HK40006665B - Novel benzylamide compound, method for producing the same, and miticide - Google Patents

Description

Novel benzamide compounds, their preparation methods and acaricides

Technical Field

This invention relates to novel benzamide compounds, their preparation methods, and acaricides containing the compounds.

Background Technology

Because mites have developed resistance to acaricides due to long-term use in recent years, it has become difficult to control them using known acaricides.

In this situation, there is an urgent need to develop novel acaricides that are expected to achieve excellent acaricidal activity.

For example, patent document (PTL) 1) discloses a compound represented by the following formula (A):

^R5 represents substituted or unsubstituted _C1-20 alkyl, substituted or unsubstituted amino, N-containing heterocycle, etc., and this compound is reported to exhibit acaricidal activity.

However, in PTL 1, urea compounds were mainly prepared, and although amide compounds in which ^R5 is alkyl, haloalkyl, aryl, or cycloalkyl were also prepared, amide compounds in which ^R5 is benzyl were not disclosed. Furthermore, PTL 1 did not disclose at all that the aforementioned compound (A) exhibited ovicidal activity.

Citation List

Patent documents

PTL 1: Japanese Patent Publication No. 2011-042611

Invention Overview

Technical issues

The objective of this invention is to provide novel benzamide compounds or salts thereof that exhibit acaricidal activity.

Another objective of the present invention is to provide a method for preparing benzamide compounds or salts thereof.

Another objective of this invention is to provide novel acaricides containing benzamide compounds or their salts.

Solution to the problem

The inventors have conducted extensive research to achieve the objectives described above and have successfully synthesized compounds or salts thereof represented by formula (1) with acaricidal activity. Further research has been conducted based on the findings described above. This invention is thus completed.

More specifically, the present invention includes the following embodiments:

Project 1:

A benzamide compound represented by formula (1):

or its salt,

Where ^R1 represents a _C1-6 alkyl or a _C1-6 haloalkyl;

^R2 and ^R3 may be the same or different and each represents hydrogen, halogen, cyano, nitro, _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 or _C3-8 cycloalkyl- _C1-6 alkyl;

R ⁴ represents hydrogen, 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 alkyl carbonyl, _{C1-6 haloalkyl} carbonyl, _C1-6 alkoxy carbonyl, _C1-6 haloalkoxy carbonyl, aryl carbonyl, aryloxy carbonyl, _C2-6 alkenyl, _C2-6 haloalkenyl, _C2-6 alkynyl, _C2-6 haloalkynyl, _C1-6 alkylsulfonyl, _C1-6 haloalkylsulfonyl, _C1-6 alkylsulfinyl _{, C1-6} haloalkylsulfinyl, _C1-6 alkylthio, C _1-6 haloalkylthio, aryl, aryl C _1-6 alkyl, arylsulfonyl, arylsulfinyl, arylthio or heterocyclic, all substituents defined as R ⁴ may optionally be further substituted;

^R5 and ^R6 may be the same or different and each represents hydrogen, halogen, _C1-6 alkyl or _C1-6 haloalkyl; ^R5 and ^R6 may be bonded to each other with or without a carbon atom to form a 3 to 8-membered ring.

^R7 , ^R8 , ^R9 , ^R10 , and ^R11 may be the same or different and each represents hydrogen, halogen, 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 alkyl carbonyl, _C1-6 haloalkyl carbonyl, aryl carbonyl, aryloxy carbonyl, _C1-6 alkoxy carbonyl, _C1-6 haloalkoxy carbonyl, _C1-6 cyanoalkyl, _C1-6 cyanoalkoxy, _C2-6 alkenyl, _C2-6 haloalkenyl, _C2-6 ynyl, _C2-6 haloynyl, _C2-6 haloynyl, C _1-6 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 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 ,} C _1-6 alkylsulfonyloxy, C1-6 haloalkylsulfonyloxy, _C1-6 alkylsulfinyloxy, _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} or heterocyclic oxy, all of which may optionally be further substituted;

^R7 and ^R8 , ^R8 and ^R9 , ^R9 and ^R10 , or ^R10 and ^R11 together with the benzene ring they are bonded to can form 3 to 8-membered rings, with or without at least one heteroatom.

X represents oxygen or sulfur; and

n represents an integer from 0 to 2.

Project 2:

The benzamide compound or its salt according to Project 1, wherein ^R1 is a _C1-6 haloalkyl group.

Project 3:

The benzamide compound or its salt according to item 1 or 2, wherein ^R2 and ^R3 are the same or different and each represents a halogen, cyano or _C1-6 alkyl.

Project 4:

The benzamide compound or its salt according to any one of items 1 to 3, wherein R ⁴ is hydrogen or C _1-6 alkyl.

Project 5:

The benzamide compound or a salt thereof according to any one of items 1 to 4, wherein ^R7 , ^R8 , ^R9 , ^R10 and ^R11 are the same or different and each represents 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.

Project 6:

The benzamide compound or its salt according to any one of the foregoing items, wherein the benzamide compound is represented by formula (1-3):

in

R ³ indicates halogen;

R ⁴ represents hydrogen, _C1-6 alkyl, or _C1-6 haloalkyl;

^R5 and ^R6 may be the same or different and each represents hydrogen or halogen;

X represents O or S;

L represents a single bond, O, or S;

^X1 , ^X2 , and ^X3 may be the same or different and each represents a halogen; and

^X4 , ^X5 , and ^X6 may be the same or different and each represents hydrogen or halogen.

Project 7:

The benzamide compound or its salt according to any one of the foregoing items, wherein ^X4 , ^X5 and ^X6 are the same or different and each represents a halogen.

Project 8:

The benzamide compound or its salt according to any one of the foregoing items, wherein ^R5 and ^R6 are the same or different and each represents hydrogen, fluorine, chlorine or bromine.

Project 9:

The benzamide compound or its salt according to any one of the foregoing items, wherein ^R5 and ^R6 are the same or different and each represents hydrogen, fluorine or chlorine.

Project 10:

The benzamide compound or its salt according to any one of the foregoing items, wherein ^R5 and ^R6 are the same or different and each represents hydrogen or fluorine.

Project 11:

The benzamide compound or its salt according to any one of the foregoing items, wherein ^R5 and ^R6 are hydrogen.

Project 12:

The benzamide compound or its salt according to any one of the foregoing items, wherein R ⁴ represents hydrogen, methyl or ethyl.

Project 13:

The benzamide compound or its salt according to any one of the foregoing items, wherein L is O or S.

Project 14:

The benzamide compound or its salt according to any one of the foregoing items, wherein X is O.

Project 15:

The benzamide compound or its salt according to any one of the foregoing items, wherein ^R3 is fluorine, chlorine or bromine.

Project 16:

The benzamide compound or its salt according to any one of the foregoing items, wherein ^R3 is fluorine or chlorine.

Project 17:

The benzamide compound or its salt according to any one of the foregoing items, wherein ^R3 is fluorine.

Project 18:

The benzamide compound or its salt according to any one of the foregoing items, wherein ^X1 , ^X2 and ^X3 are the same or different and each represents fluorine, chlorine or bromine.

Project 19:

The benzamide compound or its salt according to any one of the foregoing items, wherein ^X1 , ^X2 and ^X3 are the same or different and each represents fluorine or chlorine.

Project 20:

The benzamide compound or its salt according to any one of the foregoing items, wherein ^X4 , ^X5 and ^X6 are the same or different and each represents fluorine, chlorine or bromine.

Project 21:

The benzamide compound or its salt according to any one of the foregoing items, wherein ^X4 , ^X5 and ^X6 are the same or different and each represents fluorine or chlorine.

Project 22:

A benzamide compound selected from the group consisting of: compounds 1A-12, 1A-14, 1A-42, 1A-43, 1A-24, 1A-47, 1A-48, 1A-49, 1A-51, 1A-52, 1A-53, 1A-54, 1A-56, 1A-58, 1A-59, 1A-60, 1A-62, 1A-69, 1A-72, 1A-73, 1 A-74, 1A-75, 1A-76, 1A-77, 1A-78, 1A-82, 1A-83, 1A-91, 1A-92, 1A-112, 1A-116, 1A-117, 1A-137, 1A-138, 1B-28, 1B-39, 1B-53, 1B-54, 1B-56, 1B-79, 1B-80, 1B-86 and 1B-87 or their salts.

Project 23:

A benzamide compound selected from the group consisting of compounds 1A-14, 1A-42, 1A-47, 1A-48, 1A-49, 1A-51, 1A-54, 1A-56, 1A-58, 1A-59, 1A-62, 1A-73 and 1A-75 or salts thereof.

Project 24:

The benzamide compound or its salt according to any one of the foregoing items, wherein the benzamide compound is represented by formula (1-4):

in

R ³ indicates halogen;

R ⁴ indicates hydrogen, methyl, or ethyl;

^R5 and ^R6 may be the same or different and each represents hydrogen, halogen, _C1-6 alkyl or _C1-6 haloalkyl;

^R12 , ^R13 , ^R14 , ^R15 , and ^R16 may be the same or different and each represents hydrogen, halogen, 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 alkyl carbonyl, _C1-6 haloalkyl carbonyl, aryl carbonyl, aryloxy carbonyl, _C1-6 alkoxy carbonyl, _C1-6 haloalkoxy carbonyl, _C1-6 cyanoalkyl, _C1-6 cyanoalkoxy, _C2-6 alkenyl, _C2-6 haloalkenyl, _C2-6 ynyl, _C2-6 haloynyl, _C2-6 haloynyl, C _1-6 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 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 ,} C _1-6 alkylsulfonyloxy, C1-6 haloalkylsulfonyloxy, _C1-6 alkylsulfinyloxy, _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} or heterocyclic oxy, all of which may optionally be further substituted;

X represents oxygen or sulfur; and

^X1 , ^X2 , and ^X3 may be the same or different and each represents a halogen.

Project 25:

The benzamide compound or its salt according to any one of the foregoing items, wherein ^R3 is fluorine, chlorine or bromine.

Project 26:

The benzamide compound or its salt according to any one of the foregoing items, wherein ^X1 , ^X2 and ^X3 are the same or different and each represents fluorine, chlorine or bromine.

Project 27:

The benzamide compound or its salt according to any one of the foregoing items, wherein ^R3 is fluorine or chlorine.

Project 28:

The benzamide compound or its salt according to any one of the foregoing items, wherein ^X1 , ^X2 and ^X3 are the same or different and each represents fluorine or chlorine.

Project 29:

The benzamide compound or its salt according to any one of the foregoing items, wherein ^R3 is fluorine.

Project 30:

The benzamide compound or its salt according to any one of the foregoing items, wherein ^X1 , ^X2 and ^X3 are fluorine.

Project 31:

The benzamide compound or its salt according to any one of the foregoing items, wherein R ⁴ represents hydrogen or methyl.

Project 32:

The benzamide compound or its salt according to any one of the foregoing items, wherein R ⁴ represents hydrogen.

Project 33:

The benzamide compound or its salt according to any one of the foregoing items, wherein ^R5 and ^R6 are the same or different and each represents hydrogen or halogen.

Project 34:

The benzamide compound or its salt according to any one of the foregoing items, wherein ^R5 and ^R6 each represent hydrogen.

Project 35:

The benzamide compound or its salt according to any one of the foregoing items, wherein ^R12 , ^R13 , ^R14 , ^R15 and ^R16 are the same or different and each represents hydrogen, halogen, cyano, _C1-6 haloalkyl, _C1-6 haloalkoxy or _C1-6 alkylthio.

Project 36:

A benzamide compound selected from the group consisting of: compounds 1A-27, 1A-28, 1A-29, 1A-63, 1A-65, 1A-66, 1A-67, 1A-68, 1A-93, 1A-94, 1A-95, 1A-96, 1A-102, 1A-103, 1A-104, 1A-105, 1A-106, 1A-107, 1A-108, 1A-109, 1A-110, 1A-111, 1A-113, 1A-114, 1A-118, 1A-119, 1A-120, 1A-121, 1A-122, 1A-123, 1A-124, 1A-125, 1A-127, 1 A-128, 1A-140, 1A-141, 1A-142, 1A-143, 1A-144, 1A-145, 1A-146, 1A-147 ,1A-148,1A-149,1B-4,1B-5,1B-6,1B-11,1B-12,1B-13,1B-14,1B-15,1 B-16, 1B-17, 1B-18, 1B-19, 1B-20, 1B-21, 1B-26, 1B-27, 1B-29, 1B-30, 1B -31, 1B-32, 1B-33, 1B-34, 1B-35, 1B-37, 1B-38, 1B-40, 1B-41 and 1B-43 or their salts.

Project 37:

A method for preparing a benzamide compound or a salt thereof according to any one of the preceding items, comprising at least one step selected from the group consisting of steps (d) and (e):

Step (d): The thioether compound represented by formula (6) is obtained by reacting the thiol compound represented by formula (6) with the alkylating agent represented by formula (7):

Where ^R1 , ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 and X are as defined above, and G represents the leaving basis; and

Step (e): Reacting the sulfide compound represented by formula (1-1) with an oxidizing agent to obtain the benzamide compound represented by formula (1-2):

Where ^R1 , ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 and X are defined above, and n' represents 1 or 2.

Project 38:

A method for preparing a benzamide compound and its salt according to any one of the foregoing items, further comprising the step (c):

Step (c): Obtain the thiol compound represented by formula (6) by reacting the sulfonyl chloride compound represented by formula (5) with a reducing agent:

^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 and X are as defined above.

Project 39:

A method for preparing a benzamide compound and its salt according to any one of the foregoing items, further comprising the step (b):

Step (b): Obtain the sulfonyl chloride compound represented by formula (5) by chlorosulfonation of the amide compound represented by formula (4):

^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 and X are as defined above.

Project 40:

A method for preparing a benzamide compound and its salt according to any one of the foregoing items, further comprising the step (a):

Step (a): The amide compound represented by formula (4) is obtained by reacting the aniline compound represented by formula (2) with the benzyl carbonyl compound represented by formula (3):

^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.

Project 41:

An insecticide containing a benzamide compound or a salt thereof according to any one of the preceding items.

Project 42:

An acaricide containing a benzamide compound or a salt thereof according to any one of the preceding items.

Advantages of the present invention

Small amounts of the benzamide compound of the present invention or its salts can achieve excellent acaricidal effects.

Using this invention, benzamide compounds and their salts can be prepared easily and in excellent yields.

In addition, the present invention can be used to provide novel acaricides containing the benzamide compound or its salt thereof.

Description of the implementation plan

The invention is described below. Unless otherwise specifically stated, throughout this specification, singular expressions should be understood to encompass the concept of their plural forms. Therefore, unless otherwise specifically stated, singular articles (e.g., "a," "an," "the," etc. in the English context) should also be understood to encompass the concept of their plural forms. Furthermore, unless otherwise specifically stated, the terminology used herein should be understood to be used in the sense commonly understood by those skilled in the art. Therefore, unless otherwise defined, all terms and scientific and technical terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention pertains. In cases of conflict, this specification (including definitions) takes precedence.

1. Benzamide compounds or their salts

This invention relates to compounds represented by formula (1):

Or its salts (hereinafter sometimes referred to as “benzamide compound (1)” or “compound (1)” of ^the present invention), wherein ^R1 , ^R2 , ^R3 , ^R4 , ^R5 , R6, ^R7 , ^R8 , ^R9 , ^R10 , ^R11 , X and n are as defined above.

The terminology used in this specification will be described below.

In this specification, there is no specific limitation on the number of substituents in a group defined by "optionally substituted" or "substituted" in cases where it is substituted, and the number can be one or more. Furthermore, unless otherwise indicated, the description of each group also applies when the group is part of another group or a substituent on another group.

"C _1-6 alkyl" refers to a straight-chain or branched saturated hydrocarbon group having 1 to 6 carbon atoms.

"C _2-6 alkenyl" refers to a straight-chain or branched unsaturated hydrocarbon group with 2 to 6 carbon atoms and 1 to 3 double bonds.

"C _2-6 ynyl" refers to a straight-chain or branched unsaturated hydrocarbon group with 2 to 6 carbon atoms and containing one triple bond.

"C _3-8 cycloalkyl" refers to cycloalkyl groups having 3 to 8 carbon atoms, including those cycloalkyl groups with partially bridging structures.

"C _1-6 alkoxy" refers to "C _1-6 alkyloxy", and the definition of "C _1-6 alkyl" is the same as that of "C _1-6 alkyl" above.

"Aromatic" refers to monocyclic or polycyclic aromatic hydrocarbons.

"Heterocyclic" means a saturated, unsaturated, or aromatic heterocyclic group that has at least one nitrogen, oxygen, phosphorus, and/or sulfur atom in the ring and can be bonded at any substituted position.

The following shows specific examples of each group as used in this specification.

Examples of halogens include, but are not limited to, fluorine, chlorine, bromine, iodine, etc.

Examples of _C1-6 alkyl groups include, but are not limited to, _C1-6 straight-chain or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl.

Examples of _C1-6 haloalkyl groups include, but are not limited to, C1-6 straight-chain or branched alkyl groups substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as _fluoromethyl , chloromethyl, bromomethyl, iodomethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, and pentafluoroisobutyl.

Examples of _C1-6 alkoxy groups include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, and other _C1-6 straight-chain or branched alkoxy groups.

Examples of _C1-6 haloalkoxy groups include, but are not limited to, C1-6 straight-chain or branched alkoxy groups substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethoxy, chloromethoxy, bromomethoxy, iodomethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, pentafluoroethoxy, 3,3,3-trifluoropropoxy, _4,4,4 -trifluorobutoxy, and pentafluoroisobutoxy.

Examples of _C1-6 alkoxy- _C1-6 alkyl include, but are not limited to, methoxymethyl, ethoxymethyl, n-propoxymethyl, isopropoxymethyl, n-butoxymethyl, isobutoxymethyl, sec-butoxymethyl, tert-butoxymethyl, methoxyethyl, ethoxyethyl, methoxy-n-propyl, methoxy-n-butyl, etc., wherein the _C1-6 straight-chain or branched alkyl group is substituted with a _C1-6 straight-chain or branched alkoxy group.

Examples of _C1-6 haloalkoxy _C1-6 alkyl groups include, but are not limited to, straight-chain or branched alkoxyalkyl groups such as fluoromethoxymethyl, chloromethoxymethyl, bromomethoxymethyl, iodomethoxymethyl, difluoromethoxymethyl, trifluoromethoxymethyl, 2,2,2-trifluoroethoxymethyl, etc., which are substituted with 1 to 9, preferably 1 to 5, halogen atoms.

Examples of _C3-8 cycloalkyl groups include, but are not specifically limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.

Examples of _C3-8 cycloalkyl and _C1-6 alkyl include, but are not specifically limited to, cyclopropylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclohexylmethyl, etc.

Examples of _C1-6 alkyl carbonyl groups include, but are not limited to, methyl carbonyl (acetyl), ethyl carbonyl (propionyl), n-propyl carbonyl (butyryl), isopropyl carbonyl (isobutyryl), n-butyl carbonyl (valeryl), isobutyl carbonyl (isovaleryl), sec-butyl carbonyl, tert-butyl carbonyl, and other _C1-6 straight-chain or branched alkyl carbonyl groups.

Examples of _C1-6 haloalkyl carbonyl groups include, but are not limited to, C1-6 straight-chain or branched alkyl carbonyl groups substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethyl carbonyl, chloromethyl carbonyl, bromomethyl carbonyl, iodomethyl carbonyl, dichloromethyl carbonyl, trichloromethyl carbonyl, difluoromethyl carbonyl, trifluoromethyl carbonyl, chlorodifluoromethyl carbonyl, bromodifluoromethyl carbonyl, dichlorofluoromethyl carbonyl, 2,2,2- _{trichloroethyl} carbonyl, 2,2,2-trifluoroethyl carbonyl, and pentafluoroethyl carbonyl.

Examples of aryl carbonyl groups include, but are not limited to, substituted or unsubstituted benzoyl groups such as benzoyl, tert-butylbenzoyl, etc.; substituted or unsubstituted naphthoyl groups such as 1-naphthoyl, 2-naphthoyl, etc.

Examples of aryloxycarbonyl groups include, but are not limited to, substituted or unsubstituted phenoxycarbonyl groups such as phenoxycarbonyl, 4-diaminophenoxycarbonyl, 4-fluorophenoxycarbonyl, and 4-tert-butylphenoxycarbonyl; and substituted or unsubstituted naphthoxycarbonyl groups such as 1-naphthoxycarbonyl and 2-naphthoxycarbonyl.

Examples of _C1-6 alkoxycarbonyl groups include, but are not limited to, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, and other _C1-6 straight-chain or branched alkoxycarbonyl groups.

Examples of _C1-6 haloalkoxycarbonyl groups include, but are not limited to, C1-6 straight-chain or branched alkoxycarbonyl groups substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethoxycarbonyl, chloromethoxycarbonyl, bromomethoxycarbonyl, iodomethoxycarbonyl, dichloromethoxycarbonyl, trichloromethoxycarbonyl, difluoromethoxycarbonyl, trifluoromethoxycarbonyl, 2,2,2-trifluoroethoxymethyl, pentafluoroethoxycarbonyl, _3,3,3 -trifluoropropoxycarbonyl, 4,4,4-trifluorobutoxycarbonyl, and pentafluoroisopropoxycarbonyl.

Examples of cyano _C1-6 alkyl groups include, but are not limited to, cyanomethyl, cyanoethyl, cyano-n-propyl, cyano-isopropyl, cyano-n-butyl, cyano-isobutyl, cyano-sec-butyl, cyano-tert-butyl, cyano-n-hexyl, and other cyano-substituted _C1-6 straight-chain or branched alkyl groups.

Examples of _cyanoC1-6 alkoxy groups include cyanomethoxy, cyanoethoxy, cyano-n-propoxy, cyano-isopropoxy, cyano-n-butoxy, cyano-isobutoxy, cyano-sec-butoxy, cyano-tert-butoxy, cyano-hexyloxy, and other cyano-substituted _C1-6 straight-chain or branched alkoxy groups.

Examples of _C2-6 alkenyl groups include, but are not limited to, vinyl, allyl, 2-butenyl, 3-butenyl, 1-methylallyl, etc.

Examples of C _2-6 haloalkenyl groups include, but are not specifically 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, etc.

Examples of C _2-6 ynyl groups include, but are not limited to, ethynyl, 2-propynyl (propynyl), 1-methyl-2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, etc.

Examples of C _2-6 halogenated alkynyl groups include, but are not specifically limited to, fluoroacetylene, bromoacetylene, chloroacetylene, iodoacetylene, 3,3,3-trifluoro-1-propynyl, etc.

Examples of _C1-6 alkylsulfonyl groups include, but are not limited to, methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, and other _C1-6 straight-chain or branched alkylsulfonyl groups.

Examples of _C1-6 haloalkylsulfonyl groups include, but are not limited to, C1-6 straight-chain or branched alkylsulfonyl groups substituted with 1 to 9, preferably 1 to 5, halogen atoms, of fluoromethylsulfonyl, chloromethylsulfonyl, bromomethylsulfonyl, iodomethylsulfonyl, dichloromethylsulfonyl, trichloromethylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, chlorodifluoromethylsulfonyl, bromodifluoromethylsulfonyl, dichlorofluoromethylsulfonyl, _2,2,2 -trichloroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, pentafluoroethylsulfonyl, etc.

Examples of _C1-6 alkyl sulfinyl groups include, but are not limited to, methyl sulfinyl, ethyl sulfinyl, n-propyl sulfinyl, isopropyl sulfinyl, n-butyl sulfinyl, isobutyl sulfinyl, sec-butyl sulfinyl, tert-butyl sulfinyl, and other _C1-6 straight-chain or branched alkyl sulfinyl groups.

Examples of _C1-6 halogenated alkyl sulfinyl groups include, but are not limited to, C1-6 straight-chain or branched alkyl sulfinyl groups substituted with 1 to 9, preferably 1 to 5, halogen atoms, of fluoromethyl sulfinyl, chloromethyl sulfinyl, bromomethyl sulfinyl, iodomethyl sulfinyl, dichloromethyl sulfinyl, trichloromethyl sulfinyl, difluoromethyl sulfinyl, trifluoromethyl sulfinyl, chlorodifluoromethyl sulfinyl, bromodifluoromethyl sulfinyl, dichlorofluoromethyl sulfinyl, 2,2,2- _{trichloroethyl} sulfinyl, 2,2,2-trifluoroethyl sulfinyl, pentafluoroethyl sulfinyl, etc.

Examples of _C1-6 alkylthio groups include, but are not limited to, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, and other _C1-6 straight-chain or branched alkylthio groups.

Examples of _C1-6 haloalkylthio groups include, but are not limited to, C1-6 straight-chain or branched alkylthio groups substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethylthio, chloromethylthio, bromomethylthio, iodomethylthio, dichloromethylthio, trichloromethylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, bromodifluoromethylthio, dichlorofluoromethylthio, 2,2,2 _- trichloroethylthio, 2,2,2-trifluoroethylthio, and pentafluoroethylthio.

Examples of _C3-8 cycloalkylsulfonyl groups include, but are not specifically limited to, cyclopropylsulfonyl, cyclobutylsulfonyl, cyclopentylsulfonyl, cyclohexylsulfonyl, etc.

Examples of _C3-8 cycloalkyl sulfinyl groups include, but are not limited to, cyclopropyl sulfinyl, cyclobutyl sulfinyl, cyclopentyl sulfinyl, cyclohexyl sulfinyl, etc.

Examples of _C3-8 cycloalkyl thio groups include, but are not limited to, cyclopropyl thio, cyclobutyl thio, cyclopentyl thio, cyclohexyl thio, etc.

Examples of _C3-8 cycloalkyl and _C1-6 alkylsulfonyl groups include, but are not limited to, cyclopropylmethylsulfonyl, 2-cyclopropylethylsulfonyl, 3-cyclopropylpropylsulfonyl, cyclohexylmethylsulfonyl, etc.

Examples of _C3-8 cycloalkyl and _C1-6 alkyl sulfinyl groups include, but are not limited to, cyclopropylmethyl sulfinyl, 2-cyclopropylethyl sulfinyl, 3-cyclopropylpropyl sulfinyl, cyclohexylmethyl sulfinyl, etc.

Examples of _C3-8 cycloalkyl _C1-6 alkylthio groups include, but are not limited to, cyclopropylmethylthio, 2-cyclopropylethylthio, 3-cyclopropylpropylthio, cyclohexylmethylthio, etc.

Examples of _C1-6 alkoxy- _C1-6 alkylsulfonyl groups include, but are not limited to, methoxymethylsulfonyl, ethoxymethylsulfonyl, n-propoxymethylsulfonyl, isopropoxymethylsulfonyl, n-butoxymethylsulfonyl, sec-butoxymethylsulfonyl, tert-butoxymethylsulfonyl, methoxyethylsulfonyl, etc., wherein the _C1-6 straight-chain or branched alkylsulfonyl group is replaced by a _C1-6 straight-chain or branched alkoxy group.

Examples of _C1-6 alkoxy- _C1-6 alkyl sulfinyl groups include, but are not limited to, methoxymethyl sulfinyl, ethoxymethyl sulfinyl, n-propoxymethyl sulfinyl, isopropoxymethyl sulfinyl, n-butoxymethyl sulfinyl, sec-butoxymethyl sulfinyl, tert-butoxymethyl sulfinyl, 2-methoxyethyl sulfinyl, etc., wherein the _C1-6 straight-chain or branched alkyl sulfinyl group is substituted with a _C1-6 straight-chain or branched alkoxy group.

Examples of _C1-6 alkoxy- _C1-6 alkylthio groups include, but are not limited to, methoxymethylthio, ethoxymethylthio, n-propoxymethylthio, isopropoxymethylthio, n-butoxymethylthio, sec-butoxymethylthio, tert-butoxymethylthio, 2-methoxyethylthio, etc., wherein the _C1-6 straight-chain or branched alkylthio group is replaced by a _C1-6 straight-chain or branched alkoxy group.

Examples of C _2-6 alkenyloxy groups include, but are not limited to, vinyloxy, 1-propenyloxy, isopropenyloxy, allyloxy, 2-butenyloxy, 3-butenyloxy, 1-methylallyloxy, etc.

Examples of C _2-6 haloenoxy groups include, but are not limited to, 2,2-dichlorovinyloxy, 2,2-dibromovinyloxy, 2,2-difluorovinyloxy, 2,2-dibromovinyloxy, 3,3-difluoro-2-allyloxy, 4,4-difluoro-3-butenyloxy, 4,4,4-trifluoro-2-butenyloxy, etc.

Examples of C _2-6 alkynyloxy groups include, but are not limited to, ethynyloxy, 2-propynyloxy, 1-methyl-2-propynyloxy, 1,1-dimethyl-2-propynyloxy, 1-butynyloxy, 2-butynyloxy, 3-butynyloxy, etc.

Examples of C _2-6 haloethynyloxy groups include, but are not limited to, fluoroethynyloxy, bromoethynyloxy, chloroethynyloxy, iodoethynyloxy, 3,3,3-trifluoro-1-propynyloxy, etc.

Examples of _C1-6 alkylsulfonyloxy groups include, but are not limited to, methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy, isopropylsulfonyloxy, n-butylsulfonyloxy, isobutylsulfonyloxy, sec-butylsulfonyloxy, tert-butylsulfonyloxy, and other _C1-6 straight-chain or branched alkylsulfonyl groups.

Examples of _C1-6 halogenated alkyl sulfonyloxy groups include, but are not limited to, C1-6 straight-chain or branched alkyl sulfonyloxy groups substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethylsulfonyloxy, chloromethylsulfonyloxy, bromomethylsulfonyloxy, iodomethylsulfonyloxy, dichloromethylsulfonyloxy, trichloromethylsulfonyloxy, difluoromethylsulfonyloxy, trifluoromethylsulfonyloxy, chlorodifluoromethylsulfonyloxy, bromodifluoromethylsulfonyloxy, dichlorofluoromethylsulfonyloxy, 2,2,2-trichloroethylsulfonyloxy, 2,2,2-trifluoroethylsulfonyloxy, and _{pentafluoroethylsulfonyloxy} .

Examples of _C1-6 alkyl sulfinyloxy groups include, but are not limited to, methyl sulfinyloxy, ethyl sulfinyloxy, n-propyl sulfinyloxy, isopropyl sulfinyloxy, n-butyl sulfinyloxy, isobutyl sulfinyloxy, sec-butyl sulfinyloxy, tert-butyl sulfinyloxy, and other _C1-6 straight-chain or branched alkyl sulfinyloxy groups.

Examples of _C1-6 halogenated alkyl sulfinyloxy groups include, but are not limited to, C1-6 straight-chain or branched alkyl sulfinyloxy groups substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethyl sulfinyloxy, chloromethyl sulfinyloxy, bromomethyl sulfinyloxy, iodomethyl sulfinyloxy, dichloromethyl sulfinyloxy, trichloromethyl sulfinyloxy, difluoromethyl sulfinyloxy, trifluoromethyl sulfinyloxy, chlorodifluoromethyl sulfinyloxy, bromodifluoromethyl sulfinyloxy, _{dichlorofluoromethyl} sulfinyloxy, 2,2,2-trichloroethyl sulfinyloxy, 2,2,2-trifluoroethyl sulfinyloxy, and pentafluoroethyl sulfinyloxy.

Examples of substituted or unsubstituted amino groups include, but are not specifically limited to, amino, monoalkylamino, dialkylamino, monoacylamino, etc. Examples of alkyl groups include the _C1-6 alkyl groups mentioned above. Examples of acyl groups include the _C1-6 alkoxycarbonyl, haloalkoxycarbonyl, arylcarbonyl, etc. mentioned above.

Examples of aryl groups include, but are not specifically limited to, phenyl, 1-naphthyl, 2-naphthyl, etc.

Examples of aryl _C1-6 alkyl groups include, but are not specifically limited to, benzyl, phenylethyl, phenyl-n-propyl, etc.

Examples of aryloxy groups include, but are not limited to, phenoxy, 1-naphthyloxy, 2-naphthyloxy, etc.

Examples of aryl C _1-6 alkoxy groups include, but are not limited to, benzyloxy, phenoxyethoxy, phenoxy-n-propoxy, phenyl-n-butoxy, 1-naphthylmethoxy, 2-naphthylmethoxy, etc.

Examples of arylsulfonyl groups include, but are not limited to, phenylsulfonyl, 1-naphthylsulfonyl, 2-naphthylsulfonyl, etc.

Examples of aryl sulfinyl groups include, but are not specifically limited to, phenyl sulfinyl, 1-naphthyl sulfinyl, 2-naphthyl sulfinyl, etc.

Examples of aryl thio groups include, but are not limited to, phenyl thio, 1-naphthyl thio, 2-naphthyl thio, etc.

Examples of aryl C _1-6 alkyl sulfonyl groups include, but are not limited to, benzyl methyl sulfonyl, phenyl ethyl sulfonyl, phenyl-n-propyl sulfonyl, phenyl-n-butyl sulfonyl, 1-naphthyl methyl sulfonyl, 2-naphthyl methyl sulfonyl, etc.

Examples of aryl C _1-6 alkyl sulfinyl groups include, but are not limited to, benzyl sulfinyl, phenyl ethyl sulfinyl, phenyl-n-propyl sulfinyl, phenyl-n-butyl sulfinyl, 1-naphthylmethyl sulfinyl, 2-naphthylmethyl sulfinyl, etc.

Examples of aryl _C1-6 alkylthio groups include, but are not limited to, benzyl thio, phenyl ethyl thio, phenyl-n-propyl thio, phenyl-n-butyl thio, 1-naphthyl methyl thio, 2-naphthyl methyl thio, etc.

All the aryl groups mentioned above may optionally be further substituted. Examples of the number of substituents include, but are not specifically limited to, 1 to 20 (preferably 1 to 10 and more preferably 1 to 5).

Examples of heterocyclic groups include, but are not limited to, thiophene, furanyl, tetrahydrofuranyl, dioxolane, dioxane, pyrrolyl, pyrrololinyl, pyrrolylalkyl, oxazolyl, isoxazolyl, oxazolinyl, oxazolinyl, isoxazolinyl, thiazolyl, isothiazolyl, thiazolinyl, thiazolinyl, isothiazolinyl, pyrazolyl, pyrazolinyl, imidazolyl, imidazolinyl, imidazolinyl, oxadiazolyl, oxadiazolinyl, thiadiazolinyl, triazolyl, triazolinyl, triazolinyl Tetrazolyl, tetrazolinyl, pyridyl, dihydropyridyl, tetrahydropyridyl, piperidinyl, oxazinyl, dihydrooxazinyl, morpholinyl, thiazinyl, dihydrothiazinyl, thiamorpholino, pyridazinyl, dihydropyridazinyl, tetrahydropyridazinyl, hexahydropyridazinyl, oxadiazinyl, dihydrooxadiazinyl, tetrahydrooxadiazinyl, thiadiazolyl, thiadiazinyl, dihydrothiadiazinyl, tetrahydrothiadiazinyl, pyrimidinyl, dihydropyrimidinyl, tetrahydropyrimidinyl, hexahydropyrimidinyl Hydropyrimidinyl, pyrazinyl, dihydropyrazinyl, tetrahydropyrazinyl, piperazinyl, triazinyl, dihydrotriazinyl, tetrahydrotriazinyl, hexahydrotriazinyl, tetraazinyl, dihydrotetraazinyl, indoleyl, indolyl, isoindolyl, indazoleyl, quinazolinyl, dihydroquinazolinyl, tetrahydroquinazolinyl, carbazoleyl, benzoxazolinyl, benzoxazolinyl, benzoisoxazolinyl, benzoxisoxazolinyl, benzothiazolyl, benzoisothiazolyl, benzoisothiazolyl, benzimidazoleyl, indazolelinyl, quin Phinyl, dihydroquinolinyl, tetrahydroquinolinyl, isoquinolinyl, dihydroisoquinolinyl, tetrahydroisoquinolinyl, pyridinoindolyl, dihydrobenzoxazinyl, phylinyl, dihydrophylinyl, tetrahydrophylinyl, phthalazinyl, dihydrophthalazinyl, tetrahydrophthalazinyl, quinoxalinyl, dihydroquinoxalinyl, tetrahydroquinoxalinyl, purine, dihydrobenzotriazinyl, dihydrobenzotetraazinyl, phenothiazinylfuranyl, benzofuranyl, benzodihydropyranyl (chromanyl), benzothiopheneyl, etc.

These heterocyclic groups include those that are substituted at any substituted position by an oxo or thionyl group.

Examples of heterocyclic _C1-6 alkyl groups include, but are not specifically limited to, 2-pyridylmethyl, 3-pyridylmethyl, 2-pyrazinylmethyl, pyrimidinylmethyl, 2-quinolinylmethyl, etc.

Examples of heterocyclic groups include, but are not limited to, 2-pyridyloxy, 3-pyridyloxy, 2-pyrazinyloxy, pyrimidinyloxy, 2-quinolinylmethyloxy, etc.

All the heterocycles mentioned above may optionally be further substituted. Examples of the number of substituents include, but are not specifically limited to, 1 to 20 (preferably 1 to 10, and more preferably 1 to 5).

^R5 and ^R6, together with their bonded carbon atoms, can bond to each other, with or without at least one heteroatom, to form 3 to 8-membered rings.

Examples of heteroatoms in the specification include, but are not limited to, oxygen, sulfur, and nitrogen atoms. Examples of 3- to 8-membered rings include, but are not limited to, _C3-8 cycloalkyl groups such as cyclopropane and cycloheptane; and heterocycles such as tetrahydropyran and piperidine.

^R7 and ^R8 , ^R8 and ^R9 , ^R9 and ^R10 , or ^R10 and ^R11, together with the benzene ring they are bonded to, may or may not be bonded to each other via at least one heteroatom to form 3- to 8-membered rings. Examples of _3- to 8-membered rings include: C3-8 cycloalkyl, aryl, heterocyclic, etc. _C3-8 cycloalkyl, aryl, and heterocyclic are as defined above.

Examples of "substituents" for the groups substituted above include, but are not limited to, halogens, nitro groups, cyano groups, hydroxyl groups, formyl groups, _C1-6 alkyl groups, _C1-6 haloalkyl groups, _C1-6 alkoxy groups, _C1-6 haloalkoxy groups, _{C1-6 alkyl} groups, _C1-6 haloalkoxy groups _{, C1-6 alkyl groups, C3-8 cycloalkyl groups} , _C3-8 cycloalkyl groups, _C1-6 alkyl groups, _C1-6 alkyl carbonyl groups, C1-6 haloalkyl carbonyl groups, aryl carbonyl groups, aryloxy carbonyl groups, _C1-6 alkoxy carbonyl groups, _C1-6 haloalkoxy carbonyl groups, _C1-6 cyanoalkyl groups, _C1-6 cyanoalkoxy groups, _C2-6 alkenyl groups, _C2-6 haloalkenyl groups, _C2-6 alkynyl groups, C2-6 haloalkynyl groups, _C1-6 alkylsulfonyl groups, _C1-6 alkyl ... _1-6 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 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 alkenoxy _{, C2-6 haloalkenoxy, C2-6 alkynyloxy , C2-6 haloalkynyloxy , C1-6 alkylsulfonyloxy ,} C _1-6 haloalkylsulfonyloxy, _C1-6 alkylsulfinyloxy, _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, etc. Among these substituents, preferred substituents are halogens, nitro groups, _C1-6 alkyl groups, _C1-6 haloalkyl groups, _C1-6 alkoxy groups, _C1-6 haloalkoxy groups, _C1-6 alkylsulfonyl groups, _C1-6 haloalkylsulfonyl groups, _C1-6 alkylsulfinyl groups, _C1-6 haloalkylsulfinyl groups, _C1-6 alkylthio groups, _C1-6 haloalkylthio groups, substituted or unsubstituted amino groups, aryl groups, and heterocyclic groups, and more preferred substituents are fluorine, chlorine, nitro groups, methyl groups, ethyl groups, trifluoromethyl groups, methoxy groups, and trifluoromethoxy groups.

Preferred substituted aryl groups are halogen-substituted aryl groups, _C1-6 alkyl-substituted aryl groups, _C1-6 haloalkyl-substituted aryl groups, halogen and _C1-6 haloalkyl-substituted aryl groups, _C1-6 alkoxy-substituted aryl groups, _C1-6 haloalkoxy-substituted aryl groups, and _C1-6 alkylthio-substituted aryl groups. More preferred substituted aryl groups are chlorinated aryl groups, fluorinated aryl groups, trifluoromethyl-substituted aryl groups, chlorinated and trifluoromethyl-substituted aryl groups, trifluoromethoxy-substituted aryl groups, methoxy-substituted aryl groups, and methylthio-substituted aryl groups.

Preferred substituted heterocyclic groups are halogen-substituted heterocycles, _C1-6 alkyl-substituted heterocycles, _C1-6 haloalkyl-substituted heterocycles, _C1-6 alkoxy-substituted heterocycles, _C1-6 haloalkoxy-substituted heterocycles, and _C1-6 alkylthio-substituted heterocycles. More preferred substituted heterocyclic groups are chlorine-substituted heterocycles, fluorine-substituted heterocycles, trifluoromethyl-substituted heterocycles, trifluoromethoxy-substituted heterocycles, methoxy-substituted heterocycles, and methylthio-substituted heterocycles.

The salt of the compound represented by formula (1) can be any type of salt, as long as it is agriculturally acceptable. Examples of salts include inorganic acid salts such as hydrochloride, sulfate, and nitrate; organic acid salts such as acetate and methanesulfonate; alkali metal salts such as sodium and potassium salts; alkaline earth metal salts such as magnesium and calcium salts; quaternary ammonium salts such as dimethylammonium and triethylammonium; etc.

X represents oxygen or sulfur.

The symbol n represents an integer from 0 to 2.

In the compound (1) of the present invention, the preferred compound is a compound in which R ¹ is a C _1-6 haloalkyl group, and the more preferred compound (1) is a compound in which R ¹ is a trifluoromethyl or trifluoroethyl group.

In the compound (1) of the present invention, the preferred compound is one in which ^R2 is hydrogen, halogen or _C1-6 alkyl, and the more preferred compound (1) is one in which ^R2 is fluorine, chlorine, bromine or methyl.

In the compound (1) of the present invention, the preferred compound is one in which ^R3 is hydrogen, halogen or _C1-6 alkyl, and the more preferred compound (1) is one in which ^R3 is fluorine, chlorine, bromine, methyl or trifluoromethyl.

In the compound (1) of the present invention, the preferred compound is one in which ^R4 is hydrogen, _C1-6 alkyl, _C2-6 alkenyl, _C2-6 alkynyl or _C1-6 haloalkyl, and the more preferred compound (1) is one in which ^R4 is hydrogen, methyl, ethyl, n-propyl, n-butyl, 3,3,3-trifluoro-n-propyl, pentafluoroisopropyl or propargyl.

In the compound (1) of the present invention, the preferred compound is one in which ^R5 and ^R6 are the same or different and each represents hydrogen, halogen or _C1-6 alkyl, and the more preferred compound (1) is one in which ^R5 and ^R6 are hydrogen, fluorine, methyl, isopropyl or tert-butyl.

In the compound (1) of the present invention, the preferred compound is one in which ^R7 , ^R8 , ^R9 , ^R10 and ^R11 are: hydrogen, halogen, nitro, cyano, _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 unsubstituted aryl, substituted or unsubstituted heterocyclic or substituted or unsubstituted heterocyclic; the more preferred compound is one in which R7, ^R8 , ^R9 , ^R10 and ^R11 are: hydrogen, halogen, nitro, _C1-6 alkyl, C1-6 alkyl, _C1-6 alkylsulfonyl, C1-6 alkylsulfonyl, C1-6 alkylthio ...sulfonyl, C1-6 alkylthio, C1-6 alkylsulfonyl, C1-6 alkylsulfonyl, C1-6 alkylsulfonyl, C1-6 alkylsulfonyl, ^C1-6 alkylsulfonyl, C1-6 alkylsulfonyl, C1-6 alkylsulfonyl, C1-6 alkylsulfonyl, C1-6 alkylsulfonyl, C1-6 alkylsulfonyl, _C1-6 alkylsulfonyl, C1-6 _1-6 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 unsubstituted aryl, or substituted or unsubstituted heterocycle; and another more preferred compound ( ₁ ) is a compound wherein ^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, 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-trifluoromethylphenyl, 3-chloro-5-trifluoromethylphenyl, 4-chloro-3-trifluoromethylphenyl, 2-trifluoromethoxyphenyl, 3-trifluoromethoxyphenyl, 4-trifluoromethoxyphenyl, 4-methoxyphenyl, 2-methylphenylthio, 5-trifluoromethyl-2-pyridyl or 5-pyrimidinyl, ethylthio, n-propylthio, iso Propylthio, difluoromethylthio, 4-phenylphenyl, 4-cyanophenyl, 3-chlorophenyl, 2,3,4-trichlorophenyl, 3-trifluoromethoxyphenyl, 2,2,2-trifluoroethylthio, 2-(methylthio)-phenyl, 2,3-dichlorophenyl, 2,3,4-trifluorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 3,4-difluorophenyl, 3-(benzo[d][1,3]dioxacyclopenten-5-yl)phenyl, 3,5-dichlorophenyl, 4-(ethylthio)-phenyl, 4-acetylphenyl, or 4-(dimethylamino)-phenyl.

Alternatively, in the compound (1) of the present invention, the preferred compound is one in which ^R1 is _-CH2C ( ^X1 )( ^X2 )( ^X3 ), wherein ^X1 , ^X2 and ^X3 are the same or different and each represents a halogen; a more preferred compound (1) is one in which ^X1 , ^X2 and ^X3 are the same or different and each represents fluorine, chlorine or bromine; another more preferred compound (1) is one in which ^X1 , ^X2 and ^X3 are the same or different and each represents fluorine or chlorine; and the most preferred compound (1) is one in which ^X1 , ^X2 and ^X3 are fluorine.

In the compound (1) of the present invention, the preferred compound is one in which ^R2 is a methyl group.

In the compound (1) of the present invention, the preferred compound is a compound in which R ³ is a halogen; the more preferred compound is a compound in which R ³ is fluorine, chlorine or bromine; another more preferred compound is a compound in which R ³ is fluorine or chlorine; and the most preferred compound is a compound in which R ³ is fluorine.

In the compound (1) of the present invention, the preferred compound is a compound in which ^R4 is hydrogen, _C1-6 alkyl or _C1-6 haloalkyl; the more preferred compound (1) is a compound in which ^R4 is hydrogen, methyl or ethyl; the most preferred compound (1) is a compound in which ^R4 is hydrogen or methyl; and the most preferred compound (1) is a compound in which ^R4 is hydrogen.

In the compound (1) of the present invention, the preferred compound is one in which ^R5 and ^R6 are hydrogen or halogen; the more preferred compound is one in which ^R5 and ^R6 are the same or different and each represents hydrogen, fluorine, chlorine or bromine; another more preferred compound is one in which ^R5 and ^R6 are the same or different and each represents hydrogen, fluorine or chlorine; the still more preferred compound is one in which ^R5 and ^R6 are the same or different and each represents hydrogen or fluorine; and the most preferred compound (1) is one in which ^R5 and ^R6 are hydrogen.

In the compound (1) of the present invention, the preferred compound is one in which ^R7 , ^R8 , ^R10 and ^R11 are hydrogen.

In the compound (1) of the present invention, the preferred compound is one in which R ⁹ is -L-CH ₂ -C(X ⁴ )(X ⁵ )(X ⁶ ), wherein L is a single bond, oxygen or sulfur and X ⁴ , X ⁵ and X ⁶ are the same or different and each represents hydrogen or halogen; a more preferred compound (1) is one in which L is oxygen or sulfur and X ⁴ , X ⁵ and X ⁶ are the same or different and each represents halogen; another more preferred compound (1) is one in which L is oxygen or sulfur and X ⁴ , X ⁵ and X ⁶ are the same or different and each represents fluorine, chlorine or bromine; and a further more preferred compound (1) is one in which L is oxygen or sulfur and X ⁴ , X ⁵ and X ⁶ are the same or different and each represents fluorine or chlorine.

In the compound (1) of the present invention, the preferred compound is one in which X is oxygen or sulfur, and the more preferred compound (1) is one in which X is oxygen.

In the compound (1) of the present invention, the preferred compound is the compound in which n is 0.

In the compound (1) of the present invention, the preferred compound is one in which ^R7 , ^R8 , ^R10 and ^R11 are hydrogen atoms and ^R9 is a group of the following formula:

Where * represents the carbon atom adjacent to ^R9 ; ^R12 , ^R13 , ^R14 , ^R15 , and ^R16 are hydrogen, halogen, 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 cyanoalkyl, _C1-6 cyanoalkoxy, _C2-6 alkenyl, _C2-6 haloalkenyl, _C2-6 ynyl, _{C 2-6} 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 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} , C _2-6 haloalkynyloxy, _C1-6 alkylsulfonyloxy, C1-6 haloalkylsulfonyloxy, _C1-6 alkylsulfinyloxy, _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 alkylthio, heterocyclic, heterocyclic _{C1-6 alkyl} or heterocyclic oxy, all of which may optionally be further substituted; more preferably, compounds in which _R12 , ^R13 , ^R14 _, ^R15 and ^R16 are the same or different and ^each represents hydrogen, halogen, cyano, _C1-6 haloalkyl, C Compounds of _1-6 haloalkoxy or _C1-6 alkylthio groups; and more preferably compounds wherein ^R9 is one of the following: phenyl, 2-fluorophenyl, 2-chlorophenyl, 2-trifluoromethoxyphenyl, 2-(methylthio)phenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2-chloro-4-fluorophenyl, 2,3,4-trifluorophenyl, 2,3,4-trichlorophenyl, 3-fluorophenyl, 3-chlorophenyl, 3-trifluoromethylphenyl, 3-trifluoromethoxyphenyl, 3,4-difluorophenyl, 3,4-dichlorophenyl, 3,5-difluorophenyl, 3 5-Dichlorophenyl, 3-trifluoromethyl-4-chlorophenyl, 3-chloro-5-trifluoromethylphenyl, 3,4,5-trifluorophenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-methylphenyl, 4-methoxyphenyl, 4-trifluoromethylphenyl, 4-trifluoromethoxyphenyl, 4-cyanophenyl, 4-phenylphenyl, 4-acetylphenyl, 4-(dimethylamino)phenyl, 4-(methylthio)phenyl or 4-(ethylthio)phenyl.

When compound (1) has isomers such as optical isomers, stereoisomers, regioisomers, etc., any such isomers and mixtures thereof are included within the scope of compound (1). For example, when compound (1) has optical isomers, the optical isomers separated from the racemic mixture are also included within the scope of compound (1). Each of such isomers can be obtained as a single compound by known synthetic and separation methods (e.g., concentration, solvent extraction, column chromatography, recrystallization, etc.). 2. Method for preparing benzamide compounds and their salts.

There are no limitations on the method for preparing the benzamide compound (1) (compounds (1-1) and compounds (1-2)) of the present invention, and the benzamide compound (1) can be prepared by steps 1 to 5 as represented by reaction scheme 1 below:

[Reaction Scheme 1]

^R1 , ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 , X, and n are as defined above.

Step 1

An amide compound (hereinafter referred to as "compound (4)") represented by formula (2) can be prepared by reacting an aniline compound (hereinafter referred to as "compound (2)") represented by formula (3) with a benzyl carbonyl compound (hereinafter referred to as "compound (3)") represented by formula (reaction scheme 2):

[Reaction Scheme 2]

^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 , and X are as defined above.

Y represents a leaving group or hydroxyl group, and examples of leaving groups include: halogens, such as chlorine, bromine, and iodine; substituted or unsubstituted _C1-6 alkyl sulfonic acids; and substituted or unsubstituted aryl sulfonic acids. Examples of substituents include those mentioned above, such as halogens and _C1-6 haloalkyl groups.

Step 1A (when Y is a leaving basis)

The phenylacetamide compound represented by formula (4) (hereinafter referred to as "compound (2)") can be prepared by reacting the aniline compound represented by formula (2) (hereinafter referred to as "compound (3A)") with the benzyl carbonyl compound represented by formula (3A) (reaction scheme 3):

[Reaction Scheme 3]

^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 and X are as defined above. Y' represents the leaving group.

Examples of benzyl carbonyl compounds (3A) include, but are not limited to, substituted or unsubstituted phenylacetyl halides such as phenylacetyl chloride and phenylacetyl bromide; and substituted or unsubstituted phenyl acetates such as ethyl phenylacetate and methyl phenylacetate.

There is no specific limitation on the ratio of aniline compound (2) to benzyl carbonyl compound (3A) used in the reaction, and therefore it can be appropriately selected from a wide range. About 1 to 5 moles of benzyl carbonyl compound (3A) are typically used relative to 1 mole of aniline compound (2), and preferably about equimolar to 1.2 moles of benzyl carbonyl compound.

The reactions mentioned above can be carried out in the absence or presence of a base. In the above scenario, the reaction is preferably carried out in the presence of a base. Known bases can be widely used as bases, and examples of bases include: alkali metal carbonates such as sodium carbonate, potassium carbonate, cesium carbonate, potassium bicarbonate, and sodium bicarbonate; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; inorganic bases such as alkali metal hydrides, such as sodium hydride and potassium hydride; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium tert-butoxide; organic bases such as pyridine, triethylamine, diethylamine, dimethylamine, methylamine, imidazole, benzimidazole, diisopropylethylamine, 4-dimethylaminepyridine, and piperidine; etc. Any single base or a combination of two or more types of these bases can be used.

Relative to 1 mole of aniline compound (2), approximately 1 to 10 moles of base can usually be used in excess, and preferably approximately 1 to 5 moles of base. When using organic bases such as triethylamine and pyridine, they can be used in large excesses as reaction solvents as well.

The reactions mentioned above are carried out in a suitable solvent or in the absence of any solvent. When carrying out the reactions mentioned above in a solvent, there are no restrictions on the solvent, as long as the solvent is inactive for the reactions mentioned above. Examples of such solvents include: solvents based on fatty acids or alicyclic hydrocarbons such as n-hexane, cyclohexane, and n-heptane; solvents based on aromatic hydrocarbons such as benzene, chlorobenzene, toluene, and xylene; solvents based on halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, and carbon tetrachloride; ether-based solvents such as diethyl ether, tetrahydrofuran (THF), and 1,4-dioxane; ester solvents such as methyl acetate and ethyl acetate; acetonitrile; amide-based solvents such as N,N-dimethylformamide (DMF); and sulfoxide-based solvents such as dimethyl sulfoxide. Any of these solvents may be used alone or in combination of two or more types as needed.

There is no specific limitation on the reaction temperature for the reactions mentioned above, and it is generally in the range between -10°C and the boiling point of the solvent used, and preferably 0 to 25°C. The reaction time depends on, for example, changes in the reaction temperature, and the reaction usually ends in about 0.5 to 24 hours.

Step 1B (when Y is a hydroxyl group)

As another method to obtain phenylacetamide compound (4), compound (4) can be prepared by reacting aniline compound (2) with phenylacetic acid compound represented by formula (3B) (hereinafter referred to as "compound (3B)") (reaction scheme 4):

[Reaction Scheme 4]

^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 and X are as defined above.

There is no specific limitation on the ratio of aniline compound (2) to phenylacetic acid compound (3B) used in the reaction, and therefore it can be appropriately selected from a wide range. About 1 to 5 moles of phenylacetic acid compound (3B) are typically used relative to 1 mole of aniline compound (2), and preferably about equimolar to 1.2 moles of phenylacetic acid compound.

The reactions mentioned above can be carried out with or without the presence of a condensing agent. In the above scenario, the reactions mentioned above are preferably carried out in the presence of a condensing agent. Known condensing agents can be used as condensing agents, and examples of condensing agents include 1-ethyl-3-(3-dimethylaminopropyl)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)phosphonic acid chloride (BOP-C1), propylphosphonic anhydride (T3P), etc. Any one of these condensing agents, or a combination of two or more types thereof, can be used.

Relative to 1 mole of aniline compound (2), 1 to 10 moles of condensing agent can usually be used in excess, and preferably about 1 to 3 moles of condensing agent.

The reactions mentioned above are carried out in a suitable solvent or in the absence of any solvent. When carrying out the reactions mentioned above in a solvent, there are no restrictions on the solvent, as long as the solvent is inactive for the reactions mentioned above. Examples of such solvents include: solvents based on fatty acids or alicyclic hydrocarbons such as n-hexane, cyclohexane, and n-heptane; solvents based on aromatic hydrocarbons such as benzene, chlorobenzene, toluene, and xylene; solvents based on halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, and carbon tetrachloride; ether-based solvents such as diethyl ether, THF, and 1,4-dioxane; ester solvents such as methyl acetate and ethyl acetate; acetonitrile; amide solvents such as DMF; and sulfoxide-based solvents such as dimethyl sulfoxide. Any of these solvents may be used alone, or a combination of two or more types of these solvents may be used if necessary.

There is no specific limitation on the reaction temperature for the reactions mentioned above, and it is generally in the range between -10°C and the boiling point of the solvent used, and preferably in the range between -5°C and the boiling point of the solvent. The reaction time varies depending on, for example, the reaction temperature, and the reaction usually ends in about 0.25 to 24 hours.

Step 1C

Note that, as a method for preparing phenylacetamide compound (4), phenylacetic acid halide compound (3C) obtained by reacting phenylacetic acid compound (3B) with a halogenating agent can be used as a raw material.

The reactions mentioned above can be carried out in the presence of a base. Any of the same bases described above can be used as the base, and preferred examples of the base include organic bases such as triethylamine, pyridine, di-isopropylamine, 4-diisopropylethylamine, 4-dimethylaminopyridine, and dimethylpyridine, and this base can also be used in excess as a reaction solvent.

Examples of halogenating reagents include, but are not limited to, _POCl3 , _POBr3 , _SOCl2 , _SO2Cl2 , and oxalyl _chloride .

For 1 mole of aniline compound (2), 1 to 10 moles of halogenating agent can typically be used, and preferably about 1 to 5 moles of halogenating agent.

The reactions mentioned above are carried out in a suitable solvent or in the absence of any solvent. When carrying out the reactions mentioned above in a solvent, there are no restrictions on the solvent, as long as the solvent is inactive for the reactions mentioned above. The solvents mentioned above are listed as such solvents. Any of these solvents may be used alone or in combination of two or more types if necessary.

There is no specific limitation on the reaction temperature for the reactions mentioned above, and it is generally in the range between -10°C and the boiling point of the solvent used, and preferably in the range between -5°C and the boiling point of the solvent. The reaction time varies depending on, for example, the reaction temperature, and the reaction usually ends in about 0.25 to 24 hours.

The aniline compound (2), benzyl carbonyl compound (3A), phenylacetic acid compound (3B), and phenylacetic acid halide compound (3C) used as starting materials in step 1 are known compounds or compounds that can be easily prepared by known methods.

The compound (4) obtained by the method shown in step 1 can be easily separated from the reaction mixture to be purified by using typical separation and purification methods (e.g., filtration, solvent extraction, distillation, recrystallization, column chromatography, etc.).

After the reaction is complete, compound (4) can be provided for the next reaction without being separated from the reaction system.

Step 2 can be performed by chlorosulfonamide compound (4) (reaction scheme 5) to prepare the sulfonyl chloride compound represented by formula (5) (hereinafter referred to as "compound (5)"):

[Reaction Scheme 5]

^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 and X are as defined above.

There are no specific limitations on the reagents used for chlorosulfonation, and they include, for example, chlorosulfonic acid. When chlorosulfonic acid is used, this step can be performed in one step. For chlorosulfonation, a two-step method (including sulfonation followed by chlorination) can be used. Sulfonyl chloride compounds (5) can be prepared by reacting an amide compound with a sulfonating agent to prepare a _HOSO₂ -substituted amide compound, and then reacting the _HOSO₂ -containing amide compound with a chlorinating agent.

There are no specific restrictions on the reagents used for sulfation, and examples include chlorosulfonic acid and sulfuric acid. Examples of chlorinating agents used for chlorination include, but are not specifically limited to, chlorine, _POCl3 , _SOCl2 , _SO2Cl2 , and oxalyl _chloride .

When using chlorosulfonic acid, there is no specific limitation on the ratio of amide compound (4) to chlorosulfonic acid used in the reaction and it can be appropriately selected from a wide range. About 1 to 50 moles of chlorosulfonic acid are typically used relative to 1 mole of amide compound (4), and preferably about 1 to 20 moles of chlorosulfonic acid.

When using a sulfonating agent and a chlorinating agent, the ratio of the sulfonating agent to the chlorinating agent used in the reaction between the amide compound (4) and the sulfonating agent is not specifically limited and can be appropriately selected from a wide range. About 1 to 50 moles of the sulfonating agent are typically used relative to 1 mole of the amide compound (4), and preferably about 1 to 20 moles of the sulfonating agent. The ratio of the two used in the reaction between the amide compound (4) and the chlorinating agent is not specifically limited and can be appropriately selected from a wide range. About 1 to 50 moles of sulfuric acid are typically used relative to 1 mole of the amide compound (1), and preferably 1 to 20 moles of sulfuric acid.

The reactions mentioned above are carried out in a suitable solvent or in the absence of any solvent. When carrying out the reactions mentioned above in a solvent, there are no restrictions on the solvent, as long as the solvent is inactive for the reactions mentioned above. Examples of such solvents are listed as those described above. Any of these solvents may be used alone or in combination of two or more types if necessary.

There is no specific limitation on the reaction temperature for the reactions mentioned above, and it is generally in the range between -20°C and the boiling point of the solvent used, preferably -10°C to 150°C, and more preferably 0°C to 100°C. The reaction time varies depending on, for example, the reaction temperature, and the reaction usually ends in about 0.25 to 24 hours.

The sulfonyl chloride compound (5) obtained by the method shown in step 2 can be easily separated from the reaction mixture to be purified by using typical separation and purification methods (e.g., filtration, solvent extraction, distillation, recrystallization, column chromatography, etc.).

After the reaction is complete, sulfonyl chloride compound (5) can be provided for the next reaction without being separated from the reaction system.

Step 3

The thiol compound represented by formula (6) (hereinafter referred to as "compound (6)") can be prepared by reacting the sulfonyl chloride compound (5) with a reducing agent (reaction scheme 6):

[Reaction Scheme 6]

^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 and X are as defined above.

There are no specific limitations on the ratio of sulfonyl chloride compound (5) to reducing agent used in the reaction, and it can be appropriately selected from a wide range. About 1 to 50 moles of reducing agent are typically used relative to 1 mole of sulfonyl chloride compound (5), and more preferably about 1 to 20 moles of reducing agent.

Any commonly known reducing agent can be widely used as a reducing agent, and examples of reducing agents include: phosphorus compounds such as triphenylphosphine; reducing agents containing metals and acids (e.g., zinc and acid, tin(II) and acid, and iron and acid); and specific reducing agents such as red phosphorus, iodine, dichlorodimethylsilane-zinc-dimethylacetamide, and lithium aluminum hydride. Examples of acids include organic acids such as acetic acid; and inorganic acids such as hydrochloric acid and sulfuric acid.

The reactions mentioned above are carried out in suitable solvents. There are no restrictions on the solvent, as long as it is inactive for the reaction. Examples of such solvents are listed above. Any of these solvents may be used alone or in combination of two or more types if necessary.

There is no specific limitation on the reaction temperature for the reactions mentioned above, and it is generally in the range between -20°C and the boiling point of the solvent used, preferably -10°C to 150°C, and more preferably 20°C to 120°C. The reaction time varies depending on, for example, the reaction temperature, and the reaction usually ends in about 0.25 to 24 hours.

The thiol compounds (6) obtained by the method shown in step 3 can be easily separated from the reaction mixture to be purified by using typical separation and purification methods (e.g., filtration, solvent extraction, distillation, recrystallization, column chromatography, etc.).

After the reaction is complete, thiol compound (6) can be provided for the next reaction without being separated from the reaction system.

Method for preparing thioether compounds or salts thereof represented by formula (1-1)

Examples of methods for preparing thioether compounds represented by formula (1-1) include, but are not limited to, preparation routes 1, 2, 3, and 4 described below.

Preparation method 1 (step 4)

Thiol compounds (1-1) can be prepared by reacting a thiol compound (6) with an alkyl reagent represented by formula (7) (hereinafter referred to as "alkyl reagent (7)") (reaction scheme 7):

[Reaction Scheme 7]

^R1 , ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 and X are defined as above, and G represents the leaving basis.

Examples of leaving bases are listed below, which are the same leaving bases as those described above.

There is no specific limitation on the ratio of the thiol compound (6) to the alkyl reagent (7) used in the reaction, and it can be appropriately selected from a wide range. About 1 to 10 moles of alkyl reagent (7) are usually used relative to 1 mole of thiol compound (6), and preferably about 1 to 5 moles of alkyl reagent.

Examples of alkyl reagents (7) include, but are not limited to, _C1-6 alkyl halides such as iodomethane and ethyl bromide; _C1-6 haloalkyl halides such as trifluoroiodomethane, trifluoromethyl bromide, trifluoroiodoethane, and trifluoroethyl bromide; etc.

The reactions mentioned above can be carried out in the presence of a base. In the above scenario, the reactions mentioned above are preferably carried out in the presence of a base. As examples of bases, conventionally known bases can be widely used, and any of the same bases described above can be used.

For every 1 mole of thiol compound (6), 1 to 10 moles of base can typically be used, and preferably about 1 to 3 moles of base. When using organic bases such as triethylamine and pyridine, they can be used in large excess as reaction solvents.

The reactions mentioned above can be carried out by further adding a free radical initiator. Examples of free radical initiators include, but are not limited to, sulfurous acid, sulfites, and sulfite adducts such as Rongalit (product name, sodium formaldehyde sulfoxylate). Bases and free radical initiators can be used in combination.

When using a free radical initiator, as an addition dose, 0.1 to 10 moles of free radical initiator can typically be used relative to 1 mole of thiol compound (6), and preferably about 0.1 to 5 moles of free radical initiator.

The reactions mentioned above are carried out in appropriate solvents. Examples of solvents include: solvents based on fatty acids or alicyclic hydrocarbons such as n-hexane, cyclohexane, and n-heptane; solvents based on aromatic hydrocarbons such as benzene, chlorobenzene, toluene, and xylene; solvents based on halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, and carbon tetrachloride; ether-based solvents such as diethyl ether, THF, and 1,4-dioxane; ester-based solvents such as methyl acetate and ethyl acetate; acetonitrile; amide-based solvents such as DMF, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide-based solvents such as dimethyl sulfoxide; alcohol-based solvents, such as aprotic polar solvents like sulfolane, methanol, ethanol, and isopropanol; water; etc. Any of these solvents may be used alone or in combination of two or more types as needed.

There is no specific limitation on the reaction temperature for the reactions mentioned above, and it is generally in the range between -20°C and the boiling point of the solvent used, preferably -10°C to 60°C, and more preferably 0°C to 50°C. The reaction time varies depending on, for example, the reaction temperature, and the reaction usually ends in about 0.25 to 24 hours.

The thioether compounds (1-1) obtained by the method shown in step 4 can be readily separated from the reaction mixture to be purified by using typical separation and purification methods (e.g., filtration, solvent extraction, distillation, recrystallization, column chromatography, etc.).

After the reaction is complete, the thioether compound (1-1) can be provided for the next reaction without being separated from the reaction system.

Preparation method 2

The sulfide compound represented by formula (1-1b) (hereinafter referred to as "compound (1-1a)") can be prepared by reacting the sulfide compound represented by formula (1-1a) with the compound represented by formula (7'): R4'-G (hereinafter referred to as "compound (7')" (reaction scheme 8):

[Reaction Scheme 8]

Where ^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 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 , C1-6} alkoxycarbonyl, _C1-6 haloalkoxycarbonyl, arylcarbonyl, aryloxycarbonyl, _C2-6 alkenyl, _C2-6 haloalkenyl, _C2-6 alkynyl _{, C2-6 haloalkynyl} , C _1-6 alkylsulfonyl, _C1-6 haloalkylsulfonyl, _C1-6 alkylsulfinyl, C1-6 haloalkylsulfinyl _{, C1-6} alkylthio, _C1-6 haloalkylthio, aryl, _arylC1-6 alkyl, arylsulfonyl, arylsulfinyl, arylthio, and heterocyclic groups, and these groups may optionally be further substituted. G indicates a leaving group.

Examples of leaving bases are listed above.

There is no specific limitation on the ratio of the thioether compound (1-1a) to the compound (7’) used in the reaction, and it can be appropriately selected from a wide range. About 1 to 10 moles of the compound (7’) are usually used relative to 1 mole of the thioether compound (1-1a), and preferably about equimolar to 5 moles of the compound (7’).

The reactions mentioned above can be carried out in the presence of a base. In the above scenario, the reactions mentioned above are preferably carried out in the presence of a base. Commonly known bases can be used, and any of the same bases described above can be used as the base.

Relative to 1 mole of the sulfide compound (1-1a), a stoichiometric amount of base or an excess of base mentioned above may be used. Preferably, an excess of 1 to 10 times, and more preferably 1 to 5 times, of base may be used. When using organic bases such as triethylamine or pyridine, they may be used in large excesses as reaction solvents.

The reactions mentioned above are carried out in suitable solvents. Examples of solvents include: solvents based on fatty acids or alicyclic hydrocarbons such as n-hexane, cyclohexane, and n-heptane; solvents based on aromatic hydrocarbons such as benzene, chlorobenzene, toluene, and xylene; solvents based on halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, and carbon tetrachloride; ether-based solvents such as diethyl ether, THF, and 1,4-dioxane; ester solvents such as methyl acetate and ethyl acetate; acetonitrile; amide-based solvents such as DMF, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide-based solvents such as dimethyl sulfoxide; alcohol-based solvents, such as aprotic polar solvents like sulfolane, methanol, ethanol, and isopropanol; and water. Any of these solvents may be used alone or in combination of two or more types if necessary.

There is no specific limitation on the reaction temperature for the reactions mentioned above, and it is generally in the range between -20°C and the boiling point of the solvent used, preferably -10°C to 60°C, and more preferably 20°C to 50°C. The reaction time varies depending on, for example, the reaction temperature, and the reaction usually ends in about 0.25 to 24 hours.

The thioether compounds (1-1b) obtained by the method shown in step 4 can be readily separated from the reaction mixture to be purified by using typical separation and purification methods (e.g., filtration, solvent extraction, distillation, recrystallization, column chromatography, etc.).

After the reaction is complete, the thioether compound (1-1b) can be provided for the next reaction without being separated from the reaction system.

The thioether compound (1-1) can be prepared not only according to the preparation routes mentioned above, but also according to preparation routes 3, 4 and 5.

Preparation route 3

The thioether compound (1-1a) can be prepared by reacting an aniline compound (hereinafter referred to as "compound (8)") with a phenylacetic acid compound (3) (reaction scheme 9):

[Reaction Scheme 9]

^R1 , ^R2 , ^R3 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 , X, and Y are as defined above.

Preparation route 3A (when Y is a leaving group)

The thioether compound (1-1a) can be prepared by reacting the aniline compound (8) with the benzyl carbonyl compound (3A) (reaction scheme 10):

[Reaction Scheme 10]

^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 and X are defined above, and Y' represents the leaving basis.

Examples of benzyl carbonyl compounds (3A) include, but are not specifically limited to, those same as those in step 1A.

Aniline compounds (8) used as starting materials can be prepared according to the method described in WO2007/131680.

There is no specific limitation on the ratio of aniline compound (8) to benzyl carbonyl compound (3A) used in the reaction, and therefore it can be appropriately selected from a wide range. About 1 to 5 moles of benzyl carbonyl compound (3A) are typically used relative to 1 mole of aniline compound (8), and preferably about equimolar to 1.2 moles of benzyl carbonyl compound (3A).

The reactions mentioned above can be carried out in the absence or presence of a base. In the above scenario, the reactions mentioned above are preferably carried out in the presence of a base. As examples of bases, any of the same bases shown in step 1 above can be used. Any single one of these bases or a combination of two or more of these bases can be used.

For 1 mole of aniline compound (8), a stoichiometric amount of base or an excess of base mentioned above may be used.

Preferably, an excess of 1 to 5 times the amount of base can be used. When using organic bases such as triethylamine and pyridine, they can also be used in large excesses as reaction solvents.

The reactions mentioned above are carried out in a suitable solvent or in the absence of any solvent. When carrying out the reactions mentioned above in a solvent, any of the same solvents shown in step 1 above can be used. Any of these solvents can be used alone or in combination of two or more types if necessary.

There is no specific limitation on the reaction temperature for the reactions mentioned above, and it is generally in the range between -20°C and the boiling point of the solvent used, preferably 0 to 50°C. The reaction time varies depending on, for example, the reaction temperature, and the reaction usually ends in about 0.5 to 24 hours.

The aniline compound (8) used as a starting material is a known compound or a compound that can be easily prepared by known methods.

Thioether compounds can be readily separated from the reaction mixture to be purified using typical separation and purification methods (e.g., filtration, solvent extraction, distillation, recrystallization, column chromatography, etc.).

After the reaction is complete, the thioether compound (1-1a) can be provided for the next reaction without being separated from the reaction system.

Step 3B (when Y is a hydroxyl group)

As another method for obtaining phenylacetamide compound (1-1a), compound (1-1a) can be prepared by reacting aniline compound (8) with phenylacetic acid compound (3B) (reaction scheme 11):

[Reaction Scheme 11]

^R1 , ^R2 , ^R3 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 and X are as defined above.

There is no specific limitation on the ratio of aniline compound (8) to phenylacetic acid compound (3B) used in the reaction, and therefore it can be appropriately selected from a wide range. About 1 to 5 moles of phenylacetic acid compound (3B) are typically used relative to 1 mole of aniline compound (8), and preferably equimolar to 1.2 moles of phenylacetic acid compound (3B).

The reactions mentioned above can be carried out with or without the condensing agent. In the above scenario, the reactions mentioned above are preferably carried out in the presence of the condensing agent. Examples of condensing agents are listed, which are the same condensing agents shown in step 1B. Any single one of these condensing agents or a combination of two or more types thereof can be used.

A stoichiometric amount of condensing agent or an excess of the amount mentioned above may be used relative to 1 mole of aniline compound (8). Preferably, an excess of about 1 to 5 times the amount of condensing agent may be used.

The reactions mentioned above can be carried out in the absence or presence of a base. In the above scenario, the reactions mentioned above are preferably carried out in the presence of a base. Any of the same bases as those shown in step 1 above can be used as the base. Any single one of these bases or a combination of two or more of these bases can be used.

A stoichiometric amount of base or an excess of the amount mentioned above can be used relative to 1 mole of aniline compound (8). Preferably, an excess of about 1 to 5 times the amount of base can be used. When using organic bases such as triethylamine or pyridine, they can be used in large excesses as reaction solvents.

The reactions mentioned above are carried out in a suitable solvent or in the absence of any solvent. When carrying out the reactions mentioned above in a solvent, any of the same solvents shown in step 1 above can be used. Any of these solvents can be used alone or in combination of two or more types if necessary.

There is no specific limitation on the reaction temperature for the reactions mentioned above, and it is generally in the range between -20°C and the boiling point of the solvent used, and preferably 0 to 25°C. The reaction time varies depending on, for example, the reaction temperature, and the reaction usually ends in about 0.5 to 24 hours.

Preparation method 3C

Note that, as a method for preparing phenylacetamide compound (1-1a), a phenylacetic acid halide compound (3C) obtained by reacting phenylacetic acid compound (3B) with a halogenating agent can be used as a material.

The reactions mentioned above can be carried out in the presence of a base. Any of the same bases described above can be used as the base, and preferred examples of bases include organic bases such as triethylamine, pyridine, di-isopropylamine, 4-diisopropylethylamine, 4-dimethylaminopyridine, and dimethylpyridine. The base can be used in excess as a reaction solvent.

Examples of halogen reagents include, but are not limited to, _POCl3 , _POBr3 , _SOCl2 , _SO2Cl2 and oxalyl _chloride .

For 1 mole of aniline compound (2), 1 to 10 moles of halogenating agent can typically be used, and preferably about 1 to 5 moles of halogenating agent.

The reactions mentioned above are carried out in a suitable solvent or in the absence of any solvent. When carrying out the reactions mentioned above in a solvent, there are no restrictions on the solvent, as long as the solvent is inactive for the reactions mentioned above. As examples of such solvents, the solvents mentioned above are listed. Any of these solvents may be used alone or in combination of two or more types if necessary.

There is no specific limitation on the reaction temperature for the reactions mentioned above, and it is generally in the range between 10°C and the boiling point of the solvent used, and preferably in the range between -5°C and the boiling point of the solvent. The reaction time varies depending on, for example, the reaction temperature, and the reaction usually ends in about 0.25 to 24 hours.

Thioether compounds can be readily separated from the reaction mixture to be purified using typical separation and purification methods (e.g., filtration, solvent extraction, distillation, recrystallization, column chromatography, etc.).

After the reaction is complete, the thioether compound (1-1a) can be provided for the next reaction without being separated from the reaction system.

Preparation method 4

The thioether compound (1-1) can be prepared by reacting a thioether compound (hereinafter referred to as "compound (9)") with an amide compound represented by formula (10) (hereinafter referred to as "compound (10)") (reaction scheme 12):

[Reaction Scheme 12]

^R1 , ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 and X are defined above, and Z represents the leaving basis.

There is no specific limitation on the ratio of the thioether compound (9) to the amide compound (10) used in the reaction, and it can be appropriately selected from a wide range. About 1 to 10 moles of amide compound (10) are usually used relative to 1 mole of thioether compound (9), and preferably about equimolar to 5 moles of amide compound (10).

The reactions mentioned above can be carried out in the absence or presence of a base. In the above scenario, the reactions are preferably carried out in the presence of a base. Any of the same bases shown in step 1 above can be used as the base. Any single one of these bases or a combination of two or more of these bases can be used.

Relative to 1 mole of aniline compound (9), 1 to 10 moles of base are typically used, and preferably about 1 to 5 moles of base.

The reactions mentioned above are carried out in a suitable solvent or in the absence of any solvent. When carrying out the reactions mentioned above in a solvent, any of the same solvents shown in step 1 above can be used. Any of these solvents can be used alone or in combination of two or more types if necessary.

There is no specific limitation on the reaction temperature for the reactions mentioned above, and it is generally between -10°C and the boiling point of the solvent used, and preferably between -0°C and the boiling point of the solvent. The reaction time varies depending on, for example, the reaction temperature, and the reaction usually ends in about 0.5 to 24 hours.

Thioether compounds (9) used as starting materials can be prepared according to the methods described in EP3002279 and WO2012/176856.

Thioether compounds can be readily separated from the reaction mixture to be purified using typical separation and purification methods (e.g., filtration, solvent extraction, distillation, recrystallization, column chromatography, etc.).

After the reaction is complete, the thioether compound (1-1) can be provided for the next reaction without being separated from the reaction system.

Step 5

The benzamide compound represented by formula (1-2) (hereinafter referred to as "compound (1-2)") can be prepared by reacting the sulfide compound represented by formula (1-1) with an oxidizing agent (reaction scheme 13):

[Reaction Scheme 13]

^R1 , ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 , X and n' are as described above.

There are no specific limitations on the ratio of benzamide compound (1-1) to oxidant used in the reaction, and it can be appropriately selected from a wide range. About 1 to 10 moles of oxidant are typically used relative to 1 mole of benzamide compound (1-1), and preferably about equimolar to 5 moles of oxidant.

The reactions mentioned above can be carried out in the presence of an oxidizing agent. Any known oxidizing agent can be used, provided it can oxidize the sulfide to sulfoxide. Examples of oxidizing agents include combinations of the following: peracids such as performic acid, peracetic acid, pertrifluoroacetic acid, peroxybenzoic acid, m-chloroperoxybenzoic acid (mCPBA), and o-carbonylperoxybenzoic acid; alkyl hydroperoxides such as hydrogen peroxide, tert-butyl hydroperoxide, and cumene hydroperoxide; titanium tetraols such as tetraisopropoxide; dichromates such as sodium dichromate and potassium dichromate; and permanganates such as permanganic acid, sodium permanganate, and potassium permanganate; etc. Any single oxidizing agent or a combination of two or more of these oxidizing agents may be used.

Relative to 1 mole of benzamide compound (1-1), an excess of stoichiometric amount of oxidant or an excess of the amount mentioned above may be used. Preferably, 1 to 10 times the amount of oxidant, and more preferably about 1 to 5 times the amount of oxidant, may be used.

The reactions mentioned above can be further carried out by adding a catalyst.

The reactions mentioned above are carried out in appropriate solvents. Examples of solvents include: solvents based on fatty acids or alicyclic hydrocarbons such as n-hexane, cyclohexane, and n-heptane; solvents based on aromatic hydrocarbons such as benzene, chlorobenzene, toluene, and xylene; solvents based on halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, and carbon tetrachloride; ether-based solvents such as diethyl ether, THF, and 1,4-dioxane; ester solvents such as methyl acetate and ethyl acetate; acetonitrile; amide-based solvents such as DMF, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide-based solvents such as dimethyl sulfoxide; and alcohol-based solvents, such as sulfolane, methanol, ethanol, and isopropanol, which are aprotic polar solvents. Any of these solvents may be used alone or in combination of two or more types, if necessary.

There is no specific limitation on the reaction temperature mentioned above, and it is generally in the range between -20°C and the boiling point of the solvent used, preferably -10°C to 60°C, and more preferably 20°C to 50°C. The reaction time varies depending on, for example, the reaction temperature, and the reaction usually ends in about 0.25 to 24 hours.

The thioether compounds (1-2) obtained by the method shown in step 5 can be readily separated from the reaction mixture to be purified by using typical separation and purification methods (e.g., filtration, solvent extraction, distillation, recrystallization, chromatography, etc.).

Each compound (1) obtained after completing the reactions shown in reaction schemes 1 to 13 can be readily separated and purified from the reaction mixture by known separation and purification techniques such as filtration, solvent extraction, distillation, recrystallization and column chromatography.

When compound (1) has regioisomers, each regioisomer can be separated by commonly used separation steps (e.g., silica gel chromatography).

Pest control agents

The compound (1) of the present invention can be used as an active ingredient in pest control agents. Examples of pest control agents include agents for controlling pests, mites, nematodes, or soil pests that cause problems in farmland and horticultural fields (agricultural and horticultural insecticides, acaricides, nematicides, or soil insecticides); animal ectoparasite control agents (e.g., flea killers, acaricides (ixodicides), and pedivulicideon).

As an active ingredient for use as a pest control agent, the compound (1) of the present invention can be used as is without other components. However, it is generally preferred to use the compound by combining it with a solid carrier, liquid carrier or gaseous carrier (propellant) and optionally with surfactants and other adjuvants used in pharmaceutical preparations, and formulating the resulting mixture into various forms (e.g., oily solutions, emulsions, wettable powders, flowable formulations, granules, powders, aerosols, fumigants, etc.) according to known preparation methods.

The compound (1) of the present invention is typically contained in these formulations in proportions of 0.01 wt% to 95 wt%, and preferably 0.1 wt% to 50 wt%.

Examples of solid carriers that can be used in formulations include solid carriers in the form of fine powders or granules, such as clays (e.g., kaolin clay, diatomaceous earth, synthetic hydrated silica, bentonite, Fubasami clay, and acid clay), talc, ceramics, other inorganic minerals (e.g., diatomaceous earth, quartz, sulfur, activated carbon, calcium carbonate, and hydrated silica), and chemical fertilizers (e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and ammonium chloride); etc.

Examples of liquid carriers include water, alcohols (e.g., methanol and ethanol), ketones (e.g., acetone and methyl ethyl ketone), aromatic hydrocarbons (e.g., benzene, toluene, xylene, ethylbenzene and methylnaphthalene), aliphatic hydrocarbons (e.g., hexane, cyclohexane, kerosene and light oils), esters (e.g., ethyl acetate and butyl acetate), nitriles (e.g., acetonitrile and isobutyronitrile), ethers (e.g., diisopropyl ether and dioxane), amides (e.g., N,N-dimethylformamide and N,N-dimethylacetamide), halogenated hydrocarbons (e.g., dichloromethane, trichloroethane and carbon tetrachloride), dimethyl sulfoxide, soybean oil, cottonseed oil and other vegetable oils.

Examples of gaseous carriers include butane gas, LPG (liquefied petroleum gas), dimethyl ether, and carbon dioxide gas.

Examples of surfactants include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers, their polyoxyethylene adducts, polyethylene glycol ethers, polyol esters, sugar alcohol derivatives, etc.

Examples of adjuvants used in pharmaceutical preparations include fixatives, dispersants, and stabilizers.

Examples of fixatives and dispersants include casein, gelatin, polysaccharides (e.g., starch, gum arabic, cellulose derivatives, and alginate), lignin derivatives, bentonite, sugars, and water-soluble synthetic polymers (e.g., polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylic acid).

Examples of stabilizers include PAP (isopropyl acid phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (a mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol), vegetable oils, mineral oils, fatty acids and fatty acid esters, etc.

For the pest control agent of the present invention, the compound (1) is preferably used as is or by dilution with water or the like. The pest control agent of the present invention can be used by mixing with, for example, other pest control agents (e.g., known insecticides, nematicides, tick killers, fungicides), herbicides, plant growth regulators, synergists, soil conditioners, animal feed, etc., or can be used simultaneously with these agents without mixing.

The amount of the pest control agent of the present invention is not limited and can be appropriately selected from a wide range according to various conditions (e.g., concentration of active ingredient, form of formulation, type of disease and pest to be treated, plant type, severity of disease, application time, application method, chemicals to be used in combination (insecticides, nematicides, acaricides, fungicides, herbicides, plant growth controllers, synergists, soil conditioners, etc.) and amount and type of fertilizer).

When used as an insecticide, the compound (1) of the present invention is typically used in amounts from 0.01 g/100 ^m² to 500 g/100 ^m² , and preferably from 1 g/100 ^m² to 200 g/100 ^m² .

When used as an acaricide, the compound (1) of the present invention is typically used in amounts from 0.1 g/100 ^m² to 500 g/100 ^m² , and preferably from 1 g/100 ^m² to 200 g/100 ^m² .

When emulsions, wettable powders, flowable formulations, etc., are used by dilution with water, the concentration is from 0.1 ppm to 1,000 ppm, preferably from 1 ppm to 500 ppm. Granules, powders, etc., can be used as is without dilution.

The compound (1) of the present invention is characterized by having particularly excellent acaricidal activity and a broad activity spectrum.

The compound (1) of the present invention can be effectively used as an agricultural and horticultural insecticide, acaricide, nematicide or soil insecticide. Specifically, the compound (1) of this invention can effectively control pests such as aphids like peach aphids and cotton aphids; diamondback moths, cabbage leafminer moths, common root-cutting insects, apple leafrollers, leafhoppers, tobacco moth larvae, gypsy moths, rice leafrollers, tea leafrollers, potato beetles, cucumber leaf beetles, cotton boll weevils, planthoppers, leafhoppers, scale insects, bedbugs, whiteflies, thrips, grasshoppers, flower flies, scarab beetles, black root-cutting insects, root-cutting insects, ants, and agricultural pests; gastropods such as slugs and snails; pests that harm hygiene such as rat mites, cockroaches, houseflies, and house mosquitoes; grain storage insects such as wheat moths, bean weevils, red flour beetles, and whiteflies; pests that harm clothing such as bagworm moths, black carpet beetles, and ground-dwelling termites; and pests that harm houses and home decorations. Insects; etc., mites, such as two-spotted spider mite, carmine spider mite, citrus red spider mite, Kanzawa spider mite, European red spider mite (fruit tree mite), gentian mite, citrus gall mite, bulb mite and other plant parasitic mites; house dust mites such as Tyrophagus putrescentiae, Dermatophagoides farinae, Chelacaropsis moorei; etc., and soil pests, such as root-knot nematodes, cyst nematodes, root rot nematodes, white tip nematodes, strawberry leaf bud nematodes, pine wood nematodes and other plant parasitic nematodes; solitary worms such as isochoria; etc.

The pest control agent of the present invention can also effectively control various pests resistant to chemicals (such as organophosphates, carbamates, synthetic pyrethroids and neonicotinoids).

References cited in this document (such as scientific literature, patents, and patent applications) are incorporated herein by reference as if each document were specifically described in its entirety. As used herein, "or" is used where "at least one or more" of the terms listed in the sentence are applicable.

Example

As described above, the invention has been explained, and preferred embodiments have been shown to aid understanding. Hereinafter, the invention is described in more detail with reference to the following manufacturing examples and embodiments; however, the explanations mentioned above and the following manufacturing examples and embodiments are not intended to limit the invention, but are merely illustrative. Therefore, the scope of the invention is not limited to the embodiments and the specific embodiments described herein, but is limited only by the scope of the claims.

Preparation Example 1:

Preparation of N-(2-fluoro-4-methylphenyl)-2-(4-(trifluoromethoxy)phenyl)acetamide (4-14)

POCl₃ (1.6 mL, 17.58 mmol, 2 equivalents) was slowly added to a solution of 2-fluoro-4-methylaniline (2-14; 1.1 g, 8.79 mmol, 1 equivalent) and 2-(4-(trifluoromethoxy)phenyl)acetic acid (3b-14; _2.12 g, 9.67 mmol, 1.1 equivalents) in pyridine (10 mL) at 0 °C. The reaction was maintained at the same temperature for another 15 min. The reaction mixture was then quenched on ice, and the product was extracted with ethyl acetate. The combined organic layers were washed with 1 N HCl solution followed by a brine solution, dried over sodium sulfate, filtered, and concentrated under reduced pressure to give 2.20 g of crude product 4-14 as a yellow solid. The crude product was used as is without further purification.

¹ H NMR (CDCl ₃ ): 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).

Preparation 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 equivalents) was added to N-(2-fluoro-4-methylphenyl)-2-(4-(trifluoromethoxy)phenyl)acetamide (4-14; 2.20 g, 6.72 mmol, 1 equivalent) at a temperature below 50 °C. The reaction mixture was then stirred overnight at room temperature. The reaction mixture was then quenched in ice, and the product was extracted with ethyl acetate. The combined organic layers were washed with distilled water, dried over sodium sulfate, filtered, and concentrated under reduced pressure to give 2.60 g of crude product 5-14 as a black, viscous oil. The crude product thus obtained was used as is without any purification. ¹ H NMR (CDCl ₃ ): 9.08 (d, J = 7.6 Hz, 1H), 7.39-7.36 (m, 2H), 7.25-7.24 (m, 3H), 7.12 (d, J = 10.8 Hz, 1H), 3.79 (s, 2H), 2.71 (s, 3H).

Preparation Example 3:

Preparation of N-(2-fluoro-5-mercapto-4-methylphenyl)-2-(4-(trifluoromethoxy)phenyl)acetamide (6-14): Triphenylphosphine (4.8 g , 18.35 mmol, 3 equivalents) was added 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 equivalent) and toluene (20 mL) at room temperature. The reaction mixture was then heated to 100 °C and held for 3 hours. The reaction mixture was cooled to room temperature and all volatiles were distilled off by rotary evaporation. The crude product thus obtained was purified by column chromatography on silica gel using a mixture of ethyl acetate and n-hexane as eluent to obtain 1.0 g of the title compound 6-14 as a grayish-white solid.

¹ H NMR (CDCl ₃ ): 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).

Example 1:

N-(5-(2,2,2-trifluoroethylthio)-2-fluoro-4-methylphenyl)-2-(4-(trifluoromethoxy)phenyl)acetyl Preparation of amine (1A-14)

Cesium carbonate (0.90 g, 2.78 mmol, 1 equivalent) was added to a cooled mixture of N-(2-fluoro-5-mercapto-4-methylphenyl)-2-(4-(trifluoromethoxy)phenyl)acetamide (6-14; 1.00 g, 2.78 mmol, 1 equivalent) in DMF (10 mL), followed by sodium formaldehyde sulfoxylate (0.33 g, 2.78 mmol, 1 equivalent). Trifluoroiodoethane (0.639 g, 3.06 mmol, 1.1 equivalent) was then slowly added to this mixture at 0 °C, and the resulting mixture was stirred at room temperature for 6 hours. The reaction mixture was then poured into distilled water and extracted with dichloromethane. The combined organic layers were washed with distilled water, dried over sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography on silica gel using a mixture of ethyl acetate and n-hexane as eluent to obtain 0.95 g of the title compound 1A-14 as a pale yellow solid.

Preparation Example 4:

Preparation of N-(2-fluoro-4-methylphenyl)acetamide

A solution of acetic anhydride (4.49 g, 43.95 mmol, 1 equivalent) in chloroform (30 ml) was slowly added to a mixture of 2-fluoro-4-methylaniline (5.50 g, 43.95 mmol, 1 equivalent) in chloroform (20 ml) at 0 °C. The reaction mixture was then stirred at room temperature for 3 hours. The reaction mixture was then quenched in sodium bicarbonate solution and the product was extracted with dichloromethane. The combined organic layers were washed with sodium bicarbonate solution followed by distilled water, dried over sodium sulfate, filtered, and concentrated under reduced pressure to give 5.92 g of crude product as a white solid. The crude product thus obtained was used as is without any purification.

¹ H NMR (CDCl ₃ ): 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).

Preparation Example 5:

Preparation of 5-acetamido-4-fluoro-2-toluene-1-sulfonyl chloride

Chlorosulfonic acid (20.56 g, 176.46 mmol, 5 equivalents) was slowly added to N-(2-fluoro-4-methylphenyl)acetamide (5.90 g, 35.29 mmol, 1 equivalent), and the temperature of the reaction mixture was maintained below 50 °C. The resulting mixture was then heated to 70 °C and maintained for 4 hours. After cooling to room temperature, the reaction mixture was carefully poured into ice, the precipitate was filtered, thoroughly washed with distilled water, and dried to give 7.3 g of crude product as a light brown solid. The crude product obtained was used as is without any purification.

¹ H NMR (CDCl ₃ ): 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).

Preparation Example 6:

Preparation of N-(2-fluoro-5-mercapto-4-methylphenyl)acetamide

Zinc powder (34.44 g, 526.80 mmol, 20 equivalents) was added fractionally to a mixture of 5-acetamido-4-fluoro-2-methylbenzene-1-sulfonyl chloride (7.00 g, 26.34 mmol, 1 equivalent) and glacial acetic acid (60 ml) at room temperature. The resulting 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 a diatomaceous earth bed. The organic layer was thoroughly washed with distilled water, dried over sodium sulfate, filtered, and concentrated under reduced pressure to give 3.64 g of crude product as a pale yellow solid. The crude product was used as is without further purification.

¹ H NMR (CDCl ₃ ): 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).

Preparation Example 7:

Preparation of N-(5-(2,2,2-trifluoroethylthio)-2-fluoro-4-methylphenyl)acetamide

Cesium carbonate (5.07 g, 15.56 mmol, 1 equivalent) was added to a cooled mixture of N-(2-fluoro-5-mercapto-4-methylphenyl)acetamide (3.10 g, 15.56 mmol, 1 equivalent) in DMF (30 mL), followed by sodium formaldehyde sulfoxylate (1.84 g, 15.56 mmol, 1 equivalent). Trifluoroiodoethane (3.27 g, 15.56 mmol, 1 equivalent) was then slowly added to this mixture, and the resulting mixture was stirred at room temperature for 6 hours. The reaction mixture was then poured into distilled water and extracted with dichloromethane. The combined organic layers were washed with distilled water, dried over sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product. The crude product was purified by column chromatography on silica gel using a mixture of ethyl acetate and n-hexane as eluent to give 2.90 g of the title compound as a grayish-white solid.

¹ H NMR (CDCl ₃ ): δ 8.49 (d, J = 8.0 Hz, 1H), 7.29 (bs, 1H), 6.96 (d, J = 11.6 Hz, 1H), 3.42-3.35 (q, J = 9.6 Hz, 2H), 2.41 (s, 3H), 2.21 (s, 3H).

Preparation Example 8:

Preparation of 5-(2,2,2-trifluoroethylthio)-2-fluoro-4-methylaniline

Concentrated HCl (30 mL) was added to a mixture of N-(5-(2,2,2-trifluoroethylthio)-2-fluoro-4-methylphenyl)acetamide (2.20 g, 7.82 mmol, 1 equivalent) in ethanol/water (30 mL/4 mL). The resulting mixture was then refluxed for 6 hours. After cooling to room temperature, all volatiles were removed by vacuum distillation, and the residue was then made alkaline by slow addition of 1 N NaOH solution. The product was then extracted with ethyl acetate. The combined organic layers were then washed with distilled water followed by a brine solution, dried over sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product as a brown oil. The crude product was used as is without further purification.

¹ H NMR (CDCl ₃ ): 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).

Example 2:

Preparation of N-(5-(2,2,2-trifluoroethylthio)-2-fluoro-4-methylphenyl)-2-phenylacetamide (1A-1)

Triethylamine (0.046 g, 0.46 mmol, 1.1 equivalent) was added to a cooled solution of 5-(2,2,2-trifluoroethylthio)-2-fluoro-4-methylaniline (0.10 g, 0.42 mmol, 1 equivalent) in chloroform (10 mL), followed by the slow addition of 2-phenylacetyl chloride (0.068 g, 0.44 mmol, 1.05 equivalent). The resulting mixture was then stirred at room temperature for 14 hours. The reaction mixture was then poured into a solution of _NaHCO3 and the product was extracted with dichloromethane. The combined organic layers were then washed with distilled water followed by a brine solution, dried over sodium sulfate, filtered, and concentrated under reduced pressure to give 0.125 g of the title product as a grayish-white solid.

Example 3:

N-(5-(2,2,2-trifluoroethylthio)-2-fluoro-4-methylphenyl)-2-(2-chlorophenyl)acetamide (1A-3) preparation

Triethylamine (0.042 g, 0.42 mmol, 2.0 equivalent) was added to a cooled solution of 5-(2,2,2-trifluoroethylthio)-2-fluoro-4-methylaniline (0.05 g, 0.21 mmol, 1 equivalent) in dichloromethane (10 mL), followed by the slow addition of 2-(2-chlorophenyl)acetyl chloride (0.04 g, 0.21 mmol, 1 equivalent). The resulting mixture was then stirred at room temperature for 14 hours. The reaction mixture was then poured into a solution of _NaHCO3 and the product was extracted with dichloromethane. The combined organic layers were then washed with distilled water followed by a brine solution, dried over sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product. The crude product was purified by column chromatography on silica gel using a mixture of ethyl acetate and n-hexane as eluent to give 0.07 g of the title compound as a brown solid.

Example 4:

N-(5-(2,2,2-trifluoroethylthio)-2-fluoro-4-methylphenyl)-2-(2,5-dichlorophenyl)acetamide (1A-) 4) Preparation

POCl₃ (0.08 g, 0.52 mmol, 2.5 equivalents) was added very slowly to a cooled mixture of 5-(2,2,2-trifluoroethylthio)-2-fluoro- ₄ -methylaniline (0.05 g, 0.21 mmol, 1 equivalent) and 2-(2,5-dichlorophenyl)acetic acid (0.05 g, 0.25 mmol, 1.2 equivalents) in pyridine (3 mL). After a few minutes, the reaction mixture was poured onto ice and the product was extracted with ethyl acetate. The combined organic layers were then washed successively with 1 N HCl and distilled water, dried over sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product. The crude product thus obtained was purified by column chromatography on silica gel using a mixture of ethyl acetate and n-hexane as eluent to give 0.023 g of the title compound as a pale yellow solid.

Example 5:

2-(4-(ethylthio)phenyl)-N-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)acetyl Preparation of amine (1B-1)

POCl₃ (0.08 g, 5.348 mmol, 6.4 equivalents) was added very slowly to a cooled mixture of 5-(2,2,2-trifluoroethylthio)-2-fluoro- ₄ -methylaniline (0.20 g, 0.835 mmol, 1 equivalent) and 2-(4-(ethylthio)phenyl)acetic acid (0.186 g, 1.021 mmol, 1.2 equivalents) in pyridine (3 mL). After a few minutes, the reaction mixture was poured onto ice and the product was extracted with ethyl acetate. The combined organic layers were then washed successively with 1 N HCl and distilled water, dried over sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product. The crude product thus obtained was purified by column chromatography on silica gel using a mixture of ethyl acetate and n-hexane as eluent to give 0.18 g of the title compound as a yellow solid.

Example 6:

N-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)-2-(4-(propylthio)phenyl)acetyl Preparation of amine (1B-2)

POCl₃ (0.08 g, 5.348 mmol, 6.4 equivalents) was added very slowly to a cooled mixture of 5-(2,2,2-trifluoroethylthio)-2-fluoro- ₄ -methylaniline (0.20 g, 0.835 mmol, 1 equivalent) and 2-(4-(propylthio)phenyl)acetic acid (0.327 g, 1.556 mmol, 1.8 equivalents) in pyridine (3 mL). After a few minutes, the reaction mixture was poured onto ice and the product was extracted with ethyl acetate. The combined organic layers were then washed successively with 1 N HCl and distilled water, dried over sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product. The crude product thus obtained was purified by column chromatography on silica gel using a mixture of ethyl acetate and n-hexane as eluent to give 0.13 g of the title compound as a yellow solid.

Example 7:

N-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)-2-(4-(isopropylthio)phenyl)ethyl Preparation of amide (1B-3)

POCl₃ (0.08 g, 5.348 mmol, 6.4 equivalents) was added very slowly to a cooled mixture of 5-(2,2,2-trifluoroethylthio)-2-fluoro- ₄ -methylaniline (0.20 g, 0.835 mmol, 1 equivalent) and 2-(4-(isopropylthio)phenyl)acetic acid (0.155 g, 0.737 mmol, 0.8 equivalents) in pyridine (3 mL). After a few minutes, the reaction mixture was poured onto ice and the product was extracted with ethyl acetate. The combined organic layers were then washed successively with 1 N HCl and distilled water, dried over sodium sulfate, filtered, and concentrated under reduced pressure to give a crude product. The crude product thus obtained was purified by column chromatography on silica gel using a mixture of ethyl acetate and n-hexane as eluent to give 0.12 g of the title compound as a yellow solid.

Example 8:

Apart from the compounds obtained in Examples 1 to 7, the compounds shown in Tables 1 to 4 were prepared by methods similar to those described in Examples 1 to 7 or in the specification.

Tables 2 and 4 show the ^1H -NMR data of the compounds of the present invention obtained therefrom.

The abbreviations in Tables 1 to 4 are shown below.

F: Fluorine, Cl: Chlorine, Br: Bromine, Me: Methyl, Et: Ethyl, n-Pr: n-propyl, i-Pr: Isopropyl, n-Bu: n-Butyl, t-Bu: Tert-Butyl, n-Pent: n-Pentyl, _CF3 : Trifluoromethyl, OMe: Methoxy, OEt: Ethoxy, _OCF3 : Trifluoromethoxy, _SCF3 : Trifluoromethylthio, _SMe : Methylthio, NH2: Amino, _NO2 : Nitro, Ph: Phenyl, S: Sulfur, O: Oxygen, Ac: Acetyl, _CHF2 : Difluoromethyl.

Table 1

Table 2

Table 3

Table 4

The following are formulation examples, where “parts” refers to “parts by weight”.

Formulation Example 1: Emulsion

Ten parts of each compound of the present invention were dissolved in 45 parts of Solvesso 150 and 35 parts of N-methylpyrrolidone. Ten parts of emulsifier (trade name: Sorpol 3005X, manufactured by Toho Chemical Industry Co., Ltd.) were added. The mixture was stirred to obtain a 10% emulsion.

Formulation Example 2: Wettable Powder

Twenty parts of each compound of the present invention were added to a mixture of two parts sodium lauryl sulfate, four parts sodium lignosulfonate, 20 parts fine powder of synthetic hydrated silica, and 54 parts clay. The mixture was stirred using a juice mixer to obtain a 20% wettable powder.

Formulation Example 3: Granules

Two parts of sodium dodecylbenzenesulfonate, ten parts of bentonite, and eighty-three parts of clay were added to five parts of each compound of the present invention, and each mixture was thoroughly mixed by stirring. An appropriate amount of water was added. The resulting mixture was further stirred and granulated using a granulator. The granules were air-dried to obtain 5% granules.

Formulation Example 4: Powder

One part of each compound of the present invention was dissolved in an appropriate amount of acetone. Five parts of fine powder of synthetic hydrated silica, 0.3 parts of isopropyl phosphate (PAP), and 93.7 parts of clay were added to the solution. The mixture was stirred using a juice mixer, and the acetone was removed by evaporation to obtain a 1% powder.

Formulation Example 5: Flowable Formulation

Twenty parts of each compound of the present invention were mixed with 20 parts of water containing 3 parts of polyoxyethylene tristyrene phenyl ether phosphate triethanolamine and 0.2 parts of Rhodorsil 426R. The mixture was wet-milled using a DYNO-Mill and then mixed with 60 parts of water containing 8 parts of propylene glycol and 0.32 parts of xanthan gum to obtain a 20% aqueous suspension.

The following test examples demonstrate that the compounds of the present invention can be used as active ingredients in acaricides.

Test Example 1 (Acaricide Test against Two-spotted Tetranychus)

A piece of nonwoven fabric (4.5 × 5.5 cm) was suspended inside a plastic cup through a slit made in the cup's lid. After water was poured into the cup, the cup was covered with the lid. A bean leaf (approximately 3.5 × 4.5 cm) was then placed on the fully moistened nonwoven fabric. Another bean leaf containing two-spotted spider mites (approximately 30 mite samples) was placed on top of the first leaf, and the fabric and leaf were placed in a constant temperature chamber with a temperature of 25 ± 2 °C and a humidity of 40%.

The acaricide containing the compound of the present invention (200 ppm) is prepared by adding an aqueous solution (100 ppm) of Sorpol 355 (produced by Tobo Kagaku Co. Ltd.) to a methanol solution of the compound of the present invention.

Spray the acaricides onto the leaves, air-dry the leaves, and place them in a constant temperature chamber (25±2℃ and 50% humidity). Calculate the mortality rate of the two-spotted spider mite after 2 days.

The following compounds exhibit a mortality rate of 50% or greater:

Compound numbers: 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, 1 A-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, 1B-1, 1B-2, 1B-3, 1B-5, 1B-7, 1B-8, 1B-9, 1B-10, 1B-11, 1B-12, 1B-15, 1B-16, 1B-17, 1B-18, 1B-19, 1B-20, 1 B-22, 1B-23, 1B-24, 1B-25, 1B-26, 1B-27, 1B-28, 1B-29, 1B-30, 1B-32 , 1B-33, 1B-34, 1B-35, 1B-36, 1B-37, 1B-38, 1B-39, 1B-41, 1B-43, 1B-4 8. 1B-49, 1B-50, 1B-54, 1B-55, 1B-56, 1B-57, 1B-58, 1B-59, 1B-61, 1B -62, 1B-63, 1B-64, 1B-65, 1B-66, 1B-67, 1B-68, 1B-69, 1B-70, 1B-71, 1B-72, 1B-73, 1B-74, 1B-76, 1B-77, 1B-78, 1B-79, 1B-80, 1B-82, 1B-8 3. 1B-87, 1B-90, 1B-96, 1B-97, 1B-98, 1B-99, 1B-100, 1B-101, 1B-102.

Test Example 2 (Ovicidal Test against Two-spotted Tetranychus)

A piece of nonwoven fabric (4.5 × 5.5 cm) was suspended inside a plastic cup through a slit made in the cup's lid. After water was poured into the cup, it was covered with the lid. A bean leaf (approximately 3.5 × 4.5 cm) was then placed on the fully moistened nonwoven fabric. Twenty female adult two-spotted spider mites were placed on the top of the leaf, and the fabric and leaf were placed in a constant temperature chamber with 25 ± 2 °C, 40% humidity, and 16 L/8D.

The following day, after adjusting the number of female adults back to 20, 2 ml of an acaricide containing 200 ppm of the compound of the present invention, prepared in the same manner as in Test Example 1, was sprayed onto the leaves. The leaves were then air-dried and placed in a constant temperature chamber (25 ± 2°C and 50% humidity). Six days after spraying the acaricide, the ovicidal rate of the two-spotted spider mite was calculated. The compounds exhibiting a mortality rate of 50% or greater at 500 ppm are as follows:

Compound numbers: 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-6 9. 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, 1B-1, 1B-2, 1B-3, 1B-5, 1B-7, 1B-8, 1B-9, 1B-10, 1B-11, 1B-12, 1B-15, 1B-16, 1B -17, 1B-18, 1B-19, 1B-20, 1B-22, 1B-23, 1B-24, 1B-25, 1B-26, 1B-27, 1B-28, 1B-29, 1B-30, 1B-32, 1B-33, 1B-34, 1B-35, 1B-36, 1B-37, 1B-38, 1B-39, 1B-41, 1B-43, 1B-48, 1B-49, 1B-50, 1B-54, 1B-55, 1B-56, 1B-57, 1B-58, 1B-59 , 1B-61, 1B-62, 1B-63, 1B-64, 1B-65, 1B-66, 1B-67, 1B-68, 1B-69, 1B-70, 1B-71, 1B-72, 1B-73, 1B-74, 1B-76, 1B- 77, 1B-78, 1B-79, 1B-80, 1B-82, 1B-83, 1B-86, 1B-87, 1B-88, 1B-90, 1B-96, 1B-97, 1B-98, 1B-99, 1B-100, 1B-101.

(Note)

It should be understood that the patents, patent applications and documents cited herein are incorporated herein by reference as if their contents were specifically described herein. This application claims priority to PCT Application No. PCT/IB2016/055523 and Indian Patent Application No. 201611024522, the entire contents of which are incorporated herein by reference.

[Industrial Applicability]

This invention provides novel benzamide compounds, their preparation methods, and acaricides, and is therefore particularly applicable to the agricultural industry.

Claims (9)

1. A benzamide compound represented by formula (1): or its salt, Where ^R1 represents a _C1-6 haloalkyl group; ^R2 and ^R3 may be the same or different and each represents a halogen or a _C1-6 alkyl group; R ⁴ represents hydrogen, _C1-6 alkyl, _C1-6 haloalkyl, _C1-6 alkoxy- _C1-6 alkyl, _C1-6 haloalkoxy- _C1-6 alkyl, _C3-8 cycloalkyl- _C1-6 alkyl, or aryl _-C1-6 alkyl, and all substituents defined as R ⁴ may optionally be further substituted; ^R5 and ^R6 may be the same or different and each represents hydrogen, halogen, _C1-6 alkyl or _C1-6 haloalkyl; R ⁹ represents hydrogen, halogen, nitro, cyano, _C1-6 alkyl, _C1-6 haloalkyl, _C1-6 alkoxy, _C1-6 haloalkoxy, _C1-6 alkylsulfonyl, _C1-6 alkylthio, _C1-6 haloalkylthio, substituted or unsubstituted amino, aryl, or heterocyclic, all of which may optionally be further substituted; ^R7 and ^R8 may be the same or different and each represents hydrogen, halogen or aryl, which may optionally be further substituted; ^R10 and ^R11 may be the same or different and each represents hydrogen or halogen; X represents oxygen or sulfur; and n represents an integer from 0 to 2. 2. The benzamide compound or a salt thereof according to claim 1, wherein ^R4 is hydrogen or a _C1-6 alkyl group. 3. The benzamide compound or a salt thereof according to claim 1, wherein ^R9 represents hydrogen, halogen, nitro, _C1-6 alkyl, _C1-6 haloalkyl, _C1-6 alkoxy, _C1-6 haloalkoxy, C1-6 alkylsulfonyl, _C1-6 alkylthio, _C1-6 haloalkylthio, substituted or unsubstituted _amino , aryl or heterocyclic. 4. A method for preparing a benzamide compound or a salt thereof according to any one of claims 1 to 3, comprising at least one step selected from the group consisting of steps (d) and (e): Step (d): The thioether compound represented by formula (6) is obtained by reacting the thiol compound represented by formula (6) with the alkylating agent represented by formula (7): 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): Reacting the sulfide compound represented by formula (1-1) with an oxidizing agent to obtain the benzamide compound represented by formula (1-2): Where ^R1 , ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 and X are defined above, and n' represents 1 or 2. 5. The method for preparing benzamide compounds and their salts according to claim 4, further comprising the step (c): Step (c): Obtain the thiol compound represented by formula (6) by reacting the sulfonyl chloride compound represented by formula (5) with a reducing agent: ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 and X are as defined above. 6. The method for preparing benzamide compounds and their salts according to claim 5, further comprising the step (b): Step (b): Obtain the sulfonyl chloride compound represented by formula (5) by chlorosulfonation of the amide compound represented by formula (4): ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^R8 , ^R9 , ^R10 , ^R11 and X are as defined above. 7. The method for preparing benzamide compounds and their salts according to claim 6, further comprising the step (a): Step (a): The amide compound represented by formula (4) is obtained by reacting the aniline compound represented by formula (2) with the benzyl carbonyl compound represented by formula (3): ^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. 8. An insecticide containing a benzamide compound or a salt thereof according to any one of claims 1 to 3. 9. An acaricide containing a benzamide compound or a salt thereof according to any one of claims 1 to 3.