ice for 2 hours, washed with an aqueous sodium

thiosulfate solution and then washed with an aqueous
sodium hydrogencarbonate solution, and then dried over
anhydrous magnesium sulfate. The solvent was distilled
off under reduced pressure, and the obtained crystals
were washed with carbon tetrachloride to obtain 1.2 g of
[5-(5-amino-3-trifluoromethyl-1,2,4-triazolyl)-4-chloro-
2-methylphenyl]2,2,2-trifluoroethyl sulfoxide as white
crystals (melting point 235 to 237°C) .
EXAMPLE 3
Preparation of [5-(3-nitro-l,2,4-triazolyl)-2-
difluoromethylphenyl]2,2,2-trifluoroethyl sulfide
(Compound No. 11 of the present invention)
(1) Synthesis of 4-(3-nitro-l,2,4-triazolyl)-2-
fluorobenzaldehyde
10 ml of a N,N-dimethylformamide solution of 3.4 g
of 3-nitro-l,2,4-triazole was added dropwise to a
suspension of 1.2 g (60%) of sodium hydride and 50 ml of
N,N-dimethylformamide under cooling with ice. After
generation of hydrogen stopped, 4.3 g of 2,4-
difluorobenzaldehyde was added, followed by stirring at
7 0°C for 3 hours. The mixture was concentrated under
reduced pressure, 200 ml of water was added, and the
mixture was extracted with ethyl acetate. The ethyl
acetate layer was washed with water and dried over
anhydrous magnesium sulfate. The solvent was distilled
off under reduced pressure, and the obtained crude
crystals were washed with diisopropyl ether to obtain 1.6

g of 4-(3-nitro-l,2,4-triazolyl)-2-fluorobenzaldehyde.
(2) Synthesis of 4-(3-nitro-l,2,4-triazolyl)-2-(2,2,2-
trifluoroethylthio)benzaldehyde
0.8 g of 2,2,2-trifluoroethylmercaptan was added
dropwise under cooling with ice to a mixture of 1.6 g of
4-(3-nitro-l,2,4-triazolyl)-2-fluorobenzaldehyde, 1.3 g
of potassium carbonate and 50 ml of N,N-dimethylformamide,
followed by stirring at from 0 to 10°C for 4 hours. The
mixture was concentrated under reduced pressure, 2 00 ml
of water was added, and the mixture was extracted with
ethyl acetate. The organic layer was washed with water
and dried over anhydrous magnesium sulfate. The solvent
was distilled off under reduced pressure to obtain 1.8 g
of 4-(3-nitro-l,2,4-triazolyl)-2-(2,2,2-
trifluoroethylthio)benzaldehyde.
(3) Synthesis of [5-(3-nitro-l,2,4-triazolyl)-2-
difluoromethylphenyl]2,2,2-trifluoroethyl sulfide
2.6 g of diethylaminosulfur trifluoride was added
under cooling with ice to a mixture of 1.8 g of 4-(3-
nitro-1,2,4-triazolyl)-2-(2,2,2-
trifluoroethylthio)benzaldehyde with 20 ml of methylene
chloride, followed by reflux with heating for 6 hours.
After the mixture was cooled to room temperature, it was
poured into ice water, and the organic layer was washed
with an aqueous sodium hydrogencarbonate solution and
with water and then dried over anhydrous magnesium
sulfate. The solvent was distilled off under reduced

pressure, and the residue was purified by silica gel
column chromatography to obtain [5-(3-nitro-l,2,4-
triazolyl)-2-difluoromethylphenyl]-2,2,2-trifluoroethyl
sulfide as pale yellow crystals (melting point 74 to
76°C).
EXAMPLE 4
Preparation of [5-(5-amino-3-trifluoromethyl-1,2,4-
triazolyl)-4-fluoro-2-methylphenyl]2,2,2-trifluoroethyl
sulfide (Compound No. 1 of the present invention)
(1) Synthesis of 5-acetylthio-2-fluoro-4-
methylacetanilide
15 0 g of 2-fluoro-4-methylacetanilide was added to
500 g of chlorosulfonic acid at 50°C or lower, followed
by stirring for 1 hour. The reaction mixture was poured
into a mixture of ice water with ethyl acetate, the
organic layer was washed with water and dried over
anhydrous magnesium sulfate, and the solvent was
distilled off under reduced pressure to obtain solid
residue. The obtained solid residue was dissolved in 350
ml of acetic acid, and the obtained solution was added
dropwise to a mixture of 84 g of red phosphorus, 1 g of
iodine and 300 ml of acetic acid under reflux with
heating over a period of 1 hour, followed by reflux with
heating for 2 hours. The reaction mixture was cooled to
room temperature, the insolubles were filtered off, and
the liquid was concentrated under reduced pressure, water
was poured, and the mixture was extracted with ethyl

acetate. The organic layer was washed with water and
dried over anhydrous magnesium sulfate, and the solvent
was distilled off under reduced pressure to obtain 211 g
of 5-acetylthio-2-fluoro-4-methylacetanilide.
(2) Synthesis of 2-fluoro-4-methyl-5-mercaptoaniline
211 g of 5-acetylthio-2-fluoro-4-methylacetanilide
was dissolved in 500 ml of ethanol, and to this solution,
a solution comprising 2 00 g of potassium hydroxide and
500 ml of water was added dropwise over a period of 30
minutes, followed by reflux with heating for 5 hours.
After the reaction mixture was cooled to room temperature,
it was neutralized with diluted hydrochloric acid,
concentrated under reduced pressure and extracted with
ethyl acetate. The organic layer was dried over
anhydrous magnesium sulfate, and the solvent was
distilled off under reduced pressure to obtain 129 g of
2-fluoro-4-methyl-5-mercaptoaniline.
(3) Synthesis of 2-fluoro-4-methyl-5-(2,2,2-
trifluoroethylthio)aniline
To 1,000 ml of a N,N-dimethylformamide solution of
129 g of 2-fluoro-4-methyl-5-mercaptoaniline, 250 g of
2,2,2-trifluoroethyl iodide and 125 g of potassium
carbonate were added, and 10 g of Rongalit was further
added, followed by stirring at room temperature for 8
hours. The reaction liquid was poured into water, the
mixture was extracted with ethyl acetate, the organic
layer was dried over anhydrous magnesium sulfate, and the

solvent was distilled off under reduced pressure to
obtain 182 g of
2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)aniline.
1H-NMR data (CDC13/TMS S(ppm) value): 2.36(3H,s),
3.30(2H,q), 3.64(2H,s), 6.86(lH,d), 6.98(lH,d)
(4) Synthesis of 2-fluoro-4-methyl-5-(2,2,2-
trifluoroethylthio)phenylhydrazine
53 g of sodium nitrite was added to 300 ml of
concentrated sulfuric acid at 50°C or lower, and 300 ml
of acetic acid was added dropwise at 50°C or lower. To
this mixed solution, 100 ml of an acetic acid solution of
182 g of 2-fluoro-4-methyl-5-(2,2,2-
trifluoroethylthio)aniline was added dropwise over a
period of 2 hours at 2 0°C or lower, followed by stirring
at 2 0°C for 3 hours. The reaction mixture was added
dropwise at 5°C or lower to a mixed solution of 390 g of
tin(II) chloride dihydrate and 1,000 ml of 6N
hydrochloric acid, followed by stirring for 30 minutes.
Toluene was added to this reaction mixture, and the
reaction mixture was neutralized with a 10% aqueous
sodium hydroxide solution. The insolubles were filtered
off, and the organic layer was dried over anhydrous
magnesium sulfate and concentrated under reduced pressure
to obtain 177 g of 2-fluoro-4-methyl-5-(2,2,2-
trifluoroethylthio)phenylhydrazine.
(5) Synthesis of trifluoroacetaldehyde {2-fluoro-4-
methyl-5-(2,2,2-trifluoroethylthio)phenyl}hydrazone

A mixture of 3.1 g of 2-fluoro-4-methyl-5-(2,2,2-
trifluoroethylthio)phenylhydrazine, 1.9 g of
trifluoroacetaldehyde ethyl hemiacetal, 0.5 g of
methanesulfonic acid and 100 ml of ethanol was refluxed
with heating for 5 hours. After the reaction mixture was
cooled to room temperature, it was concentrated under
reduced pressure and extracted with ethyl acetate, and
the organic layer was dried over anhydrous magnesium
sulfate. The solvent was distilled off under reduced
pressure to obtain 3.7 g of trifluoroacetaldehyde {2-
fluoro-4-methyl-5-(2,2,2-
trifluoroethylthio)phenyl}hydrazone.
(6) Synthesis of N-{2-fluoro-4-methyl-5-(2,2,2-
trifluoroethylthio)phenyl}trifluoroacetohydrazonoyl
bromide
3.7 g of trifluoroacetaldehyde {2-fluoro-4-methyl-5-
(2 , 2,2-trifluoroethylthio)phenyl}hydrazone was dissolved
in 5 0 ml of N,N-dimethylformamide, and 2.0 g of N-
bromosuccinimide was added at room temperature, followed
by stirring at room temperature for 30 minutes. The
reaction mixture was poured into water and extracted with
ethyl acetate, and the organic layer was dried over
anhydrous magnesium sulfate. The solvent was distilled
off under reduced pressure to obtain 4.4 g of N-{2-
fluoro-4-methyl-5-(2,2,2-
trifluoroethylthio)phenyl}trifluoroacetohydrazonoyl
bromide.

(7) [5-(5-amino-3-trifluoromethyl-1,2,4-triazolyl)-4-
fluoro-2-methylphenyl]2,2,2-trifluoroethyl sulfide
To 100 ml of tetrahydrofuran, 4.5 g of S-
methylisothiourea hydroiodide, 4.4 g of N-{2-fluoro-4-
methyl-5-(2,2,2-trifluoroethyIthio)phenyl}
trifluoroacetohydrazonoyl bromide and 3.5 g of
triethylamine were added, followed by reflux with heating
for 8 hours. After the reaction mixture was cooled to
room temperature, it was concentrated under reduced
pressure and extracted with ethyl acetate, and the
organic layer was washed with water and dried over
anhydrous magnesium sulfate. The solvent was distilled
off under reduced pressure, and the obtained solid was
purified by column chromatography (eluent ethyl
acetate:hexane=4:1) to obtain 2.9 g of [5-(5-amino-3-
trifluoromethyl-1,2,4-triazolyl)-4-fluoro-2-
methylphenyl]2,2,2-trifluoroethyl sulfide as pale yellow
crystals (melting point 171 to 173°C).
EXAMPLE 5
Preparation of [5-(5-amino-3-trifluoromethyl-1,2,4-
triazolyl)-4-fluoro-2-methylphenyl]2,2,2-trifluoroethyl
sulfoxide (Compound No. 2 of the present invention)
1.9 g of [5-(5-amino-3-trifluoromethyl-1,2,4-
triazolyl)-4-fluoro-2-methylphenyl]2,2,2-trifluoroethyl
sulfide was dissolved in 100 ml of chloroform, and 1.0 g
of m-chloroperbenzoic acid was added at 0°C, followed by
stirring at room temperature for 1 hour. The solvent was

distilled off under reduced pressure, and the obtained
residue was purified by column chromatography (eluent
ethyl acetate:hexane:triethylamine=50:50:1) to obtain 1.8
g of [5-(5-amino-3-trifluoromethyl-1,2,4-triazolyl)-4-
fluoro-2-methylphenyl]2,2,2-trifluoroethyl sulfoxide as
pale yellow crystals (melting point 236 to 238°C) .
EXAMPLE 6
Preparation of [5-(5-trifluoroacetylamino-3-
trifluoromethyl-1,2,4-triazolyl)-4-fluoro-2-
methylphenyl]2,2,2-trifluoroethyl sulfide (Compound No. 5
of the present invention)
1.1 g of [5-(5-amino-3-trifluoromethyl-1,2,4-
triazolyl)-4-fluoro-2-methylphenyl]2,2,2-trifluoroethyl
sulfide was added to 50 ml of trifluoroacetic anhydride,
followed by stirring at room temperature for 12 hours.
The solvent was distilled off under reduced pressure, and
the obtained solid was purified by column chromatography
(eluent ethyl acetate:hexane=2:1) to obtain 1.1 g of [5-
(5-trifluoroacetylamino-3-trifluoromethyl-1,2,4-
triazolyl)-4-fluoro-2-methylphenyl]2,2,2-trifluoroethyl
sulfide as pale yellow crystals (melting point 122 to
125°C).
EXAMPLE 7
Preparation of [5-(5-amino-3-trifluoromethyl-1,2,4-
triazolyl)-4-fluoro-2-methylphenyl]2,2,2-trifluoroethyl
sulfoxide (Compound No. 6 of the present invention)
0.8 g of [5-(5-trifluoroacetylamino-3-

trifluoromethyl-1,2,4-triazolyl)-4-fluoro-2-
methylphenyl]2,2,2-trifluoroethyl sulfide was dissolved
in 50 ml of chloroform, and 0.3 g of m-chloroperbenzoic
acid was added at 0°C, followed by stirring at room
temperature for 1 hour. The solvent was distilled off
under reduced pressure, and the obtained solid was
purified by column chromatography (eluent ethyl
acetate:hexane=l:1) to obtain 0.6 g of [5-(5-
trifluoroacetylamino-3-trifluoromethyl-1,2,4-triazolyl)-
4-fluoro-2-methylphenyl]2,2,2-trifluoroethyl sulfoxide as
a pale yellow powder (melting point 233 to 237°C).
The structural formulae and physical properties of
the compounds [I] of the present invention synthesized in
accordance with the above Examples, including the above
Examples, are shown in Tables 7 to 10. The symbols in
the Tables denote as defined above.
The compound numbers will be referred to in the
subsequent description.








1H-NMR data (CDCl3/TMS 6(ppm) value) of the Compounds
Nos. 49, 59, 101, 128, 158, 184, 185, 193, 195 and 209
will be shown below.
Compound No. 49: 2.56(3H,s), 3.40(2H,q), 5.29(2H,s),
7.21(lH,d), 7,67(lH,d)
Compound No. 59: 1.22-1.28(3H,m), 2.55(3H,s), 3.40(2H,q),
3.46-3.55(2H,m), 4.12(1H,t), 7.20(lH,d), 7.63(lH,d)
Compound No. 101: 2.54(3H,s), 3.07(3H,d), 3.3.9(2H,q),
4.25(lH,s), 7.17(lH,d), 7.61(lH,d)
Compound No. 128: 1.32(6H,t), 2.50(3H,s), 3.25(4H,q),
3.44(2H,q), 7.19(lH,s), 7.75(lH,s)
Compound No. 158: 1.98(3H,s), 2.56(3H,s), 3.05(3H,s),
3.36(2H,q), 3.85(2H,q), 7.16(lH,d), 7.61(lH,d)

Compound No. 184: 2.29(lH,d), 2.53(3H,s), 3.39(2H,q),
3.82(2H,q), 4.20(2H,dd), 4.34(lH,s), 7.16(lH,d),
7.61 (lH,d)
Compound No. 185: 2,29(lH,t), 2.47(3H,s), 3.42-3.57(2H,m),
3.83(2H,q), 4.22(2H,d), 4.40(lH,s), 7.22(lH,s),
8.12(lH,s)
Compound No. 193: 2.30(lH,t), 2.55(3H,s), 3.40(2H,q),
4.24(2H,q),4.40(1H,S), 7.20(lH,d), 7.63(lH,d)
Compound No. 195: 1.22-1.39(lH,m), 1.48-1.57(1H,m), 2.06-
2.14(lH,m), 2.52(3H,s), 3.07(lH,dd), 3.29(lH,dd),
3.42,(2H,t), 4.75(2H,s), 7.16(lH,d), 7.65(lH,d)
Compound No. 209: 2.61(3H,s), 3.42(2H,q), 7.31(lH,d),
7.74(lH,d)
Now, an Example of Preparation of Intermediate will
be shown below.

(1) Synthesis of 5-acetylthio-2,4-dimethylacetanilide
78 g of 2-fluoro-4-methylacetanilide was added to
168 g of chlorosulfonic acid at 40°C or lower, followed
by stirring at 70°C for 2 hours. The reaction mixture
was poured into ice water/ethyl acetate, the organic
layer was washed with water and dried over anhydrous
magnesium sulfate, and the solvent was distilled off
under reduced pressure to obtain solid residue. The
obtained solid residue was dissolved in 200 ml of acetic
acid, and the resulting solution was added dropwise to a
mixed solution of 72 g of red phosphorus, 1 g of iodine

and 300 ml of acetic acid under reflux with heating over
a period of 1 hour, followed by reflux with heating
further for 4 hours. The insolubles were filtered off,
acetic acid was distilled off under reduced pressure,
water was added, and the residue was extracted with ethyl
acetate. The organic layer was washed with water and
dried over anhydrous magnesium sulfate. The solvent was
distilled off under reduced pressure to obtain 42 g of 5-
acetylthio-2,4-dimethylacetanilide.
(2) Synthesis of 2-fluoro-4-methyl-5-mercaptoaniline
42 g of 5-acetylthio-2-fluoro-4-methylacetanilide
was added to a 5% aqueous potassium hydroxide solution,
followed by reflux with heating for 18 hours. After the
reaction mixture was cooled to room temperature, it was
adjusted to have a pH 7 with diluted hydrochloric acid
and extracted with ethyl acetate. The organic layer was
dried over anhydrous magnesium sulfate, and the solvent
was distilled off under reduced pressure to obtain 25 g
of 2,4-dimethyl-5-merpcatoaniline.
(3) Synthesis of 2,4-dimethyl-5-(2,2,2-
trifluoroethylthio)aniline
To a mixed solution of 20 g of 2,4-dimethyl-5-
mercaptoaniline and 150 ml of N,N-dimethylformamide, 41 g
of 2,2,2-trifluoroethyl iodide and 24 g of potassium
carbonate were added, and 4 g of Rongalit was further
added, followed by stirring at room temperature for 24
hours. The reaction mixture was poured into water and

extracted with ethyl acetate. The organic layer was
dried over anhydrous magnesium sulfate, and the solvent
was distilled off under reduced pressure, and the
obtained residue was purified by silica gel column
chromatography (eluent hexane:ethyl acetate=5:l) to
obtain 29 g of 2,4-dimethyl-5-(2,2,2-
trifluoroethylthio)aniline.
1H-NMR data (CDCl3/TMS 5(ppm) value): 2.13(3H,s),
3.34(3H,s), 3.32(2H,q), 3.52(2H,s), 6.84(lH,s),
6.91(lH,s)
Now, formulation methods will be described in detail
with reference to typical Formulation Examples. However,
it should be understood that the types and the
proportions of the compounds and the adjuvants are not
restricted by these specific Examples and may be varied
within wide ranges. In the following description,
"part(s)" means "part(s) by weight".
FORMULATION EXAMPLE 1: Emulsifiable concentrate
Compound No. 6 (30 parts), cyclohaxanone (20 parts),
polyoxyethylene alkyl aryl ether (11 parts), calcium
alkylbenzenesulfonate (4 parts) and methylnaphthalene (35
parts) were uniformly dissolved to obtain an emulsifiable
concentrate.
FORMULATION EXAMPLE 2: Wettable powder
Compound No. 2 (10 parts), sodium salt of a
naphthalenesulfonic acid/formalin condensate (0.5 part),
polyoxyethylene alkyl aryl ether (0.5 part), diatomaceous

earth (24 parts) and clay (65 parts) were uniformly mixed
and pulverized to obtain a wettable powder.
FORMULATION EXAMPLE 3: Dust
Compound No. 6 (2 parts), diatomaceous earth (5
parts) and clay (93 parts) were uniformly mixed and
pulverized to obtain a dust.
FORMULATION EXAMPLE 4: Granule
Compound No. 2 (5 parts), sodium lauryl alcohol
sulfate (2 parts), sodium lignin sulfonate (5 parts),
carboxymethylcellulose (2 parts) and clay (86 parts) were
uniformly mixed and pulverized. Water (20 parts) was
added to this mixture (100 parts) and they were kneaded,
formed into granules of from 14 to 3 2 mesh by an
extrusion-type granulator and dried to obtain a granule
formulation.
Now, the effects of the pesticides containing the
compounds of the present invention as active ingredients
will be described with reference to Test Examples.
Comparative Compounds a and b are Compounds [VI-208] and
[VI-226] disclosed in JP-A-2000-198768:


TEST EXAMPLE 1 Miticidal test on two-spotted spider
mites (by dipping)
Wettable powders were prepared in accordance with
Formulation Example 2 and diluted with water to an active
ingredient concentration of 500 ppm. Soybean seedlings
which had been inoculated with imago two-spotted spider
mites were dipped in the resulting solutions and dried in
air. The treated seedlings were placed in a thermostatic
chamber at 25°C for 13 days, and the mite survivors were
counted for calculation of the miticidal value by using
Equation 2. The test was carried out by one series
system. The results of this test are shown in Tables 11
and 12.




TEST EXAMPLE 2 Miticidal test on two-spotted spider
mites (by soil drenching)
Wettable powders were prepared in accordance with
Formulation Example 2 and diluted with water to an active
ingredient concentration of 100 ppm. 100 g of the soil
in cups with soybean seedlings which had been inoculated

with imago two-spotted spider mites were drenched with 5
ml of the resulting solutions. The treated seedlings
were placed in a thermoplastic chamber at 25°C for 13
days, and the mite survivors were counted for calculation
of the miticidal value by using Equation 2. The results
of this test are shown in Tables 13 and 14.




TEST EXAMPLE 3 Insecticidal test on brown planthoppers
Wettable powders were prepared in accordance with
Formulation Example 2 and diluted with water to an active
ingredient concentration of 500 ppm. Germinating rice
was immersed in the resulting solutions and put in a
plastic cup with a capacity of 60 ml. Ten 4th-instar
larvae of brown planthoppers were released to the cup,
and the cup was covered and placed in a thermostatic
chamber at 25°C for 6 days, and the survivors were

counted for calculation of the insecticidal degree by-
using Equation 1. The test was carried out by one series
system. The results of this test are shown in Tables 15
and 16.





TEST EXAMPLE
Nemastatic test on southern root-knot nematodes
Compounds of the present invention (5 parts) and
Tween 2 0 (tradename for polyoxyethylene sorbitan
monolaurate) (1 part) as a spreader were dissolved n N,N-
dimethylformamide (94 parts) to prepare 5% emulsifiable
concentrates of the compounds of the present invention.
Distilled water was added to the emulsifiable
concentrates to prepare diluted solutions having a
concentration of the compounds of the present invention
of 20 ppm. 0.5 ml of the diluted solutions and 0.5 ml of
water suspensions containing 100 second stage larvae of
southern root-knot nematodes were mixed, and the mixture
were placed in a thermostatic chamber at 2 5°C for 5 days,
and the survivors were counted for calculation of the
nemastatic degree by using Equation 3. The test was
carried out by two series system. The results of this
test are shown in Tables 17 and 18.




Equation 1
Insecticidal degree (%) =
10-number of survivors in the treated area
x 100


INDUSTRIAL APPLICABILITY
3-Triazolylphenyl sulfide derivatives of the present
invention exhibit outstanding effects on various farm and
garden pests, especially on mites, pest lepidoptera, pest
hemiptera, pest coleoptera and nematodes, and they can be
widely used as insecticides, miticides and nematicides
having soil treatment activity with which safe and labor-
saving application becomes possible.
The entire disclosure of Japanese Patent Application
No. 2004-305251 filed on October 20, 2004 including
specification, claims and summary are incorporated herein
by reference in its entirety.

WE CLAIM :
1. A 3-Triazolylphenyl sulfide derivative represented by
the formula [I] :

wherein either
R is a trifluoroethyl group;
n is an integer of 1;
A1 is a trifluoromethyl group;
A3 is a methylamino group;
B2 is a halogen atom; and
B4 is a methyl group;
or
R is a trifluoroethyl group;
n is an integer of 1;
A1 is a trifluoromethyl group or a trifluoromethylthio
group;
A3 is an amino group;
B2 is a halogen atom; and
B4 is a methyl group.
2. A 3-Triazolylphenyl sulfide derivative as claimed in
Claim 1 represented by the formula [I] :


wherein
R is a trifluoroethyl group;
n is an integer of 1;
A1 is a trifluoromethyl group;
A3 is a methylamino group;
B2 is a halogen atom; and
B4 is a methyl group.
3. A 3-Triazolylphenyl sulfide derivative as claimed in
Claim 1 represented by the formula [I] :

wherein
R is a trifluoroethyl group;
n is an integer of 1 ;
A1 is a trifluoromethyl group or a trifluoromethylthio
group;

A3 is an amino group;
B2 is a halogen atom; and
B4 is a methyl group.
4. An insecticide, miticide or nematicide formulation
having soil treatment miticidal activity, for agriculture
and horticulture, comprising the 3-triazolylphenyl sulfide
derivative as claimed in Claim 2 as an active ingredient
and an adjuvant.
5. An insecticide, miticide or nematicide formulation
having soil treatment miticidal activity, for agriculture
and horticulture, comprising the 3-triazolylphenyl sulfide
derivative as claimed in Claim 3 as an active ingredient
and an adjuvant .
6. An insecticide, miticide or nematicide formulation
having soil treatment miticidal activity, for agriculture
and horticulture, comprising the 3-triazolylphenyl sulfide
derivative as claimed in Claim 1 as an active ingredient
and a diluent .
7. A miticidal formulation having soil treatment
miticidal activity, comprising the 3-triazolylphenyl
sulfide derivative as claimed in Claim 2 as an active
ingredient and water, wherein the active ingredient is
diluted with water to a concentration of
from 0.1 to 5000 ppm.

8. A miticidal formulation having soil treatment
miticidal activity, comprising the 3-triazolylphenyl
sulfide derivative as claimed in Claim 2 as an active
ingredient and water, wherein the active ingredient is
diluted with water to a concentration of from 0.1 to 500
ppm.
9. A miticidal formulation having soil treatment
miticidal activity, comprising the 3-triazolylphenyl
sulfide derivative as claimed in Claim 2 as an active
ingredient and water, wherein the active ingredient is
diluted with water to a concentration of from 0.1 to 100
ppm.
10. A miticidal formulation having soil treatment
miticidal activity, comprising the 3-triazolylphenyl
sulfide derivative as claimed in Claim 3 as an active
ingredient and water, wherein the active ingredient is
diluted with water to a concentration of from 0.1 to 5000
ppm.
11. A miticidal formulation having soil treatment
miticidal activity, comprising the 3-triazolylphenyl
sulfide derivative as claimed in Claim 3 as an active
ingredient and water, wherein the active ingredient is
diluted with water to a concentration of from 0.1 to 500
ppm.

12. A miticidal formulation having soil treatment
miticidal activity, comprising the 3-triazolylphenyl
sulfide derivative as claimed in Claim 3 as an active
ingredient and water, wherein the active ingredient is
diluted with water to a concentration of from 0.1 to 100
ppm.


ABSTRACT

To provide novel 3-triazolylphenyl sulfide
derivatives having excellent soil treatment activity as
insecticides, miticides or nematicides for agricultural
and horticultural plants.
3-Triazolylphenyl sulfide derivatives represented by
the formula [1]:

wherein R is a cyclopropylmethyl group or a
trifluoroethyl group, B2 is a hydrogen atom, a halogen
atom or a methyl group, B4 is a halogen atom, a cyano
group, a nitro group or a C1-C6 alkyl group, and each of
A1 and A3 is a hydrogen atom, a halogen atom, a C1-C6
alkyl group which may be substituted or an amino group
which may be substituted.

Documents:

01274-kolnp-2007-abstract.pdf

01274-kolnp-2007-assignment.pdf

01274-kolnp-2007-claims.pdf

01274-kolnp-2007-correspondence others 1.1.pdf

01274-kolnp-2007-correspondence others 1.2.pdf

01274-kolnp-2007-correspondence others 1.3.pdf

01274-kolnp-2007-correspondence others.pdf

01274-kolnp-2007-description complete.pdf

01274-kolnp-2007-form 1.pdf

01274-kolnp-2007-form 3 1.1.pdf

01274-kolnp-2007-form 3 1.2.pdf

01274-kolnp-2007-form 3.pdf

01274-kolnp-2007-form 5.pdf

01274-kolnp-2007-gpa 1.1.pdf

01274-kolnp-2007-gpa.pdf

01274-kolnp-2007-international publication.pdf

01274-kolnp-2007-international search report.pdf

01274-kolnp-2007-pct request.pdf

01274-kolnp-2007-priority document.pdf

1274-KOLNP-2007-ABSTRACT-1.1.pdf

1274-KOLNP-2007-ABSTRACT.pdf

1274-KOLNP-2007-AMANDED CLAIMS-1.1.pdf

1274-KOLNP-2007-AMANDED CLAIMS.pdf

1274-KOLNP-2007-ASSIGNMENT.pdf

1274-KOLNP-2007-CORRESPONDENCE-1.3.pdf

1274-kolnp-2007-correspondence-1.4.pdf

1274-KOLNP-2007-DESCRIPTION (COMPLETE)-1.1.pdf

1274-KOLNP-2007-DESCRIPTION (COMPLETE).pdf

1274-KOLNP-2007-EXAMINATION REPORT REPLY RECIEVED.pdf

1274-kolnp-2007-examination report.pdf

1274-KOLNP-2007-FORM 1-1.1.pdf

1274-KOLNP-2007-FORM 1.pdf

1274-KOLNP-2007-FORM 13.pdf

1274-kolnp-2007-form 18.pdf

1274-KOLNP-2007-FORM 2-1.1.pdf

1274-KOLNP-2007-FORM 2.pdf

1274-KOLNP-2007-FORM 3-1.2.pdf

1274-KOLNP-2007-FORM 3-1.3.pdf

1274-kolnp-2007-form 3-1.4.pdf

1274-kolnp-2007-form 5.pdf

1274-kolnp-2007-gpa.pdf

1274-kolnp-2007-granted-abstract.pdf

1274-kolnp-2007-granted-claims.pdf

1274-kolnp-2007-granted-description (complete).pdf

1274-kolnp-2007-granted-form 1.pdf

1274-kolnp-2007-granted-form 2.pdf

1274-kolnp-2007-granted-specification.pdf

1274-KOLNP-2007-OTHERS 1.2.pdf

1274-KOLNP-2007-OTHERS-1.1.pdf

1274-KOLNP-2007-OTHERS.pdf

1274-KOLNP-2007-PETITION UNDER RULE 137.pdf

1274-KOLNP-2007-PETITION UNDER RULR 137-1.1.pdf

1274-kolnp-2007-reply to examination report-1.1.pdf

1274-kolnp-2007-translated copy of priority document.pdf

abstract-01274-kolnp-2007.jpg


Patent Number 254076
Indian Patent Application Number 1274/KOLNP/2007
PG Journal Number 38/2012
Publication Date 21-Sep-2012
Grant Date 18-Sep-2012
Date of Filing 11-Apr-2007
Name of Patentee KUMIAI CHEMICAL INDUSTRY CO., LTD.
Applicant Address 4-26, IKENOHATA 1-CHOME, TAITOH-KU, TOKYO
Inventors:
# Inventor's Name Inventor's Address
1 KINPARA, SHIORI C/O KUMIAI CHEMICAL INDUSTRY CO., LTD. 4-26, IKENOHATA 1-CHOME, TAITOH-KU, TOKYO 1108782
2 YANO, HIROYUKI C/O KUMIAI CHEMICAL INDUSTRY CO., LTD. 4-26, IKENOHATA 1-CHOME, TAITOH-KU, TOKYO 1108782
3 YONEKURA, NORIHISA C/O KUMIAI CHEMICAL INDUSTRY CO., LTD. 4-26, IKENOHATA 1-CHOME, TAITOH-KU, TOKYO 1108782
4 ITOU, YOSHIHIRO C/O KUMIAI CHEMICAL INDUSTRY CO., LTD. 4-26, IKENOHATA 1 -CHOME, TAITOH-KU, TOKYO 1108782
5 TAKAHASHI, SATORU C/O KUMIAI CHEMICAL INDUSTRY CO., LTD. 4-26, IKENOHATA 1-CHOME, TAITOH-KU, TOKYO 1108782
6 HAMAGUCHI, RYUJI C/O KUMIAI CHEMICAL INDUSTRY CO., LTD. 4-26, IKENOHATA 1-CHOME, TAITOH-KU, TOKYO 1108782
7 TORIYABE, KEIJI C/O K-I CHEMICAL RESEARCH INSTITUTE CO., LTD. 4 08-1, SHIOSHINDEN, IWATA-SHI, SHIZUOKA 4371213
8 YAMAGUCHI, MIKIO C/O K-I CHEMICAL RESEARCH INSTITUTE CO., LTD. 4 08-1, SHIOSHINDEN, IWATA-SHI, SHIZUOKA 4371213
PCT International Classification Number C07D 249/14
PCT International Application Number PCT/JP2005/019315
PCT International Filing date 2005-10-20
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2004-305251 2004-10-20 Japan