Technical Field
The present invention relates to a novel benzylamide compound, method for producing the same, and miticide containing the compound.
Background Art
Due to the emergence of mites resistant to miticides in recent years as a result of long-term use of miticides, it has become difficult to accomplish control by use of known miticides.
Under such circumstances, there has been an urgent demand for the development of new types of miticides that are expected to achieve excellent miticidal activity.
For example, Patent Literature (PTL) 1) discloses a compound represented by following Formula (A):
R3 R4
^(OJnPQm R1
wherein R5 represents substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted amino, N-containing heterocycles, or the like, and reports that this compound exhibits miticidal activity.
However, in PTL 1, mainly, urea compounds are produced, and although the amide compounds where R5 is alkyl, haloalkyl, aryl, or cycloalkyl are also produced, no amide compounds where R5 is benzyl is disclosed. In addition, PTL 1 nowhere discloses that the above compound (A) exhibits ovicidal activity. Citation List Patent Literature PTL 1: Japanese Patent Application Laid-open No. 2011-042611
Summary of Invention

Technical Problem
An object of the present invention is to provide a novel benzylamide compound or a salt thereof that exhibits miticidal activity.
Another object of the present invention is to provide a method for producing the benzylamide compound or the salt thereof.
A further object of the present invention is to provide a new type of miticide containing the benzylamide compound or the salt thereof.
Solution to Problem
The present inventors conducted extensive research to achieve the above objects, and succeeded in synthesizing a compound represented by the following Formula (1) or a salt thereof that has miticidal activity. The present inventors have conducted further research based on the above findings. The present invention has thereby been accomplished.
More specifically, the present invention includes the following embodiments:
Item 1:
A benzylamide compound represented by Formula (1]

s
II (0)n
0)
R4 R5R6 R7
or a salt thereof,
wherein R1 represents Ci-6 alkyl or Ci-6 haloalkyl;
R2 and R3 are identical or different and each represent hydrogen,
halogen, cyano, nitro, Ci-6 alkyl, Ci-6 haloalkyl, Ci-6 alkoxy, Ci-6
haloalkoxy, Ci_6 alkoxy Ci_6 alkyl, Ci_6 haloalkoxy Ci_6 alkyl, C3-8
cycloalkyl or C3-8 cycloalkyl Ci-6 alkyl;

R represents hydrogen, formyl, Ci-6 alkyl, Ci-6 haloalkyl, C

1-6

alkoxy, Ci-6 haloalkoxy, Ci-6 alkoxy Ci-6 alkyl, Ci-6 haloalkoxy Ci-6 alkyl, C3-8 cycloalkyl, C3-8 cycloalkyl Ci_6 alkyl, Ci_6 alkylcarbonyl, Ci-6 haloalkylcarbonyl, Ci-6 alkoxycarbonyl, Ci-6 haloalkoxycarbonyl, arylcarbonyl, aryloxycarbonyl, C2-6 alkenyl, C2-6 haloalkenyl, C2_6 alkynyl, C2_6 haloalkynyl, Ci_6 alkylsulfonyl, Ci-6 haloalkylsulfonyl, Ci-6 alkylsulfinyl, Ci-6 haloalkylsulfinyl, Ci-6 alkylthio, Ci_6 haloalkylthio, aryl, aryl Ci_6 alkyl, arylsulfonyl, arylsulfinyl, arylthio, or heterocyclic, all the substituents defined as R4 may optionally be further substituted; R5 and R6 are identical or different and each represent hydrogen, halogen, Ci-6 alkyl, or Ci-6 haloalkyl; R5 and R6, taken together with the carbon atom, may bond to each other to form a 3- to 8-membered ring, via or not via at least one heteroatom; R7, R8, R9, R10, and R11 are identical or different and each represent hydrogen, halogen, nitro, cyano, hydroxyl, formyl, Ci-6 alkyl, Ci-6 haloalkyl, Ci_6 alkoxy, Ci_6 haloalkoxy, Ci_6 alkoxy Ci_6 alkyl, Ci-6 haloalkoxy Ci-6 alkyl, C3-8 cycloalkyl, C3-8 cycloalkyl Ci-6 alkyl, Ci-6 alkylcarbonyl, Ci_6 haloalkylcarbonyl, arylcarbonyl, aryloxycarbonyl, Ci-6 alkoxycarbonyl, Ci-6 haloalkoxycarbonyl, Ci-6 cyanoalkyl, Ci_6 cyanoalkoxy, C2_6 alkenyl, C2-6 haloalkenyl, C2_6 alkynyl, C2-6 haloalkynyl, Ci-6 alkylsulfonyl, Ci-6
haloalkylsulfonyl, Ci-6 alkylsulfinyl, Ci-6 haloalkylsulfinyl, Ci-6 alkylthio, Ci-6 haloalkylthio, C3-8 cycloalkylsulfonyl, C3-8 cycloalkylsulfinyl, C3-8 cycloalkylthio, C3-8 cycloalkyl Ci_6 alkylsulfonyl, C3-8 cycloalkyl Ci-6 alkylsulfinyl, C3-8 cycloalkyl Ci-6 alkylthio, Ci_6 alkoxy Ci_6 alkylsulfonyl, Ci_6 alkoxy Ci_6 alkylsulfinyl, Ci-6 alkoxy Ci-6 alkylthio, C2-6 alkenyloxy, C2-6 haloalkenyloxy, C2-6 alkynyloxy, C2-6 haloalkynyloxy, Ci-6 alkylsulfonyloxy, Ci-6 haloalkylsulfonyloxy, Ci-6 alkylsulfinyloxy, Ci-6 haloalkylsulfinyloxy, carboxyl, OCN, SCN, SF5, substituted or unsubstituted amino, aryl, aryl Ci_6 alkyl, aryloxy, aryl Ci_6 alkoxy, arylsulfonyl, arylsulfinyl, arylthio, aryl Ci-6 alkylsulfonyl, aryl Ci-6 alkylsulfinyl, aryl Ci-6 alkylthio, heterocyclic, heterocyclic Ci-6 alkyl, or heterocyclic oxy, all of which may optionally be further substituted;

R7 and R8, R8 and R9, R9 and R10, or R10 and R11, taken together with
the benzene ring to which they bond, may bond to each other to
form a 3- to 8-membered ring via or not via at least one
heteroatom; 5 X represents oxygen or sulfur; and
n represents an integer of 0 to 2.
Item 2:
The benzylamide compound or the salt thereof according
to Item 1, wherein R1 is C1-6 haloalkyl. 10 Item 3:
The benzylamide compound or the salt thereof according
to Item 1 or 2, wherein R2 and R3 are identical or different and
each represent halogen, cyano, or C1-6 alkyl.
Item 4:
15 The benzylamide compound or the salt thereof according
to any one of Items 1 to 3, wherein R4 is hydrogen, or C1-6 alkyl.
Item 5:
The benzylamide compound or the salt thereof according
to any one of Items 1 to 4, wherein R7, R8, R9, R10, and R11 are 20 identical or different and each represent hydrogen, halogen,
nitro, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, C1-6
alkylsulfonyl, C1-6 haloalkylsulfonyl, C1-6 alkylsulfinyl, C1-6
haloalkylsulfinyl, C1-6 alkylthio, C1-6 haloalkylthio, substituted
or unsubstituted amino, aryl, or heterocyclic. 25 Item 6:
A method for producing the benzylamide compound or the
salt thereof according to any one of Items 1 to 5, comprising at
least one step selected from the group consisting of following
steps (d) and (e):
30 step (d): obtaining a sulfide compound represented by
Formula (1-1) by reacting a thiol compound represented by Formula
(6) with an alkylating reagent represented by Formula (7):
5


R1—G
Rl/-^/R3v R" J\/R9 (7)
i^-^t
HS ^ N
R4 R5R6 R7
(6)
wherein, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and X are as defined above and G represents a leaving group; and
step (e): obtaining a benzylamide compound represented 5 by Formula (1-2) by reacting the sulfide compound represented by Formula (1-1) with an oxidizing agent:
R10 R10
*! "^r -R3X RV> /R9
V1 J" NNVT ^R8
(O)n- R4 R5R6 R7
R2 /. R3 RiiL, R9 oxidizing agent
R4 R5 R6 R7
0-1) (1-2)
wherein, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and X are as defined above. n’ represents 1 or 2. 10 Item 7:
The method for producing the benzylamide compound and the salt thereof according to Item 6, further comprising the following step (c) :
step (c): obtaining a thiol compound represented by 15 Formula (6) by reacting a sulfonylchloride compound represented by Formula (5) with a reducing agent:

R\ D R10
/R3X R1^A.
R4 R5R6 R7 (5) .R9 ^R8 reducing agent R^, D R10
-R3X RV>
R4 R5R6 R7
(6) .R9
}
CIS02


' HS^

^R8
wherein, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and X are as
defined above.
20 Item 8:
The method for producing the benzylamide compound and
the salt thereof according to Item 7, further comprising the
following step (b):
6

step (b): obtaining the sulfonylchloride compound represented by Formula (5) by chlorosulfonylating an amide compound represented by Formula (4) :

^ RWR3X R11
" CIS02-^^N/"X'"y'^R8
R4 R5R6 R7
(5)
5 wherein, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and X are as defined above. Item 9:
The method for producing the benzylamide compound and the salt thereof according to Item 8, further comprising the 10 following step (a):
step (a): obtaining the amide compound represented by Formula (4) by reacting an aniline compound represented by Formula (2) with a benzylcarbonyl compound represented by Formula (3) :
□10 D10
^N^^v^ R11 JL R9 R2 ^ R3 R11
8
N X T R'
^NH + xxi —- xx x
34

R n,5,-,6 --, R4 R5R6 R7
15
(2) (3) (4)
wherein, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and X are as defined above, and Y represents a leaving group or hydroxyl group. Item 10:
A pesticide containing the benzylamide compound or the 20 salt thereof of according to any one of Items 1 to 5. Item 11:
A miticide containing the benzylamide compound or the salt thereof of according to any one of Items 1 to 5.
25 Advantageous Effects of Invention
The benzylamide compound or the salt thereof according
to the present invention achieves an excellent miticidal effect
7

with a small amount thereof.
With the present invention, the benzylamide compound
and the salt thereof can simply be produced with an excellent
yield.
5 Additionally, with the present invention, a new type of
miticide containing the benzylamide compound or the salt thereof according to the present invention can be provided.
Description of Embodiments 10 1. benzylamide compound or a salt thereof
The present invention is directed to a compound
represented by Formula (1):

s
(6)n R4 R5R6 R^
or a salt thereof (hereinafter sometimes referred to as 15 “benzylamide compound (1) of the present invention” or “compound (1)”) ,
Wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, X and n are as defined above.
The following shows specific examples of each group as 20 used in this specification.
Examples of halogen include, but are not particularly limited to, fluorine, chlorine, bromine, iodine, and the like.
Examples of C1-6 alkyl include, but are not particularly limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 25 sec-butyl, tert-butyl, n-pentyl, n-hexyl, and like C1-6 straight-chain or branched-chain alkyl.
Examples of C1-6 haloalkyl include, but are not
particularly limited to, fluoromethyl, chloromethyl, bromomethyl,
iodomethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl,
30 pentafluoroethyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl,
8

heptafluoroisobutyl, and like C1-6 straight-chain or branched-chain alkyl substituted with 1 to 9, and preferably 1 to 5, halogen atoms.
Examples of C1-6 alkoxy include, but are not 5 particularly limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, and like C1-6 straight-chain or branched-chain alkoxy.
Examples of C1-6 haloalkoxy include, but are not particularly limited to, fluoromethoxy, chloromethoxy,
10 bromomethoxy, iodomethoxy, difluoromethoxy, trifluoromethoxy,
2,2,2-trifluoroethoxy, pentafluoroethoxy, 3,3,3-trifluoropropoxy, 4,4,4-trifluorobutoxy, heptafluoroisobutoxy, and like C1-6 straight-chain or branched-chain alkoxy substituted with 1 to 9, preferably 1 to 5, halogen atoms.
15 Examples of C1-6 alkoxy C1-6 alkyl include, but are not
particularly limited to, methoxymethyl, ethoxymethyl, n-propoxymethyl, isopropoxymethyl, n-butoxymethyl, isobutoxymethyl, sec-butoxymethyl, tert-butoxymethyl, methoxyethyl, ethoxyethyl, methoxy-n-propyl, methoxy-n-butyl, and like alkoxyalkyl in which
20 C1-6 straight-chain or branched-chain alkyl is substituted with C1-6 straight-chain or branched-chain alkoxy.
Examples of C1-6 haloalkoxy C1-6 alkyl include, but are not particularly limited to, fluoromethoxymethyl, chloromethoxymethyl, bromomethoxymethyl, iodomethoxymethyl,
25 difluoromethoxymethyl, trifluoromethoxymethyl, 2,2,2-trifluoroethoxymethyl, and like straight-chain or branched-chain alkoxyalkyl substituted with 1 to 9, preferably 1 to 5, halogen atoms.
Examples of C3-8 cycloalkyl include, but are not
30 particularly limited to, cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, cycloheptyl, cyclooctyl, and the like.
Examples of C3-8 cycloalkyl C1-6 alkyl include, but are
not particularly limited to, cyclopropylmethyl, cyclobutylethyl,
cyclopentylmethyl, cyclohexylmethyl, and the like.
35 Examples of C1-6 alkylcarbonyl include, but are not
9

particularly limited to, methylcarbonyl (acetyl), ethylcarbonyl (propionyl), n-propylcarbonyl (butyryl), isopropylcarbonyl (isobutyryl), n-butylcarbonyl (valeryl), isobutylcarbonyl (isovaleryl), sec-butylcarbonyl, tert-butylcarbonyl, and like C1-6 5 straight-chain or branched-chain alkylcarbonyl groups.
Examples of C1-6 haloalkylcarbonyl include, but are not particularly limited to, fluoromethylcarbonyl,
chloromethylcarbonyl, bromomethylcarbonyl, iodomethylcarbonyl, dichloromethylcarbonyl, trichloromethylcarbonyl,
10 difluoromethylcarbonyl, trifluoromethylcarbonyl,
chlorodifluoromethylcarbonyl, bromodifluoromethylcarbonyl, dichlorofluoromethylcarbonyl, 2,2,2-trichloroethylcarbonyl, 2,2,2-trifluoroethylcarbonyl,pentafluoroethylcarbonyl, and like C1-6 straight-chain or branched-chain alkylcarbonyl substituted
15 with 1 to 9, and preferably 1 to 5, halogen atoms.
Examples of arylcarbonyl include, but are not particularly limited to, benzoyl, tert-butylbenzoyl, and like substituted or unsubstituted benzoyl group; 1-naphthoyl, 2-naphthoyl, and the like substituted or unsubstituted naphthoyl
20 group.
Examples of aryloxycarbonyl include, but are not particularly limited to, phenoxycarbonyl, 4-diaminophenoxycarbonyl, 4-fluorophenoxycarbonyl, 4-tert-butylphenoxycarbonyl, and like substituted or unsubstituted
25 phenoxycarbonyl group; 1-naphthoxycarbonyl, 2-naphthoxycarbonyl,
and the like substituted or unsubstituted naphthoxycarbonyl group.
Examples of C1-6 alkoxycarbonyl include, but are not particularly limited to, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl,
30 isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, and
like C1-6 straight-chain or branched-chain alkoxycarbonyl groups.
Examples of C1-6 haloalkoxycarbonyl include, but are not
particularly limited to, fluoromethoxycarbonyl,
chloromethoxycarbonyl, bromomethoxycarbonyl, iodomethoxycarbonyl,
35 dichloromethoxycarbonyl, trichloromethoxycarbonyl,
10

difluoromethoxycarbonyl, trifluoromethoxycarbonyl, 2,2,2-trifluoroethoxymethyl, pentafluoroethoxycarbonyl, 3,3,3-trifluoropropoxycarbonyl, 4,4,4-trifluorobutoxycarbonyl, heptafluoroisopropoxycarbonyl, and like C1-6 straight-chain or 5 branched-chain alkoxycarbonyl substituted with 1 to 9, preferably 1 to 5, halogen atoms.
Examples of cyano C1-6 alkyl include, but are not particularly limited to, cyanomethyl, cyanoethyl, cyano-n-propyl, cyano-isopropyl, cyano-n-butyl, cyano-isobutyl, cyano-sec-butyl, 10 cyano-tert-butyl, cyano-n-hexyl, and like C1-6 straight-chain or branched-chain alkyl substituted with a cyano group.
Examples of cyano C1-6 alkoxy include cyanomethoxy, cyanoethoxy, cyano-n-propoxy, cyano-isopropoxy, cyano-n-butoxy, cyano-iso-butoxy, cyano-sec-butoxy, cyano-tert-butoxy, cyano-15 hexyloxy, and like C1-6 straight-chain or branched-chain alkoxy substituted with a cyano group.
Examples of C2-6 alkenyl include, but are not
particularly limited to, vinyl, allyl, 2-butenyl, 3-butenyl, 1-
methylallyl, and the like.
20 Examples of C2-6 haloalkenyl include, but are not
particularly limited to, 2,2-dichlorovinyl, 2,2-dibromovinyl, 2,2-difluorovinyl, 2,2-dibromovinyl, 3,3-difluoro-2-allyl, 4,4-difluoro-3-butenyl, 4,4,4-trifluoro-2-butenyl, and the like.
Examples of C2-6 alkynyl include, but are not 25 particularly limited to, ethynyl, 2-propynyl (propargyl), 1-methyl-2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, and the like.
Examples of C2-6 haloalkynyl include, but are not particularly limited to, fluoroethynyl, bromoethynyl,
chloroethynyl, iodoethynyl, 3,3,3-trifluoro-1-propynyl, and the 30 like.
Examples of C1-6 alkylsulfonyl include, but are not particularly limited to, methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, and like
35 C1-6 straight-chain or branched-chain alkylsulfonyl groups.
11

Examples of C1-6 haloalkylsulfonyl include, but are not particularly limited to, fluoromethylsulfonyl,
chloromethylsulfonyl, bromomethylsulfonyl, iodomethylsulfonyl, dichloromethylsulfonyl, trichloromethylsulfonyl, 5 difluoromethylsulfonyl, trifluoromethylsulfonyl,
chlorodifluoromethylsulfonyl, bromodifluoromethylsulfonyl, dichlorofluoromethylsulfonyl, 2,2,2-trichloroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, pentafluoroethylsulfonyl, and like C1-6 straight-chain or branched-chain alkylsulfonyl substituted
10 with 1 to 9, and preferably 1 to 5, halogen atoms.
Examples of C1-6 alkylsulfinyl include, but are not particularly limited to, methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, and like
15 C1-6 straight-chain or branched-chain alkylsulfinyl groups.
Examples of C1-6 haloalkylsulfinyl include, but are not particularly limited to, fluoromethylsulfinyl,
chloromethylsulfinyl, bromomethylsulfinyl, iodomethylsulfinyl, dichloromethylsulfinyl, trichloromethylsulfinyl,
20 difluoromethylsulfinyl, trifluoromethylsulfinyl,
chlorodifluoromethylsulfinyl, bromodifluoromethylsulfinyl, dichlorofluoromethylsulfinyl, 2,2,2-trichloroethylsulfinyl, 2,2,2-trifluoroethylsulfinyl, pentafluoroethylsulfinyl, and like C1-6 straight-chain or branched-chain alkylsulfinyl substituted
25 with 1 to 9, and preferably 1 to 5, halogen atoms.
Examples of C1-6 alkylthio include, but are not particularly limited to, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, and like C1-6 straight-chain or branched-chain
30 alkylthio.
Examples of C1-6 haloalkylthio include, but are not
particularly limited to, fluoromethylthio, chloromethylthio,
bromomethylthio, iodomethylthio, dichloromethylthio,
trichloromethylthio, difluoromethylthio, trifluoromethylthio,
35 chlorodifluoromethylthio, bromodifluoromethylthio,
12

dichlorofluoromethylthio, 2,2,2-trichloroethylthio, 2,2,2-
trifluoroethylthio, pentafluoroethylthio, and like C1-6 straight-
chain or branched-chain alkylthio substituted with 1 to 9, and
preferably 1 to 5, halogen atoms.
5 Examples of C3-8 cycloalkylsulfonyl include, but are not
particularly limited to, cyclopropylsulfonyl, cyclobutylsulfonyl, cyclopentylsulfonyl, cyclohexylsulfonyl, and the like.
Examples of C3-8 cycloalkylsulfinyl include, but are not particularly limited to, cyclopropylsulfinyl, cyclobutylsulfinyl, 10 cyclopentylsulfinyl, cyclohexylsulfinyl, and the like.
Examples of C3-8 cycloalkylthio include, but are not particularly limited to, cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, and the like.
Examples of C3-8 cycloalkyl C1-6 alkylsulfonyl include, 15 but are not particularly limited to, cyclopropylmethylsulfonyl, 2-cyclopropylethylsulfonyl, 3-cyclopropylpropylsulfonyl, cyclohexylmethylsulfonyl, and the like.
Examples of C3-8 cycloalkyl C1-6 alkylsulfinyl include, but are not particularly limited to, cyclopropylmethylsulfinyl, 20 2-cyclopropylethylsulfinyl, 3-cyclopropylpropylsulfinyl, cyclohexylmethylsulfinyl, and the like.
Examples of C3-8 cycloalkyl C1-6 alkylthio include, but are not particularly limited to, cyclopropylmethylthio, 2-cyclopropylethylthio, 3-cyclopropylpropylthio, 25 cyclohexylmethylthio, and the like.
Examples of C1-6 alkoxy C1-6 alkylsulfonyl include, but are not particularly limited to, methoxymethylsulfonyl, ethoxymethylsulfonyl, n-propoxymethylsulfonyl, isopropoxymethylsulfonyl, n-butoxymethylsulfonyl, sec-30 butoxymethylsulfonyl, tert-butoxymethylsulfonyl,
methoxyethylsulfonyl, and like alkoxyalkylsulfonyl in which C1-6 straight-chain or branched-chain alkylsulfonyl is substituted with C1-6 straight-chain or branched-chain alkoxy.
Examples of C1-6 alkoxy C1-6 alkyl sulfinyl include, but
35 are not particularly limited to, methoxymethylsulfinyl,
13

ethoxymethylsulfinyl, n-propoxymethylsulfinyl, isopropoxymethylsulfinyl, n-butoxymethylsulfinyl, sec-butoxymethylsulfinyl, tert-butoxymethylsulfinyl, 2-methoxyethylsulfinyl, and like alkoxyalkylsulfinyl in which C1-6 5 straight-chain or branched-chain alkylsulfinyl is substituted with C1-6 straight-chain or branched-chain alkoxy.
Examples of C1-6 alkoxy C1-6 alkylthio include, but are not particularly limited to, methoxymethylthio, ethoxymethylthio, n-propoxymethylthio, isopropoxymethylthio, n-butoxymethylthio, 10 sec-butoxymethylthio, tert-butoxymethylthio, 2-methoxyethylthio, and like alkoxyalkylthio in which C1-6 straight-chain or branched-chain alkylthio is substituted with C1-6 straight-chain or branched-chain alkoxy.
Examples of C2-6 alkenyloxy include, but are not 15 particularly limited to, vinyloxy, 1-propenyloxy, isopropenyloxy, allyloxy, 2-butenyloxy, 3-butenyloxy, 1-methylallyloxy, and the like.
Examples of C2-6 haloalkenyloxy include, but are not particularly limited to, 2,2-dichlorovinyloxy, 2,2-20 dibromovinyloxy, 2,2-difluorovinyloxy, 2,2-dibromovinyloxy, 3,3-difluoro-2-allyloxy, 4,4-difluoro-3-butenyloxy, 4,4,4-trifluoro-2-butenyloxy, and the like.
Examples of C2-6 alkynyloxy include, but are not particularly limited to, ethynyloxy, 2-propynyloxy, 1-methyl-2-25 propynyloxy, 1,1-dimethyl-2-propynyloxy, 1-butynyloxy, 2-butynyloxy, 3-butynyloxy, and the like.
Examples of C2-6 haloalkynyloxy include, but are not particularly limited to, fluoroethynyloxy, bromoethynyloxy, chloroethynyloxy, iodoethynyloxy, 3,3,3-trifluoro-1-propynyloxy, 30 and the like.
Examples of C1-6 alkylsulfonyloxy include, but are not particularly limited to, methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy, isopropylsulfonyloxy, n-butylsulfonyloxy,
35 isobutylsulfonyloxy, sec-butylsulfonyloxy, tert-butylsulfonyloxy,
14

and like C1-6 straight-chain or branched-chain alkylsulfonyl groups.
Examples of C1-6 haloalkylsulfonyloxy include, but are not particularly limited to, fluoromethylsulfonyloxy, 5 chloromethylsulfonyloxy, bromomethylsulfonyloxy,
iodomethylsulfonyloxy, dichloromethylsulfonyloxy, trichloromethylsulfonyloxy, difluoromethylsulfonyloxy, trifluoromethylsulfonyloxy, chlorodifluoromethylsulfonyloxy, bromodifluoromethylsulfonyloxy, dichlorofluoromethylsulfonyloxy,
10 2,2,2-trichloroethylsulfonyloxy, 2,2,2-trifluoroethylsulfonyloxy, pentafluoroethylsulfonyloxy, and like C1-6 straight-chain or branched-chain alkylsulfonyloxy substituted with 1 to 9, and preferably 1 to 5, halogen atoms.
Examples of C1-6 alkylsulfinyloxy include, but are not
15 particularly limited to, methylsulfinyloxy, ethylsulfinyloxy, n-propylsulfinyloxy, isopropylsulfinyloxy, n-butylsulfinyloxy, isobutylsulfinyloxy, sec-butylsulfinyloxy, tert-butylsulfinyloxy, and like C1-6 straight-chain or branched-chain alkylsulfinyloxy groups.
20 Examples of C1-6 haloalkylsulfinyloxy include, but are
not particularly limited to, fluoromethylsulfinyloxy, chloromethylsulfinyloxy, bromomethylsulfinyloxy, iodomethylsulfinyloxy, dichloromethylsulfinyoxy, trichloromethylsulfinyloxy, difluoromethylsulfinyloxy,
25 trifluoromethylsulfinyloxy, chlorodifluoromethylsulfinyloxy,
bromodifluoromethylsulfinyloxy, dichlorofluoromethylsulfinyloxy, 2,2,2-trichloroethylsulfinyloxy, 2,2,2-trifluoroethylsulfinyloxy, pentafluoroethylsulfinyloxy, and like C1-6 straight-chain or branched-chain alkylsulfinyloxy substituted with 1 to 9, and
30 preferably 1 to 5, halogen atoms.
Examples of substituted or unsubstituted amino include,
but are not particularly limited to, amino, monoalkylamino,
dialkylamino, monoacylamino, and the like. Examples of the alkyl
include C1-6 alkyl mentioned above, and the like. Examples of the
35 acyl include C1-6 alkoxycarbonyl, haloalkoxycarbonyl, arylcarbonyl
15

mentioned above, and the like.
Examples of aryl include, but are not particularly limited to, phenyl, 1-naphthyl, 2-naphthyl, and the like.
Examples of aryl C1-6 alkyl include, but are not 5 particularly limited to, benzyl, phenylethyl, phenyl-n-propyl, and the like.
Examples of aryloxy include, but are not particularly limited to, phenoxy, 1-naphthyloxy, 2-naphthyloxy, and the like.
Examples of aryl C1-6 alkoxy include, but are not 10 particularly limited to, benzyloxy, phenoxyethoxy, phenoxy-n-propoxy, phenyl-n-butoxy, 1-naphthylmethoxy, 2-naphthylmethoxy, and like.
Examples of arylsulfonyl include, but are not particularly limited to, phenylsulfonyl, 1-naphthylsulfonyl, 2-15 naphthylsulfonyl, and the like.
Examples of arylsulfinyl include, but are not particularly limited to, phenylsulfinyl, 1-naphthylsulfinyl, 2-naphthylsulfinyl, and the like.
Examples of arylthio include, but are not particularly 20 limited to, phenylthio, 1-naphthylthio, 2-naphthylthio, and the like.
Examples of aryl C1-6 alkylsulfonyl include, but are not particularly limited to, benzylsulfonyl, phenylethylsulfonyl, phenyl-n-propylsulfonyl, phenyl-n-butylsulfonyl, 1-25 naphthylmethylsulfonyl, 2-naphthylmethylsulfonyl, and the like.
Examples of aryl C1-6 alkylsulfinyl include, but are not
particularly limited to, benzylsulfinyl, phenylethylsulfinyl,
phenyl-n-propylsulfinyl, phenyl-n-butylsulfinyl, 1-
naphthylmethylsulfinyl, 2-naphthylmethylsulfinyl, and the like.
30 Examples of aryl C1-6 alkylthio include, but are not
particularly limited to, benzylthio, phenylethylthio, phenyl-n-propylthio, phenyl-n-butylthio, 1-naphthylmethylthio, 2-naphthylmethylthio, and the like.
All the Aryls mentioned above may optionally be further
35 substituted. Examples of the number of substituents include, but
16

are not particularly limited to, 1 to 20 (preferably 1 to 10, and more preferably 1 to 5).
Examples of a heterocyclic group include, but are not particularly limited to, thienyl, furyl, tetrahydrofuryl, 5 dioxolanyl, dioxanyl, pyrrolyl, pyrrolinyl, pyrrolidinyl,
oxazolyl, isoxazolyl, oxazolinyl, oxazolidinyl, isoxazolinyl, thiazolyl, isothiazolyl, thiazolinyl, thiazolidinyl, isothiazolinyl, pyrazolyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, oxadiazolyl, oxadiazolinyl,
10 thiadiazolinyl, triazolyl, triazolinyl, triazolidinyl, tetrazolyl, tetrazolinyl, pyridyl, dihydropyridyl, tetrahydropyridyl, piperidyl, oxazinyl, dihydroxazinyl, morpholino, thiazinyl, dihydrothiazinyl, thiamorpholino, pyridazinyl, dihydropyridazinyl, tetrahydropyridazinyl, hexahydropyridazinyl, oxadiazinyl,
15 dihydrooxadiazinyl, tetrahydrooxadiazinyl, thiadiazolyl,
thiadiazinyl, dihydrothiadiazinyl, tetrahydrothiadiazinyl, pyrimidinyl, dihydropyrimidinyl, tetrahydropyrimidinyl, hexahydropyrimidinyl, pyrazinyl, dihydropyrazinyl, tetrahydropyrazinyl, piperazinyl, triazinyl, dihydrotriazinyl,
20 tetrahydrotriazinyl, hexahydrotriazinyl, tetrazinyl,
dihydrotetrazinyl, indolyl, indolinyl, isoindolyl, indazolyl, quinazolinyl, dihydroquinazolyl, tetrahydroquinazolyl, carbazolyl, benzoxazolyl, benzoxazolinyl, benzisoxazolyl, benzisoxazolinyl, benzothiazolyl, benzisothiazolyl, benzisothiazolinyl,
25 benzimidazolyl, indazolinyl, quinolinyl, dihydroquinolinyl, tetrahydroquinolinyl, isoquinolinyl, dihydroisoquinolinyl, tetrahydroisoquinolinyl, pyridoindolyl, dihydrobenzoxazinyl, cinnolinyl, dihydrocinnolinyl, tetrahydrocinnolinyl, phthalazinyl, dihydrophthalazinyl, tetrahydrophthalazinyl, quinoxalinyl,
30 dihydroquinoxalinyl, tetrahydroquinoxalinyl, purinyl,
dihydrobenzotriazinyl, dihydrobenzotetrazinyl,
phenothiazinylfuranyl, benzofuranyl, chromanyl, benzothienyl, and
the like.
These heterocyclic groups include those substituted at
35 any substitutable position with an oxo or thioketone group.
17

Examples of heterocyclic C1-6 alkyl include, but are not
particularly limited to, 2-pyridylmethyl, 3-pyridylmethyl, 2-
pyrazinylmethyl, pyrimidinylmethyl, 2-quinolinylmethyl, and the
like.
5 Examples of heterocyclicoxy include, but are not
particularly limited to, 2-pyridyloxy, 3-pyridyloxy, 2-pyrazinyloxy, pyrimidinyloxy, 2-quinolinylmethyloxy, and the like.
All the heterocyclics mentioned above may optionally be further substituted. Examples of the number of substituents
10 include, but are not particularly limited to, 1 to 20 (preferably 1 to 10, and more preferably 1 to 5).
R5 and R6, taken together with the carbon atom to which they bond, may bond to each other to form a 3- to 8-membered ring via or not via at least one heteroatom.
15 Examples of hetero atom in the specification include,
but are not particularly limited to, an oxygen atom, a sulfur atom, a nitrogen atom, and the like. Examples of 3- to 8-membered ring include: but are not particularly limited to, cyclopropane, cycloheptane, and the like C3-8 cycloalkyl; tetrahydropyran,
20 piperidine, and the like heterocyclic.
R7 and R8, R8 and R9, R9 and R10, or R10 and R11, taken together with the benzene ring to which they bond, may bond to each other to form a 3- to 8-membered ring via or not via at least one heteroatom. Examples of the 3- to 8-membered ring
25 include: C3-8 cycloalkyl, aryl, heterocyclic, and the like. The C3-8 cycloalkyl, the aryl, and the heterocyclic are as defined above.
Examples of “substituents” for the above substituted groups include： but are not particularly limited to, the halogen,
30 nitro, cyano, hydroxyl, formyl, C1-6 alkyl, C1-6 haloalkyl, C1-6
alkoxy, C1-6 haloalkoxy, C1-6 alkoxy C1-6 alkyl, C1-6 haloalkoxy C1-6
alkyl, C3-8 cycloalkyl, C3-8 cycloalkyl C1-6 alkyl, C1-6
alkylcarbonyl, C1-6 haloalkylcarbonyl, arylcarbonyl,
aryloxycarbonyl, C1-6 alkoxycarbonyl, C1-6 haloalkoxycarbonyl, C1-6
35 cyanoalkyl, C1-6 cyanoalkoxy, C2-6 alkenyl, C2-6 haloalkenyl, C2-6
18

alkynyl, C2-6 haloalkynyl, C1-6 alkylsulfonyl, C1-6 haloalkylsulfonyl, C1-6 alkylsulfinyl, C1-6 haloalkylsulfinyl, C1-6 alkylthio, C1-6 haloalkylthio, C3-8 cycloalkylsulfonyl, C3-8 cycloalkylsulfinyl, C3-8 cycloalkylthio, C3-8 cycloalkyl C1-6 5 alkylsulfonyl, C3-8 cycloalkyl C1-6 alkylsulfinyl, C3-8 cycloalkyl C1-6 alkylthio, C1-6 alkoxy C1-6 alkylsulfonyl, C1-6 alkoxy C1-6 alkylsulfinyl, C1-6 alkoxy C1-6 alkylthio, C2-6 alkenyloxy, C2-6 haloalkenyloxy, C2-6 alkynyloxy, C2-6 haloalkynyloxy, C1-6 alkylsulfonyloxy, C1-6 haloalkylsulfonyloxy, C1-6 alkylsulfinyloxy,
10 C1-6 haloalkylsulfinyloxy, carboxyl, OCN, SCN, SF5, substituted or unsubstituted amino, aryl, aryl C1-6 alkyl, aryloxy, aryl C1-6 alkoxy, arylsulfonyl, arylsulfinyl, arylthio, aryl C1-6 alkylsulfonyl, aryl C1-6 alkylsulfinyl, aryl C1-6 alkylthio, heterocyclic, heterocyclic C1-6 alkyl, heterocyclic oxy, and the
15 like. Of these, preferable substituents are halogen, nitro, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, C1-6 alkylsulfonyl, C1-6 haloalkylsulfonyl, C1-6 alkylsulfinyl, C1-6 haloalkylsulfinyl, C1-6 alkylthio, C1-6 haloalkylthio, substituted or unsubstituted amino, aryl, and heterocyclic, and more
20 preferable substituents are fluorine, chlorine, nitro, methyl, ethyl, trifluoromethyl, methoxy, and trifluoromethoxy.
Preferable substituted aryl groups are halogen-substituted aryl, C1-6 alkyl-substituted aryl, C1-6 haloalkyl-substituted aryl, halogen and C1-6 haloalkyl-substituted aryl, C1-6
25 alkoxy-substituted aryl, C1-6 haloalkoxy-substituted aryl, and C1-6 alkylthio-substituted aryl. More preferable substituted aryl groups are chlorine-substituted aryl, fluorine-substituted aryl, trifluoromethyl-substituted aryl, chlorine- and trifluoromethyl-substituted aryl, trifluoromethoxy-substituted aryl, and methoxy-
30 substituted aryl, and methylthio-substituted aryl.
Preferable substituted heterocyclic groups are halogen-substituted heterocyclic, C1-6 alkyl-substituted heterocyclic, C1-6 haloalkyl-substituted heterocyclic, C1-6 alkoxy-substituted heterocyclic, C1-6 haloalkoxy-substituted heterocyclic, and C1-6
35 alkylthio-substituted heterocyclic. More preferable substituted
19

heterocyclic groups are chlorine-substituted heterocyclic,
fluorine-substituted heterocyclic, trifluoromethyl-substituted
heterocyclic, trifluoromethoxy-substituted heterocyclic, methoxy-
substituted heterocyclic, and methylthio-substituted heterocyclic.
5 The salts of the compounds represented by Formula (1)
may be any type of salts as long as they are agriculturally acceptable. Examples of the salts include a hydrochloride salt, a sulfate salt, a nitrate salt, and like inorganic acid salts; an acetate salt, a methanesulfonic acid salt, and like organic acid
10 salts; a sodium salt, a potassium salt, and like alkali metal
salts; a magnesium salt, a calcium salt, and like alkaline earth metal salts; dimethylammonium, triethylammonium, and like quaternary ammonium salts; and the like. X represents oxygen or sulfur.
15 Symbol n represents an integer of 0 to 2.
Among compounds (1) of the present invention, a preferable compound is a compound in which R1 is C1-6 haloalkyl, and a more preferable compound (1) is a compound in which R1 is trifluoromethyl or trifluoroethyl.
20 Among compounds (1) of the present invention, a
preferable compound is a compound in which R2 is hydrogen, halogen, or C1-6 alkyl, and a more preferable compound (1) is a compound in which R2 is fluorine, chlorine, bromine, or methyl.
Among compounds (1) of the present invention, a
25 preferable compound is a compound in which R3 is hydrogen, halogen, or C1-6 alkyl, and a more preferable compound (1) is a compound in which R3 is fluorine, chlorine, bromine, methyl or trifluoromethyl.
Among compounds (1) of the present invention, a preferable compound is a compound in which R4 is hydrogen, C1-6
30 alkyl, C2-6 alkenyl, C2-6 alkynyl, or C1-6 haloalkyl, and a more
preferable compound (1) is a compound in which R4 is hydrogen,
methyl, ethyl, n-propyl, n-butyl, 3,3,3-trifluoro-n-propyl,
heptafluoroisopropyl, or propargyl.
Among compounds (1) of the present invention, a
35 preferable compound is a compound in which R5 and R6 are identical
20

or different and each represent hydrogen, halogen, or C1-6 alkyl,
and a more preferable compound (1) is a compound in which R5 and
R6 are hydrogen, fluorine, methyl, isopropyl, or tert-butyl.
Among compounds (1) of the present invention, a
5 preferable compound is a compound in which R7, R8, R9, R10, and R11
are hydrogen, halogen, nitro, C1-6 alkyl, C1-6 haloalkyl, C1-6
alkoxy, C1-6 haloalkoxy, C1-6 alkylsulfonyl, C1-6 haloalkylsulfonyl,
C1-6 alkylsulfinyl, C1-6 haloalkylsulfinyl, C1-6 alkylthio, C1-6
haloalkylthio, substituted or unsubstituted amino, substituted or
10 unsubstituted aryl, or substituted or unsubstituted heterocyclic,
and a more preferable compound (1) is a compound in which R7, R8,
R9, R10, and R11 are hydrogen, fluorine, chlorine, bromine, nitro,
methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-pentyl,
trifluoromethyl, methoxy, ethoxy, n-propoxy, trifluoromethoxy,
15 trifluoromethylsulfonyl, trifluoromethylthio, methylsulfonyl,
methylthio, NH2, phenyl, 2-chlorophenyl, 4-chlorophenyl, 3,4-
dichlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl,
3,5-difluorophenyl, 2-chloro-4-fluorophenyl, 2-
trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-
20 trifluoromethylphenyl, 3-chloro-5-trifluoromethylphenyl, 4-
chloro-3-trifluoromethylphenyl, 2-trifluoromethoxylphenyl, 3-
trifluoromethoxylphenyl, 4-trifluoromethoxylphenyl, 4-
methoxylphenyl, 2-methylthiophenyl, 5-trifluoromethyl-2-pyridyl,
or 5-pyrimidyl.
25 When the compound (1) has isomers such as optical
isomers, stereoisomers, regioisomers, and the like,
any of the isomers and mixtures thereof are included within the scope of the compound (1). For example, when the compound (1) has optical isomers, the optical isomer separated from a racemic body 30 is also included within the scope of the compound (1). Each of such isomers may be obtained as a single compound by known synthesis and separation means (e.g., concentration, solvent extraction, column chromatography, recrystallization, etc.).
35 2. Method for producing a benzylamide compound and a salt thereof
21

5

No limitations are placed on the method for producing a benzylamide compound (1) (compound (1-1) and compound (1-2)) according to the present invention, and the benzylamide compound (1) can be produced by Steps 1 to 5 represented by Reaction Scheme 1 below: [Reaction Scheme 1]

STEP 1 RV^v-R3X R11
u
RV^WR3
IA
NH
(2)

STEP 2

Rl^^^R3 Rl1
T ^T JR^^^R3 R11
Ti ^T j{
ciso2
)10

STEP 3
STEP 5

HSA^A
N' X T R8
R4 R5R6 R7

4 R5R6 R7
(6)

STEP 4

10
15

(1-1) (1-2)
wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, X, and n are as defined above. Step 1
An amide compound (hereinafter may be referred to as “compound (4)”) represented by Formula (4) can be produced by reacting an aniline compound (hereinafter may be referred to as “compound (2)”) represented by Formula (2)) with a benzylcarbonyl compound (hereinafter may be referred to as “compound (3)”) represented by Formula (3) (Reaction Scheme 2): [Reaction Scheme 2]

22

R'

R3
NH R4

R5R6 R7

R4 R5R6 R7

5
10
15
20
25

(2) (3) (4)
wherein R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, X are as defined above.
Y represents a leaving group or a hydroxyl group, and examples of the leaving group include: halogen such as chlorine, bromine, and iodine; substituted or unsubstituted C1-6 alkyl sulfonate; and substituted or unsubstituted aryl sulfonate. Examples of the substituent include the aforementioned substituents such as the halogen and the C1-6 haloalkyl. Step 1A (when Y is a leaving group)
A phenylacetamide compound (hereinafter may be referred to as “compound (4)”) represented by Formula (4) can be produced by reacting the aniline compound (hereinafter may be referred to as “compound (2)) represented by Formula (2)) with a benzylcarbonyl compound (hereinafter may be referred to as “compound (3A) represented by Formula (3A) (Reaction Scheme 3): [Reaction Scheme 3]
RJ
NH R4
Rlz-^/R3 R11
R10

R
KX
N
R3R° R7
R4 R5k6 R7
(2) (3A) (4)
wherein R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and X are as
defined above. Y’ represents a leaving group.
Examples of the benzylcarbonyl compound (3A) include,
but are not particularly limited to, phenylacetyl chloride,
phenylacetyl bromide, and the like substituted or unsubstituted
phenylacetyl halide; and ethyl phenylacetate, methyl
phenylacetate, and the like substituted or unsubstituted
phenylacetic acid esters.
A used ratio of the aniline compound (2) and the
23

benzylcarbonyl compound (3A) in the reaction therebetween is not particularly limited and thus can appropriately be selected from a wide range. Relative to 1 mole of the aniline compound (2), typically approximately 1 to 5 moles of the benzylcarbonyl 5 compound (3A) and preferably approximately equimolar to 1.2 moles thereof is used.
The aforementioned reaction can be performed under absence or presence of a base. Among the above, the reaction is performed preferably under the presence of the base. As the base,
10 a conventionally known base can widely be used, and examples of the base include: sodium carbonate, potassium carbonate, cesium carbonate, potassium bicarbonate, sodium bicarbonate, and the like alkali metal carbonates; sodium hydroxide, potassium hydroxide, and the like alkali metal hydroxides; alkali metal
15 hydrides such as sodium hydride and potassium hydride, and the like inorganic bases; sodium methoxide, sodium ethoxide, potassium tert-butoxide, and the like alkali metal alkoxides; pyridine, triethylamine, diethylamin, dimethylamine, methylamine, imidazole, benzimidazole, diisopropylethylamine, 4-dimethylamine
20 pyridine, piperidine, and the like organic bases; and the like. Any separate one of these bases or a combination of two or more types thereof is used.
Relative to 1 mole of the aniline compound (2), typically approximately 1 to 10 moles of the base and preferably
25 approximately 1 to 5 moles thereof may excessively be used. When triethylamine, pyridine, or like an organic base is used, it can be used in large excess to serve also as a reaction solvent.
The aforementioned reaction is performed in an appropriate solvent or without any solvent. When the
30 aforementioned reaction is carried out in the solvent, no
limitations are placed on the solvent as long as the solvent is
inactive with respect to the aforementioned reaction. Examples of
such a solvent include: n-hexane, cyclohexane, n-heptane, and the
like fatty acid or alicyclic hydrocarbon-based solvents; benzene,
35 chlorobenzene, toluene, xylene, and the like aromatic
24

hydrocarbon-based solvents; methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride, and the like halogenated hydrocarbon-based solvents; diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, and the like ether-based 5 solvents; methyl acetate, ethyl acetate, and the like esters
solvents; acetonitrile; N,N-dimethylformamide (DMF) and the like amide-based solvents; and dimethyl sulfoxide and the like sulfoxide-based solvents. Any one of these solvents can be used alone or a combination of two or more types thereof can be used
10 when necessary.
Reaction temperature for the aforementioned reaction is not particularly limited, and is typically within a range between -10°C and a boiling point of the solvent used and preferably 0 to 25°C. Reaction time varies depending on, for example, the
15 reaction temperature, and the reaction typically ends in approximately 0.5 to 24 hours.

20

Step 1B (when Y is a hydroxyl group)
As another method for obtaining the phenylacetamide compound (4), the compound (4) can be produced by reacting the aniline compound (2) with a phenylacetic acid compound (hereinafter may be referred to as “compound (3B)”) represented by Formula (3B) (Reaction Scheme 4): [Reaction Scheme 4]

25
30


RsRb R7 (3B)
N
R4 R5R6 R7
(4)
(2)
wherein R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and X are as
defined above.
A used ratio of the aniline compound (2) and the
phenylacetic acid compound (3B) in the reaction therebetween is
not particularly limited and thus can appropriately be selected
from a wide range. Relative to 1 mole of the aniline compound (2),
25

typically approximately 1 to 5 moles of the phenylacetic acid compound (3B) and preferably approximately equimolar to 1.2 moles thereof is used.
The aforementioned reaction can be performed under 5 absence or presence of a condensing agent. Among the above, the aforementioned reaction is preferably performed under the presence of the condensing agent. As the condensing agent, a conventionally known condensing agent can be used, and examples of the condensing agent include 1-ethyl-3-(3-dimethylaminopropyl)
10 carbodiimide (EDCI HCl), 1-hydroxybenzotriazole (HOBT), 1-[bis(dimethylamino) methylene]-1H-1,2,3-triazolo [4, 5-b] pyridinium-3-oxide hexafluorophosphate (HATU), bis (2-oxo-3-oxazolidinyl) phosphine acid chloride (BOP-C1), propylphosphonic acid anhydride (T3P), and the like. Any separate one of these
15 condensing agents or a combination of two or more types thereof is used.
Relative to 1 mole of the aniline compound (2), typically 1 to 10 moles of the condensing agent and preferably approximately 1 to 3 moles thereof can excessively be used.
20 The aforementioned reaction is performed in an
appropriate solvent or without any solvent. When the aforementioned reaction is carried out in the solvent, no limitations are placed on the solvent as long as the solvent is inactive with respect to the aforementioned reaction. Examples of
25 such a solvent include: fatty n-hexane, cyclohexane, n-heptane, and the like acid or alicyclic hydrocarbon-based solvents; benzene, chlorobenzene, toluene, xylene, and the like aromatic hydrocarbon-based solvents; methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, and the like
30 halogenated hydrocarbon-based solvents; diethyl ether, THF, and
1,4-dioxane, and the like ether-based solvents; methyl acetate,
ethyl acetate, and the like esters solvents; acetonitrile; DMF
and the like amide solvents; and dimethyl sulfoxide and the like
sulfoxide-based solvents. Any one of these solvents can be used
35 alone or a combination of two or more types of the solvents can
26

be used when necessary.
Reaction temperature for the aforementioned reaction is not particularly limited and is typically within a range between -10°C and a boiling point of the solvent used and preferably 5 within a range between -5°C and the boiling point of the solvent. Reaction time varies depending on, for example, the reaction temperature, and the reaction typically ends in approximately 0.25 to 24 hours. Step 1C
10 Note that as a method for producing the phenylacetamide
compound (4), a phenylacetic acid halide compound (3C) obtained by reacting the phenylacetic acid compound (3B) with a halogenation reagent can be used as a raw material.
The aforementioned reaction can be performed under
15 presence of a base. As the base, any of the same bases as those described above can be used, and preferable examples of the base include triethylamine, pyridine, di-isopropylamine, 4-diisopropylethylamine, 4-dimethylamine pyridine, lutidine, and the like organic bases, and this base can also much excessively
20 be used to be also used as a reaction solvent.
Examples of the halogenation reagent includes, but are not particularly limited to, POCl3, POBr3, SOCl2, SO2Cl2, oxalyl chloride.
Relative to 1 mole of the aniline compound (2),
25 typically 1 to 10 moles of the halogenation reagent and
preferably approximately 1 to 5 moles thereof can be used.
The aforementioned reaction is performed in an appropriate solvent or without any solvent. When the aforementioned reaction is carried out in the solvent, no
30 limitations are placed on the solvent as long as the solvent is
inactive with respect to the aforementioned reaction. As such a
solvent, the aforementioned solvents are listed. Any one of these
solvents can be used alone or a combination of two or more types
thereof can be used when necessary.
35 Reaction temperature for the aforementioned reaction is
27

not particularly limited and is typically within a range between
-10°C and a boiling point of the solvent used and preferably
within a range between -5°C and the boiling point of the solvent.
Reaction time varies depending on, for example, the reaction 5 temperature, and the reaction typically ends in approximately
0.25 to 24 hours.
The aniline compound (2), the benzylcarbonyl compound
(3A), the phenylacetic acid compound (3B), and phenylacetic acid
halide compound (3C) in Step 1 used as starting materials in Step 10 1 are known compounds or compounds that can easily be produced by
a known method.
The compound (4) obtained by the method shown in Step 1
is easily isolated from a reaction mixture to be purified by use
of typical isolation means and purification means, for example, 15 filtration, solvent extraction, distillation, recrystallization,
column chromatography, etc.
After end of the reaction, the compound (4) can be
provided for next reaction without being isolated from the
reaction system. 20
Step 2
A sulfonyl chloride compound (hereinafter may be
referred to as “compound (5)”) represented by Formula (5) can be
produced by chlorosulfonating the amide compound (4) (Reaction 25 Scheme 5) :
[Reaction Scheme 5]
R10
R2VV
.. „ CISO
R4 R5R6 R7
(4)
wherein R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and X are as
defined above.
30 A reagent used for the chlorosulfonation is not
particularly limited, and for example, include chlorosulfonic
28

acid, and the like. When using chlorosulfonic acid, the step can be carried out in one step. For the chlorosulfonation, a two-step method including sulfonation and then chlorination can be used. The sulfonyl chloride compound (5) can be produced by reacting 5 the amide compound with a sulfonation reagent to produce an HOSO2-substituted amide compound and then reacting the HOSO2-containing amide compound with a chlorination agent.
The reagent used for the sulfation is not particularly limited, and for example, chlorosulfonic acid, sulfuric acid are
10 provided. Examples of the chlorinating agent used for the chlorination include, but are not particularly limited to, chlorine, POCl3, SOCl2, SO2Cl2, and oxalyl chloride.
When the chlorosulfonic acid is used, a used ratio between the amide compound (4) and the chlorosulfonic acid in the
15 reaction therebetween is not particularly limited and can
appropriately be selected from a wide range. Relative to 1 mole of the amide compound (4), typically approximately 1 to 50 moles of chlorosulfonic acid and preferably approximately 1 to 20 moles thereof is used.
20 When the sulfonation reagent and the chlorinating agent
are used, a used ratio between the sulfonation reagent and the chlorinating agent in the reaction between the amide compound (4) and the sulfonation reagent is not particularly limited and can appropriately be selected from a wide range. Relative to 1 mole
25 of the amide compound (4), typically approximately 1 to 50 moles of the sulfonation reagent and preferably approximately 1 to 20 moles thereof is used. A used ratio between the two in the reaction between the amide compound (4) and the chlorinating agent is not particularly limited, and can appropriately be
30 selected from a wide range. Relative to 1 mol of the amide
compound (1), typically approximately 1 to 50 moles of the
sulfuric acid and preferably 1 to 20 moles thereof is used.
The aforementioned reaction is performed in an
appropriate solvent or without any solvent. When the
35 aforementioned reaction is carried out in the solvent, no
29

limitations are placed on the solvent as long as the solvent is inactive with respect to the aforementioned reaction. As examples of such a solvent, the same solvents as those described above are listed. Any one of these solvents can be used alone or a 5 combination of two or more types thereof can be used when necessary.
Reaction temperature for the aforementioned reaction is not particularly limited, and is typically within a range between -20°C and a boiling point of the solvent used, preferably -10°C
10 to 150°C, and more preferably 0 to 100°C. Reaction time varies depending on, for example, the reaction temperature and the reaction typically ends in approximately 0.25 to 24 hours.
The sulfonyl chloride compound (5) obtained by the method shown in Step 2 is easily isolated from a reaction mixture
15 to be purified by use of typical isolation means and purification means, for example, filtration, solvent extraction, distillation, recrystallization, column chromatography, etc.
After end of the reaction, the sulfonyl chloride compound (5) can be provided for next reaction without being
20 isolated from the reaction system.
Step 3
A thiol compound (hereinafter may be referred to as “compound (6)”) represented by Formula (6) can be produced by 25 reacting the sulfonyl chloride compound (5) with a reducing agent (Reaction Scheme 6): [Reaction Scheme 6]
R10
R^-~/R3 R1J^\/R9 reducing agent R"Y"^r"R3X R^
R4 R5R6 R7
(5)
wherein R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and X are as
30 defined above.
A used ratio between the sulfonyl chloride compound (5)
30

and the reducing agent in the reaction therebetween is not particularly limited and can appropriately be selected from a wide range. Relative to 1 mole of the sulfonyl chloride compound (5), typically approximately 1 to 50 moles of the reducing agent 5 and more preferably approximately 1 to 20 moles thereof is used. As the reducing agent, any of conventionally known reducing agents can widely be used, and examples of the reducing agent include: triphenylphosphine and the like phosphorous compounds; reducing agents containing metal and acid such as zinc
10 and acid, tin (II) and acid, and iron and acid; and reducing agentred phosphorus, iodine, dichlorodimethylsilane-zinc-dimethylacetamide, lithium aluminum hydride, and the like specific reducing agents. Examples of the acid include acetic acid and the like organic acids; and hydrochloric acid, sulfuric
15 acid, and the like inorganic acids.
The aforementioned reaction is performed in an appropriate solvent. No limitations are placed on the solvent as long as the solvent is inactive with respect to the reaction. As examples of such a solvent, the same solvents as those described
20 above are listed. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
Reaction temperature for the aforementioned reaction is not particularly limited and is typically within a range between
25 -20°C and a boiling point of the solvent used, preferably -10°C to 150°C, and more preferably 20 to 120°C. Reaction time varies depending on, for example, the reaction temperature and the reaction typically ends in approximately 0.25 to 24 hours.
The thiol compound (6) obtained by the method shown in
30 Step 3 is easily isolated from a reaction mixture to be purified
by use of typical isolation means and purification means, for
example, filtration, solvent extraction, distillation,
recrystallization, column chromatography, etc.
After end of the reaction, the thiol compound (6) can
35 be provided for next reaction without being isolated from the
31

reaction system.
Method for producing a sulfide compound represented by Formula
(1-1) or a salt thereof
5 Examples of the method for producing the sulfide
compound represented by Formula (1-1) include, but are not
limited to, a production route 1, a production route 2, a
production route 3, a production route 4, described below, and
the like. 10
Production route 1 (Step 4)
A sulfide compound (1-1) can be produced by reacting
the thiol compound (6) with an alkyl reagent (hereinafter may be
referred to as “alkyl reagent (7)) represented by Formula (7) 15 (Reaction Scheme 7):
[Reaction Scheme 7]

R4 R5 R6 R7 R4 R5 R6 R7
(6) (1-D
wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and X are as defined above, and G represents a leaving group.
20 As examples of the leaving group, the same leaving
groups as those described above are listed.
A used ratio between the thiol compound (6) and the alkyl reagent (7) in the reaction therebetween is not particularly limited and can appropriately be selected from a
25 wide range. Relative to 1 mole of the thiol compound (6),
typically approximately 1 to 10 moles of the alkyl reagent (7) and preferably approximately 1 to 5 moles thereof is used.
Examples of the alkyl reagent (7) include, but are not particularly limited to, methyl iodide, ethyl bromide, and the
30 like C1-6 alkyl halides; trifluoromethyl iodide, trifluoromethyl
bromide, trifluoroethyl iodide, trifluoroethyl bromide, and the
32

like C1-6 haloaklyl halides; and the like.
The aforementioned reaction can be performed under presence of a base. Among the above, the aforementioned reaction is preferably performed under the presence of the base. As 5 examples of the base, conventionally known bases can widely be
used, and any of the same bases as those described above can be used.
Relative to 1 mole of the thiol compound (6), typically 1 to 10 moles of the base and preferably approximately 1 to 3
10 moles thereof can be used. When triethylamine, pyridine, or like an organic base is used, it can be used in large excess to serve also as a reaction solvent.
The aforementioned reaction can be performed by further adding a radical starting agent. Examples of the radical starting
15 agent include, but are not particularly limited to, sulfurous acid, a sulfurous acid salt, Rongalit (product name, sodium-formaldehyde-sulfoxylate), and the like sulfurous acid adducts. The base and the radical starting agent can be used in combination.
20 When the radical starting agent is used, as an additive
amount thereof, relative to 1 mole of the thiol compound (6), typically 0.1 to 10 moles of the radical starting agent and preferably approximately 0.1 to 5 moles thereof can be used. The aforementioned reaction is performed in an
25 appropriate solvent. Examples of the solvent include: n-hexane, cyclohexane n-heptane, and the like fatty acid or alicyclic hydrocarbon-based solvents; benzene, chlorobenzene, toluene, xylene, and the like aromatic hydrocarbon-based solvents; methylene chloride, 1,2-dichloroethane, chloroform, carbon
30 tetrachloride, and the like halogenated hydrocarbon-based
solvents; diethyl ether, THF, 1,4-dioxane, and the like ether-based solvents; methyl acetate, ethyl acetate, and the like ester-based solvents; acetonitrile; DMF, N,N-dimethylacetamide, N-methyl-2-pyrolidone, and the like amide-based solvents;
35 dimethyl sulfoxide and the like sulfoxide-based solvents;
33

5
10
15
20
25

alcohol-based solvents such as sulfolane, methanol, ethanol, isopropyl alcohol, and the like aprotic polar solvents; water; and the like. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
Reaction temperature for the aforementioned reaction is not particularly limited, and is typically within a range between -20°C and a boiling point of the solvent used, preferably -10°C to 60°C, and more preferably 0 to 50°C. Reaction time varies depending on, for example, the reaction temperature and the reaction typically ends in approximately 0.25 to 24 hours.
The sulfide compound (1-1) obtained by the method shown in Step 4 is easily isolated from a reaction mixture to be purified by use of typical isolation means and purification means, for example, filtration, solvent extraction, distillation, recrystallization, column chromatography, etc.
After end of the reaction, the sulfide compound (1-1) can be provided for next reaction without being isolated from the reaction system.
Production Route 2
A sulfide compound (hereinafter may be referred to as ”compound (1-1b)”) represented by Formula (1-1b) can be produced by reacting a sulfide compound (hereinafter may be referred to as “compound (1-1a)”) represented by Formula (1-1a) with a compound (hereinafter may be referred to as “compound (7’) represented by Formula (7’): R4’-G (Reaction Scheme 8): [Reaction Scheme 8]

R

-Ox

R10
R3X RVS /R9 ^R8 R4'-G (7')
H R5R6 R7 (1-1a)

30

wherein R1, R2, R3, R5, R6, R7, R8, R9, R10, R11 and X are as defined
above, and R4’ represents formyl, C1-6 alkyl, C1-6 haloalkyl, C1-6
34

alkoxy, C1-6 haloalkoxy, C1-6 alkoxy C1-6 alkyl, C1-6 haloalkoxy C1-6 alkyl, C3-8 cycloalkyl, C3-8 cycloalkyl C1-6 alkyl, C1-6 alkyl carbonyl, C1-6 haloalkyl carbonyl, C1-6 alkoxycarbonyl, C1-6 haloalkoxycarbonyl, arylcarbonyl, aryloxy carbonyl, C2-6 alkenyl, 5 C2-6 haloalkenyl, C2-6 alkynyl, C2-6 haloalkynyl, C1-6 alkylsulfonyl, C1-6 haloalkylsulfonyl, C1-6 alkylsulfinyl, C1-6 haloalkylsulfinyl, C1-6 alkylthio, C1-6 haloalkylthio, aryl, aryl C1-6 alkyl,
arylsulfonyl, arylsulfinyl, arylthio, and heterocyclic, and these groups may optionally be further substituted. G represents a
10 leaving group.
As examples of the leaving group, the leaving groups as those described above are listed.
A used ratio between the sulfide compound (1-1a) and the compound (7’) in the reaction therebetween is not
15 particularly limited and can appropriately be selected from a wide range. Relative to 1 mole of the former, typically approximately 1 to 10 moles of the latter and preferably approximately equimolar to 5 moles thereof is used.
The aforementioned reaction can be performed under
20 presence of a base. Among the above, the aforementioned reaction is preferably performed under the presence of the base. As the base, conventionally known bases can be used and any of the same bases as those described above can be used.
Relative to 1 mole of the sulfide compound (1-1a), a
25 stoichiometric amount of the base or an excessive amount thereof
over the aforementioned amount can be used. Preferably one to ten times of the base and more preferably one to five times thereof may excessively be used. When triethylamine, pyridine, or like an organic base is used, it can be used in large excess to serve
30 also as a reaction solvent.
The aforementioned reaction is performed in an
appropriate solvent. Examples of the solvent include: n-hexane,
cyclohexane, n-heptane, and the like fatty acid or alicyclic
hydrocarbon-based solvents; benzene, chlorobenzene, toluene,
35 xylene, and the like aromatic hydrocarbon-based solvents;
35

methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, and the like halogenated hydrocarbon-based solvents; diethyl ether, THF, 1,4-dioxane, and the like ether-based solvents; methyl acetate, ethyl acetate, and the like 5 esters solvents; acetonitrile; DMF, N,N-dimethylacetamide, N-methyl-2-pyrolidone, and the like amide-based solvents; dimethyl sulfoxide and the like sulfoxide-based solvents; alcohol-based solvents such as sulfolane, methanol, ethanol, and isopropyl alcohol and the like aprotic polar solvents; and water. Any one
10 of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
Reaction temperature for the aforementioned reaction is not particularly limited and is typically within a range between -20°C and a boiling point of the solvent used, preferably -10°C
15 to 60°C, and more preferably 20 to 50°C. Reaction time varies depending on, for example, the reaction temperature and the reaction typically ends in approximately 0.25 to 24 hours.
The sulfide compound (1-1b) obtained by the method shown in Step 4 is easily isolated from a reaction mixture to be
20 purified by use of typical isolation means and purification means, for example, filtration, solvent extraction, distillation, recrystallization, column chromatography, etc.
After end of the reaction, the sulfide compound (1-1b) can be provided for next reaction without being isolated from the
25 reaction system.
The sulfide compound (1-1) can be produced in accordance with not only what have been mentioned above but also production routes 3, 4, and 5. Production Route 3
30 The sulfide compound (1-1a) can be produced by reacting
an aniline compound (hereinafter may be referred to as “compound (8)”) with a phenylacetic acid compound (3) (Reaction Scheme 9): [Reaction Scheme 9]
36




H R5R6 R7 (1-1a)
S ^ NH2 (8)
wherein R1, R2, R3, R5, R6, R7, R8, R9, R10, R11, X, and Y are as defined above.

5

Production Route 3A (when Y is a leaving group)
The sulfide compound (1-1a) can be produced by reacting the aniline compound (2) with a benzylcarbonyl compound (3A) (Reaction Scheme 10): [Reaction Scheme 10]



H R5R6 R7

10
15
20
25

(8) (3A) (1-1 a)
wherein R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and X are as defined above, and Y’ represents a leaving group.
Examples of the benzylcarbonyl compound (3A) include, but are not particularly limited to, the same compounds as those of Step 1A.
The aniline compound (8) used as a starting material can be produced according to methods described in WO2007/131680. A used ratio between the aniline compound (8) and the benzylcarbonyl compound (3A) in the reaction therebetween is not particularly limited and thus can appropriately be selected from a wide range. Relative to 1 mole of the former, typically aproximately 1 to 5 moles of the latter and preferably approximately equimolar to 1.2 moles thereof is used.
The aforementioned reaction can be performed under
absence or presence of a base. Among the above, the
aforementioned reaction is preferably performed under the
presence of the base. As examples of the base, any of the same
37

bases as those shown in Step 1 above can be used. Any separate one of these bases or a combination of two or more types thereof is used.
Relative to 1 mole of the aniline compound (8), a 5 stoichiometric amount of the base or an excessive amount thereof over the aforementioned amount can excessively be used. Preferably one to five times of the base may excessively be used. When triethylamine, pyridine, or like an organic base is used, it can be used in large excess to serve 10 also as a reaction solvent.
The aforementioned reaction is performed in an appropriate solvent or without any solvent. When the
aforementioned reaction is carried out in the solvent, any of the same solvents as those shown in Step 1 above can be used. Any one 15 of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
Reaction temperature for the aforementioned reaction is not particularly limited and is typically within a range between -20°C and a boiling point of the solvent used and preferably 0 to 20 50°C. Reaction time varies depending on, for example, the reaction temperature and the reaction typically ends in approximately 0.5 to 24 hours.
The aniline compound (8) used as a starting material is a known compound or a compound that can easily be produced by a 25 known method.
The sulfide compound (1-1a) is easily isolated from a reaction mixture to be purified by use of typical isolation means and purification means, for example, filtration, solvent extraction, distillation, recrystallization, column 30 chromatography, etc.
After end of the reaction, the sulfide compound (1-1a) can be provided for next reaction without being isolated from the reaction system.
35 Step 3B (when Y is a hydroxyl group)
38

5

As another method for obtaining the phenylacetamide compound (1-1a), the compound (1-1a) can be produced by reacting the aniline compound (8) with a phenylacetic acid compound (3B) (Reaction Scheme 11): [Reaction Scheme 11]

10
15
20
25
30

R
R2

Rl
R3
R5R6 R7 (1-1a)
NH,
(8)
RsRb R7 (3B)
wherein R1, R2, R3, R5, R6, R7, R8, R9, R10, R11, and X are as defined above.
A used ratio between the aniline compound (8) and the phenylacetic acid compound (3B) in the reaction therebetween is not particularly limited and thus can appropriately be selected from a wide range. Relative to 1 mole of the former, typically approximately 1 to 5 moles of the latter and preferably equimolar to 1.2 moles thereof is used.
The aforementioned reaction can be performed under absence or presence of a condensing agent. Among the above, the aforementioned reaction is preferably performed under the presence of the condensing agent. As examples of the condensing agent, the same condensing agents as those shown in Step 1B are listed. Any separate one of these condensing agents or a combination of two or more types thereof is used.
Relative to 1 mole of the aniline compound (8), a stoichiometric amount of the condensing agent or an excessive amount thereof over the aforementioned amount can be used. Preferably approximately one to five times of the condensing agent may excessively be used.
The aforementioned reaction can be performed under
absence or presence of a base. Among the above, the
aforementioned reaction is preferably performed under the
presence of the base. As the base, any of the same bases as those
shown in Step 1 above can be used. Any separate one of these
39

bases or a combination of two or more types thereof is used. Relative to 1 mole of the aniline compound (8), a stoichiometric amount of the base or an excessive amount thereof over the aforementioned amount can be used. Preferably 5 approximately 1 to 5 times of the base can excessively be used.
When triethylamine, pyridine, or like an organic base is used, it can be used in large excess to serve also as a reaction solvent.
The aforementioned reaction is performed in an appropriate solvent or without any solvent. When the 10 aforementioned reaction is carried out in the solvent, any of the same solvents as those shown in Step 1 above can be used. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
Reaction temperature for the aforementioned reaction is 15 not particularly limited and is typically within a range between
-20°C and a boiling point of the solvent used and preferably 0 to 25°C. Reaction time varies depending on, for example, the reaction temperature and the reaction typically ends in approximately 0.5 to 24 hours. 20
Production Route 3C
Note that as a method for producing the phenylacetamide compound (1-1a), a phenylacetic acid halide compound (3C) obtained by reacting the phenylacetic acid compound (3B) with a 25 halogenation reagent can be used as a material.
The aforementioned reaction can be performed under presence of a base. As the base, any of the same bases as those described above can be used, and preferable examples of the base include triethylamine, pyridine, di-isopropylamine, 4-30 diisopropylethylamine, 4-dimethylamine pyridine, lutidine, and
the like organic bases. The bases can much excessively be used to be also used as reaction solvents.
Examples of the halogen reagent include, but are not particularly limited to, POCl3, POBr3, SOCl2, SO2Cl2, and oxalyl
35 chloride.
40

Relative to 1 mole of the aniline compound (2), typically 1 to 10 moles of the halogenation reagent and preferably approximately 1 to 5 moles thereof can be used. The aforementioned reaction is performed in an 5 appropriate solvent or without any solvent. When the
aforementioned reaction is carried out in the solvent, no limitations are placed on the solvent as long as the solvent is inactive with respect to the aforementioned reaction. As examples of such a solvent, the aforementioned solvents are listed. Any 10 one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
Reaction temperature for the aforementioned reaction is not particularly limited and is typically within a range between 10°C and a boiling point of the solvent used and preferably 15 within a range between -5°C and the boiling point of the solvent. Reaction time varies depending on, for example, the reaction temperature, and the reaction typically ends in approximately 0.25 to 24 hours.
The sulfide compound (1-1a) is easily isolated from a 20 reaction mixture to be purified by use of typical isolation means and purification means, for example, filtration, solvent extraction, distillation, recrystallization, column chromatography, etc.
After end of the reaction, the sulfide compound (1-1a) 25 can be provided for next reaction without being isolated from the reaction system.
Production Route 4
The sulfide compound (1-1) can be produced by reacting 30 a sulfide compound (hereinafter may be referred to as “compound (9)”) with an amide compound (hereinafter may be referred to as “compound (10)”) represented by Formula (10) (Reaction Scheme 12): [Reaction Scheme 12]
41

£ 0 /R3 + R10
R11 JL
x Ylf
R4 R5R6 R7 .R9 -0 3 R10
-R3X RVS
XNVT
R4 R5R6 R7 /R9

^R8


^R8
(9) (1°) (1-1)
wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and X are as defined above, and Z represents a leaving group.
A used ratio between the sulfide compound (9) and the 5 amide compound (10) in the reaction therebetween is not
particularly limited and can appropriately be selected from a wide range. Relative to 1 mole of the former, typically approximately 1 to 10 moles of the latter and preferably approximately equimolar to 5 moles thereof is used.
10 The aforementioned reaction can be performed under
absence or presence of a base. Among the above, the aforementioned reaction is preferably performed under the presence of the base. As the base, any of the same bases as those shown in Step 1 above can be used. Any separate one of these
15 bases or a combination of two or more types thereof is used. Relative to 1 mole of the aniline compound (9), typically 1 to 10 moles of the base and preferably approximately 1 to 5 moles thereof is used.
The aforementioned reaction is performed in an
20 appropriate solvent or without any solvent. When the
aforementioned reaction is carried out in the solvent, any of the same solvents as those shown in the Step 1 above can be used. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
25 Reaction temperature for the aforementioned reaction is
not particularly limited and is typically within a range between -10°C and a boiling point of the solvent used and preferably between -0°C and the boiling point of the solvent. Reaction time varies depending on, for example, the reaction temperature and
30 the reaction typically ends in approximately 0.5 to 24 hours.
The sulfide compound (9) used as a starting material
42

can be produced according to methods described in EP3002279 and WO2012/176856.
The sulfide compound (1-1) is easily isolated from a reaction mixture to be purified by use of typical isolation means 5 and purification means, for example, filtration, solvent extraction, distillation, recrystallization, column chromatography, etc.
After end of the reaction, the sulfide compound (1-1) can be provided for next reaction without being isolated from the 10 reaction system.

15

Step 5
A benzylamide compound (hereinafter may be referred to as “compound (1-2)”) represented by Formula (1-2) can be produced by reacting a sulfide compound represented by Formula (1-1) with an oxidizing agent (Reaction Scheme 13): [Reaction Scheme 13]

R9 R8
R9 R8
10 R
10 R
20
25
30

R 2^^R 3 X R 11
SN
R2,
R 3 X R 11.

oxidizing agent
S
N
R4 R5 R6 R7 (1-1)
R1>
(O)n'
4 R5 R67 RR
(1-2)
wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, X, and n’ are as described above.
A used ratio between the benzylamide compound (1-1) and the oxidizing agent in the reaction therebetweeen is not particularly limited and can appropriately be selected from a wide range. Relative to 1 mole of the former, typically approximately 1 to 10 moles of the latter and preferably approximately equimolar to 5 moles thereof is used.
The aforementioned reaction can be performed under
presence of the oxidizing agent. As the oxidizing agent, any of
known oxidizing agents can be used as long as the oxidizing agent
can achieve oxidization of sulfide into sulfoxide, and examples
of the oxidizing agent include a combination of: performic acid,
43

peracetic acid, pertrifluoroacetic acid, perbenzoic acid, m-chloroperbenzoic acid (mCPBA), o-carbonylperbenzoic acid, and the like peracids; hydrogen peroxide, t-butylhydroperoxide, cumene hydroperoxide,and the like alkyl hydroperoxides; and titanium 5 tetraisopropoxide and the like titanium tetraalkoxides;
dichromate, sodium bichromate, patassium bichromate, and the like dichromate salts; and permanganic acid, sodium permanganate, potassium permanganate, and the like permanganates; and the like. Any separate one of these oxidizing agents or a combination of
10 two or more types thereof is used.
Relative to 1 mole of the benzylamide compound (1-1), a stoichiometric amount of the oxidizing agent or an excessive amount thereof over the aforementioned amount can excessively be used. Preferably one to ten times of the oxidizing agent and more
15 preferably approximately one to five times thereof may be used.
The aforementioned reaction can further be performed by adding a catalyst.
The aforementioned reaction is performed in an appropriate solvent. Examples of the solvent include: n-hexane,
20 cyclohexane, n-heptane, and the like fatty acid or alicyclic hydrocarbon-based solvents; benzene, chlorobenzene, toluene, xylene, and the like aromatic hydrocarbon-based solvents; methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, and the like halogenated hydrocarbon-based
25 solvents; diethyl ether, THF, 1,4-dioxane, and the like ether-based solvents; methyl acetate, ethyl acetate, and the like esters solvents; acetonitrile; DMF, N,N-dimethylacetamide, N-methyl-2-pyrolidone, and the like amide-based solvents; dimethyl sulfoxide and the like sulfoxide-based solvents; alcohol-based
30 solvents such as sulfolane, methanol, ethanol, isopropyl alcohol,
and the like aprotic polar solvents. Any one of these solvents
can be used alone or a combination of two or more types thereof
can be used when necessary.
Reaction temperature for the aforementioned reaction is
35 not particularly limited, and is typically within a range between
44

-20°C and a boiling point of the solvent used, preferably -10°C
to 60°C, and more preferably 20 to 50°C. Reaction time varies
depending on, for example, the reaction temperature, and the
reaction typically ends in approximately 0.25 to 24 hours.
5 The sulfide compound (1-2) obtained by the method shown
in Step 5 is easily isolated from a reaction mixture to be purified by use of typical isolation means and purification means, for example, filtration, solvent extraction, distillation, recrystallization, chromatography, etc.
10
Each compound (1) obtained after the completion of the reactions shown in Reaction Scheme 1 to Reaction Scheme 13 may be easily isolated from the reaction mixture and purified by known isolation and purification techniques, such as filtration,
15 solvent extraction, distillation, recrystallization, and column chromatography.
When compound (1) has regioisomers, each regioisomer may be separated by a usual separation step, such as silica gel chromatography.
20
Pest-Controlling Agent
Compound (1) of the present invention may be used as an active ingredient of a pest-controlling agent. Examples of pest-controlling agents include agents (agricultural and horticultural
25 insecticide, miticides, nematicides, or soil insecticides) for
controlling pests, mites, nematode, or soil pests that all cause problems in the agricultural and horticultural fields; animal-ectoparasite-controlling agents (e.g., pulicide, ixodicide, and pedivulicideon), and the like.
30 For use as an active ingredient of a pest-controlling
agent, it is possible to use compound (1) of the present
invention as is with no additional components. However, it is
usually preferable to use the compound by combining with a solid
carrier, liquid carrier, or gaseous carrier (propellant), and
35 optionally with a surfactant and other adjuvants for
45

pharmaceutical preparation, and formulating the resulting mixture
into various forms such as oil solutions, emulsions, wettable
powders, flowable preparations, granules, dusts, aerosols,
fumigants, or the like, according to known preparation methods.
5 Compound (1) of the present invention is usually
contained in these formulations in a proportion of 0.01 to 95 wt%, and preferably 0.1 to 50 wt%.
Examples of solid carriers usable in the formulations include solid carriers in a fine powder or granular form, such as
10 clay (e.g., kaolin clay, diatomaceous earth, synthetic hydrated
silicon dioxide, bentonite, Fubasami clay, and acid clay), talc, ceramic, other inorganic minerals (e.g., celite, quartz, sulfur, active carbon, calcium carbonate, and hydrated silica), and chemical fertilizers (e.g., ammonium sulfate, ammonium phosphate,
15 ammonium nitrate, urea, and ammonium chloride); and the like. Examples of liquid carriers include water, alcohols (e.g., methanol and ethanol), ketones (e.g., acetone and
methylethylketone), aromatic hydrocarbons (e.g., benzene, toluene, xylene, ethylbenzene, and methylnaphthalene), aliphatic
20 hydrocarbons (e.g., hexane, cyclohexane, kerosene, and light oil), esters (e.g., ethyl acetate and butyl acetate), nitriles (e.g., acetonitrile and isobutyronitrile), ethers (e.g., diisopropyl ether and dioxane), acid amides (e.g., N,N-dimethylformamide and N,N-dimethylacetamide), halogenated hydrocarbons (e.g.,
25 dichloromethane, trichloroethane, and carbon tetrachloride), dimethylsulfoxide, soybean oil, cottonseed oil, and like vegetable oils, and the like.
Examples of gaseous carriers include butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide gas,
30 and the like.
Examples of surfactants include alkyl sulfates, alkyl
sulfonates, alkylaryl sulfonates, alkyl aryl ethers,
polyoxyethylene adducts thereof, polyethylene glycol ethers,
polyhydric alcohol esters, sugar alcohol derivatives, and the
35 like.
46

Examples of adjuvants for pharmaceutical preparation include fixing agents, dispersants, stabilizers, and the like.
Examples of the fixing agents and dispersants include casein, gelatin, polysaccharides (e.g., starch, gum arabic, 5 cellulose derivatives, and alginic acid), lignin derivatives,
bentonite, sugars, and water-soluble synthetic polymers (e.g., polyvinyl alcohol, polyvinyl pyrrolidone, and polyacrylic acids).
Examples of stabilizers include PAP (acidic isopropyl phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (mixture 10 of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, fatty acids, and fatty acid esters, and the like.
For the pest-controlling agent of the present invention, it is preferable to use compound (1) as is, or by diluting it 15 with water or the like. The pest-controlling agent of the present invention may be used by mixing with, for example, other pest-controlling agents, such as known insecticides, nematicides, acaricides, fungicides, herbicides, plant-growth-controlling agents, synergists, soil conditioners, animal feeds, and the like, 20 or it may be used simultaneously with these agents without mixing. The amount of the pest-controlling agent of the invention is not limited, and may be suitably selected from a wide range according to various conditions such as the
concentration of active ingredient, the form of preparation, type 25 of disease or pest to be treated, type of plant, severity of
disease, time for application, method for application, chemicals
to be used in combination (insecticide, nematicide, miticide,
fungicide, herbicide, plant growth control agent, synergist, soil
conditioner, etc.), and amount and type of fertilizer.
30 When used as a pesticide, compound (1) of the present
invention is usually used in an amount of 0.01 to 500 g/100 m2, and preferably 1 to 200 g/100 m2.
When used as a miticide, compound (1) of the present invention is usually used in an amount of 0.1 to 500 g/100 m2, and
35 preferably 1 to 200 g/100 m2.
47

When the emulsion, wettable powder, flowable preparation, or the like is used by diluting with water, the concentration is 0.1 to 1,000 ppm, and preferably 1 to 500 ppm. The granules, dusts, or the like can be used as is without 5 dilution.
Compound (1) of the present invention is characterized by having a particularly excellent miticidal activity and a broad spectrum of activity.
Compound (1) of the present invention is effectively
10 used as an agricultural and horticultural insecticide, miticide, nematicide, or a soil insecticide. Specifically, compound (1) of the present invention is effective for controlling pests, such as green peach aphids, cotton aphids, and like aphids; diamondback moths, cabbage armyworms, common cutworms,
15 codling moths, bollworms, tobacco budworms, gypsy moths, rice
leafrollers, smaller tea tortrix moths, Colorado potato beetles, cucurbit leaf beetles, boll weevils, plant hoppers, leafhoppers, scales, bugs, whiteflies, thrips, grasshoppers, anthomyiid flies, scarabs, black cutworms, cutworms, ants, and agricultural pest
20 insects; slugs, snails, and like gastropods; rat mite,
cockroaches, houseflies, house mosquitoes, and like hygiene-harming insects; angoumois grain moths, adzuki bean weevils, red flour beetles, mealworms, and like stored-grain insects; casemaking clothes moths, black carpet beetles, subterranean
25 termites, and like clothes-harming insects and house- and household-harming insects; and the like,
mites, such as two-spotted spider mites, carmine spider mites, citrus red mites, Kanzawa spider mites, European red mites (fruit tree spider mites), broad mites, pink citrus rust mites, bulb
30 mites, and like plant-parasitic mites; Tyrophagus putrescentiae, Dermatophagoides farinae, Chelacaropsis moorei, and like house dust mites; and the like, and
soil pests, such as root-knot nematodes, cyst nematodes, root-lesion nematodes, white-tip nematode, strawberry bud nematode,
35 pine wood nematode, and like plant parasitic nematodes; pill bugs,
48

sow bugs, and like isopods; and the like.
The pest-controlling agent of the present invention is also effective for controlling various pests resistant to chemicals such as organophosphorus agents, carbamate agents, 5 synthetic pyrethroid agents, and neonicotinoid agent.
Examples
The present invention is described in more detail with reference to the following Production Examples and Examples; 10 however, the present invention is not limited to these Examples.
Production Example 1:
Preparation of N-(2-fluoro-4-methylphenyl)-2-(4-(trifluoromethoxy) phenyl) acetamide (4-14)
15 To a solution of 2-fluoro-4-methylbenzenamine (2-14;
1.1 g, 8.79 mmol, 1 equiv.) and 2-(4-(trifluoromethoxy) phenyl) acetic acid (3b-14; 2.12 g, 9.67 mmol, 1.1 equiv.) in pyridine (10 ml) slowly added POCl3 (1.6 ml, 17.58 mmol, 2 equiv.) at 0 °C. The reaction was further maintained at the same temperature for
20 15 minutes. The reaction mixture was then quenched into ice and the product was then extracted with ethyl acetate. The combined organic layer was washed by 1N HCl solution followed by brine solution, dried over sodium sulfate, filtered and concentrated under reduced pressure to get 2.20 g of the crude product 4-14 as
25 yellow solid. The crude product thus obtained was further used as such without any purification.
1H NMR (CDCl3): 8.10 (t, J = 8.6 Hz, 1H), 7.39-7.37 (m, 2H), 7.25-7.23 (m, 3H), 6.92-6.85 (m, 2H), 3.75 (s, 2H), 2.29 (s, 3H).
30 Production Example 2:
Preparation of 5-(2-(4-(trifluoromethoxy) phenyl) acetamide)-4-fluoro-2-methylbenzene-1-sulfonyl chloride (5-14)
Chlorosulfonic acid (14.0 g, 120 mmol, 18 equiv.) was added to N-(2-fluoro-4-methylphenyl)-2-(4-(trifluoromethoxy)
35 phenyl) acetamide (4-14; 2.20 g, 6.72 mmol, 1 equiv.) at a
49

temperature below 50 °C. The reaction mixture was then stirred at room temperature overnight. The reaction mixture was then quenched into ice, the product was then extracted with ethyl acetate. The combined organic layer was washed by distilled water, 5 dried over sodium sulfate, filtered and concentrated under
reduced pressure to get 2.60 g of the crude product 5-14 as black viscous oil. The crude product thus obtained was further used as such without any purification.
1H NMR (CDCl3): 9.08 (d, J = 7.6 Hz, 1H), 7.39-7.36 (m, 2H), 7.25-10 7.24 (m, 3H), 7.12 (d, J = 10.8 Hz, 1H), 3.79 (s, 2H), 2.71 (s, 3H).
Production Example 3:
Preparation of N-(2-fluoro-5-mercapto-4-methylphenyl)-2-(4-15 (trifluoromethoxy) phenyl) acetamide (6-14)
To a mixture of 5-(2-(4-(trifluoromethoxy) phenyl) acetamide)-4-fluoro-2-methylbenzene-1-sulfonyl chloride (5-14; 2.60 g, 6.11 mmol, 1 equiv.) in toluene (20 ml) was added triphenyl phosphine (4.8 g, 18.35 mmol, 3 equiv.) at room 20 temperature. The reaction was then heated to 100 °C for 3 hours. The reaction mixture was cooled to room temperature and all the volatiles were distilled out by rotary evaporator. The crude product thus obtained was purified by column chromatography on silica gel with a mixture of ethyl acetate and n-hexane as an 25 eluent to obtain 1.0 g of the title compound 6-14 as an off white solid.
1H NMR (CDCl3): 8.26 (d, J = 7.6 Hz, 1H), 7.38-7.36 (m, 2H), 7.25-7.21 (m, 3H), 6.87 (d, J = 10.8 Hz, 1H), 3.74 (s, 2H), 3.30 (s, 1H), 2.25 (s, 3H). 30
Example 1:
Preparation of N-(5-(2,2,2-trifluoroethylthio)-2-fluoro-4-methylphenyl)-2-(4-(trifluoromethoxy) phenyl) acetamide (1A-14) To a cooled mixture of N-(2-fluoro-5-mercapto-4-35 methylphenyl)-2-(4-(trifluoromethoxy) phenyl) acetamide (6-14;
50

1.00 g, 2.78 mmol, 1 equiv.) in DMF (10 ml) was added cesium carbonate (0.90 g, 2.78 mmol, 1 equiv.) followed by sodium formaldehyde sulfoxylate (0.33 g, 2.78 mmol, 1 equiv.). To this mixture was then added slowly trifluoroethyl iodide (0.639 g, 5 3.06 mmol, 1.1 equiv.) at 0 °C and the resulting mixture was then stirred at room temperature for 6 hours. The reaction mixture was then poured into distilled water and extracted with dichloromethane. The combined organic layer was washed with distilled water, dried over sodium sulfate, filtered and
10 concentrated under reduced pressure to obtain a crude product. The crude product thus obtained was purified by column chromatography on silica gel with a mixture of ethyl acetate and n-hexane as an eluent to obtain 0.95 g of the title compound 1A-14 as a pale yellow solid.
15
Production Example 4:
Preparation of N-(2-fluoro-4-methylphenyl) acetamide
To a mixture of 2-fluoro-4-methylaniline (5.50 g, 43.95 mmol, 1 equiv.) in chloroform (30 ml), a solution of acetic
20 anhydride (4.49 g, 43.95 mmol, 1 equiv.) in chloroform (20 ml)
was slowly added at 0 °C. The reaction mixture was then stirred at room temperature for 3 hours. The reaction mixture was then quenched into sodium bicarbonate solution and the product was extracted with dichloromethane. The combined organic layer was
25 washed by sodium bicarbonate solution followed by distilled water, dried over sodium sulfate, filtered and concentrated under reduced pressure to get 5.92 g of the crude product as white solid. The crude product thus obtained was further used as such without any purification.
30 1H NMR (CDCl3) : δ 8.14-8.10 (m, 1H) , 7.25 (bs, 1H), 6.93-6.88 (m, 2H), 2.31 (s, 3H), 2.20 (s, 3H).
Production Example 5:
Preparation of 5-acetamido-4-fluoro-2-methylbenzene-1-sulfonyl
35 chloride
51

Chlorosulfonic acid (20.56 g, 176.46 mmol, 5 equiv.) was slowly added to N-(2-fluoro-4-methylphenyl) acetamide (5.90 g, 35.29 mmol, 1 equiv.) keeping the temperature of the reaction mixture below 50 °C. The resulting mixture was then heated to 5 70 °C for 4 hours. After cooling to room temperature, the reaction mixture was then poured carefully into ice, the precipitate was filtered, washed well with distilled water and dried to get 7.3 g of crude product as light brown solid. The crude product thus obtained was further used as such without any 10 purification.
1H NMR (CDCl3) : δ 9.09 (d, J = 7.6 Hz, 1H), 7.48 (bs, 1H), 7.14 (d, J = 10.8 Hz, 1H), 2.72 (s, 3H), 2.25 (s, 3H).
Production Example 6:
15 Preparation of N-(2-fluoro-5-mercapto-4-methylphenyl) acetamide
To a mixture of 5-acetamido-4-fluoro-2-methylbenzene-1-sulfonyl chloride (7.00 g, 26.34 mmol, 1 equiv.) in glacial acetic acid (60 ml) was portion-wise added zinc dust (34.44 g, 52 6.80 mmol, 20 equiv.) at room temperature. The resulting
20 mixture was then refluxed for 4 hours. After cooling to room temperature, the reaction mixture was diluted with distilled water and ethyl acetate and filtered through celite bed. The organic layer was washed well by distilled water, dried over sodium sulfate, filtered and concentrated under reduced pressure
25 to get 3.64 g of the crude product as pale yellow solid. The
crude product thus obtained was further used as such without any
purification.
1H NMR (CDCl3) : δ 8.25 (d, J = 7.6 Hz, 1H), 7.29 (bs, 1H), 6.89 (d,
J = 11.6 Hz, 1H), 3.34 (bs, 1H), 2.26 (s, 3H), 2.20 (s, 3H).
30
Production Example 7:
Preparation of N-(5-(2,2,2-trifluoroethylthio)-2-fluoro-4-
methylphenyl) acetamide
To a cooled mixture of N-(2-fluoro-5-mercapto-4-
35 methylphenyl) acetamide (3.10 g, 15.56 mmol, 1 equiv.) in DMF (30
52

ml) was added cesium carbonate (5.07 g, 15.56 mmol, 1 equiv.) followed by sodium formaldehyde sulfoxylate (1.84 g, 15.56 mmol, 1 equiv.). To this mixture was then added slowly trifluoroethyl iodide (3.27 g, 15.56 mmol, 1 equiv.) and the resulting mixture 5 was then stirred at room temperature for 6 hours. The reaction mixture was then poured into distilled water and extracted with dichloromethane. The combined organic layer was washed with distilled water, dried over sodium sulfate, filtered and concentrated under reduced pressure to get crude product. The
10 crude product thus obtained was purified by column chromatography on silica gel with a mixture of ethyl acetate and n-hexane as an eluent to obtain 2.90 g of the title compound as an off white solid. 1H NMR (CDCl3) : δ 8.49 (d, J = 8.0 Hz, 1H), 7.29 (bs, 1H) , 6.96 (d,
15 J = 11.6 Hz, 1H), 3.42-3.35 (q, J = 9.6 Hz, 2H), 2.41 (s, 3H), 2.21 (s, 3H).
Production Example 8:
Preparation of 5-(2,2,2-trifluoroethylthio)-2-fluoro-4-
20 methylbenzenamine
To a mixture of N-(5-(2,2,2-trifluoroethylthio)-2-fluoro-4-methylphenyl) acetamide (2.20 g, 7.82 mmol, 1 equiv.) in ethanol/water (30 ml/4 ml) was added concentrated HCl (30 ml). The resulting mixture was then refluxed for 6 hours. After
25 cooling to room temperature, all volatiles were removed by vacuum distillation and pH of the residue was then made basic by slow addition of 1N NaOH solution. The product was then extracted with ethyl acetate. The combined organic layer was then washed with distilled water followed by brine solution, dried over sodium
30 sulfate, filtered and concentrated under reduced pressure to get
crude product as a brown oil. The crude product thus obtained was
further used as such without any purification.
1H NMR (CDCl3) : δ 6.98 (d, J = 9.2 Hz, 1H), 6.86 (d, J = 11.6 Hz,
1H), 3.64 (bs, 2H), 3.32-3.25 (q, J = 9.6 Hz, 2H), 2.36 (s, 3H).
35 Example 2:
53

Preparation of N-(5-(2,2,2-trifluoroethylthio)-2-fluoro-4-methylphenyl)-2-phenylacetamide (1A-1)
To a cooled solution of 5-(2,2,2-trifluoroethylthio)-2-fluoro-4-methylbenzenamine (0.10 g, 0.42 mmol, 1 equiv.) in 5 chloroform (10 ml), triethylamine (0.046 g, 0.46 mmol, 1.1
equiv.) was added followed by slow addition of 2-phenylacetyl chloride (0.068 g, 0.44 mmol, 1.05 equiv.). The resulting mixture was then stirred at room temperature for 14 hours. The reaction mixture was then poured into NaHCO3 solution and the product was 10 extracted by dichloromethane. The combined organic layer was then washed with distilled water followed by brine solution, dried over sodium sulfate, filtered and concentrated under reduced pressure to get 0.125 g of title product as an off white solid.
15 Example 3:
Preparation of N-(5-(2,2,2-trifluoroethylthio)-2-fluoro-4-methylphenyl)-2-(2-chlorophenyl) acetamide (1A-3)
To a cooled solution of 5-(2,2,2-trifluoroethylthio)-2-fluoro-4-methylbenzenamine (0.05 g, 0.21 mmol, 1 equiv.) in
20 dichloromethane (10 ml), triethylamine (0.042 g, 0.42 mmol, 2.0
equiv.) was added followed by slow addition of 2-(2-chlorophenyl) acetyl chloride (0.04 g, 0.21 mmol, 1 equiv.). The resulting mixture was then stirred at room temperature for 14 hours. The reaction mixture was then poured into NaHCO3 solution and the
25 product was extracted by dichloromethane. The combined organic layer was then washed with distilled water followed by brine solution, dried over sodium sulfate, filtered and concentrated under reduced pressure to get crude product. The crude product thus obtained was purified by column chromatography on silica gel
30 with a mixture of ethyl acetate and n-hexane as an eluent to obtain 0.07 g of the title compound as a brown solid.
Example 4:
Preparation of N-(5-(2,2,2-trifluoroethylthio)-2-fluoro-4-35 methylphenyl)-2-(2,5-dichlorophenyl) acetamide (1A-4)
54

To a cooled mixture of 5-(2,2,2-trifluoroethylthio)-2-fluoro-4-methylbenzenamine (0.05 g, 0.21 mmol, 1 equiv.) and 2-(2,5-dichlorophenyl)acetic acid (0.05 g, 0.25 mmol, 1.2 equiv.) in pyridine (3 ml), POCl3 (0.08 g, 0.52 mmol, 2.5 equiv.) was 5 added very slowly. After few minutes, the reaction mixture was
poured into ice and the product was extracted with ethyl acetate. The combined organic layer was then washed with 1N HCl followed with distilled water, dried over sodium sulfate, filtered and concentrated under reduced pressure to get crude product. The 10 crude product thus obtained was purified by column chromatography on silica gel with a mixture of ethyl acetate and n-hexane as an eluent to obtain 0.023 g of the title compound as a light yellow solid.
15 Example 5:
The compounds shown in Tables 1 and 2, other than the
compounds obtained in Examples 1 to 4, were produced by methods
similar to the methods described in Examples 1 to 4 or methods
described in the description.
20 Tables 2 show 1H-NMR data of the thus obtained
compounds of the present invention.
The abbreviations in Tables 1 and 2 are as indicated below.
25 F: fluoro, Cl: chloro, Br: bromo, Me: methyl, Et: ethyl, n-Pr:
normal-propyl, i-Pr: isopropyl, n-Bu: normal-butyl, t-Bu: tert-butyl, n-Pent: normal-pentyl, CF3: trifluoromethyl, OMe: methoxy, OEt: ethoxy, OCF3: trifluoromethoxy, SCF3: trifluoromethylthio, SMe: methylthio, NH2: amino, NO2: nitro, Ph: phenyl, S: sulfur
30 atom, O: oxygen atom.
55


Table 1

S. No. R2 R3 R4 R5
H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H Me H H H H H R6 R7 R８ R9 R10 R11 X n
1A-1 Me F H
H H H H H H O 0
1A-2 Me F H
H H H Cl H H O 0
1A-3 Me F H
H Cl H H H H O 0
1A-4 Me F H
H Cl H H Cl H O 0
1A-5 Me F H
H H Cl Cl H H O 0
1A-6 Me F H
H H Cl H Cl H O 0
1A-7 Me F H
H Cl Cl H H H O 0
1A-8 Me F H
H Cl H Cl H H O 0
1A-9 Me F H
H H Cl H H H O 0
1A-10 Me F H
H H H t-Bu H H O 0
1A-11 Me F H
H Cl H H H Cl O 0
1A-12 Me F H
H H H CF3 H H O 0
1A-13 Me F H
H H H F H H O 0
1A-14 Me F H
H H H OCF3 H H O 0
1A-15 Me F H
H F H F H F O 0
1A-16 Me F H
H Br H OMe H H O 0
1A-17 Me F H
H H F H H H O 0
1A-18 Me F H
H F H H H H O 0
1A-19 Me F H
H H OCF3 H H H O 0
1A-20 Me F H
H F H H H F O 0
1A-21 Me F H
H Me H H H H O 0
1A-22 Me F H
H Me H Me H Me O 0
1A-23 Me F H
H H H Br H H O 0
1A-24 Me F H
H H H OMe H H O 0
1A-25 Me F H
H H H OEt H H O 0
1A-26 Me F H
H H H O-n-Pr H H O 0
1A-27 Me F H
H H H 3,4-Cl2-Ph H H O 0
1A-28 Me F H
H H H 4-OCF3-Ph H H O 0
1A-29 Me F H
H H H 4-CF3-Ph H H O 0
1A-30 Me F H
H H H i-Pr H H O 0
1A-31 Me F H
H H H NH2 H H O 0
1A-32 Me F H
H H H NO2 H H O 0
1A-33 Me F H
i-Pr H H Cl H H O 0
1A-34 Me F H
Me H H Cl H H O 0
1A-35 Me F H
H H H Cl H H O 1
1A-36 Me F H
H H H Cl H H O 2
1A-37 Me F H
H H H OCF3 H H O 1
1A-38 Me F H
H H H OCF3 H H O 2
1A-39 Me F H
H H H CF3 H H O 1
56

1A-40 Me F H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H H Me Me H H H CF3 H H O 2
1A-41 Me F Me
H H H Cl H H O 0
1A-42 Me F Me
H H H OCF3 H H O 0
1A-43 Me F Me
H H H CF3 H H O 0
1A-44 Me Br H
H H H Cl H H O 0
1A-45 Me F Et
H H H Cl H H O 0
1A-46 Me F H
H H H n-Pr H H O 0
1A-47 Me F H
H H H SCF3 H H O 0
1A-48 Me F Et
H H H OCF3 H H O 0
1A-49 Me F Me
H H H SCF3 H H O 0
1A-50 Me Br Me
H H H Cl H H O 0
1A-51 Me Br Me
H H H OCF3 H H O 0
1A-52 Me Br Me
H H H CF3 H H O 0
1A-53 Me Br H
H H H CF3 H H O 0
1A-54 Me Br H
H H H OCF3 H H O 0
1A-55 Me Cl Et
H H H Cl H H O 0
1A-56 Me Cl Me
H H H OCF3 H H O 0
1A-57 Me Cl Me
H H H Cl H H O 0
1A-58 Me Cl Et
H H H OCF3 H H O 0
1A-59 Me Cl H
H H H OCF3 H H O 0
1A-60 Me Cl H
H H H CF3 H H O 0
1A-61 Me Cl H
H H H Cl H H O 0
1A-62 Me Cl H
H H H SCF3 H H O 0
1A-63 Me F H
H H H 4-Cl-Ph H H O 0
1A-64 Me F H
H H H 5-CF3-2-Py H H O 0
1A-65 Me F H
H H H Ph H H O 0
1A-66 Me F H
H H H 3,5-F2-Ph H H O 0
1A-67 Me F H
H H H 2-SMe-Ph H H O 0
1A-68 Me F H
H H H 2-Cl-Ph H H O 0
1A-69 Me F H
H H H Me H H O 0
1A-70 Me F H
H H H Et H H O 0
1A-71 Me F H
H H H n-pent H H O 0
1A-72 Me F Me
H H H SMe H H O 0
1A-73 Me Br Me
H H H SCF3 H H O 0
1A-74 Me Br Me
H H H SMe H H O 0
1A-75 Me Br H
H H H SCF3 H H O 0
1A-76 Me F H
H H H SMe H H O 0
1A-77 Me Br H
H H H SMe H H O 0
1A-78 Me F Et
H H H SMe H H O 0
1A-79 F Me H
H H H Cl H H O 0
1A-80 F Me H
H H H OCF3 H H O 0
1A-81 F Me H
H H H CF3 H H O 0
1A-82 Me Cl Me
H H H CF3 H H O 0
1A-83 Me Cl Et
H H H CF3 H H O 0
1A-84 F Me H
H H H SCF3 H H O 0
1A-85 Me Br Et
H H H Cl H H O 0
1A-86 Me F Me
H H H Cl H H O 0
57

1A-87 Me F Et Me Me Me Me H H H H H H H H H H H H H H H
H H H H H
H H
H H
H H H H H H
H H H H H F H H H H H Cl H H O 0
1A-88 Me Br Me
H H H Cl H H O 0
1A-89 Me Br H
H H H Cl H H O 0
1A-90 Me F H
H H H Cl H H O 0
1A-91 Me F n-Pr
H H H CF3 H H O 0
1A-92 Me F n-Bu
H H H CF3 H H O 0
1A-93 Me F Me
H H H 3,4-Cl2-Ph H H O 0
1A-94 Me F Et
H H H 3,4-Cl2-Ph H H O 0
1A-95 Me F Me
H H H Ph H H O 0
1A-96 Me F Et
H H H Ph H H O 0
1A-97 Me F Propargyl
H H H CF3 H H O 0
1A-98 Me F i-Pr
H H H CF3 H H O 0
1A-99 F Me H
H H H 4-OCF3-Ph H H O 0
1A-100 F Me H
H H H 4-CF3-Ph H H O 0
1A-101 Me F Heptafluoro-i-Pr
H H H CF3 H H O 0
1A-102 Me F H
H H H 4-F-Ph H H O 0
1A-103 Me F H
H H H 4-OMe-Ph H H O 0
1A-104 Me F H
H H H 3-OCF3-Ph H H O 0
1A-105 Me F H
H H H 3-Cl, 5-CF3-Ph H H O 0
1A-106 Me F H
H H H 2-OCF3-Ph H H O 0
1A-107 Me F H
H H H 3-CF3-Ph H H O 0
1A-108 Me F H
H H H 3-F-Ph H H O 0
1A-109 Me F H
H H H 2-F-Ph H H O 0
1A-110 Me F Me
H H H 4-Cl, 3-CF3-Ph H H O 0
1A-111 Me F Me
H H H 2-Cl, 4-F-Ph H H O 0
1A-112 Me F 3,3,3-trifluoro-n-Pr
H H H CF3 H H O 0
1A-113 Me F H
H H H 2-Cl, 4-F-Ph H H O 0
1A-114 Me F H
H H H 4-Cl, 3-CF3-Ph H H O 0
1A-115 Me F H
H H H 5-Pyrimidyl H H O 0
1A-116 Me F H
H H H CF3 H H S 0
1A-117 Me F Me
H H H CF3 H H S 0
1A-118 Me F Me
H H H 3-F-Ph H H O 0
1A-119 Me F Me
H H H 3-CF3-Ph H H O 0
1A-120 Me F Me
H H H 3-Cl, 5-CF3-Ph H H O 0
1A-121 Me F Me
H H H 3-OCF3-Ph H H O 0
1A-122 Me F Me
H H H 4-OMe-Ph H H O 0
1A-123 Me F Me
H H H 4-F-Ph H H O 0
1A-124 Me F Me
H H H 2-F-Ph H H O 0
1A-125 Me F Me
H H H 2-OCF3-Ph H H O 0
1A-126 Me F H
F H H Cl H H O 0
1A-127 Me F Me
H H H 4-Cl-Ph H H O 0
1A-128 Me F Me
H H H 2-Cl-Ph H H O 0
58

1A-129 Me F Me F H H H H H H H F F H H H H H H H H H H H F H H Cl H H O 0
1A-130 Me F Me
H H H n-Pr H H O 0
1A-131 Me F Me
H H Cl Cl H H O 0
1A-132 Me F Me
H F H H H F O 0
1A-133 Me F Me
H H H Et H H O 0
1A-134 Me F Et
H H H SO2Me H H O 0
1A-135 Me F Me
H H H SO2Me H H O 0
1A-136 Me F H
H H H SO2Me H H O 0
1A-137 Me F H
F H H CF3 H H O 0
1A-138 Me F Me
F H H CF3 H H O 0
1A-139 Me F Me
H H H CN H H O 0
1A-140 Me F H
H H H 2,4-Cl2-Ph H H O 0
1A-141 Me F H
H H H 3,4,5-F3-Ph H H O 0
1A-142 Me F H
H H H 4-Br-Ph H H O 0
1A-143 Me F H
H H H 3,5-Cl2-Ph H H O 0
1A-144 Me F H
H H H 4-SMe-Ph H H O 0
1A-145 Me F H
H H H 4-Me-Ph H H O 0
1A-146 Me F Me
H H H 4-SMe-Ph H H O 0
1A-147 Me F Me
H H H 3,5-Cl2-Ph H H O 0
1A-148 Me F Me
H H H 4-Br-Ph H H O 0
1A-149 Me F Me
H H H 4-Me-Ph H H O 0
Table 2

S. No. 1H NMR
1A-1 CDCl3: δ 8.50 (d, J = 7.6 Hz, 1H), 7.43-7.40 (m, 2H), 7.37-7.33 (m, 3H), 7.27-7.24 (bs, 1H), 6.90 (d, J = 11.2 Hz, 1H), 3.77 (s, 2H), 3.37 (q, J = 9.6 Hz, 2H), 2.39 (s, 3H).
1A-2 CDCl3: δ 8.47 (d, J = 8.0 Hz, 1H), 7.39-7.37 (m, 2H), 7.29-7.27 (m, 2H), 7.24 (bs, 1H), 6.93 (d, J = 11.6 Hz, 1H), 3.73 (s, 2H), 3.37 (q, J = 9.6 Hz, 2H), 2.40 (s, 3H).
1A-3 CDCl3: δ 8.59 (d, J = 8.0 Hz, 1H), 7.47-7.41 (m, 3H), 7.33-7.28 (m, 2H), 6.92 (d, J = 11.6 Hz, 1H), 3.89 (s, 2H), 3.37 (q, J = 9.7 Hz, 2H), 2.40 (s, 3H).
1A-4 CDCl3: δ 8.47 (d, J = 8.0 Hz, 1H), 7.42-6.42 (m, 2H), 7.28-7.26 (m, 2H), 6.95 (d, J = 11.6 Hz, 1H), 3.84 (s, 2H), 3.37 (q, J = 9.6 Hz, 2H), 2.41 (s, 3H).
1A-5 DMSO-d6: δ 10.02 (s, 1H), 8.06 (d, J = 7.6 Hz, 1H), 7.60 (d, J = 4.0 Hz, 2H), 7.32 (d, J = 8.0 Hz, 1H), 7.25 (d, J = 11.6 Hz, 1H), 3.82-3.76 (m, 4H), 2.37 (s, 3H).
1A-6 CDCl3: δ 8.47 (d, J = 8.0 Hz, 1H), 7.34 (s, 1H), 7.26-7.25 (m, 3H), 7.96 (d, J = 11.6 Hz, 1H), 3.70 (s, 2H), 3.37 (q, J = 9.6 Hz, 2H), 2.42 (s, 3H).
1A-7 CDCl3: δ 8.47 (d, J = 7.6 Hz, 1H), 7.46 (d, J = 9.2 Hz, 1H), 7.39 (bs, 1H), 7.33 (d, J = 6.8 Hz, 1H), 7.27-7.23 (m, 1H), 6.95 (d, J = 11.2 Hz, 1H), 3.93 (s, 2H), 3.37 (q, J = 9.6 Hz, 2H), 2.41 (s, 3H).
1A-8 CDCl3: δ 8.47 (d, J = 8.0 Hz, 1H), 7.47 (d, J = 2.0 Hz, 1H), 7.38 (bs, 1H), 7.36 (d, J = 8.6 Hz, 1H), 7.29 (d, J = 8.4 Hz, 1H), 6.95 (d, J = 11.6 Hz, 1H), 3.85 (s, 2H), 3.37 (q, J = 9.6 Hz, 2H), 2.41 (s, 3H).
1A-9 CDCl3: δ 8.48 (d, J = 8.0 Hz, 1H), 7.32 (m, 3H), 7.26-7.23 (m, 2H), 6.93 (d, J = 11.6 Hz, 1H), 3.73 (s, 2H), 3.37 (q, J = 9.7 Hz, 2H), 2.41 (s, 3H).
1A-10 CDCl3: δ 8.50 (d, J = 8.0 Hz, 1H), 7.42 (d, J = 8.4 Hz, 2H), 7.28-7.25 (m, 3H), 6.90 (d, J = 11.2 Hz, 1H), 3.73 (s, 2H), 3.37 (q, J = 9.7 Hz, 2H), 2.39 (s, 3H), 1.33 (s, 9H).
1A-11 CDCl3: δ 8.50 (d, J = 8.0 Hz, 1H), 7.40 (d, J = 8.0 Hz, 2H), 7.37 (bs, 1H), 7.22 (d, J = 8.4 Hz, 1H), 6.94 (d, J = 11.6 Hz, 1H), 4.14 (s, 2H), 3.37 (q, J = 9.7 Hz, 2H), 2.41 (s, 3H).
59

1A-12 CDCl3: δ 8.47 (d, J = 7.6 Hz, 1H), 7.66 (d, J = 8.0 Hz, 2H), 7.48 (d, J = 8.0 Hz, 2H), 7.27 (bs, 1H), 6.94 (d, J = 11.2 Hz, 1H), 3.82 (s, 2H), 3.37 (q, J = 9.6 Hz, 2H), 2.41 (s, 3H).
1A-13 CDCl3: δ 8.49 (d, J = 7.6 Hz, 1H), 7.33-7.29 (m, 2H), 7.23 (bs, 1H), 7.10 (t, J = 8.6 Hz, 2H), 6.92 (d, J = 11.6 Hz, 1H), 3.74 (s, 2H), 3.37 (q, J = 9.6 Hz, 2H), 2.40 (s, 3H).
1A-14 CDCl3: δ 8.48 (d, J = 8.0 Hz, 1H), 7.38 (d, J = 8.4 Hz, 2H), 7.27-7.24 (m, 3H), 6.94 (d, J = 11.6 Hz, 1H), 3.76 (s, 2H), 3.37 (q, J = 9.6 Hz, 2H), 2.41 (s, 3H).
1A-15 CDCl3: δ 8.49 (d, J = 7.6 Hz, 1H), 7.40 (bs, 1H), 6.97 (d, J = 11.6 Hz, 1H), 6.75 (t, J = 7.8 Hz, 2H), 3.77 (s, 2H), 3.36 (q, J = 9.6 Hz, 2H), 2.42 (s, 3H).
1A-16 CDCl3: δ 8.49 (d, J = 7.6 Hz, 1H), 7.38 (bs, 1H), 7.32 (d, J = 8.4 Hz, 1H), 7.18 (d, J = 2.8 Hz, 1H), 6.94-6.89 (m, 2H), 3.83 (s, 2H), 3.81 (s, 3H), 3.38 (q, J = 9.6 Hz, 2H), 2.40 (s, 3H).
1A-17 CDCl3: δ 8.48 (d, J = 7.6 Hz, 1H), 7.38 (q, J = 7.0 Hz, 1H), 7.12 (d, J = 7.6 Hz, 2H), 7.07-7.03 (m, 2H), 6.92 (d, J = 11.6 Hz, 1H), 3.76 (s, 2H), 3.37 (q, J = 9.6 Hz, 2H), 2.40 (s, 3H).
1A-18 CDCl3: δ 8.49 (d, J = 7.6 Hz, 1H), 7.40-7.31 (m, 3H), 7.20-7.11 (m, 2H), 6.93 (d, J = 11.6 Hz, 1H), 3.78 (s, 2H), 3.37 (q, J = 9.6 Hz, 2H), 2.40 (s, 3H).
1A-19 CDCl3: δ 8.50 (d, J = 8.0 Hz, 1H), 7.43 (bs, 1H), 7.32-7.28 (m, 2H), 6.99-6.94 (m, 3H), 3.83 (s, 2H), 3.36 (q, J = 9.6 Hz, 2H), 2.41 (s, 3H).
1A-20 CDCl3: δ 8.48 (d, J = 8.0 Hz, 1H), 7.44 (t, J = 8.4 Hz, 1H), 7.29 (d, J = 8.0 Hz, 1H), 7.22-7.20 (m, 2H), 6.93 (d, J = 11.6 Hz, 1H), 3.78 (s, 2H), 3.37 (q, J = 9.7 Hz, 2H), 2.41 (s, 3H).
1A-21 CDCl3: δ 8.47 (d, J = 8.0 Hz, 1H), 7.28-7.26 (m, 4H), 7.18 (bs, 1H), 6.88 (d, J = 11.2 Hz, 1H), 3.78 (s, 2H), 3.38 (q, J = 9.6 Hz, 2H), 2.39 (s, 3H), 2.35 (s, 3H).
1A-22 CDCl3: δ 8.43 (d, J = 7.6 Hz, 1H), 7.18 (bs, 1H), 6.95 (s, 2H), 6.87 (d, J = 11.2 Hz, 1H), 3.77 (s, 2H), 3.38 (q, J = 9.6 Hz, 2H), 2.39 (s, 3H), 2.31-2.30 (m, 9H).
1A-23 CDCl3: δ 8.47 (d, J = 8.0 Hz, 1H), 7.53 (d, J = 8.0 Hz, 2H), 7.26-7.21 (m, 3H), 6.93 (d, J = 11.6 Hz, 1H), 3.71 (s, 2H), 3.37 (q, J = 9.7 Hz, 2H), 2.40 (s, 3H).
1A-24 CDCl3: δ 8.49 (d, J = 7.6 Hz, 1H), 7.27-7.24 (m, 3H), 6.94 (d, J = 8.4 Hz, 2H), 6.90 (d, J = 11.6 Hz, 1H), 3.83 (s, 3H), 3.70 (s, 2H), 3.38 (q, J = 9.6 Hz, 2H), 2.39 (s, 3H).
1A-25 CDCl3: δ 8.49 (d, J = 8.0 Hz, 1H), 7.28-7.22 (m, 3H), 6.94-6.88 (m, 3H), 4.07-4.02 (m, 2H), 3.70 (s, 2H), 3.38 (q, J = 9.6 Hz, 2H), 2.39 (s, 3H), 1.43 (t, J = 8.0 Hz, 3H).
1A-26 CDCl3: δ 8.49 (d, J = 7.6 Hz, 1H), 7.28-7.22 (m, 3H), 6.94-6.88 (m, 3H), 3.93 (t, J = 6.6 Hz, 2H), 3.70 (s, 2H), 3.38 (q, J = 8.8 Hz, 2H), 2.39 (s, 3H), 1.86-1.17 (m, 2H), 1.04 (s, 3H).
1A-27 CDCl3: δ 8.50 (d, J = 8.0 Hz, 1H), 7.68 (d, J = 1.6 Hz, 1H), 7.58 (d, J = 8.4 Hz, 2H), 7.51 (d, J = 8.4 Hz, 1H), 7.44-7.41 (m, 3H), 7.29 (bs, 1H), 6.92 (d, J = 11.2 Hz, 1H), 3.81 (s, 2H), 3.38 (q, J = 9.6 Hz, 2H), 2.40 (s, 3H).
1A-28 CDCl3: δ 8.51 (d, J = 7.6 Hz, 1H), 7.62-7.59 (m, 4H), 7.42 (d, J = 8.4 Hz, 2H), 7.30 (d, J = 8.0 Hz, 3H), 6.92 (d, J = 11.6 Hz, 1H), 3.81 (s, 2H), 3.38 (q, J = 9.6 Hz, 2H), 2.40 (s, 3H).
1A-29 CDCl3: δ 8.51 (d, J = 7.6 Hz, 1H), 7.70 (bs, 4H), 7.65 (d, J = 8.0 Hz, 2H), 7.45 (d, J = 8.0 Hz, 2H), 7.32 (bs, 1H), 6.92 (d, J = 11.6 Hz, 1H), 3.82 (s, 2H), 3.38 (q, J = 9.6 Hz, 2H), 2.40 (s, 3H).
1A-30 CDCl3: δ 8.48 (d, J = 8.0 Hz, 1H), 7.00-6.73 (m, 5H), 6.89 (d, J = 7.6 Hz, 1H), 3.73 (s, 2H), 3.37 (q, J = 9.6 Hz, 2H), 2.96-2.89 (m, 1H), 2.39 (s, 3H), 1.26 (d, J = 6.8 Hz, 6H).
1A-31 CDCl3: δ 8.49 (d, J = 8.0 Hz, 1H), 7.31 (bs, 1H), 7.10 (d, J = 8.4 Hz, 2H), 6.89 (d, J = 11.6 Hz, 1H), 6.72 (d, J = 8.4 Hz, 2H), 3.72 (bs, 2H), 3.65 (s, 2H), 3.38 (q, J = 9.6 Hz, 2H), 2.39 (s, 3H).
1A-32 CDCl3: δ 8.46 (d, J = 8.0 Hz, 1H), 8.26 (d, J = 8.0 Hz, 2H), 7.54 (d, J = 8.4 Hz, 2H), 7.31 (bs, 1H), 6.96 (d, J = 11.6 Hz, 1H), 3.86 (s, 2H), 3.36 (q, J = 9.6 Hz, 2H), 2.42 (s, 3H).
1A-33 CDCl3: δ 8.49 (d, J = 8.0 Hz, 1H), 7.35-7.28 (m, 5H), 6.93 (d, J = 11.2 Hz, 1H), 3.37 (q, J = 9.6 Hz, 2H), 2.99 (d, J = 10.0 Hz, 1H), 2.48-2.40 (m, 4H), 1.10 (d, J = 6.8 Hz, 3H), 0.75 (d, J = 6.8 Hz, 3H).
1A-34 CDCl3: δ 7.38 (s, 1H), 7.32 (d, J = 3.6 Hz, 2H), 7.22 (d, J = 8.8 Hz, 2H), 7.02 (d, J = 8.8 Hz, 2H), 3.42-2.25 (m, 2H), 2.09 (s, 3H), 1.59 (s, 3H), 1.44 (s, 3H).
1A-35 CDCl3: δ 8.77 (d, J = 7.6 Hz, 1H), 7.38 (d, J = 8.0 Hz, 2H), 7.32-7.21 (m, 3H), 6.98 (d, J = 11.2 Hz, 1H), 3.75 (s, 2H), 3.61-3.50 (m, 1H), 3.44-3.33 (m, 1H), 2.37 (s, 3H).
60

1A-36 CDCl3: δ 8.96 (d, J = 7.6 Hz, 1H), 7.39 (d, J = 8.4 Hz, 2H), 7.29-7.26 (m, 3H), 7.07 (d, J = 11.2 Hz, 1H), 3.91 (q, J = 8.8 Hz, 2H), 3.76 (s, 2H), 2.64 (s, 3H).
1A-37 CDCl3: δ 8.79 (d, J = 7.6 Hz, 1H), 7.38 (d, J = 8.8 Hz, 2H), 7.32 (bs, 1H), 7.26-7.24 (m, 2H), 6.98 (d, J = 10.8 Hz, 1H), 3.78 (s, 2H), 3.58-3.50 (m, 1H), 3.44-3.33 (m, 1H), 2.38 (s, 3H).
1A-38 CDCl3: δ 8.97 (d, J = 7.6 Hz, 1H), 7.38 (d, J = 8.4 Hz, 2H), 7.29-7.25 (m, 3H), 7.07 (d, J = 10.8 Hz, 1H), 3.90 (q, J = 8.9 Hz, 2H), 3.79 (s, 2H), 2.65 (s, 3H).
1A-39 CDCl3: δ 8.78 (d, J = 7.6 Hz, 1H), 7.66 (d, J = 8.0 Hz, 2H), 7.48 (d, J = 8.0 Hz, 2H), 7.35 (bs, 1H), 6.99 (d, J = 11.2 Hz, 1H), 3.84 (s, 2H), 3.60-3.49 (m, 1H), 3.44-3.32 (m, 1H), 2.38 (s, 3H).
1A-40 CDCl3: δ 8.96 (d, J = 9.5 Hz, 1H), 7.67 (d, J = 8.0 Hz, 2H), 7.48 (d, J = 7.6 Hz, 2H), 7.31 (bs, 1H), 7.08 (d, J = 11.2 Hz, 1H), 3.90 (q, J = 8.9 Hz, 2H), 3.85 (s, 2H), 2.65 (s, 3H).
1A-41 CDCl3: δ 7.26 (s, 1H), 7.21 (d, J = 8.4 Hz, 2H), 7.07 (d, J = 10.0 Hz, 1H), 6.96 (d, J = 8.4 Hz, 2H), 3.45-3.34 (m, 2H), 3.28-3.21 (m, 5H), 2.51 (s, 3H).
1A-42 CDCl3: δ 7.30 (d, J = 7.6 Hz, 1H), 7.10-7.04 (m, 5H), 3.48-3.38 (m, 2H), 3.29-3.17 (m, 5H), 2.51 (s, 3H).
1A-43 CDCl3: δ 7.53 (d, J = 8.0 Hz, 2H), 7.32 (d, J = 7.6 Hz, 1H), 7.19 (d, J = 7.6 Hz, 2H), 7.11 (d, J = 10.4 Hz, 1H), 3.49 (q, J = 13.2 Hz, 2H), 3.30-3.23 (m, 5H), 2.54 (s, 3H).
1A-44 CDCl3: δ 8.49 (s, 1H), 7.53 (s, 1H), 7.39 (d, J = 8.4 Hz, 2H), 7.31 (d, J = 11.2 Hz, 2H), 7.26 (s, 1H), 3.76 (s, 2H), 3.44 (q, J = 9.6 Hz, 2H), 2.35 (s, 3H).
1A-45 CDCl3: δ 7.22-7.19 (m, 3H), 7.07 (d, J = 10.0 Hz, 1H), 6.95 (d, J = 8.4 Hz, 2H), 3.74-3.66 (m, 2H), 3.42 (s, 2H), 3.26-3.19 (m, 2H), 2.51 (s, 3H), 0.84 (t, J = 8.8 Hz, 3H).
1A-46 CDCl3: δ 8.50 (d, J = 8.0 Hz, 1H), 7.20-7.26 (m, 5H), 6.88 (d, J = 11.6 Hz, 1H), 3.73 (s, 2H), 3.41-3.34 (m, 2H), 2.58 (t, J = 7.6 Hz, 2H), 2.39 (s, 3H), 1.68-1.60 (m, 2H), 0.94 (t, J = 7.2 Hz, 3H).
1A-47 CDCl3: δ 8.47 (d, J = 8.0 Hz, 1H), 7.68 (d, J = 8.0 Hz, 2H), 7.40 (d, J = 8.0 Hz, 2H), 7.29 (bs, 1H), 6.93 (d, J = 11.2 Hz, 1H), 3.79 (s, 2H), 3.33 (q, J = 9.6 Hz, 2H), 2.41 (s, 3H).
1A-48 CDCl3: δ 7.26 (d, J = 6.4 Hz, 1H), 7.09-7.04 (m, 5H), 3.77-3.63 (m, 2H), 3.44-3.34 (m, 2H), 3.29-3.20 (m, 2H), 2.48 (s, 3H), 0.86 (t, J = 9.6 Hz, 3H).
1A-49 CDCl3: δ 7.51 (d, J = 8.0 Hz, 2H), 7.31 (d, J = 7.6 Hz, 1H), 7.08 (d, J = 8.0 Hz, 2H), 7.04 (d, J = 14.4 Hz, 1H), 3.48 (s, 2H), 3.29-3.22 (s, 5H), 2.51 (s, 3H).
1A-50 CDCl3: δ 7.58 (s, 1H), 7.51 (d, J = 8.0 Hz, 2H), 7.29 (s, 1H), 7.19-7.18 (m, 2H), 3.46 (d, J = 14.8 Hz, 1H), 3.37 (d, J = 14.8 Hz, 1H), 3.29-3.22 (m, 2H), 3.19 (s, 3H), 2.48 (s, 3H).
1A-51 CDCl3: δ 7.57 (s, 1H), 7.21 (s, 1H), 7.09 (s, 4H), 3.40 (d, J = 15.2 Hz, 1H), 3.32-3.25 (m, 3H), 3.19 (s, 3H), 2.48 (s, 3H).
1A-52 CDCl3: δ 7.57 (s, 1H), 7.21 (d, J = 8.4 Hz, 2H), 7.16 (s, 1H), 6.98 (d, J = 8.4 Hz, 2H), 4.77 (d, J = 15.2 Hz, 1H), 3.30-3.24 (m, 3H), 3.18 (s, 3H), 2.47 (s, 3H).
1A-53 CDCl3: δ 8.48 (s, 1H), 7.68 (d, J = 8.0 Hz, 2H), 7.50 (d, J = 8.0 Hz, 3H), 7.33 (s, 1H), 3.84 (d, J = 8.0 Hz, 2H), 3.45 (q, J = 9.6 Hz, 2H), 2.36 (s, 3H).
1A-54 CDCl3: δ 8.50 (s, 1H), 7.52 (bs, 1H), 7.40 (d, J = 8.4 Hz, 2H), 7.32-7.26 (m, 3H), 3.80 (s, 2H), 3.45 (q, J = 9.4 Hz, 2H), 2.35 (s, 3H).
1A-55 CDCl3: δ 7.40 (s, 1H), 7.21 (d, J = 8.4 Hz, 2H), 7.11 (s, 1H), 6.96 (d, J = 8.0 Hz, 2H), 4.04-3.95 (m, 1H), 3.43-3.35 (m, 2H), 3.28-3.18 (m, 3H), 2.48 (s, 3H), 1.09 (t, J = 7.2 Hz, 3H).
1A-56 CDCl3: δ 7.39 (s, 1H), 7.30 (s, 1H), 7.11-7.05 (m, 4H), 3.42-3.25 (m, 4H), 3.19 (s, 3H), 2.48 (s, 3H).
1A-57 CDCl3: δ 7.39 (s, 1H), 7.21 (d, J = 8.4 Hz, 2H), 7.17 (s, 1H), 6.97 (d, J = 8.4 Hz, 2H), 3.38 (d, J = 15.2 Hz, 1H), 3.27 (q, J = 9.6 Hz, 3H), 3.18 (s, 3H), 2.48 (s, 3H).
1A-58 CDCl3: δ 7.40 (s, 1H), 7.17 (s, 1H), 7.10-7.05 (m, 4H), 4.01-3.99 (m, 1H), 3.42-3.37 (m, 2H), 3.30-3.22 (m, 3H), 2.49 (s, 3H), 1.10 (t, J = 7.2 Hz, 3H).
1A-59 CDCl3: δ 8.53 (s, 1H), 7.54 (bs, 1H), 7.40 (d, J = 8.4 Hz, 2H), 7.28-7.26 (m, 2H), 7.16 (s, 1H), 3.80 (s, 2H), 3.44 (q, J = 9.6 Hz, 2H), 2.36 (s, 3H).
1A-60 CDCl3: δ 8.51 (s, 1H), 7.68 (d, J = 8.0 Hz, 2H), 7.54 (bs, 1H), 7.49 (d, J = 8.4 Hz, 2H), 7.18 (s, 1H), 3.85 (s, 2H), 3.44 (q, J = 9.6 Hz, 2H), 2.36 (s, 3H).
61

1A-61 CDCl3: δ 8.52 (s, 1H), 7.55 (bs, 1H), 7.39 (d, J = 8.4 Hz, 2H), 7.29 (d, J = 8.4 Hz, 2H), 7.17 (s, 1H), 3.76 (s, 2H), 3.44 (q, J = 9.6 Hz, 2H), 2.36 (s, 3H).
1A-62 CDCl3: δ 8.53 (s, 1H), 7.71 (d, J = 8.0 Hz, 2H), 7.52 (bs, 1H), 7.43 (d, J = 8.0 Hz, 2H), 7.16 (s, 1H), 3.82 (s, 2H), 3.44 (q, J = 9.6 Hz, 2H), 2.36 (s, 3H).
1A-63 CDCl3: δ 8.47 (d, J = 7.6 Hz, 1H), 7.60-7.52 (m, 3H), 7.41 (d. J = 8.4 Hz, 2H), 7.26-7.21 (m, 4H), 6.95-6.90 (m, 1H), 3.71 (s, 2H), 3.37 (q, J = 9.8 Hz, 2H), 2.40 (s, 3H).
1A-64 CDCl3: δ 8.50 (d, J = 8.0 Hz, 1H), 8.44 (s, 1H), 7.92 (d, J = 8.4 Hz, 1H), 7.41 (d, J = 8.4 Hz, 2H), 7.31 (bs, 1H), 7.20 (d, J = 8.4 Hz, 2H), 7.04 (d, J = 8.8 Hz, 1H), 6.94 (d, J = 11.6 Hz, 1H), 3.79 (s, 2H), 3.38 (q, J = 9.6 Hz, 2H), 2.41 (s, 3H).
1A-65 CDCl3: δ 8.51 (d, J = 8.0 Hz, 1H), 7.65-7.60 (m, 3H), 7.48-7.35 (m, 5H), 7.32 (bs, 1H), 6.91 (d, J = 11.6 Hz, 2H), 3.81 (s, 2H), 3.38 (q, J = 9.6 Hz, 2H), 2.40 (s, 3H).
1A-66 CDCl3: δ 8.50 (d, J = 8.0 Hz, 1H), 7.59 (d, J = 8.4 Hz, 2H), 7.44 (d, J = 8.0 Hz, 2H), 7.30 (bs, 1H), 7.11 (d, J = 8.8 Hz, 2H), 6.93 (d, J = 11.2 Hz, 1H), 6.82-6.78 (m, 1H), 3.81 (s, 2H), 3.38 (q, J = 9.7 Hz, 2H), 2.40 (s, 3H).
1A-67 CDCl3: δ 8.52 (d, J = 8.0 Hz, 1H), 7.47 (d, J = 8.0 Hz, 2H), 7.40 (d, J = 8.0 Hz, 2H), 7.41-7.21 (m, 5H), 6.92 (d, J = 11.2 Hz, 1H), 3.82 (s, 2H), 3.39 (q, J = 9.7 Hz, 2H), 2.41 (s, 3H), 2.37 (s, 3H).
1A-68 CDCl3: δ 8.52 (d, J = 8.0 Hz, 1H), 7.50-7.47 (m, 3H), 7.41 (d, J = 8.0 Hz, 2H), 7.35-7.29 (m, 4H), 6.92 (d, J = 11.6 Hz, 1H), 3.82 (s, 2H), 3.38 (q, J = 9.6 Hz, 2H), 2.41 (s, 3H).
1A-69 CDCl3: δ 8.49 (d, J = 7.6 Hz, 1H), 7.26 (bs, 1H), 7.22-7.51 (m, 4H), 6.89 (d, J = 11.6 Hz, 1H), 3.72 (s, 2H), 3.38 (q, J = 9.6 Hz, 2H), 2.39 (s, 3H), 2.38 (s, 3H).
1A-70 CDCl3: δ 8.49 (d, J = 8.0 Hz, 1H), 7.28-7.12 (m, 5H), 6.99 (d, J = 11.2 Hz, 1H), 3.73 (s, 2H), 3.37 (q, J = 9.6 Hz, 2H), 2.67 (q, J = 7.6 Hz, 2H), 2.39 (s, 3H), 1.25 (m, 3H).
1A-71 CDCl3: δ 8.50 (d, J = 8.0 Hz, 1H), 7.28-7.22 (m, 5H), 6.89 (d, J = 11.6 Hz, 1H), 3.73 (s, 2H), 3.38 (q, J = 9.7 Hz, 2H), 2.62 (t, J = 8.0 Hz, 2H), 2.39 (s, 3H), 1.66-1.58 (m, 2H), 1.28-1.36 (m, 4H), 0.91-0.80 (m, 3H).
1A-72 CDCl3: δ 7.23 (d, J = 7.6 Hz, 1H), 7.13 (d, J = 8.0 Hz, 2H), 7.07 (d, J = 10.4 Hz, 1H), 6.94 (d, J = 8.4 Hz, 2H), 3.46-3.33 (m, 2H), 3.26-3.19 (m, 5H), 2.50 (s, 3H), 2.45 (s, 3H).
1A-73 CDCl3: δ 7.57 (s, 1H), 7.53 (d, J = 8.0 Hz, 2H), 7.22 (s, 1H), 7.12 (d, J = 8.4 Hz, 2H), 3.45-3.26 (m, 4H), 3.19 (s, 3H), 2.48 (s, 3H).
1A-74 CDCl3: δ 7.56 (s, 1H), 7.13 (d, J = 8.4 Hz, 2H), 7.08 (s, 1H), 6.95 (d, J = 8.4 Hz, 2H), 3.42-3.38 (m, 1H), 3.27-3.19 (m, 3H), 3.17 (s, 3H), 2.46 (s, 3H), 2.45 (s, 3H).
1A-75 CDCl3: δ 8.50 (s, 1H), 7.72 (d, J = 8.0 Hz, 2H), 7.50 (bs, 1H), 7.44 (d, J = 8.0 Hz, 2H), 7.32 (s, 1H), 3.83 (s, 2H), 3.45 (q, J = 9.4 Hz, 2H), 2.35 (s, 3H).
1A-76 CDCl3: δ 8.478 (d, J = 7.6 Hz, 1H), 7.242-7.298 (m, 5H), 6.911 (d, J = 11.6 Hz, 1H), 3.719 (s, 2H), 3.373 (q, J = 9.6 Hz, 2H), 2.497 (s, 3H), 2.398 (s, 3H).
1A-77 CDCl3: δ 8.50 (s, 1H), 7.58 (bs, 1H), 7.32-7.29 (m, 5H), 3.74 (s, 2H), 3.46 (q, J = 9.6 Hz, 2H), 2.50 (s, 3H), 2.35 (s, 3H).
1A-78 CDCl3: δ 7.16 (d, J = 7.6 Hz, 1H), 7.13 (d, J = 8.0 Hz, 2H), 7.08 (d, J = 10.0 Hz, 1H), 6.93 (d, J = 8.0 Hz, 2H), 3.76-3.62 (m, 2H), 3.41 (d, J = 14.8 Hz, 1H), 3.30 (d, J = 14.8 Hz, 1H), 3.20 (q, J = 9.6 Hz, 2H), 2.51 (s, 3H), 2.45 (s, 3H), 1.08 (t, J = 7.2 Hz, 3H).
1A-79 CDCl3: δ 7.95 (d, J = 7.6 Hz, 1H), 7.40 (d, J = 8.4 Hz, 2H), 7.30 (d, J = 8.4 Hz, 2H), 8.90 (d, J = 9.2 Hz, 1H), 8.75 (bs, 1H), 3.75 (s, 2H), 3.50 (q, J = 9.6 Hz, 2H), 1.93 (s, 3H).
1A-80 CDCl3: δ 7.98 (d, J = 7.6 Hz, 1H), 7.40 (d, J = 8.4 Hz, 2H), 7.29-7.27 (m, 2H), 8.90 (d, J = 9.2 Hz, 1H), 8.75 (bs, 1H), 3.78 (s, 2H), 3.39 (q, J = 9.6 Hz, 2H), 1.98 (s, 3H).
1A-81 CDCl3: δ 7.92 (d, J = 6.8 Hz, 1H), 7.69 (d, J = 8.4 Hz, 2H), 7.50 (d, J = 8.0 Hz, 2H), 6.91 (d, J = 9.6 Hz, 1H), 6.75 (bs, 1H), 3.83 (s, 2H), 3.39 (q, J = 9.6 Hz, 2H), 2.02 (s, 3H).
1A-82 CDCl3: δ 7.51 (d, J = 8.4 Hz, 2H), 7.40 (s, 1H), 7.21 (s, 1H), 7.17 (d, J = 8.4 Hz, 2H), 3.43 (d, J = 16.0 Hz, 1H), 3.36 (d, J = 15.6 Hz, 1H), 3.30-3.20 (m, 2H), 3.17 (s, 3H), 2.48 (s, 3H).
1A-83 CDCl3: δ 7.50 (d, J = 8.0 Hz, 2H), 7.42 (s, 1H), 7.16 (d, J = 8.4 Hz, 2H), 7.14 (s, 1H), 4.05-3.96 (m, 1H), 3.47-3.31 (m, 3H), 3.23 (q, J = 9.4 Hz, 2H), 2.49 (s, 3H), 1.24 (t, J = 7.2 Hz, 3H).
62

1A-84 CDCl3: δ 8.00 (d, J = 8.4 Hz, 1H), 7.72 (d, J = 7.6 Hz, 2H), 7.44 (d, J = 8.0 Hz, 2H), 6.88 (d, J = 9.6 Hz, 1H), 6.74 (bs, 1H), 3.81 (s, 2H), 3.39 (q, J = 9.4 Hz, 2H), 1.96 (s, 3H).
1A-85 CDCl3: δ 7.56 (s, 1H), 7.20 (d, J = 8.4 Hz, 2H), 6.89 (d, J = 8.4 Hz, 2H), 6.56 (s, 1H), 4.07-3.96 (m, 1H), 3.25-3.37 (m, 2H), 3.08-2.97 (m, 2H), 2.46 (s, 3H), 1.37 (t, J = 6.8 Hz, 3H), 1.06 (t, J = 7.2 Hz, 3H).
1A-86 CDCl3: δ 7.83 (d, J = 8.0 Hz, 1H), 7.27-7.24 (m, 3H), 6.98 (d, J = 8.4 Hz, 1H), 6.86 (d, J = 8.0 Hz, 1H), 4.14-3.97 (m, 1H), 3.92-3.49 (m, 2H), 3.05 (s, 3H), 2.38 (s, 3H), 1.25 (d, J = 6.8 Hz, 3H).
1A-87 CDCl3: δ 7.20-7.09 (m, 3H), 6.94-6.75 (m, 3H), 3.91-3.30 (m, 4H), 3.08-3.04 (m, 1H), 3.52-3.49 (m, 3H), 1.37-1.35 (m, 3H), 1.05 (t, J = 6.8 Hz, 3H).
1A-88 CDCl3: δ 7.56 (s, 1H), 7.20 (d, J = 8.4 Hz, 2H), 6.91 (d, J = 8.4 Hz, 2H), 6.68 (s, 1H), 3.34-3.29 (m, 1H), 3.15 (s, 3H), 3.05 (q, J = 9.4 Hz, 2H), 2.44 (s, 3H), 1.38 (d, J = 6.8 Hz, 3H).
1A-89 CDCl3: 8.48 (s, 1H), 7.50 (bs, 1H), 7.38 (d, J = 8.4 Hz, 2H), 7.32 (d, J = 8.8 Hz, 3H), 3.71 (q, J = 7.2 Hz, 1H), 3.46 (q, J = 9.6 Hz, 2H), 2.35 (s, 3H), 1.62 (d, J = 6.8 Hz, 3H).
1A-90 CDCl3: δ 8.48 (d, J = 8.0 Hz, 1H), 7.36 (d, J = 8.4 Hz, 2H), 7.31 (d, J = 8.4 Hz, 2H), 7.18 (bs, 1H), 6.91 (d, J = 11.6 Hz, 1H), 3.71 (q, J = 7.2 Hz, 1H), 3.38 (q, J = 9.6 Hz, 2H), 2.40 (s, 3H), 1.59 (d, J = 6.8 Hz, 3H).
1A-91 CDCl3: δ 8.50 (d, J = 8.0 Hz, 2H), 7.23 (d, J = 8.4 Hz, 1H), 7.15 (d, J = 8.0 Hz, 2H), 7.08 (d, J = 10.0 Hz, 1H), 3.68-3.40 (m, 4H), 3.25-3.17 (m, 2H), 2.51 (s, 2H), 1.50-1.41 (m, 3H), 0.90-0.84 (m, 3H).
1A-92 CDCl3: δ 7.49 (d, J = 8.0 Hz, 2H), 7.20 (d, J = 7.6 Hz, 1H), 7.15 (d, J = 8.0 Hz, 2H), 7.09 (d, J = 10.0 Hz, 1H), 3.73-3.66 (m, 2H), 3.62-3.54 (m, 2H), 3.25-3.18 (m, 2H), 2.52 (s, 3H). 1.46-1.41 (m, 2H) 1.32-1.22 (m, 2H), 0.862 (t, J = 7.6 Hz, 3H)
1A-93 CDCl3: δ 7.63 (d, J = 3.0 Hz, 1H), 7.48 (d, J = 8.4 Hz, 1H), 7.42 (d, J = 8.0 Hz, 2H), 7.36(s, 1H), 7.30 (d, J = 7.2 Hz, 1H), 7.13-7.08 (m, 3H), 3.53-3.42 (m, 2H), 3.26-3.20 (m, 5H), 2.52(s, 3H).
1A-94 CDCl3: δ 7.63 (d, J = 2.4 Hz, 1H), 7.48 (d, J = 8.4 Hz, 1H), 7.40-7.36 (m, 3H), 7.24 (d, J = 8.4 Hz, 1H), 7.12-7.09 (m, 3H), 3.78-3.65 (m, 2H), 3.50-3.37 (m, 2H), 3.25-3.17 (m, 2H), 2.52 (s, 3H). 1.10 (t, J = 7.2 Hz, 3H).
1A-95 CDCl3: δ 7.55 (d, J = 7.6 Hz, 2H), 7.47 (d, J = 8.0 Hz, 2H), 7.42(t, J = 7.6 Hz, 2H), 7.33 (t, J = 7.2 Hz, 1H),7.28(s,1H),7.14-7.06 (m, 3H), 3.55-3.42 (m, 2H), 3.24(s, 3H), 3.16 (s, 2H), 2.51 (s, 3H).
1A-96 CDCl3: δ 7.56 (d, J = 7.2 Hz, 2H), 7.46 (d, J = 8.0 Hz, 2H), 7.42 (t, J = 7.2 Hz, 2H), 7.33 (d, J = 7.6 Hz, 1H),7.20(d, J = 7.6 Hz, 1H), 7.09(d, J = 8.4 Hz, 3H),3.80-3.65 (m, 2H), 3.51-3.37 (m, 2H), 3.22-3.14 (m, 2H), 2.51 (s, 3H). 1.10(t, J = 7.6 Hz, 3H).
1A-97 CDCl3: δ 7.45-7.53 (m, 2H), 7.29 (s, 1H), 7.18-7.06 (m, 3H), 6.90-6.72 (m, 1H), 5.06-4.84 (m, 1H), 3.59-3.37 (m, 1H), 3.01-2.87 (m, 2H), 2.49 (s, 3H), 2.18-1.90 (m, 2H).
1A-98 CDCl3: δ 7.50 (d, J = 8.0 Hz, 2H), 7.15-7.10 (m, 4H), 4.97 (m, 1H), 3.93-3.44 (m, 2H), 3.21-3.14 (m, 2H), 2.53 (s, 3H), 1.10 (d, J = 6.8 Hz, 3H), 0.98 (d, J = 6.8 Hz, 3H).
1A-99 CDCl3: δ 7.99 (d, J = 7.2 Hz, 1H), 7.62 (t, J = 7.2 Hz, 4H), 7.45 (d, J = 8.0 Hz, 2H), 7.31 (d, J = 8.0 Hz, 2H), 6.89 (d, J = 9.2 Hz, 1H), 6.84 (s, 1H), 3.83 (s, 2H), 3.43-3.36 (m, 2H), 1.98 (s, 3H).
1A-100 CDCl3: δ 7.99 (d, J = 7.2 Hz, 1H), 7.73 (s, 4H), 7.67 (d, J = 7.6 Hz, 2H), 7.48 (d, J = 8.0 Hz, 2H), 6.90 (d, J = 9.2 Hz, 1H), 6.84 (bs, 1H), 3.84 (s, 2H), 3.43-3.36 (m, 2H), 1.99 (s, 3H).
1A-101 CDCl3: δ 8.51 (d, J = 9.2 Hz, 1H), 7.73 (d, J = 8.0 Hz, 1H), 7.53 (d, J = 7.6 Hz, 1H), 7.32 (s, 1H), 6.98 (d, J = 8.8 Hz, 1H), 6.86(d, J = 12.0 Hz, 1H), 3.64 (s, 2H), 3.36-3.25 (m, 2H), 2.37 (s, 3H).
1A-102 CDCl3: δ 8.50 (d, J = 7.6 Hz, 1H), 7.59-7.54 (m, 4H), 7.41 (d, J = 8.0 Hz, 2H), 7.31 (bs, 1H),7.14 (t, J = 8.8 Hz, 2H), 6.92 (d, J = 11.6 Hz, 1H), 3.80 (s, 2H), 3.42-3.34 (m, 2H), 2.40 (s, 3H).
1A-103 CDCl3: δ 8.50 (d, J = 8.0 Hz, 1H), 7.59 (d, J = 8.0 Hz, 2H), 7.54 (d, J = 8.8 Hz, 2H), 7.38 (d, J = 8.0 Hz, 2H), 7.32 (bs, 1H), 7.14 (t, J = 8.8 Hz, 2H), 6.92 (d, J = 11.6, 1H), 3.86 (s, 3H), 3.79 (s, 2H), 3.15-3.34 (m, 2H) 2.40 (s , 3H) .
1A-104 CDCl3: δ 7.61 (d, J = 8.0 Hz, 2H), 7.53 (d, J = 8.4 Hz, 1H), 7.48 (d, J = 8.0 Hz, 1H), 7.44 (d, J = 7.6, 4H), 7.31 (bs, 1H), 7.22 (d, J = 8.0 Hz, 1H), 6.92 (d, J = 11.6 Hz, 1H), 3.82 (s, 2H), 3.34-3.34 (m, 2H), 2.40 (s, 3H).
1A-105 CDCl3: δ 8.50 (d, J = 7.6 Hz, 1H), 7.73 (d, J = 14.4 Hz, 2H), 7.61 (d, J = 8.0 Hz, 3H), 7.46 (d, J = 8.0 Hz, 2H), 7.30 (bs, 1H), 6.93 (d, J = 11.6 Hz, 1H), 3.82 (s, 2H), 3.34-3.41 (m, 2H) 2.41 (s, 3H).
1A-106 CDCl3: δ 8.53 (d, J = 8.0 Hz, 1H), 7.51 (d, J = 8.0 Hz, 2H), 7.45-7.36 (m, 6H), 7.19-7.12 (m, 1H), 6.92 (d, J
63

= 11.2 Hz, 1H), 3.82 (s, 2H), 3.38 (q, J = 9.6 Hz, 2H), 2.40 (s, 3H).

1A-107 CDCl3: δ 8.50 (d, J = 7.6 Hz, 1H), 7.84 (s, 1H), 7.77 (d, J = 7.6 Hz, 1H), 7.63 (t, J = 7.6 Hz, 3H), 7.57 (t, J = 7.6 Hz, 1H),7.45 (d, J = 8.4 Hz, 2H), 7.33 (s, 1H), 6.92 (d, J = 12.8 Hz, 1H), 3.82 (s, 2H), 3.38 (q, J = 9.6 Hz, 2H), 2.41 (s , 3H).
1A-108 CDCl3: δ 8.51 (d, J = 7.6 Hz, 1H), 7.62 (d, J = 8.0 Hz, 2H), 7.44-7.36 (m, 4H), 7.31-7.26 (m, 2H), 7.07-7.04 (m, 1H), 6.92 (d, J = 11.6 Hz, 1H), 3.81 (s, 2H), 3.38 (q, J = 8.8 Hz, 2H), 2.40 (s, 3H).
1A-109 CDCl3: δ 8.50 (d, J = 8.0 Hz, 1H), 7.60 (d, J = 6.8 Hz, 2H), 7.47-7.41 (m, 3H), 7.34-7.31 (m, 2H), 7.26-7.14 (m, 2H), 6.92 (d, J = 11.2 Hz, 1H), 3.81 (s, 2H), 3.38 (q, J = 9.6 Hz, 2H), 2.40 (s, 3H).
1A-110 CDCl3: δ 7.85 (s, 1H), 7.64 (d, J = 6.4 Hz, 1H), 7.55 (d, J = 8.4 Hz, 1H), 7.44 (d, J = 8.0 Hz, 2H), 7.31 (d, J = 8.0 Hz, 1H), 7.15 (d, J = 8.0 Hz, 2H), 7.10 (d, J = 10.4 Hz, 1H), 3.54-3.43 (m, 2H), 3.28-3.24 (m, 5H), 2.52 (s, 3H).
1A-111 CDCl3: δ 7.69-7.65 (m, 2H), 7.57-7.53 (m, 1H), 7.49-7.44 (m, 1H), 7.32 (s, 1H), 7.29 (s, 2H), 7.09 (d, J = 6.8 Hz, 2H), 3.57-3.48 (m, 2H), 3.29-3.22 (m, 5H), 2.51 (s, 3H).
1A-112 CDCl3: δ 7.58 (d, J = 8.0 Hz, 2H), 7.19-7.11 (m, 4H), 3.75-3.83 (m, 1H), 3.70-3.66 (m, 1H), 3.52-3.40 (m, 2H), 3.27-3.20 (m, 2H), 2.53 (s, 3H), 2.15-2.09 (m, 2H), 1.79-1.71 (m, 2H).
1A-113 CDCl3: δ 8.52 (d, J = 8.0 Hz, 1H), 7.46-7.40 (m, 4H), 7.34-7.30 (m, 2H), 7.25-7.22 (m, 1H), 7.08-7.03 (m, 1H), 6.93 (d, J = 11.6 Hz, 1H), 3.82 (s, 2H), 3.38 (q, J = 9.6 Hz, 2H), 2.41 (s, 3H).
1A-114 CDCl3: δ 8.50 (d, J = 8.0 Hz, 1H), 7.89 (d, J = 1.6 Hz, 1H), 7.79 (d, J = 8.0 Hz, 1H), 7.57-7.61 (m, 3H), 7.45 (d, J = 8.0 Hz, 2H), 7.31 (bs, 1H), 6.93 (d, J = 11.6 Hz, 1H), 3.82 (s, 2H), 3.38 (q, J = 9.6 Hz, 2H), 2.40 (s, 3H).
1A-115 CDCl3: δ 9.22 (s, 1H), 8.97 (s, 2H), 8.50 (d, J = 8.0 Hz, 1H), 7.63 (d, J = 8.0 Hz, 2H), 7.51 (d, J = 8.0 Hz, 2H), 7.33 (bs, 1H), 6.94 (d, J = 11.6 Hz, 1H), 3.84 (s, 2H), 3.37 (q, J = 9.6 Hz, 2H), 2.41 (s, 3H).
1A-116 CDCl3: δ 8.69 (d, J = 7.6 Hz, 1H), 8.42 (bs, 1H), 7.68 (d, J = 8.0 Hz, 2H), 7.51 (d, J = 8.0 Hz, 2H), 6.98 (d, J = 11.2 Hz, 1H), 4.31 (s, 2H), 3.39 (q, J = 9.6 Hz, 2H), 2.44 (s, 3H).
1A-117 CDCl3: δ 7.54 (d, J = 8.4 Hz, 2H), 7.13-7.10 (m, 3H), 7.03 (d, J = 10.0 Hz, 1H), 4.14-3.95 (m, 2H), 3.66 (s, 3H), 3.19-3.05 (m, 2H), 2.49 (s, 3H).
1A-118 CDCl3: δ 7.45 (d, J = 8.0 Hz, 2H), 7.41-7.30 (m, 3H), 7.28 (s, 1H), 7.23 (s, 1H), 7.11 (d, J = 8.0 Hz, 2H), 7.04-7.00 (m, 1H), 3.54-3.42 (m, 2H), 3.29-3.18 (m, 5H), 2.49 (s, 3H).
1A-119 CDCl3: δ 7.37-7.32 (m, 5H), 7.19-7.12 (m, 2H), 7.09-7.06 (m, 2H), 7.04 (s, 1H), 3.55-3.44 (m, 2H), 3.30-3.19 (m, 5H), 2.51 (s, 3H).
1A-120 CDCl3: δ 7.68 (d, J = 14.0 Hz, 2H), 7.57 (s, 1H), 7.45 (d, J = 8.4 Hz, 2H), 7.32 (d, J = 7.6 Hz, 1H), 7.15 (d, J = 8.4 Hz, 2H), 7.10 (d, J = 10.0 Hz, 1H), 3.49 (m, 2H), 3.33-3.19 (m, 5H), 2.52 (s, 3H).
1A-121 CDCl3: δ 7.79 (s, 1H), 7.73 (d, J = 7.6 Hz, 1H), 7.60-7.52 (m, 2H), 7.48 (d, J = 8.0 Hz, 2H), 7.31-7.27 (m, 1H), 7.19-7.10 (m, 3H), 3.55-3.43 (m, 2H), 3.27-3.19 (m, 5H), 2.50 (s, 3H).
1A-122 CDCl3: δ 7.48 (d, J = 8.8 Hz, 2H), 7.42 (d, J = 8.4 Hz, 2H), 7.29-7.24 (m, 1H), 7.19-7.14 (m, 1H), 7.09-7.06 (m, 2H), 6.96 (d, J = 8.4 Hz, 2H), 3.86 (s, 3H), 3.53-3.40 (m, 2H), 3.23-3.16 (m, 5H), 2.48 (s, 3H).
1A-123 CDCl3: δ 7.52-7.48 (m, 2H), 7.42 (d, J = 8.0 Hz, 2H), 7.29-7.27 (m, 1H), 7.14-7.07 (m, 5H), 3.53-3.41 (m, 2H), 3.23-3.20 (m, 5H), 2.51 (s, 3H).
1A-124 CDCl3: δ 7.43-7.38 (m, 3H), 7.33-7.27 (m, 2H), 7.14-7.06 (m, 5H), 3.52-3.44 (m, 2H), 3.24-3.17 (m, 5H), 2.48 (s, 3H).
1A-125 CDCl3: δ 7.40-7.32 (m, 5H), 7.19-7.12 (m, 2H), 7.09-7.04 (m, 3H), 3.55-3.44 (m, 2H), 3.28-3.21 (m, 5H), 2.51 (s, 3H).
1A-126 CDCl3: δ 8.46 (d, J = 8.0 Hz, 1H), 8.26 (bs, 1H), 7.62 (d, J = 8.8 Hz, 2H), 7.47 (d, J = 8.8 Hz, 2H), 7.03 (d, J = 11.2 Hz, 1H), 3.40-3.33 (m, 2H), 2.44 (s, 3H).
1A-127 CDCl3: δ 7.49-7.35 (m, 4H), 7.29-7.28 (m, 2H), 7.11-7.06 (m, 2H), 6.91 (d, J = 8.8 Hz, 2H), 3.50-3.33 (m, 2H), 3.28-3.21 (m, 5H), 2.51 (s, 3H).
1A-128 CDCl3: δ 7.45 (d, J = 6.8 Hz, 1H), 7.33-7.27 (m, 6H), 7.10-7.06 (m, 3H), 3.56-3.44 (m, 2H), 3.24-3.20 (m, 5H), 2.51 (s, 3H).
1A-129 CDCl3: δ 7.30 (d, J = 8.4 Hz, 2H), 7.18-7.14 (m, 3H), 6.89 (d, J = 10.4 Hz, 1H), 3.28-3.21 (m, 5H), 2.47 (s,
64

3H).
1A-130 CDCl3: δ 7.21 (d, J = 7.6 Hz, 1H), 7.06-7.03 (m, 3H), 6.91 (d, J = 8.0 Hz, 2H), 3.48-3.34 (m, 2H), 3.25-3.14 (m, 5H), 3.54-2.49 (m, 5H), 1.62-1.50 (m, 2H), 0.84 (t, J = 7.2 Hz, 3H).
1A-131 CDCl3: δ 7.69-7.67 (m, 1H), 7.35 (d, J = 7.6 Hz, 1H), 7.12 (d, J = 11.2 Hz, 1H), 6.94-6.83 (m, 2H), 3.56-3.30 (m, 2H), 3.35-3.12 (m, 5H), 2.54 (s, 3H).
1A-132 CDCl3: δ 7.50 (d, J = 7.6 Hz, 1H), 7.22-7.14 (m, 1H), 7.11 (d, J = 10.0 Hz, 1H), 6.83 (t, J = 9.4 Hz, 2H), 3.45 (s, 2H), 3.35 (q, J = 9.4 Hz, 2H), 3.25 (s, 3H), 2.51 (s, 3H).
1A-133 CDCl3: δ 7.19 (d, J = 7.6 Hz, 1H), 7.06 (d, J = 7.6 Hz, 3H), 6.92 (d, J = 8.0 Hz, 2H), 3.48-3.34 (m, 2H), 3.21-3.13 (m, 5H), 2.59 (q, J = 7.6 Hz, 2H), 2.50 (s, 3H), 1.24-1.14 (m, 3H).
1A-134 CDCl3: δ 7.86-7.75 (m, 2H), 7.50-7.37 (m, 1H), 7.22 (d, J = 8.0 Hz, 2H), 6.98-6.08 (m, 1H), 3.37-3.25 (m, 2H), 3.21-3.17 (m, 5H), 2.55-2.41 (m, 5H), 1.17-1.13 (m, 3H).
1A-135 CDCl3: δ 8.05 (s, 1H), 7.82-7.76 (m, 2H), 7.18-7.16 (m, 1H), 7.16-7.12 (m, 1H), 6.94-6.89 (m, 1H), 3.73-3.58 (m, 2H), 3.40-3.36 (m, 2H), 3.22 (s, 3H), 3.10-2.98 (m, 3H), 2.47 (s, 3H).
1A-136 CDCl3: δ 8.46 (d, J = 8.0 Hz, 1H), 7.96 (d, J = 8.4 Hz, 2H), 7.56 (d, J = 8.0 Hz, 2H), 7.32 (s, 1H), 6.95 (d, J = 11.6 Hz, 1H), 3.85 (s, 2H), 3.40-3.32 (m, 2H), 3.06 (s, 3H), 2.42 (s, 3H).
1A-137 CDCl3: δ 8.44 (d, J = 7.6 Hz, 1H), 8.31 (s, 1H), 7.82 (d, J = 8.4 Hz, 2H), 7.78 (s, 1H), 7.76 (s, 1H), 7.03 (d, J = 11.2 Hz, 1H), 3.40-3.33 (m, 2H), 2.45 (s, 3H).
1A-138 CDCl3: δ 7.58 (d, J = 8.0 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 7.20 (d, J = 7.6 Hz, 1H), 6.84 (d, J = 10.0 Hz, 1H), 3.32-3.20 (m, 5H), 2.47 (s, 3H).
1A-139 CDCl3: δ 7.53 (d, J = 12.4 Hz, 1H), 7.49 (d, J = 6.4 Hz, 1H), 7.16-7.12 (m, 2H), 7.07 (d, J = 8.4 Hz, 1H), 6.91 (d, J = 8.4 Hz, 1H), 3.43-3.35 (m, 2H), 3.18 (d, J = 9.6 Hz, 2H), 2.40 (s, 3H), 1.41 (d, J = 6.4 Hz, 3H).
1A-140 CDCl3: δ 8.52 (d, J = 8.0 Hz, 1H), 7.50 (d, J = 1.6 Hz, 1H), 7.46-7.40 (m, 4H), 7.30 (d, J = 2.0 Hz, 1H), 7.31-7.26 (m, 2H), 6.93 (d, J = 11.6 Hz, 1H), 3.82 (s, 2H), 3.38 (q, J = 10.0 Hz, 2H), 2.41 (s, 3H).
1A-141 CDCl3: δ 8.50 (d, J = 8.0 Hz, 1H), 7.54 (d, J = 8.0 Hz, 2H), 7.43 (d, J = 7.6 Hz, 2H), 7.29 (bs, 1H), 7.21-7.16 (m, 2H), 6.93 (d, J = 11.6 Hz, 1H), 3.81 (d, J = 4.8 Hz, 2H), 3.37 (q, J = 9.6 Hz, 2H), 2.41 (s, 3H).
1A-142 CDCl3: δ 8.49 (q, J = 4.8 Hz, 1H), 7.69-7.40 (m, 5H), 7.30 (bs, 1H), 7.26-7.21 (m, 3H), 6.99-6.90 (m, 1H), 3.81 (d, J = 6.8 Hz, 2H), 3.41-3.27 (m, 2H), 2.40 (s, 3H).
1A-143 CDCl3: δ 8.50 (d, J = 7.6 Hz, 1H), 7.58 (d, J = 8.4 Hz, 2H), 7.46 (d, J = 1.6 Hz, 2H), 7.43 (d, J = 8.0 Hz, 2H), 7.35 (t, J = 1.6 Hz, 1H), 7.29 (bs, 1H), 6.92 (d, J = 11.6 Hz, 1H), 3.81 (s, 2H), 3.38 (q, J = 9.6 Hz, 2H), 2.40 (s, 3H).
1A-144 CDCl3: δ 8.50 (d, J = 7.6 Hz, 1H), 7.61 (d, J = 8.4 Hz, 2H), 7.53 (d, J = 8.4 Hz, 2H), 7.40 (d, J = 7.6 Hz, 2H), 7.34 (d, J = 8.4 Hz, 3H), 6.91 (d, J = 11.6 1H), 3.80 (s, 2H), 3.38 (q, J = 9.6 Hz, 2H), 2.53 (s, 3H), 2.40 (s, 3H).
1A-145 CDCl3: δ 8.50 (d, J = 7.6 Hz, 1H), 7.62 (d, J = 8.0 Hz, 2H), 7.50 (d, J = 8.0 Hz, 2H), 7.39 (d, J = 8.0 Hz, 2H), 7.32 (bs, 1H), 7.27-7.26 (m, 2H), 6.91 (d, J = 11.6 1H), 3.80 (s, 2H), 3.38 (q, J = 9.6 Hz, 2H), 2.40 (s, 6H).
1A-146 CDCl3: δ 7.48 (d, J = 8.4 Hz, 2H), 7.44 (d, J = 8.4 Hz, 2H), 7.31 (d, J = 8.4 Hz, 2H), 7.27 (s, 1H), 7.08 (t, J = 5.6 Hz, 3H), 3.50 (s, 1H), 3.45 (s, 1H), 3.23 (s, 3H), 3.20 (d, J = 10.0 Hz, 2H), 2.52 (s, 6H).
1A-147 CDCl3: δ 7.42 (q, J = 6.5 Hz, 4H), 7.32 (s, 2H), 7.14 (s, 3H), 3.23 (m, 7H), 2.52 (s, 3H).
1A-148 CDCl3: δ 7.56 (d, J = 6.0 Hz, 1H), 7.44-7.40 (m, 2H), 7.37-7.32 (m, 2H), 7.29-7.26 (m, 1H), 7.12-7.06 (m, 2H), 6.91 (d, J = 8.4 Hz, 2H), 3.49-3.28 (m, 2H), 3.28-3.18 (m, 5H), 2.51 (s, 3H).
1A-149 CDCl3: δ 7.45 (d, J = 8.0 Hz, 4H), 7.23 (d, J = 8.4 Hz, 3H), 7.09-7.06 (m, 3H), 3.47 (m, 2H), 3.23 (s, 3H), 3.20-3.16 (m, 2H), 2.50 (s, 3H), 2.39 (s, 3H).
Below are Preparation Examples in which the “parts” refers to “parts by weight.”
5 Preparation Example 1: Emulsions
65

10 parts of each compound of the invention was dissolved in 45 parts of Solvesso 150 and 35 parts of N-methylpyrrolidone. 10 parts of an emulsifier (trade name: Sorpol 3005X, produced by Toho Chemical Industry Co., Ltd.) was added 5 thereto. The mixtures were mixed by stirring to give 10% emulsions.
Preparation Example 2: Wettable powders
20 parts of each compound of the invention was added to 10 a mixture of 2 parts of sodium lauryl sulfate, 4 parts of
sodiumlignin sulfonate, 20 parts of fine powder of synthetic hydrated silicon dioxide, and 54 parts of clay. The mixtures were mixed by stirring with a juice mixer to give 20% wettable powders.
15 Preparation Example 3: Granules
2 parts of sodium dodecylbenzenesulfonate, 10 parts of bentonite, and 83 parts of clay were added to 5 parts of each compound of the invention, and each mixture was sufficiently mixed by stirring. An appropriate amount of water was added
20 thereto. The resulting mixtures were further stirred and
granulated with a granulator. The granules were air-dried to give 5% granules.
Preparation Example 4: Dusts
25 1 part of each compound of the invention was dissolved
in an appropriate amount of acetone. 5 parts of fine powder of synthetic hydrated silicon dioxide, 0.3 parts of acidic isopropyl phosphate (PAP), and 93.7 parts of clay were added thereto. The mixtures were mixed by stirring with a juice mixer, and acetone
30 was removed by evaporation to give 1% dust.
Preparation Example 5: Flowable preparations
20 parts of each compound of the invention was mixed
with 20 parts of water containing 3 parts of polyoxyethylene
35 tristyrylphenyl ether phosphoric acid ester triethanolamine and
66

0.2 parts of Rhodorsil 426R. The mixtures were subjected to wet pulverization with a DYNO-Mill, and mixed with 60 parts of water containing 8 parts of propylene glycol and 0.32 parts of xanthan gum to give 20% suspensions in water.
Test Examples are given below to demonstrate that the compounds of the invention are useful as an active ingredient for miticides.
Test Example 1 (Miticidal test on Two-Spotted Spider Mites) A piece of non-woven fabric (4.5x5.5cm) was suspended inside a plastic cup through an incision made in the lid of the plastic cup. After water was poured into the cup, the cup was covered with the lid. A kidney bean leaf (about 3.5x4.5 cm) was then placed on the sufficiently soaked, non-woven fabric. Another kidney bean leaf with two-spotted spider mites (about 30 mite samples) was placed on top of the first leaf, and the fabric and leaves were placed in a thermostatic chamber having a temperature of 25±2° C and a humidity of 40%.
Miticidal formulations containing the compound of the invention (200 ppm) were prepared by adding an aqueous solution (100 ppm) of Sorpol 355 (manufactured by Tobo Kagaku Co. Ltd.) to a methanol solution of the compound of the invention. These miticidal formulations were sprayed onto the leaves, and the leaves were air-dried and placed in a thermostatic chamber (25±2° C and a humidity of 50%). The mortality rate of the two-spotted spider mites was calculated after 2 days.
The compounds that exhibited the mortality rate of 50% or more are as follows:
Compound Nos.: 1A-2, 1A-5, 1A-8, 1A-12, 1A-13, 1A-14, 1A-15, 1A-20, 1A-23, 1A-24, 1A-27, 1A-28, 1A-30, 1A-33, 1A-42, 1A-43, 1A-45, 1A-46, 1A-47, 1A-48, 1A-49, 1A-50, 1A-51, 1A-52, 1A-53, 1A-54, 1A-55, 1A-56, 1A-57, 1A-58, 1A-59, 1A-60, 1A-62, 1A-63, 1A-65, 1A-67, 1A-68, 1A-72, 1A-73, 1A-74, 1A-75, 1A-76, 1A-77, 1A-78, 1A-82, 1A-83, 1A-85, 1A-86, 1A-87, 1A-88, 1A-90, 1A-91, 1A-92,

1A-93, 1A-94, 1A-95, 1A-96, 1A-97, 1A-103, 1A-104, 1A-107, 1A-108, 1A-109, 1A-111, 1A-112, 1A-113, 1A-114, 1A-116, 1A-117, 1A-118, 1A-119, 1A-120, 1A-121, 1A-122, 1A-123, 1A-126, 1A-127, 1A-128.
Test Example 2 (Ovicidal test on Two-Spotted Spider Mites)
A piece of non-woven fabric (4.5x5.5cm) was suspended inside a plastic cup through an incision made in the lid of the plastic cup. After water was poured into the cup, the cup was covered with the lid. A kidney bean leaf (about 3.5x4.5 cm) was then placed on the sufficiently soaked, non-woven fabric. Twenty female adults of two-spotted spider mite were placed on the top of the leaf, and the fabric and leaf were placed in a thermostatic chamber having a temperature of 25±2° C and a humidity of 40% and 16L8D.
The next day, after the number of the female adults was adjusted once more to 20, 2 ml of a miticidal formulation containing the compound of the invention (200 ppm) prepared in the same manner as in test example 1 was sprayed onto the leaf, and the leaf was air-dried and placed in a thermostatic chamber (25±2° C and a humidity of 50%). The ovicidal rate of the two-spotted spider mites was calculated 6 days after the spraying of the miticidal formulation. The compounds that exhibited a mortality of 50% or more at 500 ppm are as follows:
Compound Nos.: 1A-2, 1A-8, 1A-12, 1A-13, 1A-14, 1A-20, 1A-23, 1A-27, 1A-33, 1A-42, 1A-43, 1A-47, 1A-48, 1A-49, 1A-50, 1A-51, 1A-52, 1A-53, 1A-54, 1A-55, 1A-56, 1A-57, 1A-58, 1A-59, 1A-60, 1A-61, 1A-63, 1A-65, 1A-67, 1A-68, 1A-69, 1A-70, 1A-71, 1A-72, 1A-73, 1A-74, 1A-76, 1A-77, 1A-78, 1A-82, 1A-83, 1A-85, 1A-86, 1A-87, 1A-88, 1A-90, 1A-91, 1A-93, 1A-94, 1A-95, 1A-96.

We Claim:
A benzylamide compound represented by Formula (1)
or a salt thereof,
wherein R1 represents Ci-6 alkyl or Ci-6 haloalkyl;
R2 and R3 are identical or different and each represent
hydrogen, halogen, cyano, nitro, Ci-6 alkyl, Ci-6 haloalkyl,
Ci-6 alkoxy, Ci_6 haloalkoxy, Ci_6 alkoxy Ci_6 alkyl, Ci_6
haloalkoxy Ci-6 alkyl, C3-8 cycloalkyl or C3-8 cycloalkyl Ci-6
alkyl;
R4 represents hydrogen, formyl, Ci-6 alkyl, Ci-6 haloalkyl, Ci-
6 alkoxy, Ci_6 haloalkoxy, Ci_6 alkoxy Ci_6 alkyl, Ci_6
haloalkoxy Ci-6 alkyl, C3-8 cycloalkyl, C3-8 cycloalkyl Ci-6
alkyl, Ci-6 alkylcarbonyl, Ci_6 haloalkylcarbonyl, Ci_6
alkoxycarbonyl, Ci-6 haloalkoxycarbonyl, arylcarbonyl,
aryloxycarbonyl, C2-6 alkenyl, C2-6 haloalkenyl, C2-6 alkynyl,
C2-6 haloalkynyl, Ci-6 alkylsulfonyl, Ci-6 haloalkylsulfonyl,
Ci-6 alkylsulfinyl, Ci-6 haloalkylsulfinyl, Ci-6 alkylthio, Ci-6
haloalkylthio, aryl, aryl Ci-6 alkyl, arylsulfonyl,
arylsulfinyl, arylthio, or heterocyclic, all the
substituents defined as R4 may optionally be further
substituted;
R5 and R6 are identical or different and each represent
hydrogen, halogen, Ci-6 alkyl, or Ci-6 haloalkyl; R5 and R6,
taken together with the carbon atom to which they bond, may
bond to each other to form a 3- to 8-membered ring, via or
not via at least one heteroatom;
R7, R8, R9, R10, and R11 are identical or different and each

represent hydrogen, halogen, nitro, cyano, hydroxyl, formyl, Ci-6 alkyl, Ci-6 haloalkyl, Ci_6 alkoxy, Ci_6 haloalkoxy, Ci_6 alkoxy Ci-6 alkyl, Ci-6 haloalkoxy Ci-6 alkyl, C3-8 cycloalkyl, C3-8 cycloalkyl Ci-6 alkyl, Ci-6 alkylcarbonyl, Ci-6 haloalkylcarbonyl, arylcarbonyl, aryloxycarbonyl, Ci-6 alkoxycarbonyl, Ci-6 haloalkoxycarbonyl, Ci-6 cyanoalkyl, Ci-6 cyanoalkoxy, C2_6 alkenyl, C2_6 haloalkenyl, C2_6 alkynyl, C2-6 haloalkynyl, Ci-6 alkylsulfonyl, Ci-6 haloalkylsulfonyl, Ci-6 alkylsulfinyl, Ci-6 haloalkylsulfinyl, Ci-6 alkylthio, Ci-6 haloalkylthio, C3-8 cycloalkylsulfonyl, C3-8 cycloalkylsulfinyl, C3-8 cycloalkylthio, C3-8 cycloalkyl Ci_6 alkylsulfonyl, C3-8 cycloalkyl Ci-6 alkylsulfinyl, C3-8 cycloalkyl Ci_6 alkylthio, Ci_6 alkoxy Ci_6 alkylsulfonyl, Ci_6 alkoxy Ci-6 alkylsulfinyl, Ci-6 alkoxy Ci-6 alkylthio, C2-6 alkenyloxy, C2_6 haloalkenyloxy, C2_6 alkynyloxy, C2_6 haloalkynyloxy, Ci-6 alkylsulfonyloxy, Ci-6 haloalkylsulfonyloxy, Ci-6 alkylsulfinyloxy, Ci-6 haloalkylsulfinyloxy, carboxyl, OCN, SCN, SF5, substituted or unsubstituted amino, aryl, aryl Ci-6 alkyl, aryloxy, aryl Ci-6 alkoxy, arylsulfonyl, arylsulfinyl, arylthio, aryl Ci_6 alkylsulfonyl, aryl Ci-6 alkylsulfinyl, aryl Ci-6 alkylthio, heterocyclic, heterocyclic Ci_6 alkyl, or heterocyclic oxy, all of which may optionally be further substituted; R7 and R8, R8 and R9, R9 and R10, or R10 and R11, taken together with the benzene ring to which they bond, may bond to each other to form a 3- to 8-membered ring via or not via at least one heteroatom; X represents oxygen or sulfur; and n represents an integer of 0 to 2.
2. The benzylamide compound or the salt thereof according to claim 1, wherein R1 is Ci-6 haloalkyl.

3. The benzylamide compound or the salt thereof according to claim 1 or 2, wherein R2 and R3 are identical or different and each represent halogen, cyano, or C1-6 alkyl.
5 4. The benzylamide compound or the salt thereof according to any one of claims 1 to 3, wherein R4 is hydrogen, or C1-6 alkyl. 5. The benzylamide compound or the salt thereof according to
any one of claims 1 to 4, wherein R7, R8, R9, R10, and R11 are
10 identical or different and each represent hydrogen, halogen,
nitro, C1-6 alkyl, C1-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, C1-6 alkylsulfonyl, C1-6 haloalkylsulfonyl, C1-6 alkylsulfinyl, C1-6 haloalkylsulfinyl, C1-6 alkylthio, C1-6 haloalkylthio, substituted or unsubstituted amino, aryl, or heterocyclic.

15
20

6. A method for producing the benzylamide compound or the salt
thereof according to any one of claims 1 to 5, comprising at
least one step selected from the group consisting of
following steps (d) and (e):
step (d): obtaining a sulfide compound represented by
Formula (1-1) by reacting a thiol compound represented by
Formula (6) with an alkylating reagent represented by
Formula (7):

10
R
Rl/^/R-3.. R
R^^^R3 R11
XX
HS

25

'i0AA
(7)
N' x T R8
R4 R5R6 R7
R4 R5R6 R7
(6) 0-1)
wherein, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and X are as defined above and G represents a leaving group; and step (e): obtaining a benzylamide compound represented by Formula (1-2) by reacting the sulfide compound represented

71

by Formula (1-1) with an oxidizing agent
R10
R9 oxidizing agent R2V
*~ R1.
s — N XT R
(6)n. R4 R5 R6 R7
(1-2)
wherein, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and X are as defined above, n' represents 1 or 2.
7. The method for producing the benzylamide compound and the salt thereof according to claim 6, further comprising the following step (c):
step (c): obtaining a thiol compound represented by Formula (6) by reacting a sulfonylchloride compound represented by Formula (5) with a reducing agent:

CISO

R10 R10
s u .R3 xR 11 I „R9 ^R8 reducing agent HS 3 .R3 xR 11 I .R9
J









^R8
£. R4 R5 (5) R6 R7 R4 R5 (6) R6 R7
wherein, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and X are as defined above.
The method for producing the benzylamide compound and the salt thereof according to claim 7, further comprising the following step (b):
step (b): obtaining the sulfonylchloride compound represented by Formula (5) by chlorosulfonylating an amide compound represented by Formula (4):

wherein, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and X are as defined above.
The method for producing the benzylamide compound and the salt thereof according to claim 8, further comprising the following step (a) :
step (a): obtaining the amide compound represented by Formula (4) by reacting an aniline compound represented by Formula (2) with a benzylcarbonyl compound represented by Formula (3):
wherein, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and X are as defined above, and Y represents a leaving group or hydroxyl group.
A pesticide containing the benzylamide compound or the salt thereof of according to any one of claims 1 to 5.
A miticide containing the benzylamide compound or the salt thereof of according to any one of claims 1 to 5.