U.S. patent application number 15/122660 was filed with the patent office on 2017-05-18 for fused heterocyclic compound and pest control application thereof.
The applicant listed for this patent is Sumitomo Chemical Company, Limited. Invention is credited to Hajime MIZUNO, Hiroshi OKAMOTO, Takamasa TANABE.
Application Number | 20170135348 15/122660 |
Document ID | / |
Family ID | 54055403 |
Filed Date | 2017-05-18 |
United States Patent
Application |
20170135348 |
Kind Code |
A1 |
TANABE; Takamasa ; et
al. |
May 18, 2017 |
FUSED HETEROCYCLIC COMPOUND AND PEST CONTROL APPLICATION
THEREOF
Abstract
Provided are: a fused heterocyclic compound by formula (1) or an
N-oxide thereof, having excellent control effects against pests: a
pest control composition containing the abovementioned compound and
an inert carrier; and a pest control method for applying an
effective dose of the abovementioned compound to a pest or pest
habitat. ##STR00001##
Inventors: |
TANABE; Takamasa;
(Takarazuka-shi, Hyogo, JP) ; MIZUNO; Hajime;
(Takarazuka-shi, Hyogo, JP) ; OKAMOTO; Hiroshi;
(Takarazuka-shi, Hyogo, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Sumitomo Chemical Company, Limited |
Tokyo |
|
JP |
|
|
Family ID: |
54055403 |
Appl. No.: |
15/122660 |
Filed: |
March 6, 2015 |
PCT Filed: |
March 6, 2015 |
PCT NO: |
PCT/JP2015/056647 |
371 Date: |
August 31, 2016 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A01N 43/90 20130101;
A61P 33/00 20180101; A61P 33/14 20180101; C07D 471/04 20130101 |
International
Class: |
A01N 43/90 20060101
A01N043/90; C07D 471/04 20060101 C07D471/04 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 7, 2014 |
JP |
2014-044688 |
Claims
1. A fused heterocyclic compound represented by formula (1):
##STR00054## wherein R.sup.1 represents a hydrogen atom, a C1-C3
alkyl group which may be optionally substituted with one or more
halogen atom(s), a halogen atom, a C1-C3 alkoxy group, a C2-C4
alkoxycarbonyl group, a S(O).sub.mR.sup.2, a NR.sup.3R.sup.4, a
nitro group or a cyano group; R.sup.2 represents a C1-C3 alkyl
group; R.sup.3 and R.sup.4 are the same or different from each
other, and each represents a hydrogen atom or a C1-C3 alkyl group;
n is 0, 1 or 2; and m is 0, 1 or 2 or N-oxide thereof.
2. The compound according to claim 1 wherein R.sup.1 represents a
hydrogen atom, a C1-C3 alkyl group which may be optionally
substituted with one or more halogen atom(s), a halogen atom, a
C1-C3 alkoxy group, or a S(O).sub.mR.sup.2.
3. The compound according to claim 1 wherein R.sup.1 represents a
hydrogen atom, a halogen atom, a C1-C3 perfluoroalkyl group, a
C1-C3 alkoxy group, or a S(O).sub.mR.sup.2.
4. The compound according to claim 1 wherein R.sup.1 represents a
hydrogen atom, a chlorine atom, a bromine atom, a methyl group, a
trifluoromethyl group, a methoxy group, a methylsulfanyl group, a
methylsulfinyl group or a methylsulfonyl group.
5. The compound according to claim 1 wherein R.sup.1 represents a
hydrogen atom, a chlorine atom, a bromine atom, a trifluoromethyl
group, a methoxy group, a methylsulfanyl group or a methylsulfonyl
group.
6. The compound according to claim 1 wherein R.sup.1 represents a
hydrogen atom.
7. The compound according to claim 1, wherein n is 2.
8. A composition for controlling a pest comprising the compound
according to claim 1 and an inert carrier.
9. A method for controlling a pest, which comprises a step of
applying an effective amount of the compound according to claim 1
to a pest or a habitat where the pest lives.
10. A method for producing a fused heterocyclic compound
represented by formula (1), comprising a step of reacting a
compound represented by formula (M1) with a compound represented by
formula (M2): ##STR00055## wherein R.sup.1 represents a hydrogen
atom, a C1-C3 alkyl group which may be optionally substituted with
one or more halogen atom(s), a halogen atom, a C1-C3 alkoxy group,
a C2-C4 alkoxycarbonyl group, a S(O).sub.mR.sup.2, a
NR.sup.3R.sup.4, a nitro group or a cyano group; R.sup.2 represents
a C1-C3 alkyl group; R.sup.3 and R.sup.4 are the same or different
from each other, and each represents a hydrogen atom or a C1-C3
alkyl group; n is 0, 1 or 2; m is 0, 1 or 2; and X is a halogen
atom.
11. The method according to claim 10 wherein the step of reacting
the compound represented by formula (M1) with the compound
represented by formula (M2) is carried out in presence of base.
12. The method according to claim 11 wherein the base is alkali
metal hydride, alkaline-earth metal hydride, or alkali metal
carbonate.
Description
TECHNICAL FIELD
[0001] This application claims priority to and the benefit of
Japanese Patent Application No. 2014-044688, filed Mar. 7, 2014,
the entire contents of which is incorporated herein by
reference.
[0002] The present inventions relates to a certain kind of fused
heterocyclic compound and a pest control application thereof.
BACKGROUND ART
[0003] Hitherto, many compounds have been studied to control pests
and have been applied to a practical use.
[0004] Also, a certain kind of fused heterocyclic compound has been
known (see e.g., Patent Literature 1).
RELATED ART DOCUMENTS
Patent Documents
[0005] [Patent Literature-1]: WO 2013/018928 pamphlet
SUMMARY OF INVENTION
Problems to be Solved by Invention
[0006] An object of the present invention is to provide a compound
having an excellent efficacy on controlling pests and a method for
controlling pests using the same.
Means to Solve Problems
[0007] The present inventors have intensively studied to solve the
above-mentioned problem and found out that a fused heterocyclic
compound represented by the below-mentioned formula (1) has an
excellent efficacy on controlling pests.
[0008] The present invention provides: [0009] [1] A fused
heterocyclic compound represented by formula (1):
##STR00002##
[0009] wherein [0010] R.sup.1 represents a hydrogen atom, a C1-C3
alkyl group which may be optionally substituted with one or more
halogen atom(s), a halogen atom, a C1-C3 alkoxy group, a C2-C4
alkoxycarbonyl group, a S(O).sub.mR.sup.2, a NR.sup.3R.sup.4, a
nitro group or a cyano group; [0011] R.sup.2 represents a C1-C3
alkyl group; [0012] R.sup.3 and R.sup.4 are the same or different
from each other, and each represents a hydrogen atom or a C1-C3
alkyl group; [0013] n is 0, 1 or 2; and [0014] m is 0, 1 or 2 or
N-oxide thereof (hereinafter, the fused heterocyclic compound
represented by formula (1) or N-oxide thereof is referred to as
"Present compound"). [0015] [2] The compound according to [1]
wherein R.sup.1 represents a hydrogen atom, a C1-C3 alkyl group
which may be optionally substituted with one or more halogen
atom(s), a halogen atom, a C1-C3 alkoxy group, or a
S(O).sub.mR.sup.2. [0016] [3] The compound according to [1] wherein
R.sup.1 represents a hydrogen atom, a halogen atom, a C1-C3
perfluoroalkyl group, a C1-C3 alkoxy group, or a S(O).sub.mR.sup.2.
[0017] (4) The compound according to [1] wherein R.sup.1 represents
a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, a
trifluoromethyl group, a methoxy group, a methylsulfanyl group, a
methylsulfinyl group or a methylsulfonyl group. [0018] [5] The
compound according to [1] wherein R.sup.1 represents a hydrogen
atom, a chlorine atom, a bromine atom, a trifluoromethyl group, a
methoxy group, a methylsulfanyl group or a methylsulfonyl group.
[0019] [6] The compound according to [1] wherein R.sup.1 represents
a hydrogen atom. [0020] [7] The compound according to any one of
[1] to [6] wherein n is 2. [0021] [8] A composition for controlling
a pest comprising the compound according to any one of [1] to [7]
and an inert carrier. [0022] [9] A method for controlling a pest,
which comprises a step of applying an effective amount of the
compound according to any one of [1] to [7] to a pest or a habitat
where the pest lives. [0023] [10] A method for producing a fused
heterocyclic compound represented by formula (1), comprising a step
of reacting a compound represented by formula (M1) with a compound
represented by formula (M2): wherein
##STR00003##
[0024] R.sup.1 represents a hydrogen atom, a C1-C3 alkyl group
which may be optionally substituted with one or more halogen
atom(s), a halogen atom, a C1-C3 alkoxy group, a C2-C4
alkoxycarbonyl group, a S(O).sub.mR.sup.2, a NR.sup.3R.sup.4, a
nitro group or a cyano group; [0025] R.sup.2 represents a C1-C3
alkyl group; [0026] R.sup.3 and R.sup.4 are the same or different
from each other, and each represents a hydrogen atom or a C1-C3
alkyl group; [0027] n is 0, 1 or 2; [0028] m is 0, 1 or 2; and
[0029] X is a halogen atom. [0030] [11] The method according to
[10] wherein the step of reacting the compound represented by
formula (M1) with the compound represented by formula (M2) is
carried out in presence of base. [0031] [12] The method according
to claim [11] wherein the base is alkali metal hydride,
alkaline-earth metal hydride, or alkali metal carbonate.
MODE FOR CARRYING OUT THE INVENTION
[0032] In the present compound, the N-oxide includes a compound
represented by formula (1-1).
##STR00004##
wherein each symbol is the same as defined in formula (1).
[0033] In the present compound, the term "halogen atom" represents
a fluorine atom, a chlorine atom, a bromine atom and an iodine
atom.
[0034] In the present compound, the term of "C1-C3 alkyl group"
includes, for example, a methyl group, an ethyl group, a propyl
group, and an isopropyl group.
[0035] In the present compound, the term of "C1-C3 alkyl group
which may be optionally substituted with one or more halogen
atom(s)" represents a C1-C3 alkyl group wherein at least one
hydrogen atom may be optionally substituted with a halogen atom,
each the halogen atom may be the same or different from each other,
and includes, for example, a fluoromethyl group, a chloromethyl
group, a bromomethyl group, a iodomethyl group, a difluoromethyl
group, a dichloromethyl group, a trifluoromethyl group, a
chlorodifluoromethyl group, a bromodifluoromethyl group, a
trichloromethyl group, a 2-fluoroethyl group, a 2-chloroethyl
group, a 2-bromoethyl group, a 2,2-difluoroethyl group, a
2,2,2-trifluoroethyl group, a pentafluoroethyl group, a
heptafluoropropyl group, and a heptafluoroisopropyl group.
[0036] The above-mentioned "C1-C3 alkyl group which may be
optionally substituted with one or more halogen atom(s)" is also
expressed by the term of "C1-C3 haloalkyl group", and in the
present compound, the term of "C1-C3 haloalkyl group" represents a
C1-C3 alkyl group wherein at least one hydrogen atom is substituted
with a halogen atom, and when two or more hydrogen atoms are
substituted with halogen atoms, each the halogen atom may be the
same or different from each other.
[0037] The term "C1-C3 haloalkyl group" includes, for example, a
fluoromethyl group, a chloromethyl group, bromomethyl group, a
iodomethyl group, a difluoromethyl group, a dichloromethyl group, a
trifluoromethyl group, a chlorodifluoromethyl group, a
bromodifluoromethyl group, a trichloromethyl group, a 2-fluoroethyl
group, a 2-chloroethyl group, a 2-bromoethyl group, a
2,2-difluoroethyl group, a 2,2,2-trifluoroethyl group, a
pentafluoroethyl group, a heptafluoropropyl group and a
heptafluoroisopropyl group.
[0038] The term of "C1-C3 perfluoroalkyl group" represents a C1-C3
alkyl group wherein all hydrogen atoms are substituted with a
fluorine atom and specifically includes, for example, a
trifluoromethyl group, a pentafluoroethyl group, a
heptafluoropropyl group, and a heptafluoroisopropyl group.
[0039] In the present compound, the term of "C1-C3 alkoxy group"
includes, for example, a methoxy group, an ethoxy group, a
propyloxy group, and an isopropoxy group.
[0040] In the present compound, the term of "amino group" defined
by NR.sup.3R.sup.4 represents a group wherein R and R.sup.4 both
represent a hydrogen atom.
[0041] In the present compound, the term of "C1-C3 alkylamino
group" defined by NR.sup.3R.sup.4 includes, for example, a
methylamino group, an ethylamino group, a propylamino group, and an
isopropylamino group.
[0042] In the present compound, the term of "di(C1-C3 alkyl)amino
group" defined by NR.sup.3R.sup.4 includes, for example, a
N,N-dimethylamino group, a N,N-diethylamino group, a
N,N-dipropylamino group, a N,N-diisopropylamino group, a
N-methyl-N-ethylamino group, a N-methyl-N-propylamino group, a
N-methyl-N-isopropylamino group, a N-ethyl-N-propylamino group, and
a N-ethyl-N-isopropylamino group.
[0043] In the present compound, the term of "C2-C4 alkoxycarbonyl
group" represents a group wherein the C1-C3 alkoxy group is
attached to a carbonyl group, and includes, for example, a
methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl
group, and an isopropoxycarbonyl group.
[0044] In the present compound, the term of "S(O).sub.mR.sup.1"
represents a C1-C3 alkylsulfanyl group when m is 0, a C1-C3
alkylsulfinyl group when m is 1, and a C1-C3 alkylsulfonyl group
when m is 2.
[0045] The C1-C3 alkylsulfanyl group includes, for example, a
methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl
group, and an isopropylsulfanyl group.
[0046] The C1-C3 alkylsulfinyl group includes, for example, a
methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl
group, and an isopropylsulfinyl group.
[0047] The C1-C3 alkylsulfonyl group includes, for example, a
methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl
group, an isopropylsulfonyl group.
[0048] The present compound (1) encompasses a compound labeled with
isotope(s) (such as .sup.3H, .sup.13C, .sup.14C, .sup.15N,
.sup.18F, .sup.35S and .sup.125I) or the deuterium exchange
product.
[0049] Example of the embodiment of the present compound includes
the followings: [0050] a compound of formula (1) wherein n is 0
(n=0); [0051] a compound of formula (1) wherein n is 1 (n=1);
[0052] a compound of formula (1) wherein n is 2 (n=2); [0053] a
compound of formula (1) wherein R.sup.1 represents a hydrogen atom
or a halogen atom; [0054] a compound of formula (1) wherein R.sup.1
represents a hydrogen atom, a chlorine atom or a bromine atom;
[0055] a compound of formula (1) wherein R.sup.1 represents a
hydrogen atom; [0056] a compound of formula (1) wherein R.sup.1
represents a halogen atom; [0057] a compound of formula (1) wherein
R.sup.1 represents a chlorine atom or a bromine atom; [0058] a
compound of formula (1) wherein R.sup.1 represents a C1-C3 alkyl
group which may be optionally substituted with one or more halogen
atom(s); [0059] a compound of formula (1) wherein R.sup.1
represents a C1-C3 alkyl group substituted with one or more halogen
atom(s); [0060] a compound of formula (1) wherein R.sup.1
represents a C1-C3 alkyl group or a C1-C3 perfluoroalkyl group;
[0061] a compound of formula (1) wherein R.sup.1 represents a
methyl group or a trifluoromethyl group; [0062] a compound of
formula (1) wherein R.sup.1 represents a C1-C3 alkyl group; [0063]
a compound of formula (1) wherein R.sup.1 represents a methyl
group; [0064] a compound of formula (1) wherein R.sup.1 represents
a C1-C3 haloalkyl group; [0065] a compound of formula (1) wherein
R.sup.1 represents a C1-C3 perfluoroalkyl group; [0066] a compound
of formula (1) wherein R.sup.1 represents a trifluoromethyl group;
[0067] a compound of formula (1) wherein R.sup.1 represents an
alkoxy group; [0068] a compound of formula (1) wherein R.sup.1
represents a methoxy group; [0069] a compound of formula (1)
wherein R.sup.1 represents a S(O).sub.mR.sup.2; [0070] a compound
of formula (1) wherein R.sup.1 represents a methylsulfanyl group, a
methylsulfinyl group or a methylsulfonyl group; [0071] a compound
of formula (1) wherein R.sup.1 represents a C1-C3 alkylsulfanyl
group or a C1-C3 alkylsulfonyl group; [0072] a compound of formula
(1) wherein R.sup.1 represents a methylsulfanyl group or a
methylsulfonyl group; [0073] a compound of formula (1) wherein
R.sup.1 represents a C1-C3 alkylsulfanyl group; [0074] a compound
of formula (1) wherein R.sup.1 represents a methylsulfanyl group;
[0075] a compound of formula (1) wherein R.sup.1 represents a C1-C3
alkylsulfonyl group; [0076] a compound of formula (1) wherein
R.sup.1 represents a methylsulfonyl group; [0077] a compound of
formula (1) wherein R.sup.1 represents a NR.sup.3R.sup.4; [0078] a
compound of formula (1) wherein R.sup.1 represents an amino group,
a C1-C3 alkylamino group, a di(C1-C3)alkylamino group or a nitro
group; [0079] a compound of formula (1) wherein R.sup.1 represents
an amino group or a nitro group; [0080] a compound of formula (1)
wherein R.sup.1 represents an amino group, a C1-C3 alkylamino group
or di(C1-C3)alkylamino group; [0081] a compound of formula (1)
wherein R.sup.1 represents an amino group; [0082] a compound of
formula (1) wherein R.sup.1 represents a C2-C4 alkoxycarbonyl group
or a cyano group; [0083] a compound of formula (1) wherein R.sup.1
represents a C2-C4 alkoxycarbonyl group; [0084] a compound of
formula (1) wherein R.sup.1 represents a methoxycarbonyl group;
[0085] a compound of formula (1) wherein R.sup.1 represents a cyano
group; [0086] a compound of formula (1) wherein R.sup.1 represents
a hydrogen atom or a halogen atom, and n=2; [0087] a compound of
formula (1) wherein R.sup.1 represents a hydrogen atom, a chlorine
atom or a bromine atom, and n=2; [0088] a compound of formula (1)
wherein R.sup.1 represents a hydrogen atom, and n=2; [0089] a
compound of formula (1) wherein R.sup.1 represents a halogen atom,
and n=2; [0090] a compound of formula (1) wherein R.sup.1
represents a chlorine atom or a bromine atom, and n=2; [0091] a
compound of formula (1) wherein R.sup.1 represents a C1-C3 alkyl
group which may be optionally substituted with one or more halogen
atom(s), and n=2; [0092] a compound of formula (1) wherein R.sup.1
represents a C1-C3 alkyl group which is substituted with one or
more halogen atom(s), and n=2; [0093] a compound of formula (1)
wherein R.sup.1 represents a C1-C3 alkyl group or a C1-C3
perfluoroalkyl group, and n=2; [0094] a compound of formula (1)
wherein R.sup.1 represents a methyl group or a trifluoromethyl
group, and n=2; [0095] a compound of formula (1) wherein R.sup.1
represents a C1-C3 alkyl group, and n=2; [0096] a compound of
formula (1) wherein R.sup.1 represents a methyl group, and n=2;
[0097] a compound of formula (1) wherein R.sup.1 represents a C1-C3
haloalkyl group, and n=2; [0098] a compound of formula (1) wherein
R.sup.1 represents a C1-C3 perfluoroalkyl group, and n=2; [0099] a
compound of formula (1) wherein R.sup.1 represents a
trifluoromethyl group, and n=2; [0100] a compound of formula (1)
wherein R.sup.1 represents an alkoxy group, and n=2; [0101] a
compound of formula (1) wherein R.sup.1 represents a methoxy group,
and n=2; [0102] a compound of formula (1) wherein R.sup.1
represents a S(O).sub.mR.sup.2, and n=2; [0103] a compound of
formula (1) wherein R.sup.1 represents a methylsulfanyl group, a
methylsulfinyl group, or a methylsulfonyl group, and n=2; [0104] a
compound of formula (1) wherein R.sup.1 represents a C1-C3
alkylsulfanyl group or a C1-C3 alkylsulfonyl group, and n=2; [0105]
a compound of formula (1) wherein R.sup.1 represents a
methylsulfanyl group or a methylsulfonyl group, and n=2; [0106] a
compound of formula (1) wherein R.sup.1 represents a C1-C3
alkylsulfanyl group, and n=2; [0107] a compound of formula (1)
wherein R.sup.1 represents a methylsulfanyl group, and n=2; [0108]
a compound of formula (1) wherein R.sup.1 represents a C1-C3
alkylsulfonyl group, and n=2; [0109] a compound of formula (1)
wherein R.sup.1 represents a methylsulfonyl group, and n=2; [0110]
a compound of formula (1) wherein R.sup.1 represents a
NR.sup.3R.sup.4, and n=2; [0111] a compound of formula (1) wherein
R.sup.1 represents an amino group, a C1-C3 alkylamino group, a
di(C1-C3)alkylamino group or a nitro group, and n=2; [0112] a
compound of formula (1) wherein R.sup.1 represents an amino group
or a nitro group, and n=2; [0113] a compound of formula (1) wherein
R.sup.x represents an amino group, a C1-C3 alkylamino group or a
di(C1-C3)alkylamino group, and n=2; [0114] a compound of formula
(1) wherein R.sup.1 represents an amino group, and n=2; [0115] a
compound of formula (1) wherein R.sup.z represents a C2-C4
alkoxycarbonyl group or a cyano group, and n=2; a compound of
formula (1) wherein R.sup.1 represents a C2-C4 alkoxycarbonyl
group, and n=2; [0116] a compound of formula (1) wherein R.sup.1
represents a methoxycarbonyl group, and n=2; [0117] a compound of
formula (1) wherein R.sup.1 represents a cyano group, and n=2;
[0118] a compound of formula (1) wherein R.sup.1 represents a
hydrogen atom, a C1-C3 alkyl group which may be optionally
substituted with one or more halogen atom(s), a halogen atom, a
C1-C3 alkoxy group, a S(O).sub.mR.sup.2, a C2-C4 alkoxycarbonyl
group, an amino group, or a nitro group; [0119] a compound of
formula (1) wherein R.sup.3 represents a hydrogen atom, a halogen
atom, a C1-C3 alkyl group, a C1-C3 perfluoroalkyl group, a C1-C3
alkoxy group, a S(O).sub.mR.sup.2, a C2-C4 alkoxycarbonyl group, an
amino group, or a nitro group; [0120] a compound of formula (1)
wherein R.sup.1 represents a hydrogen atom, a chlorine atom, a
bromine atom, a methyl group, a trifluoromethyl group, a methoxy
group, a methylsulfanyl group, a methylsulfinyl group, a
methylsulfonyl group, a methoxycarbonyl group, an amino group or a
nitro group; [0121] a compound of formula (1) wherein R.sup.1
represents a hydrogen atom, a chlorine atom, a bromine atom, a
methyl group, a trifluoromethyl group, a methoxy group, a
methylsulfanyl group, a methylsulfonyl group, a methoxycarbonyl
group, an amino group or a nitro group; [0122] a compound of
formula (1) wherein R.sup.1 represents a hydrogen atom, a C1-C3
alkyl group which may be optionally substituted with one or more
halogen atom(s), a halogen atom, a C1-C3 alkoxy group, or a
S(O).sub.mR.sup.2; [0123] a compound of formula (1) wherein R.sup.1
represents a hydrogen atom, a halogen atom, a C1-C3 alkyl group, a
C1-C3 perfluoroalkyl group, a C1-C3 alkoxy group, or a
S(O).sub.mR.sup.2; [0124] a compound of formula (1) wherein R.sup.1
represents a hydrogen atom, a chlorine atom, a bromine atom, a
methyl group, a trifluoromethyl group, a methoxy group, a
methylsulfanyl group, a methylsulfinyl group, or a methylsulfonyl
group; [0125] a compound of formula (1) wherein R.sup.1 represents
a hydrogen atom, a chlorine atom, a bromine atom, a methyl group, a
trifluoromethyl group, a methoxy group, a methylsulfanyl group, or
a methylsulfonyl group; [0126] a compound of formula (1) wherein
R.sup.1 represents a hydrogen atom, a halogen atom, a C1-C3
haloalkyl group, a C1-C3 alkoxy group, or a S(O).sub.mR.sup.2;
[0127] a compound of formula (1) wherein R.sup.1 represents a
hydrogen atom, a halogen atom, a C1-C3 perfluoroalkyl group, a
C1-C3 alkoxy group or a S(O).sub.mR.sup.2; [0128] a compound of
formula (1) wherein R.sup.1 represents a hydrogen atom, a chlorine
atom, a bromine atom, a trifluoromethyl group, a methoxy group, a
methylsulfanyl group, a methylsulfinyl group, or methylsulfonyl
group; [0129] a compound of formula (1) wherein R.sup.1 represents
a hydrogen atom, a chlorine atom, a bromine atom, a trifluoromethyl
group, a methoxy group, a methylsulfanyl group or a methylsulfonyl
group; [0130] a compound of formula (1) wherein R.sup.1 represents
a hydrogen atom, a C1-C3 alkyl group which may be optionally
substituted with one or more halogen atom(s), a halogen atom, a
C1-C3 alkoxy group, a S(O).sub.mR.sup.2, a C2-C4 alkoxycarbonyl
group, an amino group, or a nitro group, and n=2; [0131] a compound
of formula (1) wherein R.sup.1 represents a hydrogen atom, a
halogen atom, a C1-C3 alkyl group, a C1-C3 perfluoroalkyl group, a
C1-C3 alkoxy group, a S(O).sub.mR.sup.2, a C2-C4 alkoxycarbonyl
group, an amino group, or a nitro group, and n=2; [0132] a compound
of formula (1) wherein R.sup.1 represents a hydrogen atom, a
halogen atom, a C1-C3 alkyl group, a C1-C3 perfluoroalkyl group, a
C1-C3 alkoxy group, a S(O).sub.mR.sup.2, a C2-C4 alkoxycarbonyl
group, an amino group, or a nitro group, and n=2; [0133] a compound
of formula (1) wherein R.sup.1 represents a hydrogen atom, a
chlorine atom, a bromine atom, a methyl group, a trifluoromethyl
group, a methoxy group, a methylsulfanyl group, a methylsulfinyl
group, a methylsulfonyl group, a methoxycarbonyl group, an amino
group, or a nitro group, and n=2; [0134] a compound of formula (1)
wherein R.sup.1 represents a hydrogen atom, a chlorine atom, a
bromine atom, a methyl group, a trifluoromethyl group, a methoxy
group, a methylsulfanyl group, a methylsulfonyl group, a
methoxycarbonyl group, an amino group, or a nitro group, and n=2;
[0135] a compound of formula (1) wherein R.sup.1 represents a
hydrogen atom, a C1-C3 alkyl group which may be optionally
substituted with one or more halogen atom(s), a halogen atom, a
C1-C3 alkoxy group, or a S(O).sub.mR.sup.2, and n=2; [0136] a
compound of formula (1) wherein R.sup.1 represents a hydrogen atom,
a halogen atom, a C1-C3 alkyl group, a C1-C3 perfluoroalkyl group,
a C1-C3 alkoxy group, or a S(O).sub.mR.sup.2 and n=2; [0137] a
compound of formula (1) wherein R.sup.1 represents a hydrogen atom,
a chlorine atom, a bromine atom, a methyl group, a trifluoromethyl
group, a methoxy group, a methylsulfanyl group, a methylsulfinyl
group, or a methylsulfonyl group, and n=2; [0138] a compound of
formula (1) wherein R.sup.1 represents a hydrogen atom, a chlorine
atom, a bromine atom, a methyl group, a trifluoromethyl group, a
methoxy group, a methylsulfanyl group, or a methylsulfonyl group,
and n=2; a compound of formula (1) wherein R.sup.1 represents a
hydrogen atom, a halogen atom, a C1-C3 haloalkyl group, a C1-C3
alkoxy group or a S(O).sub.mR.sup.2, and n=2; [0139] a compound of
formula (1) wherein R.sup.1 represents a hydrogen atom, a halogen
atom, a C1-C3 perfluoroalkyl group, a C1-C3 alkoxy group, or a
S(O).sub.mR.sup.2, and n=2; [0140] a compound of formula (1)
wherein R.sup.1 represents a hydrogen atom, a chlorine atom, a
bromine atom, a trifluoromethyl group, a methoxy group, a
methylsulfanyl group, a methylsulfinyl group, or a methylsulfonyl
group, and n=2; and [0141] a compound of formula (1) wherein
R.sup.1 represents a hydrogen atom, a chlorine atom, a bromine
atom, a trifluoromethyl group, a methoxy group, a methylsulfanyl
group, or a methylsulfonyl group, and n=2.
[0142] Next, a process for preparing the present compound is
explained.
[0143] The present compound and intermediate compounds for
producing the same can be prepared, for example, according to any
process described in (Process 1) to (Process 7) below.
(Process 1)
[0144] A present compound (1b) as a compound of formula (1) wherein
n=1 and a present compound (1c) as a compound of formula (1)
wherein n=2 can be prepared by reacting a present compound (1a) as
a compound of formula (1) wherein n=0 with an oxidizing agent.
##STR00005##
[wherein, each symbol is the same as defined in formula (1)]
[0145] Firstly, the process for preparing the present compound (1b)
from the present compound (1a) is described.
[0146] The reaction is usually carried out in the presence of
solvent.
[0147] Examples of the solvent to be used in the reaction include
aliphatic halogenated hydrocarbons such as dichloromethane and
chloroform; nitriles such as acetonitrile; alcohols such as
methanol and ethanol; acetic acid; water; and mixed solvents
thereof.
[0148] Examples of the oxidizing agent to be used include sodium
periodate, m-chloroperoxybenzoic acid and hydrogen peroxide.
[0149] If an aqueous hydrogen peroxide solution is used as the
oxidizing agent, the reaction may be also carried out, if
necessary, in the presence of a base or a catalyst.
[0150] Examples of the base to be used in the reaction include
sodium carbonate.
[0151] Examples of the catalyst to be used in the reaction include
tungstic acid and sodium tungstate.
[0152] In the reaction, the oxidizing agent is used usually within
a range from 1 to 1.2 molar ratio(s) as opposed to 1 mole of the
present compound (1a).
[0153] When the reaction uses an aqueous hydrogen peroxide solution
and a base, the aqueous hydrogen peroxide solution is used usually
within a range from 1 to 1.2 molar ratio(s), and the base is used
usually within a range from 0.01 to 1 molar ratio(s), as opposed to
1 mole of the present compound (1a).
[0154] When the reaction uses an aqueous hydrogen peroxide solution
and a catalyst, the aqueous hydrogen peroxide solution is used
usually within a range from 1 to 1.2 molar ratio(s), and the
catalyst is used usually within a range from 0.01 to 0.5 molar
ratio(s), as opposed to 1 mole of the present compound (1a).
[0155] The reaction temperature is usually within a range from -20
to 80.degree. C. The reaction period of the reaction is usually
within a range from 0.1 to 12 hour(s).
[0156] When the reaction is completed, the reaction mixtures are
extracted with organic solvent(s), and the resulting organic layers
are, if necessary, washed with an aqueous solution of a reducing
agent (such as sodium sulfite and sodium thiosulfate) and an
aqueous solution of a base (such as sodium hydrogen carbonate). The
washed organic layers are dried and concentrated to isolate the
present compound (1b). The isolated present compound (1b) may be
further purified, for example, by chromatography and
recrystallization.
[0157] Next, the process for preparing the present compound (1c)
from the present compound (1b) is described.
[0158] The reaction is usually carried out in the presence of
solvent.
[0159] Examples of the solvent to be used in the reaction include
aliphatic halogenated hydrocarbons such as dichloromethane and
chloroform; nitriles such as acetonitrile; alcohols such as
methanol and ethanol; acetic acid; water; and mixed solvents
thereof.
[0160] Examples of the oxidizing agent to be used include
m-chloroperoxybenzoic acid and an aqueous hydrogen peroxide
solution.
[0161] The reaction may be carried out, if necessary, in the
presence of a base or a catalyst.
[0162] Examples of the base to be used in the reaction include
sodium carbonate.
[0163] Examples of the catalyst to be used in the reaction include
sodium tungstate.
[0164] In the reaction, the oxidizing agent is used usually within
a range from 1 to 4 molar ratio(s) as opposed to 1 mole of the
present compound (1b). Preferably, the oxidizing agent is used
within a range from 1 to 2 molar ratio(s) as opposed to 1 mole of
the present compound (1b).
[0165] When the reaction uses an aqueous hydrogen peroxide solution
and a base, the aqueous hydrogen peroxide solution is used usually
within a range from 1 to 4 molar ratio(s), and the base is used
usually within a range from 0.01 to 1 molar ratio(s), as opposed to
1 mole of the present compound (1b).
[0166] When the reaction uses an aqueous hydrogen peroxide solution
and a catalyst, the aqueous hydrogen peroxide solution is used
usually within a range from 1 to 1.2 molar ratio(s), and the
catalyst is used usually within a range from 0.01 to 0.5 molar
ratio(s), as opposed to 1 mole of the present compound (1b).
[0167] The reaction temperature is usually within a range from -20
to 120.degree. C. The reaction period of the reaction is usually
within a range from 0.1 to 12 hour(s).
[0168] When the reaction is completed, the reaction mixtures are
extracted with organic solvent(s), and the resulting organic layers
are, if necessary, washed with an aqueous solution of a reducing
agent (such as sodium sulfite and sodium thiosulfate) and an
aqueous solution of a base (such as sodium hydrogen carbonate). The
organic layers are dried and concentrated to isolate the present
compound (1c). The present compound (1c) may be further purified,
for example, by chromatography and recrystallization.
[0169] Also, the present compound (1c) may be prepared in one step
(one-pot) by reacting the present compound (1a) with an oxidizing
agent.
[0170] The reaction is usually carried out in the presence of
solvent.
[0171] Examples of the solvent to be used in the reaction include
aliphatic halogenated hydrocarbons such as dichloromethane and
chloroform; nitriles such as acetonitrile; alcohols such as
methanol and ethanol; acetic acid; water; and mixed solvents
thereof.
[0172] Examples of the oxidizing agent to be used include
m-chloroperoxybenzoic acid and an aqueous hydrogen peroxide
solution.
[0173] If an aqueous hydrogen peroxide solution is used as the
oxidizing agent for the reaction, the reaction may be also carried
out, if necessary, in the presence of a base or a catalyst.
[0174] Examples of the base to be used in the reaction include
sodium carbonate.
[0175] Examples of the catalyst to be used in the reaction include
tungstic acid and sodium tungstate.
[0176] In the reaction, the oxidizing agent is used usually within
a range from 2 to 5 molar ratios as opposed to 1 mole of the
present compound (1a).
[0177] When the reaction uses an aqueous hydrogen peroxide solution
and a base, the aqueous hydrogen peroxide solution is used usually
within a range from 2 to 5 molar ratios, and the base is used
usually within a range from 0.01 to 1 molar ratio(s), as opposed to
1 mole of the present compound (1a).
[0178] When the reaction uses an aqueous hydrogen peroxide solution
and a catalyst, the aqueous hydrogen peroxide solution is used
usually within a range from 2 to 5 molar ratios, and the catalyst
is used usually within a range from 0.01 to 0.5 molar ratio(s), as
opposed to 1 mole of the present compound (1a).
[0179] The reaction temperature is usually within a range from 0 to
120.degree. C. The reaction period of the reaction is usually
within a range from 0.1 to 12 hour(s).
[0180] When the reaction is completed, the reaction mixtures are
extracted with organic solvent(s), and the resulting organic layers
are, if necessary, washed with an aqueous solution of a reducing
agent (such as sodium sulfite and sodium thiosulfate) and an
aqueous solution of a base (such as sodium hydrogen carbonate). The
organic layers are dried and concentrated to isolate the present
compound (1c). The isolated present compound (1c) may be further
purified, for example, by chromatography and recrystallization.
(Process 2)
[0181] The present compound can be prepared by reacting a compound
represented by formula (M1) (hereinafter, referred to as "compound
(M1)") with a compound represented by formula (M2) (hereinafter,
referred to as "compound (M2)").
##STR00006##
[wherein, X represents a halogen atom, and the other symbols are
the same as defined in formula (1)]
[0182] The compound (M2) has been known or can be prepared
according to the known method.
[0183] The present compound (1a) can be prepared by reacting a
compound (M1a) as the compound (M1) wherein n=0, with the compound
(M2).
[0184] The present compound (1b) can be prepared by reacting a
compound (M1b) as the compound (M1) wherein n=1, with the compound
(M2).
[0185] The present compound (1c) can be prepared by reacting a
compound (M1c) as the compound (M1) wherein n=2, with the compound
(M2).
[0186] The reaction is usually carried out in the presence of
solvent. Examples of the solvent to be used in the reaction include
ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and
methyl tert-butyl ether; halogenated hydrocarbons such as
dichloromethane, chloroform, carbon tetrachloride,
1,2-dichloroethane, chlorobenzene; aromatic hydrocarbons such as
toluene, benzene and xylene; esters such as ethyl acetate and butyl
acetate; nitriles such as acetonitrile; aprotic polar solvents such
as N,N-dimethylformamide, N-methylpyrrolidone,
1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide; and
nitrogen-containing aromatic compounds such as pyridine and
quinoline; and mixed solvents thereof.
[0187] Examples of the base to be used include an alkali metal
hydrides such as sodium hydride and potassium hydride;
alkaline-earth metal hydrides such as calcium hydride; and alkali
metal carbonates such as sodium carbonate and potassium carbonate;
and organic bases such as triethylamine, diisopropylethylamine,
pyridine, 4-dimethylaminopyridine.
[0188] In the reaction, the compound (M2) is used usually within a
range from 1 to 2 molar ratio(s), and the base is used usually
within a range from 1 to 5 molar ratio(s), as opposed to 1 mole of
the compound (M1).
[0189] The reaction temperature is usually within a range from 0 to
120.degree. C. The reaction period of the reaction is usually
within a range from 0.1 to 24 hour(s).
[0190] When the reaction is completed, the reaction mixtures are
poured into water and are then extracted with organic solvent(s),
and the resulting organic layers are concentrated; the reaction
mixtures are poured into water and the resulting solids are
collected by filtration; alternatively, the solids formed in the
reaction mixture are collected by filtration, to give the present
compound. The isolated present compound may be further purified,
for example, by recrystallization and chromatography.
(Process 3)
[0191] The compound (M1b) as the compound (M1) wherein n=1 and the
compound (M1c) as the compound (M1) wherein n=2 can be prepared by
reacting the compound (M1a) as the compound (M1) wherein n=0 with
an oxidizing agent.
##STR00007##
[wherein, X represents a halogen atom]
[0192] The reaction can be carried out according to the reaction
described in Process 1 by replacing the present compound (1a), the
present compound (1b) or the present compound (1c) with the
compound (M1a), the compound (M1b) or the compound (M1c)
respectively.
Process 4
[0193] The Compound (M1a) as the compound (M1) wherein n=0 can be
prepared according to the below-mentioned scheme.
##STR00008##
[wherein, X represents a halogen atom]
[0194] A compound represented by formula (M7) (hereinafter,
referred to as "compound (M7)") can be prepared by reacting a
compound represented by formula (M6) (hereinafter, referred to as
"compound (M6)") with a chlorinating agent.
[0195] Examples of the compound (M6) include
3,6-difluoropyridine-2-carboxylic acid and
3,6-dichloropyridine-2-carboxylic acid, both which are commercially
available compounds.
[0196] The reaction is usually carried out in presence of
solvent.
[0197] Examples of the solvent to be used in the reaction include
aromatic hydrocarbons such as toluene and xylene; aliphatic
halogenated hydrocarbons such as dichloromethane and chloroform;
and mixed solvents thereof.
[0198] Examples of the chlorinating agent to be used include
thionyl chloride, oxalyl chloride and phosphoryl chloride.
[0199] In the reaction, the chlorinating agent is used usually
within a range from 1 to 15 molar ratio(s) as opposed to 1 mole of
the compound (M6).
[0200] The reaction temperature is usually within a range from 0 to
150.degree. C. The reaction period of the reaction is usually
within a range from 0.1 to 24 hours.
[0201] When the reaction is completed, the reaction solvents are
distilled off to isolate the compound (M7).
[0202] The compound represented by formula (M9) (hereinafter,
referred to as "compound (M9)") can be prepared by reacting the
compound (M7) with a compound represented by formula (M8)
(hereinafter, referred to as "compound (M8)").
[0203] N2-Methyl-5-(trifluoromethyl)pyridine-2,3-diamine, which is
indicated as compound (M8), can be prepared by a method described
in WO 2010/125985.
[0204] The reaction is usually carried out in the presence of
solvent.
[0205] Examples of the solvent to be used in the reaction include
ethers such as tetrahydrofuran, ethyleneglycol dimethyl ether,
methyl tert-butyl ether and 1,4-dioxane; aliphatic hydrocarbons
such as hexane, heptane and octane; aromatic hydrocarbons such as
toluene and xylene; halogenated hydrocarbons such as chlorobenzene;
esters such as ethyl acetate and butyl acetate; nitriles such as
acetonitrile; aprotic polar solvents such as N,N-dimethylformamide,
N-methylpyrrolidone and dimethyl sulfoxide; and mixed solvents
thereof.
[0206] In the reaction, if necessary, a base may be added.
[0207] Examples of the base to be used include alkali metal
carbonates such as sodium carbonate and potassium carbonate;
tertiary amines such as triethylamine and
N,N-diisopropylethylamine; and nitrogen-containing aromatic
compounds such as pyridine and 4-dimethylaminopyridine.
[0208] In the reaction, the compound (M7) is used usually within a
range from 1 to 3 molar ratio(s), and the base is used usually
within a range from 1 to 10 molar ratio(s), as opposed to 1 mole of
the compound (M8).
[0209] The reaction temperature is usually within a range from -20
to 100.degree. C. The reaction period of the reaction is usually
within a range from 0.1 to 24 hours.
[0210] When the reaction is completed, water is poured to the
reaction mixtures and the resulting mixtures are extracted with
organic solvent(s), and the resulting organic layers are worked up
(for example, drying and concentration) to isolate the compound
(M9). The isolated compound (M9) may be further purified, for
example, by chromatography and recrystallization.
[0211] Also, the compound (M9) can be prepared by reacting the
compound (M6) with the compound (M8) in the presence of a
condensing agent.
[0212] The reaction is usually carried out in the presence of
solvent.
[0213] Examples of the solvent to be used in the reaction include
ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran and
methyl tert-butyl ether; halogenated hydrocarbons such as
dichloromethane, chloroform, carbon tetrachloride,
1,2-dichloroethane and chlorobenzene; aromatic hydrocarbons such as
toluene, benzene and xylene; halogenated hydrocarbons such as
chlorobenzene; esters such as ethyl acetate and butyl acetate;
nitriles such as acetonitrile; aprotic polar solvents such as
N,N-dimethylformamide, N-methylpyrrolidone,
1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide;
nitrogen-containing aromatic compounds such as pyridine and
quinoline; and mixed solvents thereof.
[0214] Examples of the condensing agent to be used in the reaction
include carbodiimides such as
1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride salt
and 1,3-dicyclohexylcarbodiimide.
[0215] In the reaction, if necessary, a catalyst may be added.
[0216] Examples of the catalyst to be used in the reaction include
1-hydroxybenzotriazole.
[0217] In the reaction, the compound (M6) is used usually within a
range from 1 to 2 molar ratio(s), the condensing agent is used
usually within a range from 1 to 5 molar ratio(s), and the catalyst
is used usually within a range from 0.01 to 1 molar ratio(s), as
opposed to 1 mole of the compound (M8).
[0218] The reaction temperature is usually within a range from 0 to
120.degree. C. The reaction period of the reaction is usually
within a range from 0.1 to 24 hours.
[0219] When the reaction is completed, the reaction mixtures are
poured into water and are then extracted with organic solvent(s),
and the resulting organic layers are concentrated; the reaction
mixtures are poured into water and the resulting solids are
collected by filtration; alternatively, the solids formed in the
reaction mixture are collected by filtration, to give the compound
(M9). The isolated compound (M9) may be further purified, for
example, by recrystallization and chromatography.
[0220] A compound represented by formula (M10) (hereinafter,
referred to as "compound (M10)") may be prepared by performing an
intermolecular condensation of the compound (M9).
[0221] The reaction is usually carried out in the presence of
solvent.
[0222] Examples of the solvent to be used in the reaction include
ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran and
methyl tert-butyl ether; halogenated hydrocarbons such as
dichloromethane, chloroform, carbon tetrachloride,
1,2-dichloroethane and chlorobenzene; aromatic hydrocarbons such as
toluene, benzene and xylene; esters such as ethyl acetate and butyl
acetate; nitriles such as acetonitrile; aprotic polar solvents such
as N,N-dimethylformamide, N-methylpyrrolidone,
1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide;
nitrogen-containing aromatic compounds such as pyridine and
quinoline; and mixed solvents thereof.
[0223] In the reaction, if necessary, a condensation agent, an
acid, a base or a chlorinating agent may be added.
[0224] Examples of the condensation agent to be used include acid
anhydrides such as acetic anhydride, trifluoroacetic anhydride;
1-ethyl-3-(3-dimethylaminopropyl)carbodiimide; a mixture of
triphenylphosphine, base and carbon tetrachloride or carbon
tetrabromide; and a mixture of triphenylphosphine and azodiesters
such as diethyl azodicarboxylate.
[0225] Examples of the acid to be used include sulfonic acids such
as para-toluenesulfonic acid; carboxylic acids such as acetic acid;
and polyphosphoric acid.
[0226] Examples of the base to be used include pyridine, picoline,
2,6-lutidine and 1,8-diazabicyclo[5.4.0]-7-undecene (hereinafter,
sometimes referred to as DBU), nitrogen-containing heterocyclic
compounds such as 1,5-diazabicyclo[4.3.0]-5-nonene; tertiary amines
such as triethylamine and N,N-diisopropylethylamine; and inorganic
bases such as tripotassium phosphate, potassium carbonate and
sodium hydride.
[0227] Examples of the chlorinating to be used include phosphoryl
chloride.
[0228] In the reaction, when a condensation agent is used, the
condensation agent is used usually within a range from 1 to 5 molar
ratio(s), and when an acid is used, the acid is used usually within
a range from 0.1 to 5 molar ratio(s), and when a base is used, the
base is used usually within a range from 1 to 5 molar ratio(s), and
when a chlorinating agent is used, the chlorinating agent is used
usually within a range from 1 to 5 molar ratio(s), as opposed to 1
mole of the compound (M9).
[0229] The reaction temperature is usually within a range from 0 to
200.degree. C. The reaction period of the reaction is usually
within a range from 0.1 to 24 hours.
[0230] When the reaction is completed, the reaction mixtures are
poured into water and are then extracted with organic solvent(s),
and the resulting organic layers are concentrated; the reaction
mixtures are poured into water and the resulting solids are
collected by filtration; alternatively, the solids formed in the
reaction mixture are collected by filtration, to give the compound
(10). The isolated compound (10) may be further purified, for
example, by recrystallization and chromatography.
[0231] A compound represented by formula (M1a) (hereinafter
referred to as "compound (M1a)") can be prepared by reacting the
compound (M10) with ethyl mercaptan in the presence of a base.
[0232] The reaction is usually carried out in the presence of
solvent. Examples of the solvent to be used in the reaction include
ethers such as tetrahydrofuran, ethyleneglycol dimethyl ether,
methyl tert-butyl ether and 1,4-dioxane; aromatic hydrocarbons such
as toluene and xylene; nitriles such as acetonitrile; aprotic polar
solvents such as N,N-dimethylformamide, N-methylpyrrolidone and
dimethyl sulfoxide; and mixed solvents thereof.
[0233] Examples of the base to be used include alkali metal
carbonates such as sodium carbonate and potassium carbonate; and an
alkali metal hydrides such as sodium hydride.
[0234] In the reaction, the ethyl mercaptan is used usually within
a range from 1 to 10 molar ratio(s), the base is used usually
within a range from 1 to 10 molar ratio(s), as opposed to 1 mole of
the compound (M10). Preferably, the ethyl mercaptan is used within
a range from 1.0 to 1.1 molar ratio(s) and the base is used within
a range from 1 to 2 molar ratio(s), as opposed to 1 mole of
compound the (M10).
[0235] The reaction temperature is usually within a range from -20
to 150.degree. C. The reaction period of the reaction is usually
within a range from 0.5 to 24 hours.
[0236] When the reaction is completed, the reaction mixtures are
extracted with organic solvent(s), and the resulting organic layers
are worked up (for example, drying and concentration) to isolate
the compound (M1a). The isolated compound (M1a) may be further
purified, for example, by chromatography and recrystallization.
(Process 5)
[0237] The present compound (1d) as the compound of formula (1)
wherein R.sup.1 represents a C1-C3 alkoxy group can be prepared,
for example, according to the below-mentioned scheme.
##STR00009##
[wherein, X represents a halogen atom, R.sup.a represents a C1-C3
alkyl group, V represents a chlorine atom, a bromine atom or an
iodine atom, and the other symbols are the same as defined in the
formula (1)]
[0238] A compound represented by formula (M3) (hereinafter referred
to as "compound (M3)") can be prepared by reacting the compound
(M1) with semicarbazide hydrochloride in the presence of a
base.
[0239] The reaction is usually carried out in the presence of
solvent.
[0240] Examples of the solvent to be used in the reaction include
nitriles such as acetonitrile; and aprotic polar solvents such as
N,N-dimethylformamide, N-methylpyrrolidone,
1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide; and mixed
solvents thereof.
[0241] Examples of the base to be used in the reaction include
alkali metal carbonates such as sodium carbonate and potassium
carbonate; tertiary amines such as triethylamine and
diisopropylethyl; and nitrogen-containing aromatic compounds such
as pyridine and 4-dimethylaminopyridine.
[0242] In the reaction, semicarbazide hydrochloride is used usually
within a range from 1 to 3 molar ratio(s) and the base is used
usually within a range from 1 to 10 molar ratio(s), as opposed to 1
mole of compound (M1).
[0243] The reaction temperature is usually within a range from -20
to 100.degree. C. The reaction period of the reaction is usually
within a range from 0.1 to 24 hours.
[0244] When the reaction is completed, the reaction mixtures are
poured into water and extracted with organic solvent(s), and the
resulting organic layers are concentrated; the reaction mixtures
are poured into water and the resulting solids are collected by
filtration; alternatively, the solids formed in the reaction
mixtures are collected by filtration, to give the compound (M3).
The isolated compound (M3) may be further purified, for example, by
recrystallization and chromatography.
[0245] A compound represented by formula (M4) (hereinafter,
referred to as "compound (M4)") can be prepared by reacting the
compound (M3) with formic acid or trialkyl orthoformate.
[0246] Examples of the trialkyl orthoformate to be used in the
reaction include trimethyl orthoformate and triethyl
orthoformate.
[0247] The reaction is usually carried out in the presence of
solvent.
[0248] Examples of the solvent to be used in the reaction include
halogenated hydrocarbons such as 1,2-dichloroethane and
chlorobenzene; aromatic hydrocarbons such as toluene, benzene and
xylene; aprotic polar solvents such as N,N-dimethylformamide,
N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and dimethyl
sulfoxide; alcohols such as methanol, ethanol and n-butanol; and
mixed solvents thereof.
[0249] When formic acid is used in the reaction, the formic acid is
used usually within a range from 1 to 10 molar ratio(s) as opposed
to 1 mole of the compound (M3).
[0250] When trialkyl orthoformate is used in the reaction, the
trialkyl orthoformate is used usually within a range from 1 to 10
molar ratio(s) as opposed to 1 mole of the compound (M3).
[0251] The reaction temperature is usually within a range from 0 to
150.degree. C. The reaction period of the reaction is usually
within a range from 0.1 to 24 hours.
[0252] When the reaction is completed, the reaction mixtures are
poured into water and extracted with organic solvent(s), and the
resulting organic layers are concentrated; the reaction mixtures
are poured into water and the resulting solids are collected by
filtration; alternatively, the solids formed in the reaction
mixtures are collected by filtration, to give the compound (M4).
The isolated compound (M4) may be further purified, for example, by
recrystallization and chromatography.
[0253] The present compound (1d) can be prepared by reacting the
compound (M4) with a compound represented by formula (M5)
(hereinafter referred to as "compound (M5)") in the presence of a
base.
[0254] Examples of the compound (M5) include iodomethane,
iodoethane, 1-iodopropane, and 2-iodopropane, any of which are a
commercially available compound.
[0255] The reaction is usually carried out in the presence of
solvent.
[0256] Examples of the solvent to be used in the reaction include
ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and
methyl tert-butyl ether; halogenated hydrocarbons such as
dichloromethane, chloroform, carbon tetrachloride,
1,2-dichloroethane, chlorobenzene; aromatic hydrocarbons such as
toluene, benzene and xylene; aprotic polar solvents such as
N,N-dimethylformamide, N-methylpyrrolidone,
1,3-dimethyl-2-imidazolidinone and dimethyl sulfoxide; and mixed
solvents thereof.
[0257] Examples of the base to be used include an alkali metal such
as sodium hydride and alkaline-earth metal hydrides such as
potassium hydride and calcium hydride; and alkali metal carbonates
such as sodium carbonate and potassium carbonate; and organic bases
such as triethylamine, diisopropylethylamine, pyridine,
4-dimethylaminopyridine.
[0258] In the reaction, the compound (M5) is used usually within a
range from 1 to 10 molar ratio(s), the base is used usually within
a range from 0.1 to 5 molar ratio(s), as opposed to 1 mole of the
present compound (M4).
[0259] The reaction temperature is usually within a range from -20
to 120.degree. C. The reaction period of the reaction is usually
within a range from 0.1 to 24 hours.
[0260] When the reaction is completed, the reaction mixtures are
poured into water and extracted with organic solvent(s), and the
resulting organic layers are concentrated; the reaction mixtures
are poured into water and the resulting solids are collected by
filtration; alternatively, the solids formed in the reaction
mixtures are collected by filtration, to give the present compound
(1d). The isolated present compound (1d) may be further purified,
for example, by recrystallization and chromatography.
Process 6
[0261] The present compound (1g) as the compound of formula (1)
wherein n is 2, R.sup.1 represents S(O).sub.mR.sup.2 and m is 2,
and the present compound (f) as the compound of formula (1) wherein
n is 2, R.sup.1 represents S(O).sub.mR.sup.2 and m is s can be
prepared by reacting the present compound (1e) as the compound of
formula (1) wherein n is 2, R.sup.1 represents S(O).sub.mR.sup.2
and m is 0 with an oxidizing agent.
##STR00010##
[wherein, the symbols are the same as defined in formula (1)]
[0262] The present compound (1f) can be prepared by reacting the
present compound (1e) with an oxidizing agent.
[0263] The reaction is usually carried out in the presence of
solvent.
[0264] Examples of the solvent to be used in the reaction include
aliphatic halogenated hydrocarbons such as dichloromethane and
chloroform; nitriles such as acetonitrile; alcohols such as
methanol and ethanol; acetic acid; water; and mixed solvents
thereof.
[0265] Examples of the oxidizing agent to be used include sodium
periodate, m-chloroperoxybenzoic acid and hydrogen peroxide.
[0266] If an aqueous hydrogen peroxide solution is used as the
oxidizing agent, the reaction may be also carried out, if
necessary, in the presence of a base or a catalyst.
[0267] Examples of the base to be used in the reaction include
sodium carbonate.
[0268] Examples of the catalyst to be used in the reaction include
tungstic acid and sodium tungstate.
[0269] In the reaction, the oxidizing agent is used usually within
a range from 1 to 1.2 molar ratio(s) as opposed to 1 mole of the
present compound (1e).
[0270] When the reaction uses an aqueous hydrogen peroxide solution
and a base, the aqueous hydrogen peroxide solution is used usually
within a range from 1 to 1.2 molar ratio(s), and the base is used
usually within a range from 0.01 to 1 molar ratio(s), as opposed to
1 mole of the present compound (1e).
[0271] When the reaction uses an aqueous hydrogen peroxide solution
and a catalyst, the aqueous hydrogen peroxide solution is used
usually within a range from 1 to 1.2 molar ratio(s), and the
catalyst is used usually within a range from 0.01 to 0.5 molar
ratio(s), as opposed to 1 mole of the present compound (1e).
[0272] The reaction temperature is usually within a range from -20
to 80.degree. C. The reaction period of the reaction is usually
within a range from 0.1 to 12 hours.
[0273] When the reaction is completed, the reaction mixtures are
extracted with organic solvent(s), and the resulting organic layers
are, if necessary, washed with an aqueous solution of a reducing
agent (such as sodium sulfite and sodium thiosulfate) and an
aqueous solution of a base (such as sodium hydrogen carbonate). The
washed organic layers are dried and concentrated to isolate the
present compound (1f). The isolated present compound (1f) may be
further purified, for example, by chromatography and
recrystallization.
[0274] The present compound (1g) can be prepared by reacting the
present compound (1f) with an oxidizing agent.
[0275] The reaction is usually carried out in the presence of
solvent.
[0276] Examples of the solvent to be used in the reaction include
aliphatic halogenated hydrocarbons such as dichloromethane and
chloroform; nitriles such as acetonitrile; alcohols such as
methanol and ethanol; acetic acid; water; and mixed solvents
thereof.
[0277] Examples of the oxidizing agent to be used include sodium
periodate, m-chloroperoxybenzoic acid and aqueous hydrogen peroxide
solution.
[0278] The reaction may be carried out, if necessary, in the
presence of a base or a catalyst.
[0279] Examples of the base to be used in the reaction include
sodium carbonate.
[0280] Examples of the catalyst to be used in the reaction include
sodium tungstate.
[0281] In the reaction, the oxidizing agent is used usually within
a range from 1 to 4 molar ratio(s) as opposed to 1 mole of the
present compound (1f). Preferably, the oxidizing agent is used
within a range from 1 to 2 molar ratio(s) as opposed to 1 mole of
the present compound (1f).
[0282] When the reaction uses an aqueous hydrogen peroxide solution
and a base, the aqueous hydrogen peroxide solution is used usually
within a range from 1 to 4 molar ratio(s), and the base is used
usually within a range from 0.01 to 0.5 molar ratio(s), as opposed
to 1 mole of the present compound (1f).
[0283] When the reaction uses an aqueous hydrogen peroxide solution
and a catalyst, the aqueous hydrogen peroxide solution is used
usually within a range from 1 to 4 molar ratio(s), and the catalyst
is used usually within a range from 0.01 to 0.5 molar ratio(s), as
opposed to 1 mole of the present compound (1f).
[0284] The reaction temperature is usually within a range from -20
to 120.degree. C. The reaction period of the reaction is usually
within a range from 0.1 to 12 hour(s).
[0285] When the reaction is completed, the reaction mixtures are
extracted with organic solvent(s), and the resulting organic layers
are, if necessary, washed with an aqueous solution of a reducing
agent (such as sodium sulfite and sodium thiosulfate) and an
aqueous solution of a base (such as sodium hydrogen carbonate). The
washed organic layers are dried and concentrated to isolate the
present compound (1g). The isolated present compound (1g) may be
further purified, for example, by chromatography and
recrystallization.
[0286] Also, the present compound (1g) may be prepared in one step
(one-pot) by reacting the present compound (1e) with an oxidizing
agent.
[0287] The reaction is usually carried out in the presence of
solvent.
[0288] Examples of the solvent to be used in the reaction include
aliphatic halogenated hydrocarbons such as dichloromethane and
chloroform; nitriles such as acetonitrile; alcohols such as
methanol and ethanol; acetic acid; water; and mixed solvents
thereof.
[0289] Examples of the oxidizing agent to be used include
m-chloroperoxybenzoic acid and an aqueous hydrogen peroxide
solution.
[0290] If an aqueous hydrogen peroxide solution is used as the
oxidizing agent for the reaction, the reaction may be also carried
out, if necessary, in the presence of a base or a catalyst.
[0291] Examples of the base to be used in the reaction include
sodium carbonate.
[0292] Examples of the catalyst to be used in the reaction include
tungstic acid and sodium tungstate.
[0293] In the reaction, the oxidizing agent is used usually within
a range from 2 to 5 molar ratios as opposed to 1 mole of the
present compound (1e).
[0294] When the reaction uses an aqueous hydrogen peroxide solution
and a base, the aqueous hydrogen peroxide solution is used usually
within a range from 2 to 5 molar ratios, and the base is used
usually within a range from 0.01 to 1 molar ratio(s), as opposed to
1 mole of the present compound (1e).
[0295] When the reaction uses an aqueous hydrogen peroxide solution
and a catalyst, the aqueous hydrogen peroxide solution is used
usually within a range from 2 to 5 molar ratios, and the catalyst
is used usually within a range from 0.01 to 0.5 molar ratio(s), as
opposed to 1 mole of the present compound (1e).
[0296] The reaction temperature is usually within a range from 0 to
120.degree. C. The reaction period of the reaction is usually
within a range from 0.1 to 12 hour(s).
[0297] When the reaction is completed, the reaction mixtures are
extracted with organic solvent(s), and the resulting organic layers
are, if necessary, washed with an aqueous solution of a reducing
agent (such as sodium sulfite and sodium thiosulfate) and an
aqueous solution of a base (such as sodium hydrogen carbonate). The
organic layers are dried and concentrated to isolate the present
compound (1g). The present compound (1g) may be further purified,
for example, by chromatography and recrystallization.
Process 7
[0298] The N-oxide compound represented by formula (1n)
(hereinafter, referred to as "present compound (1n)") can be
prepared, for example, according to the below-mentioned
synthesis.
##STR00011##
[wherein, the symbols are the same as defined in the formula
(1)]
[0299] Firstly, the process for preparing a compound represented by
formula (M1n) (hereinafter referred to as "compound (Mn)") from the
compound (M1c).
[0300] The reaction is usually carried out in the presence of
solvent.
[0301] Examples of the solvent to be used in the reaction include
aliphatic halogenated hydrocarbons such as dichloromethane and
chloroform.
[0302] Examples of the oxidizing agent to be used include
m-chloroperoxybenzoic acid.
[0303] In the reaction, the oxidizing agent is used usually within
a range from 1 to 10 molar ratio(s) as opposed to 1 mole of
compound (M1c).
[0304] The reaction temperature is usually within a range from -20
to 80.degree. C. The reaction period of the reaction is usually
within a range from 0.1 to 12 hour(s).
[0305] When the reaction is completed, the reaction mixtures are
extracted with organic solvent(s), and the resulting organic layers
are, if necessary, washed with an aqueous solution of a reducing
agent (such as sodium sulfite and sodium thiosulfate) and an
aqueous solution of a base (such as sodium hydrogen carbonate). The
organic layers are dried and concentrated to isolate the compound
(M1n). The compound (M1n) may be further purified, for example, by
chromatography and recrystallization.
[0306] Next, the process for preparing the present compound (1n)
from the compound (M1n) is described.
[0307] The present compound (1n) can be prepared according to a
method described in process 2 or Process 5 by using the compound
(M1n) in place of the compound (M1).
[0308] Next, specific examples of the present compound are shown
below.
##STR00012## [0309] a present compound of formula (1) wherein n and
R1 represent a combination thereof listed in Tables 1 to 3:
TABLE-US-00001 [0309] TABLE 1 R.sup.1 n R.sup.1 n H 0 CF.sub.3 0 H
1 CF.sub.3 1 H 2 CF.sub.3 2 F 0 CF.sub.2CF.sub.3 0 F 1
CF.sub.2CF.sub.3 1 F 2 CF.sub.2CF.sub.3 2 Cl 0
CF.sub.2CF.sub.2CF.sub.3 0 Cl 1 CF.sub.2CF.sub.2CF.sub.3 1 Cl 2
CF.sub.2CF.sub.2CF.sub.3 2 Br 0 CF(CF.sub.3).sub.2 0 Br 1
CF(CF.sub.3).sub.2 1 Br 2 CF(CF.sub.3).sub.2 2 I 0 CH.sub.2CF.sub.3
0 I 1 CH.sub.2CF.sub.3 1 I 2 CH.sub.2CF.sub.3 2 CH.sub.3 0
OCH.sub.3 0 CH.sub.3 1 OCH.sub.3 1 CH.sub.3 2 OCH.sub.3 2
CH.sub.2CH.sub.3 0 OCH.sub.2CH.sub.3 0 CH.sub.2CH.sub.3 1
OCH.sub.2CH.sub.3 1 CH.sub.2CH.sub.3 2 OCH.sub.2CH.sub.3 2
CH.sub.2CH.sub.2CH.sub.3 0 OCH.sub.2CH.sub.2CH.sub.3 0
CH.sub.2CH.sub.2CH.sub.3 1 OCH.sub.2CH.sub.2CH.sub.3 1
CH.sub.2CH.sub.2CH.sub.3 2 OCH.sub.2CH.sub.2CH.sub.3 2
CH(CH.sub.3).sub.2 0 OCH(CH.sub.3).sub.2 0 CH(CH.sub.3).sub.2 1
OCH(CH.sub.3).sub.2 1 CH(CH.sub.3).sub.2 2 OCH(CH.sub.3).sub.2
2
TABLE-US-00002 TABLE 2 R.sup.1 n R.sup.1 n SCH.sub.3 0
S(O).sub.2CH.sub.2CH.sub.3 0 SCH.sub.3 1 S(O).sub.2CH.sub.2CH.sub.3
1 SCH.sub.3 2 S(O).sub.2CH.sub.2CH.sub.3 2 SCH.sub.2CH.sub.3 0
S(O).sub.2CH.sub.2CH.sub.2CH.sub.3 0 SCH.sub.2CH.sub.3 1
S(O).sub.2CH.sub.2CH.sub.2CH.sub.3 1 SCH.sub.2CH.sub.3 2
S(O).sub.2CH.sub.2CH.sub.2CH.sub.3 2 SCH.sub.2CH.sub.2CH.sub.3 0
S(O).sub.2CH(CH.sub.3).sub.2 0 SCH.sub.2CH.sub.2CH.sub.3 1
S(O).sub.2CH(CH.sub.3).sub.2 1 SCH.sub.2CH.sub.2CH.sub.3 2
S(O).sub.2CH(CH.sub.3).sub.2 2 SCH(CH.sub.3).sub.2 0 NH.sub.2 0
SCH(CH.sub.3).sub.2 1 NH.sub.2 1 SCH(CH.sub.3).sub.2 2 NH.sub.2 2
S(O)CH.sub.3 0 NHCH.sub.3 0 S(O)CH.sub.3 1 NHCH.sub.3 1
S(O)CH.sub.3 2 NHCH.sub.3 2 S(O)CH.sub.2CH.sub.3 0
NHCH.sub.2CH.sub.3 0 S(O)CH.sub.2CH.sub.3 1 NHCH.sub.2CH.sub.3 1
S(O)CH.sub.2CH.sub.3 2 NHCH.sub.2CH.sub.3 2
S(O)CH.sub.2CH.sub.2CH.sub.3 0 NHCH.sub.2CH.sub.2CH.sub.3 0
S(O)CH.sub.2CH.sub.2CH.sub.3 1 NHCH.sub.2CH.sub.2CH.sub.3 1
S(O)CH.sub.2CH.sub.2CH.sub.3 2 NHCH.sub.2CH.sub.2CH.sub.3 2
S(O)CH(CH.sub.3).sub.2 0 NHCH(CH.sub.3).sub.2 0
S(O)CH(CH.sub.3).sub.2 1 NHCH(CH.sub.3).sub.2 1
S(O)CH(CH.sub.3).sub.2 2 NHCH(CH.sub.3).sub.2 2 S(O).sub.2CH.sub.3
0 N(CH.sub.3).sub.2 0 S(O).sub.2CH.sub.3 1 N(CH.sub.3).sub.2 1
S(O).sub.2CH.sub.3 2 N(CH.sub.3).sub.2 2
TABLE-US-00003 TABLE 3 R.sup.1 n R.sup.1 n
N(CH.sub.2CH.sub.3).sub.2 0 N(CH.sub.2CH.sub.3)CH(CH.sub.3).sub.2 0
N(CH.sub.2CH.sub.3).sub.2 1 N(CH.sub.2CH.sub.3)CH(CH.sub.3).sub.2 1
N(CH.sub.2CH.sub.3).sub.2 2 N(CH.sub.2CH.sub.3)CH(CH.sub.3).sub.2 2
N(CH.sub.2CH.sub.2CH.sub.3).sub.2 0 C(O)OCH.sub.3 0
N(CH.sub.2CH.sub.2CH.sub.3).sub.2 1 C(O)OCH.sub.3 1
N(CH.sub.2CH.sub.2CH.sub.3).sub.2 2 C(O)OCH.sub.3 2
N[CH(CH.sub.3).sub.2].sub.2 0 C(O)OCH.sub.2CH.sub.3 0
N[CH(CH.sub.3).sub.2].sub.2 1 C(O)OCH.sub.2CH.sub.3 1
N[CH(CH.sub.3).sub.2].sub.2 2 C(O)OCH.sub.2CH.sub.3 2
N(CH.sub.3)CH.sub.2CH.sub.3 0 C(O)OCH.sub.2CH.sub.2CH.sub.3 0
N(CH.sub.3)CH.sub.2CH.sub.3 1 C(O)OCH.sub.2CH.sub.2CH.sub.3 1
N(CH.sub.3)CH.sub.2CH.sub.3 2 C(O)OCH.sub.2CH.sub.2CH.sub.3 2
N(CH.sub.3)CH.sub.2CH.sub.2CH.sub.3 0 C(O)OCH(CH.sub.3).sub.2 0
N(CH.sub.3)CH.sub.2CH.sub.2CH.sub.3 1 C(O)OCH(CH.sub.3).sub.2 1
N(CH.sub.3)CH.sub.2CH.sub.2CH.sub.3 2 C(O)OCH(CH.sub.3).sub.2 2
N(CH.sub.3)CH(CH.sub.3).sub.2 0 NO.sub.2 0
N(CH.sub.3)CH(CH.sub.3).sub.2 1 NO.sub.2 1
N(CH.sub.3)CH(CH.sub.3).sub.2 2 NO.sub.2 2
N(CH.sub.2CH.sub.3)CH.sub.2CH.sub.2CH.sub.3 0 CN 0
N(CH.sub.2CH.sub.3)CH.sub.2CH.sub.2CH.sub.3 1 CN 1
N(CH.sub.2CH.sub.3)CH.sub.2CH.sub.2CH.sub.3 2 CN 2
##STR00013## [0310] a present compound of formula (1-1) wherein
R.sup.1 represents a residue listed in Table 4:
TABLE-US-00004 [0310] TABLE 4 R.sup.1 R.sup.1 H
S(O)CH(CH.sub.3).sub.2 F S(O).sub.2CH.sub.3 Cl
S(O).sub.2CH.sub.2CH.sub.3 Br S(O).sub.2CH.sub.2CH.sub.2CH.sub.3 I
S(O).sub.2CH(CH.sub.3).sub.2 CH.sub.3 NH.sub.2 CH.sub.2CH.sub.3
NHCH.sub.3 CH.sub.2CH.sub.2CH.sub.3 NHCH.sub.2CH.sub.3
CH(CH.sub.3).sub.2 NHCH.sub.2CH.sub.2CH.sub.3 CF.sub.3
NHCH(CH.sub.3).sub.2 CF.sub.2CF.sub.3 N(CH.sub.3).sub.2
CF.sub.2CF.sub.2CF.sub.3 N(CH.sub.2CH.sub.3).sub.2
CF(CF.sub.3).sub.2 N(CH.sub.2CH.sub.2CH.sub.3).sub.2
CH.sub.2CF.sub.3 N[CH(CH.sub.3).sub.2].sub.2 OCH.sub.3
N(CH.sub.3)CH.sub.2CH.sub.3 OCH.sub.2CH.sub.3
N(CH.sub.3)CH.sub.2CH.sub.2CH.sub.3 OCH.sub.2CH.sub.2CH.sub.3
N(CH.sub.3)CH(CH.sub.3).sub.2 OCH(CH.sub.3).sub.2
N(CH.sub.2CH.sub.3)CH.sub.2CH.sub.2CH.sub.3 SCH.sub.3
N(CH.sub.2CH.sub.3)CH(CH.sub.3).sub.2 SCH.sub.2CH.sub.3
C(O)OCH.sub.3 SCH.sub.2CH.sub.2CH.sub.3 C(O)OCH.sub.2CH.sub.3
SCH(CH.sub.3).sub.2 C(O)OCH.sub.2CH.sub.2CH.sub.3 S(O)CH.sub.3
C(O)OCH(CH.sub.3).sub.2 S(O)CH.sub.2CH.sub.3 NO.sub.2
S(O)CH.sub.2CH.sub.2CH.sub.3 CN
[0311] The pests on which a compound of the present invention has a
control efficacy include, for example, harmful arthropods such as
harmful insects and harmful mites, and harmful nematodes such as
roundworm. Specific examples of the pests are follows:
Hemiptera:
[0312] Delphacidae (for example, Laodelphax striatellus,
Nilaparvata lugens, or Sogatella furcifera),
[0313] Deltocephalidae (for example, Nephotettix cincticeps,
Nephotettix virescens, or Empoasca onukii),
[0314] Aphididae (for example, Aphis gossypii, Myzus persicae,
Brevicoryne brassicae, Aphis spiraecola, Macrosiphum euphorbiae,
Aulacorthum solani, Rhopalosiphum padi, Toxoptera citricidus, or
Hyalopterus pruni),
[0315] Pentatomidae (for example, Nezara antennata, Riptortus
clavetus, Leptocorisa chinensis, Eysarcoris parvus, or Halyomorpha
mista),
[0316] Aleyrodidae (for example, Trialeurodes vaporariorum, Bemisia
tabaci, Dialeurodes citri, or Aleurocanthus spiniferus),
[0317] Coccoidea (for example, Aonidiella aurantii, Comstockaspis
perniciosa, Unaspis citri, Ceroplastes rubens, Icerya purchasi,
Planococcus Kraunhiae, Pseudococcus longispinis, Pseudaulacaspis
Pentagona),
[0318] Tingidae,
[0319] Cimicoidea (for example, Cimex lectularius, Cimex
hemipterus), and
[0320] Psyllidae;
[0321] and the others.
Lepidoptera:
[0322] Pyralidae (for example, Chilo suppressalis, Tryporyza
incertulas, Cnaphalocrocis medinalis, Notarcha derogata, Plodia
interpunctella, Ostrinia furnacalis, Hellula undalis, or Pediasia
teterrellus),
[0323] Noctuidae (for example, Spodoptera litura, Spodoptera
exigua, Mythimna separata, Mamestra brassicae, Agrotis ipsilon,
Plusia nigrisigna, Trichoplusia spp., Heliothis spp., or
Helicoverpa spp.),
[0324] Pieridae (for example, Pieris rapae),
[0325] Adokisofiesu genus,
[0326] Tortricidae (for example, Grapholita molesta, Leguminivora
glycinivorelia, Matsumuraeses azukivora, Adoxophyes orana fasciata,
Adoxophyes honmai, Homona magnanima, Archips fuscocupreanus, or
Cydia pomonella).
[0327] Gracillariidiae (for example, Caloptilia theivora, or
Phyllonorycter ringoneella),
[0328] Carposinidae (for example, Carposina niponensis),
[0329] Lyonetiidae (for example, Lyonetia spp.),
[0330] Lymantriidae (for example, Lymantria spp., or Euproctis
spp.),
[0331] Yponomeutidae (for example, Plutella xylostella),
[0332] Gelechiidae (for example, Pectinophora gossypiella, or
Phthorimaea operculella),
[0333] Arctiidae (for example, Hyphantria cunea), and
[0334] Tineidae (for example, Tinea translucens, or Tineola
bisselliella);
[0335] and the others.
Thysanoptera:
[0336] Thysanopterae (for Example, Frankliniella occidentalis,
Thrips palmi, Scirtothrips dorsalis, Thrips tabaci, Frankliniella
intonsa),
[0337] and the others.
Diptera:
[0338] House mosquitoes (Culex spp.) (for example, Culex pipiens
pallens, Culex tritaeniorhynchus, or Culex quinquefasciatus),
[0339] Aedes spp. (for example, Aedes aegypti, or Aedes
albopictus),
[0340] Anopheles spp. (for example, Anopheles sinensis),
[0341] Chironomidae,
[0342] Muscidae (for example, Musca domestica, or Muscina
stabulans),
[0343] Calliphoridae,
[0344] Sarcophagidae,
[0345] Fanniidae,
[0346] Anthiomyiidae (for example, Delia platura, or Delia
antiqua),
[0347] Agromyzidae (for example, Agromyza oryzae, Hydreilia
griseola, Liriomyza sativae, Liriomyza trifolii, or Chromatomyia
horticola),
[0348] Chloropidae (for example, Chlorops oryzae),
[0349] Tephritidae (for example, Dacus cucurbitae, or Ceratitis
capitata),
[0350] Drosophilidae,
[0351] Phoridae (for example, Megaselia spiracularis),
[0352] Psychodidae (for example, Clogmia albipunctata),
[0353] Sciaridae,
[0354] Simuliidae,
[0355] Tabanidae (for example, Tabanus trigonus),
[0356] Hippoboscidae,
[0357] Stomoxyidae,
[0358] and the others.
Coleoptera:
[0359] Corn root worms (Diabrotica spp.) (for example, Diabrotica
virgifera virgifera, or Diabrotica undecimpunctata howardi),
[0360] Scarabaeidae (for example, Anomala cuprea, Anomala
rufocuprea, or Popillia japonica),
[0361] Curculionidae (for example, Sitophilus zeamnais,
Lissorhoptrus oryzophilus, Callosobruchuys chienensis, Echinocnemus
squameus, Anthonomus grandis, or Sphenophorus venatus),
[0362] Tenebrionidae (for example, Tenebrio molitor, or Tribolium
castaneum),
[0363] Chrysomelidae (for example, Oulema oryzae, Aulacophora
femoralis, Phyllotreta striolata, or Leptinotarsa
decemlineata),
[0364] Dermestidae (for example, Anthrenus verbasci, Dermestes
maculates),
[0365] Anobiidae (for Example, Lasioderma serricorne),
[0366] Epilachna (for example, Epilachna vigintioctopunctata),
[0367] Scolytidae (for example, Lyctus brunneus, or Tomicus
piniperda),
[0368] Bostrichidae,
[0369] Ptinidae,
[0370] Cerambycidae (for example, Anoplophora malasiaca),
[0371] Elateridae (Agriotes spp.),
[0372] Paederus fuscipes
[0373] and the others.
Orthoptera:
[0374] Locusta migratoria, Gryllotalpa africana, Oxya yezoensis,
Oxya japonica, Grylloidea and the others.
Siphonaptera:
[0375] Ctenocephalides fells, Ctenocephalides canis, Pulex
irritans, Xenopsylla cheopis, and the others.
Anoplura:
[0376] Pediculus humanus corporis, Phthirus pubis, Haematopinus
eurysternus, Dalmalinia ovis, Haematopinus suis, Linognathus
setosus and the others.
Mallophaga:
[0377] Dalmalinia ovis, Dalmalinia bovis, Menopon gallinae,
Trichodectes canis, Felicola subrostrata and the others.
Hymenoptera:
[0378] Formicidae (for example, Monamorium pharaosis, Formica fusca
japanica, Ochetellus glaber, Pristomyrex pungens, Pheidole noda,
Acromyrmnex spp., Solenopsis spp., Linepithema humile),
[0379] Vespidae,
[0380] Betylidae,
[0381] Tenthredinidae (for example, Athalia rosae, Athalia
japonica),
[0382] and the others.
Blattariae:
[0383] Blattella germanica, Periplaneta fuliginosa, Periplaneta
americana, Periplaneta brunnea, Blatta orientalis, and the
others.
Isoptera:
[0384] Reticulitermes speratus, Coptotermes formosanus,
Incisitermes minor, Cryptotermes domesticus, Odontotermes
formosanus, Neotermes koshunensis, Glyptotermes satsumensis,
Glyptotermes nakajimai, Glyptotermes fuscus, Glyptotermes kodamai,
Glyptotermes kushimensis, Hodotermnopsis japonica, Coptotermes
guangzhoensis, Reticulitermes miyatakei, Reticulitermes flaviceps
amamianus, Reticulitermes sp., Nasutitermes takasagoensis,
Pericapritermes nitobei, Sinocapritermes mushae, and the
others.
Acarina:
[0385] Tetranychidae (for example, Tetranychus urticae, Tetranychus
kanzawai, Panonychus citri, Panonychus ulmi, or Oligonychus
spp.);
[0386] Ericphyidae (for example, Aculops pelekassi, Phyllocoptruta
citri, Aculops lycopersici, Calacarus carinatus, Acaphylla
theavagrans, Eriophyes chibaensis, Aculus schlechtendiali);
[0387] Tarsonemidae (for example, Polyphagotarsonemus latus);
[0388] Tenuipalpidae (for Example, Brevipalpus phoenicis);
[0389] Tuckerellidae;
[0390] Ixodidae (for Example, Haemaphysalis longicornis,
Haemaphysalis flava, Dermacentor taiwanicus, Dermacentor
variabilis, Ixodes ovatcus, Ixodes persulcatus, Ixodes scapularis,
Amblyomma americanum, Boophilus microplus, Rhipicephalus
sanguineus),
[0391] Acaridae (for example, Tyrophagus putreacentiae, or
Tyrophagus similis),
[0392] Pyroglyphidae (for example, Dermatophagoides farinae, or
Dermatophagoides ptrenyssnus),
[0393] Cheyletidae (for example, Cheyletus eruditus, Cheyletus
malaccensis, Cheyletus moorei, or Cheyletiella yasguri),
[0394] Sarcoptidae (for example, Octodectes cynotis, or Sacroptes
scabiei),
[0395] Demodex folliculorum (for example, Demodex canis);
[0396] Lisatrophoridae,
[0397] Oribatid mites,
[0398] Dermanyssidae (for example, Ornithonyssus bacoti,
Ornithonyssus sylvairum, or Dermanyssus gallinae),
[0399] Trombiculidae (for example, Leptotrombidium akamushi),
Araneae:
[0400] Spiders (for example, Chiracanthium japonicum, or
Latrodectus hasseltii).
Chilopoda:
[0401] Thereuonema hilgendorfi, or Scolopendra subspinipes and the
others,
Diplopoda:
[0402] Oxidus gracilis, or Nedyopus tambanus and the others.
Isopoda:
[0403] Armadillidium vulgare and the others.
Gastropoda:
[0404] Limax marginatus, or Limax flavus and the others,
Roundworms:
[0405] Aphelenchoides besseyi, Nothotylenchus acris, Meloidogyne
incognita, Meloidogyne hapla, Meioidogyne javanica, Heterodera
glycines, Globodera rostochiensis, Pratylenchus coffeae, or
Pratylenchus neglectus and the others.
[0406] The pest described in herein includes a pest having lowered
pesticide susceptibility against existing pesticide, thus having
acquired pesticide resistance.
[0407] The agent for controlling pests of the present invention
comprises the present compound and an inert active carrier. The
agent for controlling pests is usually prepared by mixing the
present compound with an inert active carrier such as solid
carrier, liquid carrier or gaseous carrier, and if necessary,
adding surfactants and the other auxiliary agents for formulation,
to formulate into emulsifiable concentrates, oil solutions, dust
formulations, dry flowables, fine granules, granules, wettable
powders, water-soluble powders, flowables, microcapsules, aerosols,
smoking agents, poison baits, resin formulations, shampoo
formulations, paste-like formulations, foams, carbon dioxide
formulations and tablets and the others. Such formulations may be
processed into mosquito repellent coils, electric mosquito
repellent mats, liquid mosquito formulations, smoking agents,
fumigants, sheet formulations, spot-on formulations or formulations
for oral treatment.
[0408] The agent for controlling pests of the present invention
comprises usually 0.01 to 95% by weight of the present
compound.
[0409] Examples of the above-mentioned solid carrier to be used in
the formulation include fine powders or granules of clays (for
example, kaolin clay, diatomaceous earth, bentonite, Fubasami clay,
or acid white clay), synthetic hydrated silicon oxides, talcs,
ceramics, other inorganic minerals (for example, sericite, quartz,
sulfur, active carbon, calcium carbonate or hydrated silica) or
chemical fertilizers (for example, ammonium sulfate, ammonium
phosphate, ammonium nitrate, urea or ammonium chloride) and the
others; as well as synthetic resins (for Example, polyester resins
such as polypropylene, polyacrylonitrile, polymethylmethacrylate
and polyethylene terephthalate; nylon resins (for Example, nylon-6,
nylon-11 and nylon-66); polyamide resins; polyvinyl chloride,
polyvinylidene chloride, vinyl chloride-propylene copolymers, and
the others).
[0410] Examples of the above-mentioned liquid carriers include
water; alcohols (for example, methanol, ethanol, isopropyl alcohol,
butanol, hexanol, benzyl alcohol, ethylene glycol, propylene glycol
or phenoxy ethanol); ketones (for Example, acetone, methyl ethyl
ketone or cyclohexanone); aromatic hydrocarbons (for example,
toluene, xylene, ethyl benzene, dodecyl benzene, phenyl xylyl
ethane or methylnaphthalene); aliphatic hydrocarbons (for example,
hexane, cyclohexane, kerosene or light oil); esters (for example,
ethyl acetate, butyl acetate, isopropyl myristate, ethyl oleate,
diisopropyl adipate, diisobutyl adipate or propylene glycol
monomethyl ether acetate); nitriles (for Example, acetonitrile or
isobutyronitrile); ethers (for example, diisopropyl ether,
1,4-dioxane, ethyleneglycol dimethyl ether, diethyleneglycol
dimethyl ether, diethylene glycol monomethyl ether, propylene
glycol monomethyl ether, dipropylene glycol monomethyl ether or
3-methoxy-3-methyl-1-butanol); acid amides (for Example,
N,N-dimethylformamide or N,N-dimethylacetamide); halogenated
hydrocarbons (for Example, dichloromethane, trichloroethane or
carbon tetrachloride); sulfoxides (for Example, dimethyl
sulfoxide); propylene carbonate; and vegetable oils (for Example,
soybean oil or cottonseed oil).
[0411] Examples of the above-mentioned gaseous carrier include
fluorocarbon, butane gas, liquefied petroleum gas (LPG), dimethyl
ether, and carbon dioxide gas.
[0412] Examples of the surfactants include nonionic surfactants
such as polyoxyethylenated alkyl ethers, polyoxyethylenated alkyl
aryl ethers and polyethylene glycol fatty acid esters; and anionic
surfactants such as alkyl sulfonates, alkylbenzene sulfonates and
alkyl sulfates.
[0413] Examples of the other auxiliary agents for formulation
include a binder, a dispersant and a stabilizer. Specific examples
include casein, gelatin, polysaccharides (for example, starch, gum
arabic, cellulose derivatives and alginic acid), lignin
derivatives, bentonite, water-soluble synthetic polymers (for
example, polyvinyl alcohol, polyvinyl pyrrolidone and polyacrylic
acids), PAP (acidic isopropyl phosphate), BHT
(2,6-di-tert-butyl-4-methylphenol), BHA (a mixture of
2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol).
[0414] Examples of base material of the resin formulation include
polyvinyl chloride polymers, polyurethane and the others, and a
plasticizer such as phthalate esters (for example, dimethyl
phthalate, dioctyl phthalate), adipic acid esters and stearic acid
may be added to these base materials, if necessary. The resin
formulation can be prepared by mixing the compound of the present
invention with the above-mentioned base material, kneading the
mixture, followed by molding it by injection molding, extrusion
molding or pressure molding and the like. The resultant resin
formulation can be subjected to further molding or cutting
procedure and the like, if necessary, to be processed into shapes
such as a plate, film, tape, net or string shape. These resin
formulations can be processed into animal collars, animal ear tags,
sheet products, trap strings, gardening supports and other
products.
[0415] Examples of a base material for the poison baits include
bait ingredients such as grain powder, vegetable oil, saccharide
and crystalline cellulose, and if necessary, with addition of
antioxidants such as dibutylhydroxytoluene and nordihydroguaiaretic
acid, preservatives such as dehydroacetic acid, accidental
ingestion inhibitors for children and pets such as a chili powder,
insect attraction fragrances such as cheese flavor, onion flavor
and peanut oil.
[0416] The method for controlling pests of the present invention is
conducted by applying an effective amount of the present compound
to a pest directly and/or a habitat thereof (for example, plant
bodies, soil, an interior of house, animal bodies). In the method
for controlling pests of the present invention, the present
compound is usually used in the form of a pest controlling
agent.
[0417] When an agent for controlling pests of the present invention
is used for controlling pests in an agricultural field, the
application dose as an amount of the present compound is usually
within a range from 1 to 10,000 g per 10,000 m.sup.2. The
emulsifiable concentrate, the wettable powder, or the flowable
formulation etc. of an agent for controlling pests of the present
invention is usually applied by diluting it with water in such a
way that a concentration of the active ingredient is within a range
from 0.01 to 10,000 ppm. The granular formulation, or the dust
formulation etc., is usually applied as itself without diluting
it.
[0418] These formulations or a water dilution thereof can be
sparged directly to pests or plants to be protected from pests, and
also may be applied to the soil of crop land in order to control
pests which live there. When applying to soil, the soil may be soil
where the plants are cultivated or the soil where the plants are to
be cultivated.
[0419] The resin preparation which is processed into a sheet or a
string may be applied by winding a crop with a sheet or a string of
the resin preparation, putting a string of the resin preparation
around a crop so that the crop is surrounded by the string, or
laying a sheet of the resin preparation on the soil surface near
the root of a crop.
[0420] The area to which the agent for controlling pests of the
present invention is applied includes, for Example, paddy fields,
cultivated lands, tea gardens, orchards and non-crop lands. Also,
the agent for controlling pests of the present invention may be
used in a raising seedling tray, a raising seedling box, a raising
seedling ridging, a raising seedling mat, and a water culture
medium in hydroponic farm and the others. The method for
cultivating plant in paddy fields and cultivated lands may be
till-farming (i.e., tillage) or no-till faring.
[0421] When the agent for controlling pests of the present
invention is used to control pests that live inside a house, the
application dose as an amount of the present compound is usually
within a range from 0.01 to 1,000 mg per 1 m.sup.2 of an area to be
treated, in the case of using it on a planar area. In the case of
using it spatially, the application dose as an amount of the
present compound is usually within a range from 0.01 to 500 mg per
1 m.sup.3 of the space to be treated. When the agent for
controlling pests of the present invention is formulated into
emulsifiable concentrates, wettable powders, flowables or the
others, such formulations are usually applied after diluting it
with water in such a way that a concentration of the active
ingredient is within a range from 0.1 to 10,000 ppm, and then
sparging it. In the case of being formulated into oil solutions,
aerosols, smoking agents, poison baits and the others, such
formulations are used as itself without diluting it.
[0422] When the agent for controlling pests of the present
invention is sued for controlling external parasites of livestock
such as cows, horses, pigs, sheep, goats and chickens and small
animals such as dogs, cats, rats and mice, the pest control agent
of the present invention can be applied to the animals by a known
method in the veterinary field. Specifically, when systemic control
is intended, the pest control agent of the present invention is
administered to the animals as a tablet, a mixture with feed or a
suppository, or by injection (including intramuscular,
subcutaneous, intravenous and intraperitoneal injections). On the
other hand, when non-systemic control is intended, the pest control
agent of the present invention is applied to the animals by means
of spraying of the oil solution or aqueous solution, pour-on or
spot-on treatment, or washing of the animal with a shampoo
formulation, or by putting a collar or ear tag made of the resin
formulations to the animal. In the case of administering to an
animal body, the dose of the present compound is usually within a
range from 0.1 to 1,000 mg per 1 kg of an animal body weight.
[0423] The agent for controlling pests of the present invention can
be used in agricultural lands where the below-mentioned plants
(hereinafter referred to as "present plants") are cultivated.
[0424] Crops:
corn, rice, wheat, barley, rye, triticale, oat, sorghum, cotton,
soybean, peanut, arachis, common bean (kidney bean), lima bean,
adzuki bean, cowpea, mung bean, urd bean, scarlet runner bean, rice
bean, moth bean, tepary bean, broad bean, pea, chick pea, lentils,
lupin, pigeon pea, buckwheat, beet, rapeseed, sunflower, sugarcane,
tobacco, hop, and the others;
[0425] Vegetables:
solanaceous vegetables (for example, eggplant, tomato, pimento,
pepper, bell pepper and potato), cucurbitaceous vegetables (for
example, cucumber, pumpkin, zucchini, water melon and melon),
cruciferous vegetables (for example, Japanese radish, white turnip,
horseradish, kohlrabi, Chinese cabbage, cabbage, leaf mustard,
broccoli and cauliflower), asteraceous vegetables (for example,
burdock, crown daisy, artichoke and lettuce), liliaceous vegetables
(for example, green onion, onion, garlic and asparagus), ammiaceous
vegetables (for example, carrot, parsley, celery and parsnip),
chenopodiaceous vegetables (for example, spinach and Swiss chard),
lamiaceous vegetables (for example, Perilla frutescens, mint,
basil, and lavender), strawberry, sweet potato, Dioscorea japonica,
colocasia, and the others;
[0426] Fruits:
pomaceous fruits (for example, apple, pear, Japanese pear, Chinese
quince and quince), stone fleshy fruits (for example, peach, plum,
nectarine, Prunus mume, cherry fruit, apricot and prune), citrus
fruits (for example, Citrus unshiu, orange, lemon, lime and
grapefruit), nuts (for example, chestnut, walnuts, hazelnuts,
almond, pistachio, cashew nuts and macadamia nuts), berry fruits
(for example, blueberry, cranberry, blackberry and raspberry),
grape, kaki persimmon, olive, Japanese plum, banana, coffee, date
palm, coconuts, oil palm, and the others;
[0427] Trees Other than Fruit Trees:
tea, mulberry, flowering plant (for example, dwarf azalea,
camellia, hydrangea, sasanqua, Illicium anisatum, cherry trees,
tulip tree, crape myrtle and fragrant olive), roadside trees (for
example, ash, birch, dogwood, Eucalyptus, Ginkgo biloba, lilac,
maple, Quercus, poplar, Judas tree, Liquidambar formosana, plane
tree, zelkova, Japanese arborvitae, fir wood, hemlock, juniper,
Pinus, Picea, Taxus cuspidate, elm and Japanese horse chestnut),
Sweet viburnum, Podocarpus macrophyllus, Japanese cedar, Japanese
cypress, croton, Japanese spindletree and Photinia glabra) and the
others;
[0428] Lawn:
sods (for example, Zoysia japonica, Zoysia matrella),
bermudagrasses (for example, Cynodon dactylon), bent glasses (for
example, Agrostis gigantea, Agrostis stolonifera, Agrostis
capillaris), blueglasses (for example, Poa pratensis, Poa
trivialis), festucae (for example, Festuca arundinacea Schreb.,
Festuca rubra L. var. commutata Gaud., Festuca rubra L. var.
genuina Hack), ryegrassses (for example, Lolium multiflorum Lam,
Lolium perenne L), Dactylis glomerata, Phleum pratense, and the
others;
[0429] forage crop:alfalfa and the others;
[0430] Others:
flowers (for example, rose, carnation, chrysanthemum, Eustoma,
gypsophila, gerbera, marigold, salvia, petunia, verbena, tulip,
aster, gentian, lily, pansy, cyclamen, orchid, lily of the valley,
lavender, stock, ornamental cabbage, primula, poinsettia,
gladiolus, cattleya, daisy, cymbidium and begonia),
[0431] bio-fuel plants (for example, jatropha, curcas, safflower,
Camelina, switch grass, Miscanthus giganteus, Phalaris arundinacea,
Arundo donax, Kenaf (Hibiscus cannabinus), cassava (Manihot
esculenta), willow (Salicaceae), algae, etc.),
ornamental foliage plants, and the others.
[0432] The present plant includes a plant bred by a hybrid
technology.
[0433] Also, the present plant includes also genetically modified
plants that are prepared by a genetic engineering technology.
[0434] The present plant also includes a plant on which tolerance
to herbicide has been conferred by a genetic engineering technology
or a classical breeding method.
[0435] The present plant also includes a plant on which a
capability of producing selective toxins to pests has been
conferred by genetic engineering technology.
[0436] The present plant also includes plants on which a capability
of producing antipathogenic substances has been conferred by
genetic engineering technology.
[0437] The present plant also includes plants on which advantageous
characters such as characters improved in oil stuff ingredients or
characters having reinforced amino acid content have been
conferred.
[0438] Typical examples of an application method of the agent for
controlling pests of the present invention to the present plant to
be protected from feeding by pests include an application to stem
and leaf, flower organ or ear of plants; an application to plant
seeds or vegetative propagation organs (such as seed potatoes,
bulbs, tubers, scaly bulbs, stem-segments); and an application to
nursery (including a cutting) and the others.
[0439] Typical examples of an application method of the agent for
controlling pests of the present invention to the stem and leaf,
flower organ or ear of plants include an application method to a
surface of plants such as foliage application and trunk tree
application, and also an application to flower organ or whole
plants at times of flowering including before flowering, during
flowering and after flowering, and in the case of crops as plant,
includes an application method to ear or whole plants at times of
sprouting.
[0440] Typical examples of an application method of the agent for
controlling pests of the present invention to plant seeds or
vegetative propagation organs include a method of dressing,
smearing or soaking of seeds or vegetative propagation organs, a
method of smearing of seeds or vegetative propagation organs into
liquid formulation, and a method of coating of seeds or vegetative
propagation organs (such as a film coating treatment, a pellet
coating treatment).
[0441] In the method, the dose of the present compound may be
applied usually within a range from 0.2 to 5,000 g, and preferably
within a range from 0.5 to 1,000 g per 100 kg of seeds or
vegetative propagation organs of the plants. Preferred dosage form
includes aqueous liquid suspension formulations such as
emulsifiable concentrates, wettable powders, flowables, and
microcapsules. In particular, the plant to be applied by the method
includes among the present plants, soybean, corn, cotton, wheat,
barley, rye, triticale, oat, rice, sorghum, arachis, pulses other
than soybean and arachis, beet, rapeseed, sunflower, potato,
sugarcane and vegetables.
[0442] When applying to sugarcane, the present agent may be applied
to stem-segments of sugarcane in a cultivation of sugarcane.
[0443] The present compound can be mixed or combined with known
pesticides, miticides, nematicides, fungicides, plant growth
regulators and synergists. Also, the agent for controlling pests of
the present invention may be used in combination with known
herbicides. Each of the active ingredient as the pesticides,
miticides, nematicides, fungicides, herbicide or synergists include
the followings:
Active Ingredient as Pesticides
(1) Organophosphorous Compound
[0444] acephate, Aluminium phosphide, butathiofos, cadusafos,
chlorethoxyfos, chlorfenvinphos, chlorpyrifos, chlorpyrifos-methyl,
cyanophos (abbrev. CYAP), diazinon, dichiofenthion (abbrev. ECP),
dichlorvos (abbrev. DDVP), dimethoate, dimethylvinphos, disulfoton,
EPN, ethion, ethoprophos, etrimfos, fenthion (abbrev. MPP),
fenitrothion (abbrev. MEP), fosthiazate, formothion, Hydrogen
phosphide, isofenphos, isoxathion, malathion, mesulfenfos,
methidathion (abbrev. DMTP), monocrotophos, naled (abbrev. BRP,
oxydeprofos (abbrev. ESP), parathion, phosalone, phosmet (abbrev.
PMP), pirimiphos-methyl, pyridafenthion, quinaiphos, phenthoate
(abbrev. PAP), profenofos, propaphos, prothiofos, pyraclorfos,
salithion, sulprofos, tebupirimfos, temephos, tetrachlorvinphos,
terbufos, thiometon, trichlorphon (abbrev. DEP), vamidothion,
phorate, and cadusafos.
(2) Carbamate Compounds
[0445] alanycarb, bendiocarb, benfuracarb, BPMC, carbaryl,
carbofuran, carbosulfan, cloethocarb, ethiofencarb, fenobucarb,
fenothiocarb, fenoxycarb, furathiocarb, isoprocarb (abbrev. MIPC),
metolcarb, methomyl, methiocarb, NAC, oxamyl, pirimicarb, propoxur
(abbrev. PHC), XMC, thiodicarb, xylylcarb, and aldicarb.
(3) Pyrethroid Compounds
[0446] acrinathrin, allethrin, benfluthrin, beta-cyfluthrin,
bifenthrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin,
deltamethrin, esfenvalerate, ethofenprox, fenpropathrin,
fenvalerate, flucythrinate, flufenoprox, flumethrin, fluvalinate,
halfenprox, imiprothrin, permethrin, prallethrin, pyrethrins,
resmethrin, sigma-cypermethrin, silafluofen, tefluthrin,
tralomethrin, transfluthrin, tetramethrin, phenothrin,
cyphenothrin, alpha-cypermethrin, zeta-cypermethrin,
Lambda-cyhalothrin, gamma-cyhalothrin, furamethrin,
tau-fluvalinate, metofluthrin, profluthrin, dimefluthrin,
2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl (EZ)-(1RS,3RS;
1RS,3SR)-2,2-dimethyl-3-prop-1-enyl cyclopropanecarboxylate,
2,3,5,6-tetrafluoro-4-methylbenzyl (EZ)-(1RS,3RS;
1RS,3SR)-2,2-dimethyl-3-prop-1-enyl cyclopropanecarboxylate,
2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl (1RS,3RS;
1RS,3SR)-2,2-dimethyl-3-(2-methyl-1-propenyl)-cyclopropanecarboxylate,
and 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl (EZ)-(1RS,3RS;
1RS,3SR)-2,2-dimethyl-3-(2-cyano-1-propenyl)-cyclopropanecarboxylate.
(4) Nereis Toxin Compounds
[0447] cartap, bensultap, thiocyclam, monosultap, and bisultap.
(5) Neonicotinoid Compounds
[0448] imidacioprid, nitenpyram, acetamiprid, thiamethoxam,
thiacloprid, dinotefuran, and clothianidin.
(6) Benzoylurea Compounds
[0449] chlorfluazuron, bistrifluron, diafenthiuron, diflubenzuron,
fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron,
novaluron, noviflumuron, teflubenzuron, triflumuron, and
triazuron.
(7) Phenylpyrazole Compounds
[0450] acetoprole, ethiprole, fipronil, vaniliprole, pyriprole, and
pyrafluprole.
(8) Bt Toxins
[0451] live spores and crystal toxins originated from Bacillus
thuringiensis and a mixture thereof.
(9) Hydrazine Compounds
[0452] chromafenozide, halofenozide, methoxyfenozide, and
tebufenozide.
(10) Organochlorine Compounds
[0453] aldrin, dieldrin, dienochlor, endosulfan, methoxychlor.
(11) Other Pesticide Active Ingredients
[0454] machine oil, nicotine-sulfate; avermectin-B, bromopropylate,
buprofezin, chlorphenapyr, cyantraniliprole, cyromazine, D-D
(1,3-Dichloropropene), emamectin-benzoate, fenazaquin,
flupyrazofos, hydroprene, methoprene, indoxacarb, metoxadiazone,
milbemycin-A, pymetrozine, pyridalyl, pyriproxyfen, spinosad,
sulfluramid, tolfenpyrad, triazamate, flubendiamide, lepimectin,
arsenic acid, benclothiaz, calcium cyanamide, calcium polysulfide,
chlordane, DDT, DSP, flufenerim, flonicamid, flurimfen,
formetanate, metam-ammonium, metam-sodium, methyl bromide,
potassium oleate, protrifenbute, spiromesifen, sulfoxaflor, sulfur,
metaflumizone, spirotetramat, pyrifluquinazone, spinetoram,
chlorantraniliprole, tralopyril, and cyantraniliprole.
[0455] a compound represented by the following formula (K):
##STR00014##
[wherein, [0456] R.sup.100 represents a bromine atom or a
trifluoromethyl group; [0457] R.sup.200 represents a chlorine atom,
a bromine atom or a methyl group; and
[0458] R.sup.300 represents a chlorine atom, a bromine atom or a
cyano group], and [0459] a compound represented by the following
formula (L):
##STR00015##
[0459] [wherein,
[0460] R.sup.1000 represents a chlorine atom, a bromine atom or an
iodine atom].
Active Ingredient as Miticides
[0461] acequinocyl, amitraz, benzoximate, bifenazate,
bromopropylate, chinomethionat, chlorobenzilate, CPCBS
(chlorfenson), clofentezine, cyflumetofen, kelthane (which is also
referred to as dicofol), etoxazole, fenbutatin oxide, fenothiocarb,
fenpyroximate, fluacrypyrim, fluproxyfen, hexythiazox, propargite
(abbrev. BPPS), polynactins, pyridaben, pyrimidifen, tebufenpyrad,
tetradifon, spirodiclofen, spiromesifen, spirotetramat,
amidoflumet, cyenopyrafen and the others.
Active Ingredient as Nematicides
[0462] DCIP, fosthiazate, levamisol, methyisothiocyanate, morantel
tartarate, imicyafos and the others.
Active Ingredient as the Fungicides:
[0463] azole fungicide compounds such as propiconazole,
prothioconazole, triadimenol, prochloraz, penconazole,
tebuconazole, flusilazole, diniconazole, bromuconazole,
epoxiconazole, difenoconazole, cyproconazole, metconazole,
triflumizole, tetraconazole, myclobutanil, fenbuconazole,
hexaconazole, fluquinconazole, triticonazole, bitertanol, imazalil,
flutriafol and the others;
[0464] cyclic amine fungicide compounds such as fenpropimorph,
tridemorph, fenpropimorph and the others;
[0465] benzimidazole fungicide compounds such as carbendazim,
benomyl, thiabendazole, thiophanate-methyl and the others;
[0466] procymidone; cyprodinil; pyrimethanil; diethofencarb;
thiuram; fluazinam; mancozeb; iprodione; vinclozolin;
chlorothalonil; captan; mepanipyrim; fenpiclonil; fludioxonil;
dichlofluanid; folpet; kresoxim-methyl; azoxystrobin;
trifloxystrobin; fluoxastrobin; picoxystrobin; pyraclostrobin;
dimoxystrobin; pyribencarb; spiroxamine; quinoxyfen; fenhexamid;
famoxadone; fenamidone; zoxamide; ethaboxam; amisulbrom;
iprovalicarb; benthiavalicarb; cyazofamid; mandipropamid; boscalid;
penthiopyrad; metrafenone; fluopiran; bixafen; cyflufenamid;
proquinazid; isotianil; tiadinil and the others.
Active Ingredient as Herbicides
[0467] (1) herbicidal phenoxyfatty acid compounds [0468] 2,4-D,
MCP, MCPB, phenothiol, mecoprop, fluroxypyr, triclopyr, clomeprop,
naproanilide and the others; [0469] (2) herbicidal benzoic acid
compounds [0470] 2,3,6-TBA, dicamba, clopyralid, picloram,
aminopyralid, quinclorac, quinmerac, and the others; [0471] (3)
herbicidal urea compounds [0472] diuron, linuron, chlortoluron,
isoproturon, fluometuron, isouron, tebuthiuron, methabenzthiazuron,
cumyluron, daimuron, methyl-daimuron and the others; [0473] (4)
herbicidal triazine compounds [0474] atrazine, ametoryn, cyanazine,
simazine, propazine, simetryn, dimethametryn, prometryn,
metribuzin, triaziflam, indaziflam and the others; [0475] (5)
herbicidal bipyridinium compounds [0476] paraquat, diquat and the
others; [0477] (6) herbicidal hydroxy benzonitrile compounds [0478]
bromoxynil, ioxynil and the others; [0479] (7) herbicidal
dinitroaniline compounds [0480] pendimethalin, prodiamine,
trifluralin and the others; [0481] (8) herbicidal organophosphorus
compounds [0482] amiprofos-methyl, butamifos, bensulide,
piperophos, anilofos, glyphosate, glufosinate, glufosinate-P,
bialaphos and the others; [0483] (9) herbicidal carbamate compounds
[0484] di-allate, tri-allate, EPTC, butylate, benthiocarb,
esprocarb, molinate, dimepiperate, swep, chlorpropham,
phenmedipham, phenisopham, pyributicarb, asulam and the others;
[0485] (10) herbicidal acid amide compounds [0486] propanil,
propyzamide, bromobutide, etobenzanid and the others; [0487] (11)
herbicidal chloroacetoanilide compounds [0488] acetochlor,
alachlor, butachlor, dimethenamid, propachlor, metazachlor,
metolachlor, pretilachlor, thenylchlor, pethoxamid and the others;
[0489] (12) herbicidal diphenylether compounds [0490]
acifluozfen-sodium, bifenox, oxyfluorfen, lactofen, fomesafen,
chlomethoxynil, acionifen and the others; [0491] (13) herbicidal
cyclic imide compounds [0492] oxadiazon, cinidon-ethyl,
carfentrazone-ethyl, surfentrazone, flumiclorac-pentyl,
flumioxazin, pyraflufen-ethyl, oxadiargyl, pentoxazone,
fluthiacet-methyl, butafenacil, benzfendizone, bencarbazone and the
others; [0493] (14) herbicidal pyrazole compounds [0494]
benzofenap, pyrazolate, pyrazoxyfen, topramezone, pyrasulfotole and
the others; [0495] (15) herbicidal triketone compounds [0496]
isoxaflutole, benzobicyclon, sulcotrione, mesotrione, tembotrione,
tefuryltrione and the others; [0497] (16) herbicidal
aryloxyphenoxypropionate compounds [0498] clodinafop-propargyl,
cyhalofop-butyl, diclofop-methyl, fenoxaprop-ethyl,
fluazifop-butyl, haloxyfop-methyl, quizalofop-ethyl, metamifop and
the others; [0499] (17) herbicidal trione oxime compounds [0500]
alloxydim-sodium, sethoxydim, butroxydim, clethodim, cloproxydim,
cycloxydim, tepraloxydim, tralkoxydim, profoxydim and the others;
[0501] (18) herbicidal sulfonylurea compounds [0502] chlorsulfuron,
sulfometuron-methyl, metsulfuron-methyl, chlorimuron-ethyl,
tribenuron-methyl, triasulfuron, bensulfuron-methyl,
thifensulfuron-methyl, pyrazosulfuron-ethyl, primisulfuron-methyl,
nicosulfuron, amidosulfuron, cinosuifuron, imazosulfuron,
rimsulfuron, halosulfuron-methyl, prosulfuron,
ethametsulfuron-methyl, triflusulfuron-methyl, flazasulfuron,
cyclosulfamuron, flupyrsulfuron, sulfosufuron, azimsulfuron,
ethoxysulfuron, oxasulfuron, iodosulfuron-methyl-sodium,
foramsulfuron, mesosulfuron-methyl, trifloxysulfuron,
tritosulfuron, orthosulfamuron, flucetosulfuron, propyrisulfuron
and the others; [0503] (19) herbicidal imidazolinone compounds
[0504] imazamethabenz-methyl, imazamethapyr, imazamox, imazapyr,
imazaquin, imazethapyr and the others; [0505] (20) herbicidal
sulfonamide compounds [0506] flumetsulam, metosulam, diclosulam,
florasulam, cloransulam-methyl, penoxsulam, pyroxsulam and the
others; [0507] (21) herbicidal pyrimidinyloxy benzoate compounds
[0508] pyrithiobac-sodium, bispyribac-sodium, pyriminobac-methyl,
pyribenzoxim, pyriftalid, pyrimisulfan and the others; [0509] (22)
other kinds of herbicidal compounds [0510] bentazon, bromacil,
terbacil, chlorthiamid, isoxaben, dinoseb, amitrole, cinmethylin,
tridiphane, dalapon, diflufenzopyr-sodium, dithiopyr, thiazopyr,
flucarbazone-sodium, propoxycarbazone-sodium, mefenacet,
flufenacet, fentrazamide, cafenstrole, indanofan, oxaziclomefone,
benfuresate, ACN, pyridate, chloridazon, norflurazon, flurtamone,
diflufenican, picolinafen, beflubutamid, clomazone, amicarbazone,
pinoxaden, pyraclonil, pyroxasulfone, thiencarbazone-methyl,
aminocyclopyrachlor, ipfencarbazone, methiozolin and the others;
and the others.
Active Ingredient as the Synergists
[0511] piperonyl butoxide, sesamex, sulfoxide,
N-(2-ethylhexyl)-8,9,10-trinorborn-5-ene-2,3-dicarboximide (MGK
264), N-declyimidazole, WARF-antiresistant, TBPT, TPP, IBP, PSCP,
methyl iodide (CH.sub.3I), t-phenylbutenone, diethylmaleate, DMC,
FDMC, ETP, ETN and the others.
EXAMPLES
[0512] The following Examples including Preparation Examples,
Formulation Examples and Test Examples, serve to illustrate the
present invention in more detail, which should not intend to limit
the present invention.
[0513] Firstly, with regard to a preparation of the present
compound, the Preparation Examples are shown below.
Preparation Example 1
[0514] (1) To a mixture of 3,6-dichloropyridine-2-carboxylic acid
50 g, N,N-dimethylformamide 1 mL and toluene 130 mL is added
thionyl chloride 49 mL at room temperature. The mixtures were
heated under reflux for 5 hours with stirring, and then the
reaction mixture was allowed to cool to a room temperature. The
reaction mixture was concentrated under reduced pressure to give an
intermediate 1. (2) To a mixture of
N2-methyl-5-(trifluoromethyl)pyridin-2,3-diamine (which is prepared
by a method described in WO 2010/125985) 50 g and tetrahydrofuran
90 mL was added dropwise a mixture of a whole amount of the
intermediate 1 obtained above and tetrahydrofuran 90 mL at
0.degree. C. The reaction mixture was stirred at room temperature
for 5 hours, and then to the reaction mixture was added hexane 200
mL. The precipitated solids were filtered off and placed in a
saturated sodium carbonate solution, and extracted with ethyl
acetate. The organic layers were dried over anhydrous sodium
sulfate and then concentrated under reduced pressure to give the
following intermediate 2 105 g.
##STR00016##
7.82 (1H, d), 7.50 (1H, d), 5.06 (1H, d), 3.08 (3H, d).
[0515] (3) A mixture of the intermediate 2 105 g and acetic acid
350 mL was heated under reflux for 4 hours with stirring. The
mixtures were allowed to cool to a room temperature and then
thereto was added water. The precipitated solids were filtered off
and dried under reduced pressure to give the following intermediate
3 84 g.
##STR00017##
[0516] .sup.1H-NMR (CDCl.sub.3) .delta.: 8.77 (1H, s), 8.40 (1H,
d), 7.92 (1H, d), 7.49 (1H, d), 4.02 (3H, 8).
(4) To a mixture of the intermediate 3 54 q, 60% sodium hydride
(dispersion in paraffin liquid) 6.9 g and tetrahydrofuran 800 mL
was added dropwise ethyl mercaptan 12 mL at 0.degree. C. The
reaction mixture was stirred at 0.degree. C. for 3 hours, and
thereto was added water. The precipitated solids washed with water
and hexane and the obtained solids were dried under reduced
pressure to give the following intermediate 4 as crude product 51
g.
##STR00018##
[0517] .sup.1H-NMR (CDCl.sub.3) .delta.: 8.74 (1H, s), 8.40 (1H,
s), 7.75 (1H, d), 7.42 (1H, d), 4.11 (3H, s), 2.97 (2H, q), 1.36
(3H, t).
(5) To a mixture of the intermediate 4 as crude product 50 g and
chloroform 450 mL was added 75% m-chloromethylbenzoic acid 66 g at
0.degree. C. The mixtures were stirred at 0.degree. C. for 5 hours
and then to the reaction mixture was added saturated aqueous sodium
hydrogen carbonate solution and the resulting mixture was extracted
with chloroform. The organic layers were washed with brine and
dried over anhydrous sodium sulfate. The resulting organic layers
were concentrated under reduced pressure and the resulting residue
was recrystallized from chloroform and hexane to give the following
intermediate 5 50 g.
##STR00019##
[0518] .sup.1H-NMR (CDCl.sub.3) .delta.: 8.78 (1H, d), 8.48 (1H,
d), 8.32 (1H, d), 7.73 (1H, d), 3.93 (3H, s), 3.86 (2H, q), 1.36
(3H, t).
(6) To a mixture of the intermediate 5 400 mg and pyridine 3 ml
added 1H-1,2,4-triazole 101 mg at room temperature. The mixtures
were heated to 90.degree. C. and stirred for 10 hours, and then
water was poured to the reaction mixture and the reaction mixture
was extracted with ethyl acetate. The organic layers were washed
with water and brine and dried over anhydrous sodium sulfate. The
resulting organic layers were concentrated under reduced pressure.
The resulting residues were subjected to a silica gel column
chromatography to give the following present compound 1 160 mg.
##STR00020##
Preparation Example 2
[0519] To a mixture of the intermediate 5 500 mg, 60% sodium
hydride (dispersion in paraffin liquid) 60 mg and
N,N-dimethylformamide 2.5 mL was added 3-chloro-1H-1,2,4-triazole
141 mg at 0.degree. C. for 2.5 hours. To the reaction mixture was
then added saturated aqueous sodium hydrogen carbonate solution and
the mixtures were extracted with ethyl acetate. The organic layers
were washed with water and brine, and dried over anhydrous sodium
sulfate. The resulting organic layers were concentrated under
reduced pressure. The resulting residues were subjected to a silica
gel column chromatography to give the following present compound 2
435 mg.
##STR00021##
Preparation Example 3
[0520] To a mixture of the intermediate 5 300 mg, potassium
carbonate 133 mg and N,N-dimethylformamide 3 mL was added
3-bromo-1H-1,2,4-triazole 132 mg at 0.degree. C. The mixtures were
stirred at 0.degree. C. for 2.5 hours, and to the reaction mixture
was added saturated aqueous sodium hydrogen carbonate solution and
extracted with ethyl acetate. The organic layers were washed with
water and brine and dried over anhydrous sodium sulfate. The
resulting organic layers were concentrated under reduced pressure.
The resulting residues were subjected to a silica gel column
chromatography to give the following present compound 3 370 mg.
##STR00022##
Preparation Example 4
[0521] To a mixture of the intermediate 5 500 mg, 60% sodium
hydride (dispersion in paraffin liquid) 60 mg and
N,N-dimethylformamide 2.5 mL was added 3-methyl-1H-1,2,4-triazole
(which was prepared by a method described in US 2006/0293304 A1)
113 mg. The mixtures were stirred at 0.degree. C. for 2.5 hours. To
the reaction mixture was then added saturated aqueous sodium
hydrogen carbonate solution, and the mixtures were extracted with
ethyl acetate. The organic layers were washed with water and brine
and dried over anhydrous sodium sulfate. The resulting organic
layers were concentrated under reduced pressure. The resulting
residues were subjected to a silica gel column chromatography to
give the present compound 4 153 mg.
##STR00023##
Preparation Example 5
[0522] To a mixture of the intermediate 5 300 mg, 60% sodium
hydride (dispersion in paraffin liquid) 36 mg and
N,N-dimethylformamide 1.5 mL was added
3-trifluoromethyl-1H-1,2,4-triazole (which was prepared by a method
described in US 2010/0063063 A1) 112 mg at 0.degree. C. The
mixtures were stirred at 0.degree. C. for 2.5 hours, and to the
reaction mixture was then added saturated aqueous sodium hydrogen
carbonate solution and extracted with ethyl acetate. The organic
lays were washed with water and brine and dried over anhydrous
sodium sulfate. The resulting organic layers were concentrated
under reduced pressure. The resulting residues were subjected to a
silica gel column chromatography to give the following present
compound 5 326 mg.
##STR00024##
Preparation Example 6
[0523] (1) A mixture of the intermediate 5 2.0 g,
diisopropylethylamine 1.7 mL and N-methylpyrrolidone 10 mL was
added semicarbazide hydrochloride 1.1 g at room temperature. The
mixtures were heated at 70.degree. C. for 5 hours and allowed to
cool to a room temperature. To the reaction mixtures was added
triethyl orthoformate 10 mL, and The mixtures were heated at
100.degree. C. for 4 hours with stirring. To the reaction mixtures
were added 2N hydrochloric acid 10 mL and water 30 mL. The
precipitated solids were filtered off and dried under reduced
pressure to give the following intermediate 6 2.1 g.
##STR00025##
(2) To a mixture of the intermediate 6 1.2 g, potassium carbonate
600 mg and N-methylpyrrolidone 4.3 mL was added iodomethane 170
.mu.L at 0.degree. C. The reaction mixtures were raised to a room
temperature and stirred for 5 hours. To the resulting mixtures was
added water and the mixtures were extracted with ethyl acetate. The
organic layers were dried over anhydrous sodium sulfate and then
concentrated under reduced pressure. The resulting residues were
subjected to a silica gel column chromatography to give the
following present compound 6 740 mg.
##STR00026##
Preparation Example 7
[0524] To a mixture of the intermediate 5 500 mg, 60% sodium
hydride (dispersion in paraffin liquid) 54 mg and
N,N-dimethylformamide 2.5 mL was added
3-(methyl-thio)-1H-1,2,4-triazole (which as prepared by a method
described in Heteroatom Chemistry, 2009, 20 volume, pages 405-410)
185 mg at 0.degree. C. The mixtures were stirred at 0.degree. C.
for 4.5 hours, and to the reaction mixtures was added saturated
aqueous sodium hydrogen carbonate solution, and the mixtures were
extracted with ethyl acetate. The organic layers were washed with
water and brine and dried over anhydrous sodium sulfate. The
resulting organic layers were concentrated under reduced pressure.
To the resulting solids was added chloroform 2 mL and the solids
were filtered. The solids were washed with hexane and dried under
reduced pressure to give the following present compound 7 270
mg.
##STR00027##
Preparation Example 8
[0525] To a mixture of the present compound 7 430 mg and chloroform
6 mL was added 75% m-chloromethyl benzoic acid 440 mg at 0.degree.
C. The mixtures were stirred at room temperature for 12 hours, and
then washed with saturated aqueous sodium sulfite solution and
saturated aqueous sodium hydrogen carbonate solution. The mixtures
were extracted with chloroform and the resulting organic layers
were dried over anhydrous sodium sulfate, and then concentrated
under reduced pressure. The resulting residues were subjected to a
silica gel column chromatography to give the following present
compound 8 250 mg.
##STR00028##
Preparation Example 9
[0526] To a mixture of the intermediate 5 500 mg, 60% sodium
hydride (dispersion in paraffin liquid) 60 mg and
N,N-dimethylformamide 2.5 mL was added 3-amino-1H-[1,2,4]triazole
115 mg at 0.degree. C. The mixtures were stirred at room
temperature for 11 hours, and to the reaction mixtures was then
added saturated aqueous sodium hydrogen carbonate solution and the
mixtures were extracted with ethyl acetate. The organic layers were
washed with water and brine, and then dried over anhydrous sodium
sulfate. The resulting organic layers were concentrated under
reduced pressure. The resulting residues were subjected to a silica
gel column chromatography to give the following present compound 9
364 mg.
##STR00029##
Preparation Example 10
[0527] To a mixture of the intermediate 5 500 mg, 60% sodium
hydride (dispersion in paraffin liquid) 60 mg and
N,N-dimethylformamide 2.5 mL was added 3-nitro-1H-1,2,4-triazole
156 mg at 0.degree. C. The mixtures were stirred at room
temperature for 11 hours, and to the reaction mixtures was then
added saturated aqueous sodium hydrogen carbonate solution, and the
mixtures were extracted with ethyl acetate. The organic layers were
washed with water and brine and dried over anhydrous sodium
sulfate. The resulting organic layers were concentrated under
reduced pressure. The resulting residues were subjected to a silica
gel column chromatography to give the following present compound 10
518 mg.
##STR00030##
Preparation Example 11
[0528] To a mixture of the intermediate 5 1.1 g, 60% sodium hydride
(dispersion in paraffin liquid) 119 mg and N-methylpyrrolidone 5 mL
was added methyl 1H-1,2,4-triazole-3-carboxylate 613 mg. The
mixtures were stirred at room temperature for 12 hours, and to the
reaction mixtures was added saturated aqueous sodium hydrogen
carbonate solution, and the mixtures were extracted with ethyl
acetate. The organic layers were washed with water and brine and
dried over anhydrous sodium sulfate. The resulting organic layers
were concentrated under reduced pressure. The resulting residues
were subjected to a silica gel column chromatography to give the
following present compound 11 633 mg.
##STR00031##
Preparation Example 12
[0529] To a mixture of the intermediate 5 300 mg, 60% sodium
hydride (dispersion in paraffin liquid) 40 mg and
N,N-dimethylformamide 5 mL was added 3-cyano-1H-1,2,4-triazole 94
mg at 0.degree. C. The mixtures were stirred at room temperature
for 12 hours, and to the reaction mixtures was then added aqueous
sodium hydrogen carbonate solution, and the mixtures were extracted
with ethyl acetate. The organic layers were washed with water and
brine and dried over anhydrous sodium sulfate. The resulting
organic layers were concentrated under reduced pressure. The
resulting residues were subjected to a silica gel column
chromatography to give the following present compound 12 28 mg.
##STR00032##
Preparation Example 13
[0530] To a mixture of the intermediate 4 as crude product 370 mg,
60% sodium hydride (dispersion in paraffin liquid) 48 mg and
N,N-dimethylformamide 5 mL was added 1H-1,2,4-triazole 83 mg at
0.degree. C. The mixtures were stirred at 100.degree. C. for 12
hours, and to the reaction was added saturated aqueous sodium
hydrogen carbonate solution, and the mixtures were extracted with
ethyl acetate. The organic layers were washed with water and brine
and dried over anhydrous sodium sulfate. The resulting organic
layers were concentrated under reduced pressure. The resulting
residues were subjected to a silica gel column chromatography to
give the following present compound 13 300 mg.
##STR00033##
Preparation Example 14
[0531] The following present compound 14 was prepared according to
the method described in the preparation Example 13 using
3-chloro-1H-1,2,4-triazole in place of 1H-1,2,4-triazole.
##STR00034##
Preparation Example 15
[0532] The following present compound 15 was prepared according to
the method described in the preparation Example 13 using
3-bromo-1H-1,2,4-triazole in place of 1H-1,2,4-triazole.
##STR00035##
Preparation Example 16
[0533] The following present compound 16 was prepared according to
the method described in the preparation Example 13 using
3-(trifluoromethyl)-1H-1,2,4-triazole in place of
1H-1,2,4-triazole.
##STR00036##
Preparation Example 17
[0534] The following present compound 17 was prepared according to
the method described in the preparation Example 1.3 using
3-(methylthio)-1H-1,2,4-triazole in place of 1H-1,2,4-triazole.
##STR00037##
Preparation Example 18(1)
[0535] To a mixture of the intermediate 4 as crude product 3.0 g
and chloroform 25 mL was added 75% m-chloromethyl benzoic acid 1.9
g at 0.degree. C. The mixtures were stirred at 0.degree. C. for 5
hours, and to the reaction mixtures was then added saturated
aqueous sodium hydrogen carbonate solution, and the mixtures were
extracted with chloroform. The organic layers were washed with
brine and dried over anhydrous sodium sulfate. The resulting
organic layers were concentrated under reduced pressure and the
resulting residues were subjected to a silica gel column
chromatography to give the following intermediate 7 2.6 g.
##STR00038##
[0536] .sup.1H-NMR (CDCl.sub.3) .delta.: 8.79 (1H, d), 8.62 (1H,
d), 8.36 (1H, d), 7.69 (1H, d), 4.38 (3H, s), 3.70-3.60 (1H, m),
3.16-3.06 (1H, m), 1.47 (3H, t).
Preparation Example 18(2)
[0537] To a mixture of the intermediate 7 200 mg, 60% sodium
hydride (dispersion in paraffin liquid) 25 mg and
N,N-dimethylformamide 4 mL was added 1H-1,2,4-triazole 43 mg at
0.degree. C. The mixtures were stirred at tom temperature for 12
hours, and to the reaction mixtures was then added saturated
aqueous sodium hydrogen carbonate solution, and the mixtures were
extracted with ethyl acetate. The organic layers were washed with
water and brine, and dried over anhydrous sodium sulfate. The
resulting organic layers were concentrated under reduced pressure.
The resulting residues were subjected to a silica gel column
chromatography to give the following present compound 18 75 mg.
##STR00039##
Preparation Example 19
[0538] The following present compound 19 was prepared according to
the method described in the preparation Example 18(2) using
3-chloro-1H-1,2,4-triazole in place of 1H-1,2,4-triazole.
##STR00040##
Preparation Example 20
[0539] The following present compound 20 was prepared according to
the method described in the preparation Example 18(2) using
3-bromo-1H-1,2,4-triazole in place of 1H-1,2,4-triazole.
##STR00041##
Preparation Example 21
[0540] The following present compound 21 was prepared according to
the method described in the preparation Example 18(2) using
3-(trifluoromethyl)-1H-1,2,4-triazole in place of
1H-1,2,4-triazole.
##STR00042##
Preparation Example 22
[0541] The following present compound 22 was prepared according to
the method described in the preparation Example 18(2) using
3-(methylthio)-1H-1,2,4-triazole in place of 1H-1,2,4-triazole.
##STR00043##
Preparation Example 23(1)
[0542] To a mixture of the intermediate 5 2.0 g and chloroform 10
mL was added 75% m-chloromethyl benzoic acid 3.4 g at 0.degree. C.
The reaction mixtures were stirred at 50.degree. C. for 10 hours.
The mixtures were allowed to cool to a room temperature, and to the
reaction mixtures was then added saturated aqueous sodium hydrogen
carbonate solution, and the mixtures were dried over anhydrous
sodium sulfate. The resulting organic layers were concentrated
under reduced pressure and the resulting residues were subjected to
a silica gel column chromatography to give the following
intermediate 8 1.1 g.
##STR00044##
[0543] .sup.1H-NMR (CDCl.sub.3) .delta.: 8.48 (1H, s), 8.46 (1H,
d), 7.92 (1H, s), 7.76 (1H, d), 4.33 (3H, s), 3.70 (2H, q), 1.36
(3H, t).
Preparation Example 23(2)
[0544] To a mixture of the intermediate 8 100 mg, potassium
carbonate 50 mg and N,N-dimethylformamide 2.0 mL was added
1H-1,2,4-triazole 25 mg at 0.degree. C. The mixtures were stirred
at room temperature for 12 hours, and to the reaction mixtures was
then added saturated aqueous sodium hydrogen carbonate solution,
and the mixtures were extracted with ethyl acetate. The organic
layers were washed with water and brine and dried over anhydrous
sodium sulfate. The resulting organic layers were concentrated
under reduced pressure. The resulting residues were subjected to a
silica gel column chromatography to give the following present
compound 23 80 mg.
##STR00045##
Preparation Example 24
[0545] The following present compound 24 was prepared according to
the method described in the preparation Example 23(2) using
3-chloro-1H-1,2,4-triazole in place of 1H-1,2,4-triazole.
##STR00046##
Preparation Example 25
[0546] The following present compound 25 was prepared according to
the method described in the preparation Example 23(2) using
3-bromo-1H-1,2,4-triazole in place of 1H-1,2,4-triazole.
##STR00047##
Preparation Example 26
[0547] The following present compound 26 was prepared according to
the method described in the preparation Example 23(2) using
3-(trifluoromethyl)-1H-1,2,4-triazole in place of
1H-1,2,4-triazole.
##STR00048##
Preparation Example 27
[0548] The following present compound 27 was prepared according to
the method described in the preparation Example 23(2) using
3-(methylthio)-1H-1,2,4-triazole in place of 1H-1,2,4-triazole.
##STR00049##
[0549] The physical values of the present compounds described in
the above-mentioned Preparation Examples are shown in Table 5.
TABLE-US-00005 TABLE 5 Present compound Physical property 1
.sup.1H-NMR (CDCl.sub.3) .delta.: 9.16 (1H, s), 8.81 (1H, br s),
8.72 (1H, d), 8.36 (1H, br s), 8.31 (1H, d), 8.21 (1H, s), 3.93
(3H, s), 3.82 (2H, q), 1.39 (3H, t). 2 .sup.1H-NMR (DMSO-D.sub.6)
.delta.: 9.67 (1H, s), 8.95 (1H, br s), 8.77 (1H, d), 8.75 (1H, br
s), 8.29 (1H, d), 3.96-3.89 (5H, m), 1.26 (3H, t). 3 .sup.1H-NMR
(CDCl.sub.3) .delta.: 9.04 (1H, s), 8.81 (1H, br s), 8.73 (1H, d),
8.35 (1H, br s), 8.26 (1H, d), 3.92 (3H, s), 3.81 (2H, q), 1.39
(3H, t). 4 .sup.1H-NMR (CDCl.sub.3) .delta.: 9.03 (1H, s), 8.80
(1H, br s), 8.68 (1H, d), 8.35 (1H, br s), 8.22 (1H, d), 3.92 (3H,
s), 3.81 (2H, q), 2.54 (3H, s), 1.39 (3H, t). 5 .sup.1H-NMR
(DMSO-D.sub.6) .delta.: 9.90 (1H, s), 8.95 (1H, br s), 8.81 (1H,
d), 8.76 (1H, br s), 8.41 (1H, d), 3.99-3.91 (5H, m), 1.26 (3H, t).
6 .sup.1H-NMR (CDCl.sub.3) .delta.: 8.88 (1H, s), 8.80 (1H, br s),
8.66 (1H, d), 8.35 (1H, br s), 8.14 (1H, d), 4.13 (3H, s), 3.91
(3H, s), 3.80 (2H, q), 1.38 (3H, t). 7 .sup.1H-NMR (CDCl.sub.3)
.delta.: 9.06 (1H, s), 8.80 (1H, br s), 8.68 (1H, d), 8.35 (1H, br
s), 8.21 (1H, d), 3.91 (3H, s), 3.80 (2H, q), 2.71 (3H, s), 1.39
(3H, t). 8 .sup.1H-NMR (CDCl.sub.3) .delta.: 9.27 (1H, s), 8.82
(1H, br s), 8.80 (1H, d), 8.41 (1H, d), 8.37 (1H, br s), 3.93 (3H,
s), 3.82 (2H, q), 3.39 (3H, s), 1.40 (3H, t). 9 .sup.1H-NMR
(CDCl.sub.3) .delta.: 8.80 (1H, br s), 8.63 (1H, d), 8.35 (1H, br
s), 8.29 (1H, d), 7.66 (1H, s), 6.45 (2H, br s), 3.88 (3H, s), 3.70
(2H, q), 1.37 (3H, t). 10 .sup.1H-NMR (CDCl.sub.3) .delta.: 9.24
(1H, s), 8.85-8.82 (2H, m), 8.43 (1H, d), 8.37 (1H, br s), 3.93
(3H, s), 3.82 (2H, q), 1.40 (3H, t). 11 .sup.1H-NMR (CDCl.sub.3)
.delta.: 9.24 (1H, s), 8.82 (1H, br s), 8.77 (1H, d), 8.45 (1H, d),
8.36 (1H, br s), 4.09 (3H, s), 3.94 (3H, s), 3.82 (2H, q), 1.40
(3H, t). 12 .sup.1H-NMR (CDCl.sub.3) .delta.: 9.24 (1H, s),
8.83-8.79 (2H, m), 8.37-8.32 (2H, m), 3.92 (3H, s), 3.82 (2H, q),
1.40 (3H, t). 13 .sup.1H-NMR (CDCl.sub.3) .delta.: 9.09 (1H, s),
8.79-8.77 (1H, br m), 8.44-8.42 (1H, br m), 8.15 (1H, s), 8.04 (1H,
d), 8.00 (1H, d), 4.11 (3H, s), 3.03 (2H, q), 1.38 (3H, t). 14
.sup.1H-NMR (CDCl.sub.3) .delta.: 8.98 (1H, s), 8.78 (1H, d), 8.43
(1H, d), 8.00 (1H, d), 7.96 (1H, d), 4.09 (3H, s), 3.03 (2H, q),
1.38 (3H, t). 15 .sup.1H-NMR (CDCl.sub.3) .delta.: 8.96 (1H, s),
8.78 (1H, d), 8.43 (1H, d), 7.99 (2H, s), 4.08 (3H, s), 3.03 (2H,
q), 1.38 (3H, t). 16 .sup.1H-NMR (CDCl.sub.3) .delta.: 9.15 (1H,
d), 8.79 (1H, d), 8.44 (1H, d), 8.07 (1H, d), 8.02 (1H, d), 4.10
(3H, s), 3.04 (2H, q), 1.39 (3H, t). 17 .sup.1H-NMR (CDCl.sub.3)
.delta.: 9.00 (1H, s), 8.77 (1H, t), 8.43 (1H, t), 7.97 (2H, s),
4.08 (3H, s), 3.01 (2H, q), 2.70 (3H, s), 1.37 (3H, t). 18
.sup.1H-NMR (CDCl.sub.3) .delta.: 9.20 (1H, s), 8.88 (1H, d), 8.82
(1H, d), 8.40 (1H, d), 8.30 (1H, d), 8.22 (1H, s), 4.41 (3H, s),
3.74-3.64 (1H, m), 3.22-3.12 (1H, m), 1.50 (3H, t). 19 .sup.1H-NMR
(CDCl.sub.3) .delta.: 9.09 (1H, s), 8.89 (1H, d), 8.82 (1H, d),
8.40 (1H, d), 8.24 (1H, d), 4.40 (3H, s), 3.75-3.64 (1H, m),
3.21-3.11 (1H, m), 1.50 (3H, t). 20 .sup.1H-NMR (CDCl.sub.3)
.delta.: 9.07 (1H, s), 8.89 (1H, d), 8.82 (1H, d), 8.40 (1H, d),
8.26 (1H, d), 4.39 (3H, s), 3.74-3.64 (1H, m), 3.21-3.11 (1H, m),
1.50 (3H, t). 21 .sup.1H-NMR (CDCl.sub.3) .delta.: 9.25 (1H, d),
8.93 (1H, d), 8.83 (1H, d), 8.41 (1H, d), 8.34 (1H, d), 4.41 (3H,
s), 3.76-3.66 (1H, m), 3.23-3.13 (1H, m), 1.50 (3H, t). 22
.sup.1H-NMR (CDCl.sub.3) .delta.: 9.10 (1H, s), 8.84 (1H, d), 8.81
(1H, d), 8.39 (1H, d), 8.22 (1H, d), 4.39 (3H, s), 3.73-3.63 (1H,
m), 3.20-3.11 (1H, m), 2.72 (3H, s), 1.49 (3H, t). 23 .sup.1H-NMR
(CDCl.sub.3) .delta.: 9.14 (1H, s), 8.70 (1H, d), 8.50 (1H, d),
8.34 (1H, d), 8.21 (1H, s), 7.96 (1H, s), 4.33 (3H, s), 3.69 (2H,
q), 1.38 (3H, t). 24 .sup.1H-NMR (CDCl.sub.3) .delta.: 9.05 (1H,
s), 8.71 (1H, d), 8.50 (1H, s), 8.27 (1H, d), 7.95 (1H, s), 4.32
(3H, s), 3.68 (2H, q), 1.38 (3H, t). 25 .sup.1H-NMR (CDCl.sub.3)
.delta.: 9.02 (1H, s), 8.71 (1H, d), 8.50 (1H, s), 8.29 (1H, d),
7.95 (1H, s), 4.32 (3H, s), 3.68 (2H, q), 1.38 (3H, t). 26
.sup.1H-NMR (CDCl.sub.3) .delta.: 9.22 (1H, s), 8.76 (1H, d), 8.51
(1H, s), 8.39 (1H, d), 7.96 (1H, s), 4.33 (3H, s), 3.69 (2H, q),
1.39 (3H, t). 27 .sup.1H-NMR (CDCl.sub.3) .delta.: 9.04 (1H, s),
8.65 (1H, d), 8.50 (1H, s), 8.23 (1H, d), 7.95 (1H, s), 4.31 (3H,
s), 3.67 (2H, q), 2.70 (3H, s), 1.37 (3H, t).
[0550] Next, the formulation examples of the present compound are
shown below. The "parts" represents "part by weight" unless
otherwise specified.
Formulation Example 1
[0551] Into a mixture of 35 parts of xylene and 35 parts of
N,N-dimethylformamide, 10 parts of each of the present compounds 1
to 27 is dissolved, and then 14 parts of polyoxyethylene styryl
phenyl ether and 6 parts of calcium dodecylbenzene sulfonate are
added, followed by mixing them to obtain each formulation.
Formulation Example 2
[0552] Four (4) parts of sodium lauryl sulfate, 2 parts of calcium
lignin sulfonate, 20 parts of synthetic hydrated silicon oxide fine
powder and 54 parts of diatomaceous earth are mixed, and further 20
parts of each of the present compounds is added, followed by mixing
them to obtain each wettable powders.
Formulation Example 3
[0553] To 2 parts of each of the present compounds 1 to 27, 1 part
of synthetic hydrated silicon oxide fine powder, 2 parts of calcium
lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay
are added, followed by mixing, granulation with a granulator and
forced-air drying to obtain each granular formulation.
Formulation Example 4
[0554] Into an appropriate amount of acetone, 1 part of each the
present compounds 1 to 27 is dissolved, and then 5 parts of
synthetic hydrous silicon oxide fine powder, 0.3 parts of isopropyl
acid phosphate and 93.7 parts of fubasami clay are added, followed
by mixing with stirring thoroughly and removal of acetone from the
mixture by evaporation to obtain each of powder formulation.
Formulation Example 5
[0555] A mixture of 35 parts of polyoxyethylene alkyl ether sulfate
ammonium salt and white carbon (weight ratio of 1:1), 10 parts of
each of the present compounds 1 to 27, and 55 parts of water are
mixed, followed by finely grounding by a wet grinding method to
obtain each flowable formulation.
Formulation Example 6
[0556] Into a mixture of 5 parts of xylene and 5 parts of
trichloroethane, 0.1 parts of each of the present compounds 1 to 27
is dissolved, and the resulting mixture is then mixed with 89.9
parts of deodorized kerosene to obtain each oil solution.
Formulation Example 7
[0557] Into 0.5 mL of acetone, 10 mg of each of the present
compounds 1 to 27 is dissolved and the solution is added dropwise
to 5 g of a solid feed powder for an animal (solid feed powder for
rearing and breeding CE-2, manufactured by CLEA Japan, Inc.),
followed by mixing the resulting mixture uniformly, and then by
drying them by evaporation of acetone to obtain each poison
bait.
Formulation Example 8
[0558] Into an aerosol can, 0.1 part of each of the present
compound 1 to 27 and 49.9 parts of Neothiozole (Chuo Kasei Co.,
Ltd.) are placed. After mounting an aerosol valve, 25 parts of
dimethylether and 25 parts of LPG are filled, followed by shaking
and further mounting an actuator to obtain an oily aerosol.
Formulation Example 9
[0559] A mixture of 0.6 part of each of the present compounds 1 to
27, 0.01 part of BHT (2,6-di-tert-butyl-4-methylphenol), 5 parts of
xylene, 3.39 parts of deodorized kerosine and 1 part of an
emulsifier {Rheodol MO-60 (registered trademark of Kao
Corporation)} and 50 parts of distilled water are filled into an
aerosol container, and a valve part is attached. Then, 40 parts of
a propellant (LPG) is filled therein through the valve under
pressure to obtain an aqueous aerosol.
Formulation Example 10
[0560] Zero point one (0.1) parts of each of the present compounds
1 to 27 are mixed into 2 mL of propylene glycol, and the resulting
solution is impregnated into a porous ceramic plate having a size
of 4.0 cm.times.4.0 cm and a thickness of 1.2 cm, to obtain thermal
fumigants.
Formulation Example 11
[0561] Five (5) parts of each of the present compounds 1 to 27, and
95 parts of ethylene-methyl methacrylate copolymer (the ratio of
the methyl methacrylate in the copolymer: 10 weight %), Acryft
(registered by trademark) WD 301, manufactured by Sumitomo Chemical
Co. Ltd.) are melted and kneaded with a closed type pressure
kneader, and the resulting kneaded product is extruded from an
extrusion molding machine through a molding die to obtain a
rod-shaped molded product having a length of 15 cm and a diameter
of 3 mm.
Formulation Example 12
[0562] Five (5) parts of each of the present compounds 1 to 27, and
95 parts of plasticized polyvinyl chloride resin are melted and
kneaded with a closed type pressure kneader, and the resulting
kneaded product is extruded from an extrusion molding machine
through a molding die to obtain a rod-shaped molded product having
a length of 15 cm and a diameter of 3 mm.
Formulation Example 13
[0563] One hundred (100) mg of each of the present compounds 1 to
27, 68.75 mg of lactose, 237.5 mg of corn starch, 43.75 mg of
microcrystalline cellulose, 18.75 mg of polyvinylpyrrolidone, 28.75
mg of sodium carbomethyl starch and 25 mg of magnesium stearate are
mixed, and the resulting mixture was compressed to an appropriate
size to obtain a tablet.
Formulation Example 14
[0564] Twenty five (25) mg of each of the present compounds 1 to
27, 60 mg of lactose, 25 mg of corn starch, 6 mg of carmellose
calcium and an appropriate amount of 5% of hydroxypropyl
methylcellulose are mixed, and the resulting mixture are filled
into a hard shell gelatin capsule or a hydroxypropyl
methylcellulose capsule to obtain capsules.
Formulation Example 15
[0565] To 100 mg of each of the present compounds 1 to 27, 500 mg
of fumaric acid, 2,000 mg of granulated sugar, 13,000 mg of
sorbitol (70% solution), 100 mg of Veegum K (manufactured by
Vanderbilt Co.), 35 mg of perfume and 500 mg of coloring agent, a
distilled water is added such that a final volume is set to be 100
mL, followed by mixing them to obtain a suspension for oral
administration.
Formulation Example 16
[0566] Into a mixture of 85% by weight of polysorbate, 3% by weight
of benzyl alcohol and 30% by weight of propylene glycol, 5% by
weight of each of the present compounds 1 to 27 is dissolved, and
phosphate buffer is added thereto such that a pH of the solution is
set to be 6.0 to 6.5, and water is added as the rest parts to
obtain the solution for oral administration.
Formulation Example 17
[0567] To a mixture of 57% by weight of fractional distillated palm
oil and 3% by weight of polysorbate 85, 5% by weight of aluminum
distearate is added, and heated to disperse it. The resulting
mixture is cooled to room temperature, and 25% by weight of
saccharin is dispersed in an oil vehicle. Ten (10) % by weight of
each of the present compounds 1 to 27 is divided thereto to obtain
a paste for oral administration.
Formulation Example 18
[0568] Five (5) % by weight of each of the present compounds 1 to
27 is mixed with 95% by weight of limestone filler, followed by a
wet granulation of the resulting mixture to obtain a granule for
oral administration.
Formulation Example 19
[0569] Into 80 parts of diethylene glycol monomethyl ether, 5 parts
of each of the present compounds 1 to 27 is dissolved, and 15 parts
of propylene carbonate is added thereto, and the resulting mixture
is mixed to obtain a spot-on solution.
Formulation Example 20
[0570] Into 70 parts of diethylene glycol monomethyl ether, 10
parts of each of the present compounds 1 to 27 is dissolved, and 20
parts of 2-octyldodecanol is added thereto, and the resulting
mixture is mixed to obtain a pour-on solution.
Formulation Example 21
[0571] To 0.5 parts of each of the present compounds 1 to 27, 60
parts of Nikkol (registered by trademark) TEALS-42 (manufactured by
Nikko Chemical Co. Ltd.: 42% of aqueous solution of lauryl sulfuric
acid triethanol amine) and 20 parts of propylene glycol are added,
and the resulting mixture is mixed with stirring thoroughly, and
19.5 parts of water is then added thereto and the resulting mixture
is further mixed with stirring thoroughly to obtain a hydrogenous
solution of shampoo formulation.
Formulation Example 22
[0572] Zero point fifteen (0.15)% by weight of each of the present
compounds 1 to 27, 95% by weight of animal feed, as well as 4.85%
by weight of a mixture of dibasic calcium phosphate, diatomaceous
earth, aerosol and carbonate (or chalk) are mixed with stirring
thoroughly to obtain a premix for animal feed.
Formulation Example 23
[0573] Seven point two (7.21 g of each of the present compounds 1
to 27, and 92.8 g of Hosco (registered trademark) S-55
(manufactured by Maruishi Pharmaceuticals) are melted and mixed at
100.degree. C., and the resulting mixture was poured into a
suppository mold, followed by performing a cooling solidification
to obtain a suppository.
[0574] Also, the formulation Examples of the agent for controlling
pests comprising the present compound are shown below. The "parts"
represents "part by weight" unless otherwise specified.
Formulation Example 1A
[0575] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 1 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 2A
[0576] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 2 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 3A
[0577] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 3 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 4A
[0578] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 4 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 5A
[0579] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 5 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 6A
[0580] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 6 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 7A
[0581] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 7 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 8A
[0582] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 8 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 9A
[0583] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 9 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 10A
[0584] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 10 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 11A
[0585] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 11 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 12A
[0586] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 12 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 13A
[0587] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 13 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 14A
[0588] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 14 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 15A
[0589] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 15 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 16A
[0590] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 16 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 17A
[0591] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 17 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 18A
[0592] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 18 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 19A
[0593] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 19 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 20A
[0594] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 20 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 21A
[0595] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 21 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 22A
[0596] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 220 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 23A
[0597] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 23 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 24A
[0598] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 24 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 25A
[0599] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 25 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 26A
[0600] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 26 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 27A
[0601] Zero point one (0.1) part of any one of the compounds
selected from the following compounds A1 to A100, 10 parts of the
present compound 27 and 89.9 parts of dimethyl sulfoxide are mixed
to obtain each solution.
Formulation Example 28A
[0602] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 1
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 29A
[0603] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 2
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 30A
[0604] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 3
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 31A
[0605] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 4
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 32A
[0606] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 5
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 33A
[0607] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 6
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 34A
[0608] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 7
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 35A
[0609] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 8
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 36A
[0610] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 9
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 37A
[0611] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 10
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 38A
[0612] Ten (1.0) parts of any one of the compounds selected from
the following compounds A1 to A100, 0.1 part of the present
compound 11 and 89.9 parts of dimethyl sulfoxide are mixed to
obtain each solution.
Formulation Example 39A
[0613] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 12
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 40A
[0614] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 13
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 41A
[0615] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 14
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 42A
[0616] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 15
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 43A
[0617] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 16
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 44A
[0618] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 17
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 45A
[0619] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 18
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 46A
[0620] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 19
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 47A
[0621] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 20
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 48A
[0622] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 21
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 49A
[0623] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 22
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 50A
[0624] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 23
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 51A
[0625] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 24
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 52A
[0626] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 25
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 53A
[0627] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 26
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 54A
[0628] Ten (10) parts of any one of the compounds selected from the
following compounds A1 to A100, 0.1 part of the present compound 27
and 89.9 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 55A
[0629] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 1
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 56A
[0630] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 2
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 57A
[0631] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 3
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 58A
[0632] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 4
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 59A
[0633] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 5
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 60A
[0634] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 6
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 61A
[0635] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 7
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 62A
[0636] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 8
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 63A
[0637] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 9
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 64A
[0638] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 10
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 65A
[0639] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 11
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 66A
[0640] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 12
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 67A
[0641] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 13
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 68A
[0642] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 14
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 69A
[0643] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 15
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 70A
[0644] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 16
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 71A
[0645] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 17
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 72A
[0646] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 18
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 73A
[0647] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 19
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 74A
[0648] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 20
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 75A
[0649] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 21
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 76A
[0650] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 22
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 77A
[0651] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 23
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 78A
[0652] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 24
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 79A
[0653] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 25
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 80A
[0654] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 26
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
Formulation Example 81A
[0655] Four (4) parts of any one of the compounds selected from the
following compounds A1 to A100, 4 parts of the present compound 27
and 92 parts of dimethyl sulfoxide are mixed to obtain each
solution.
[0656] The compounds A1 to A100 that are used in the
above-mentioned formulation Examples are shown below.
Pyrethrin (compound A1); Allethrin (compound A2); Prallethrin
(compound A3); Imiprothrin (compound A4); Resmethrin (compound A5);
Tetramethrin (compound A6); Phenothrin (compound A7); Cyphenothrin
(compound A8); Flumethrin (compound A9); Metofluthrin (compound
A10); Transfluthrin (compound A11); Profluthrin (compound A12);
Dimefluthrin (compound A13); Empenthrin (compound A14); Flumethrin
(compound A15); Meperfluthrin (compound A16);
2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl=2,2-dimethyl-3-(2-cyano-1-pro-
penyl)-cyclopropanecarboxylate (compound A17);
2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl=2,2-dimethyl-3-(3,3,3-trifluo-
ro-1-propenyl)-cyclopropanecarboxylate (compound A18);
2,3,5,6-tetrafluoro-4-propargylbenzyl=2,2,3,3-tetramethylcyclpropanecarbo-
xylate (compound A19); Acrinathrin (compound A20); bifenthrin
(compound A21); Cycloprothrin (compound A22); Cyfluthrin (compound
A23); beta-Cyfluthrin (compound A24); cyhalothrin (compound A25);
lambda-cyhalothrin (compound A26); gamma-cyhalothrin (compound
A27); Cypermethrin (compound A28); alpha-Cypermethrin (compound
A29); beta-Cypermethrin (compound A30); theta-Cypermethrin
(compound A31); zeta-Cypermethrin (compound A32); Deltamethrin
(compound A33); Ethofenprox (compound A34); Fenpropathrin (compound
A35); Fenvalerate (compound A36); Esfenvalerate (compound A37);
Flucythrinate (compound A38); Fluvalinate (compound A39);
tau-Fluvalinate (compound A40); Halfenprox (compound A41);
Permethrin (compound A42); Silafluofen (compound A43); Tefluthrin
(compound A44); Tralomethrin (compound A45); Protrifenbute
(compound A46); Fenitrothion (compound A47); Dichlorvos (compound
A48); Propoxur (compound A49); Imidacloprid (compound A50);
Clothianidin (compound A51); Thiametoxam (compound A52);
Dinotefuran (compound A53); Acetamiprid (compound A54); Thiacloprid
(compound ASS); Nitenpyram (compound A56); Ethiprole (compound
A57); Fipronil (compound A58); Acetoprole (compound A59);
Vaniliprole (compound A60); Pyriprole (compound A61); Pyrafluprole
(compound A62); Abamectin (compound A63); Emamectin (compound A64);
Emamectin Benzoate (compound A65); Milbemycin (compound A66);
Doramectin (compound A67); Lepimectin (compound A68); Bistrifluron
(compound A69); Diflubenzuron (compound A70); Pyriproxyfen
(compound A71); Hexaflumuron (compound A72); Hydroplane (compound
A73); Methoprene (compound A74); Cyromazine (compound A75);
Etoxazole (compound A76); Noviflumuron (compound A77); Amitraz
(compound A78); Chlorfenapyr (compound A79); Metoxadiazone
(compound A80); Amidoflumet (compound A81); Spirotetramat (compound
A82); Sulfoxaflor (compound A83); Pymetrozin (compound A84);
Pyridalyl (compound A85); Flupyradifurone (compound A86);
Indoxacarb (compound A87); Piperonyl butoxide (compound A88);
N-(2-ethylhexyl)-5-norbornene-2,3-dicarboximide (compound A89);
##STR00050##
Chlorantraniliprole (compound A94); Cyantraniliprole (compound
A95); Flubendiamide (compound A96); triflumezopyrim (compound
A97);
##STR00051##
[0657] Next, Test Examples are used to show an efficacy of the
present compounds on controlling pests.
Test Example 1
[0658] Each of the present compounds 1 to 4, 6 to 13, 18, 19, and
22 to 27 was made to a formulation according to the Formulation
example 5 and was then diluted with water so that the active
ingredient concentration was set to 200 ppm to prepare the diluted
solution.
[0659] Cucumber seedling (on the developmental stage of the first
true leaf) was planted in a polyethylene cup and 30 heads of cotton
aphid (Aphis gossypii) (all stages of life) were released onto the
leaves of the cucumber and allowed to stand for 1 day. The diluted
solutions 20 mL were sprayed into the seedling.
[0660] Cucumber (cv; Sagami-hanjiro-fushinari) was grown in a
polyethylene cup until the first true leaf was developed.
Approximately 30 heads of cotton aphid (Aphis gossypii) (including
the adults and the larvae) was released onto the leaves of the
cabbage and next day, the above-mentioned testing drug dilutions 20
mL were sprayed.
[0661] After 6 days, the number of the surviving insects that were
parasitic on the leaves of the cucumber was examined and the
controlling value was calculated by the following equation.
Controlling value
(%)={1-(Cb.times.Tai)/(Cai.times.Tb)}.times.100
wherein the symbols in the formula represent the following
descriptions.
[0662] Cb: Number of the insects before treatment in untreated
area;
[0663] Cai: Number of the surviving parasitic insects at the time
of the observation in untreated area;
[0664] Tb: Number of the insects before treatment in treated
area;
[0665] Tai: Number of the surviving parasitic insects at the time
of the observation in treated area;
[0666] Here the "untreated area" represents an area that was
sprayed by a diluted solution of the formulation described in the
Formulation Example 5 without the present compound with water in
the same amount as that of the treated area.
[0667] As a result, the treated area that was treated with each of
the diluted solutions of the present compounds 1 to 4, 6 to 13, 18,
19 and 22 to 27 respectively showed 90% or greater as the
controlling value.
Test Example 2
[0668] Each of the present compounds 1, 4, 6, 8, 12, and 23 to 27
was made to a formulation according to the Formulation example 5
and was then diluted with water so that the active ingredient
concentration was set to 200 ppm to prepare the diluted
solution.
[0669] Cucumber seedling (on the developmental stage of the second
true leaf) was planted in a polyethylene cup, and the diluted
solutions 5 m were irrigated into the plant foot, and the plants
were held at 25.degree. C. in a greenhouse for 7 days.
Approximately 30 heads of cotton aphid (Aphis gossypii) (all stages
of life) were inoculated onto the cucumber leaves and the plants
were held in a greenhouse for additional 6 days, and then the
number of the surviving insects that were parasitic on the cucumber
leaves was examined and the controlling value was calculated by the
following equation.
Controlling value
(%)={1-(Cb.times.Tai)/(Cai.times.Tb)}.times.100
wherein the symbols in the formula represent the following
descriptions.
[0670] Cb: Number of the insects before treatment in untreated
area;
[0671] Cai: Number of the surviving parasitic insects at the time
of the observation in untreated area;
[0672] Tb: Number of the insects before treatment in treated
area;
[0673] Tai: Number of the surviving parasitic insects at the time
of the observation in treated area;
[0674] Here the "untreated area" represents an area that was
sprayed by a diluted solution of the formulation described in the
Formulation Example 5 without the present compound with water in
the same amount as that of the treated area.
[0675] As a result, the treated area that was treated with each of
the diluted solutions of the present compounds 1, 4, 6, 8, 12, and
23 to 27 respectively showed 90% or greater as the controlling
value.
Test Example 3
[0676] Each of the present compounds 1, 2, 4, 6, 8, 9, and 23 was
made to a formulation according to the Formulation example 5 and
was then diluted with water so that the active ingredient
concentration was set to 200 ppm to prepare the diluted
solution.
[0677] Rice seedling (on the developmental stage of the second true
leaf) was planted in a polyethylene cup, and the diluted solutions
10 mL were sprayed. After air drying, 20 heads of 3rd to 4th instar
larvae of brown planthopper (Nilaparvata lugens) were released onto
the rice leaves and the plants were held at 25.degree. C. in a
greenhouse.
[0678] After 6 days, the number of the surviving insects that were
parasitic on the leaves of the rice was examined and the
controlling value was calculated by the following equation.
Controlling value
(%)={1-(Cb.times.Tai)/(Cai.times.Tb)}.times.100
wherein the symbols in the formula represent the following
descriptions.
[0679] Cb: Number of the insects before treatment in untreated
area;
[0680] Cai: Number of the surviving parasitic insects at the time
of the observation in untreated area;
[0681] Tb: Number of the insects before treatment in treated
area;
[0682] Tai: Number of the surviving parasitic insects at the time
of the observation in treated area;
[0683] Here the "untreated area" represents an area that was
sprayed by a diluted solution of the formulation described in the
Formulation Example 5 without the present compound with water in
the same amount as that of the treated area.
[0684] As a result, the treated area that was treated with each of
the diluted solutions of the present compounds 1, 2, 4, 6, 8, 9 and
23 respectively showed 90% or greater as the controlling value.
Test Example 4
[0685] Each of the present compounds 1 to 10, 12, 18, 23 to 25, and
27 was made to a formulation according to the Formulation example 5
and was then diluted with water so that the active ingredient
concentration was set to 200 ppm to prepare the diluted
solution.
[0686] Rice seedling (two weeks after sowing, on the developmental
stage of the second true leaf) was planted in a polyethylene cup,
and the diluted solutions 5 mL were irrigated into the plant foot,
and the plants were held at 25.degree. C. in a greenhouse for 7
days. Twenty (20) heads of 3rd to 4th instar larvae of brown
planthopper (Nilaparvata lugens) were released onto the rice leaves
and the plants were held at 25.degree. C. in a greenhouse for
additional 6 days, and then the number of the surviving insects
that were parasitic on rice leaves was examined and the controlling
value was calculated by the following equation.
Controlling value
(%)={1-(Cb.times.Tai)/(Cai.times.Tb)}.times.100
wherein the symbols in the formula represent the following
descriptions.
[0687] Cb: Number of the insects before treatment in untreated
area;
[0688] Cai: Number of the surviving parasitic insects at the time
of the observation in untreated area;
[0689] Tb: Number of the insects before treatment in treated
area;
[0690] Tai: Number of the surviving parasitic insects at the time
of the observation in treated area;
[0691] Here the "untreated area" represents an area that was
sprayed by a diluted solution of the formulation described in the
Formulation Example 5 without the present compound with water in
the same amount as that of the treated area.
[0692] As a result, the treated area that was treated with each of
the diluted solutions containing the present compounds 1 to 10, 12,
18, 23 to 25, and 27 respectively showed 90% or greater as the
controlling value.
Test Example 5
[0693] The present compound 1 was made to a formulation according
to the Formulation example 5 and was then diluted with water so
that the active ingredient concentration was set to 200 ppm to
prepare the diluted solution.
[0694] Tomato seedling (on the developmental stage of the third
true leaf) was planted in a polyethylene cup, and Tobacco whitefly
(Bemisia tabaci) adults were released and then made lay eggs during
72 hours.
[0695] The tomato seedling was held in a greenhouse for 8 days, and
when larvae were enclosed from the delivered eggs, thereto was
sprayed the diluted solution in ratio of 20 mL/cup and the plants
were held at 25.degree. C. in a greenhouse. After 7 days, the
number of the surviving insects on the tomato leaves was examined
and the controlling value was calculated by the following
equation.
Controlling value
(%)={1-(Cb.times.Tai)/(Cai.times.Tb)}.times.100
wherein the symbols in the formula represent the following
descriptions.
[0696] Cb: Number of the insects before treatment in untreated
area;
[0697] Cai: Number of the surviving parasitic insects at the time
of the observation in untreated area;
[0698] Tb: Number of the insects before treatment in treated
area;
[0699] Tai: Number of the surviving parasitic insects at the time
of the observation in treated area;
[0700] Here the "untreated area" represents an area that was
sprayed by a diluted solution of the formulation described in the
Formulation Example 5 without the present compound with water in
the same amount as that of the treated area.
[0701] As a result, the treated area that was treated with the
diluted solution of the present compound 1 showed 90% or greater as
the controlling value.
Test Example 6
[0702] Each of the present compounds 1 to 16 and 18 to 27 was made
to a formulation according to the Formulation example 5 and was
then diluted with water so that the active ingredient concentration
was set to 200 ppm to prepare the diluted solution.
[0703] A cabbage in the third leaf stage was planted in a
polyethylene cup, and thereto was sprayed the diluted solution in a
ratio of 20 mL/cup. After spraying, the plants were air-dried, and
the stem and leaf thereof was cut and then was installed in a 50 mL
cup, and five heads of cabbage moth (Plutella xylostella) at the
second instar larval stages were released into the cup and the cup
was covered with the lid. The cup was held at 25.degree. C. and
after 5 days, the number of died insects was counted and the
mortality of insects was calculated by the following equation.
Mortality of insects (%)=(Number of dead insects/Number of tested
insects).times.100
[0704] As a result, the treated area that was treated with each of
the diluted solutions of the present compounds 1 to 16 and 18 to 27
respectively showed 80% or greater as the mortality of insects.
Test Example 7
[0705] Each of the present compounds 1 and 11 was made to a
formulation according to the Formulation example 5 and was then
diluted with water so that the active ingredient concentration was
set to 200 ppm to prepare the diluted solution.
[0706] An apple plant was planted in a polyethylene cup, and grown
until the seventh true leaf or the eighth true leaf was developed.
To the apple plant was sprayed the diluted solution in a ratio of
20 mL/cup. After spraying, the plants were air-dried, and 60 heads
of summer fruit tortrix (Adoxophyes orana fasciata) at the first
instar larval stage were released into the cup. The cup was
hollowed out the bottom and pasted with filter paper, and then was
turn upside down and covered. After 7 days, the number of died
insects was counted and the mortality of insects was calculated by
the following equation.
Mortality of insects (%)=(Number of dead insects/Number of tested
insects).times.100
[0707] As a result, the treated area that was treated with each of
the diluted solutions of the present compounds 1 and 11
respectively showed 90% or greater as the mortality of insects.
Test Example 8
[0708] Each of the present compounds 1 to 3, 5, 7, 8, 11, 13 to 16,
21 and 22 was made to a formulation according to the Formulation
example 5 and was then diluted with water so that the active
ingredient concentration was set to 500 ppm to prepare the diluted
solution. The bottom of the polyethylene cup having 5.5 cm diameter
was matted with the same size of a filter paper, and 0.7 mL of the
diluted solution was added dropwise to the filter paper and 30 mg
sucrose as bait was placed in the cup uniformly. Ten (10) heads of
female adult housefly (Musca domestica) were released into the
polyethylene cup and the cup was covered with the lid. After 24
hours, the life and death of housefly was examined and the number
of died insects was counted and the mortality of insects was
calculated by the following equation.
Mortality of insects (%)=(Number of dead insects/Number of tested
insects).times.100
[0709] As a result, the treated area that was treated with each of
the diluted solutions of the present compounds 1 to 3, 5, 7, 8, 11,
13 to 16, 21 and 22 respectively showed 100% as the mortality of
insects.
Test Example 9
[0710] Each of the present compounds 1 to 3, 5, 7, and 13 was made
to a formulation according to the Formulation example 5 and was
then diluted with water so that the active ingredient concentration
was set to 500 ppm to prepare the diluted solution. The bottom of
the polyethylene cup having 5.5 cm diameter was matted with the
same size of a filter paper, and 0.7 mL of the diluted solution was
added dropwise to the filter paper and 30 mg sucrose as bait was
placed in the cup uniformly. Two (2) heads of male adult German
cockroach (Blattella germanica) were released into the polyethylene
cup and the cup was covered with the lid. After 6 days, the life
and death of German cockroach was examined and the number of died
insects was counted and the mortality of insects was calculated by
the following equation.
Mortality of insects (%)=(Number of dead insects/Number of tested
insects).times.100
[0711] As a result, the treated area that was treated with each of
the diluted solutions of the present compounds 1 to 3, 5, 7, and 13
respectively showed 100% as the mortality of insects.
Test Example 10
[0712] Each of the present compounds 1 to 3, 5, 7, 8, 11, 14 to 17,
21, and 22 was made to a formulation according to the Formulation
example 5 and was then diluted with water so that the active
ingredient concentration was set to 500 ppm to prepare the diluted
solution. Zero point seven (0.7) mL of the diluted solution was
added to 100 mL of ion-exchanged water (the active ingredient
concentration of 3.5 ppm). Twenty (20) heads of last instar larvae
of house mosquito (Culex pipiens pallens) were released into the
solutions, and after 1 day, the life and death of house mosquito
was examined, and the number of died insects was counted and the
mortality of insects was calculated by the following equation.
Mortality of insects (%)=(Number of dead insects/Number of tested
insects).times.100
[0713] As a result, the treated area that was treated with each of
the diluted solutions of the present compounds 1 to 3, 5, 7, 8, 11,
14 to 17, 21, and 22 respectively showed 95% or greater as the
mortality of insects.
Test Example 11
[0714] Two (2) mg of a sample of the present compound 1 was weighed
into a screw tube (manufactured by Maruemu, No. 5; 27.times.55 mm),
and 0.2 mL of acetone was added thereto and the tube was covered
with the lid and then the sample was dissolved. The screw tube is
rotated and inverted and the solutions were coated on the whole of
the inner wall of the tube uniformly. The lid was removed from the
tube and the tube was air-dried for about 2 hours and 5 heads of
unfed young mites group of Longicornis (Haemaphysalis longicornis)
were released into the tube and then the lid was covered. After 2
days, the number of died insects was counted and the mortality of
insects was calculated by the following equation.
Mortality of insects (%)=(Number of dead insects/Number of tested
insects).times.100
[0715] As a result, the treated area that was treated with the
diluted solution of the present compound 1 showed 60% or greater as
the mortality of insects.
Test Example 12
[0716] Into 5 mL of propylene carbonate, 5 mg of the present
compound 1 was dissolved into propylene carbonate so as to be 0.1%
w/v of the solution. On the previous day before administering the
solution, the tested mites (Longicornis, young mites) were
inoculated in mouse. Before a drop treatment, the nonparasitic
mites were removed.
[0717] On the whole surface of the body of the mouse, 200 .mu.L of
the solution was instilled via a pipette. On the other hand, as a
control group, 200 L of only propylene carbonate was instilled. The
test was performed three times per each group. After 2 days of the
instillation, the number of died insects was counted and the
mortality of insects was calculated by the following
formulation.
Mortality of insects (%)=(Number of dead insects/Number of
parasitic insects before the instillation).times.100
[0718] As a result, the treated are that was treated with the
diluted solutions of the present compound 1 showed 50% or greater
as the mortality of insects.
Test Example 13
[0719] The present compounds 1 and 2 were dissolved in acetone and
then the 10% w/v acetone solutions were prepared.
[0720] A droplet (1.0 .mu.L) of the solution was topically applied
onto the ventral prothorax of each female American cockroaches
(Periplaneta americana). Then, the treated individuals were
transferred to a clean polyethylene cup (bottom diameter: 12 cm,
height: 10 cm) with some food and water. Each treatment consisted
of 2 replications of 5 cockroaches/polyethylene cup. The mortality
was determined on 7 days after treatment at 25.degree. C.
Mortality of insects (%)=(Number of dead insects/Number of tested
insects).times.100
[0721] As a result, the treated area that was treated with the
acetone solutions of the present compounds 1 and 2 respectively
showed 100% 100% as the mortality of insects.
Test Example 14
[0722] The compound 112 (hereinafter, referred to as "compound
112"), described in Table 40 of WO 2013/018928 pamphlet, and the
present compound 1 were dissolved in acetone and then the acetone
solutions of the designated concentration were prepared.
[0723] A droplet (1.0 .mu.L) of the solution was topically applied
onto the ventral prothorax of each female American cockroaches
(Periplaneta americana). Then, the treated individuals were
transferred to a clean polyethylene cup (bottom diameter: 12 cm,
height: 10 cm) with some food and water. Each treatment consisted
of 2 replications of 5 roaches/polyethylene cup. The mortality was
determined on 7 days after treatment at 25.degree. C.
Mortality of insects (%)=(Number of dead insects/Number of tested
insects).times.100
[0724] The result is shown in Table 6.
TABLE-US-00006 TABLE 6 Concentration of the compound Morality (%)
(w/v %) Present compound 1 Compound 112 4 -- 100% 2 100% 70% 1 100%
-- 0.5 100% -- 0.25 100% --
Compound 112:
##STR00052##
[0725] Present Compound 1:
##STR00053##
[0726] INDUSTRIAL APPLICABILITY
[0727] The present compound shows an excellent control effect
against a pest.
* * * * *