WO2018138692A1

WO2018138692A1 - Novel fungicidal carbamate compounds

Info

Publication number: WO2018138692A1
Application number: PCT/IB2018/050512
Authority: WO
Inventors: Surendra Kumar KUMAWAT; Ashish BHATT; Pramod Kumar CHAUHAN; Md. Jawed Ashraf; Amit CHOUHAN; Rajesh Kumar Singh; Manish Kumar SINGH; Bhupender Kumar SATOLIYA; Tetsuya Imai
Original assignee: Insecticides (India) Limited; Oat Agrio Co., Ltd.
Priority date: 2017-01-30
Filing date: 2018-01-29
Publication date: 2018-08-02
Also published as: TW201831457A

Abstract

An object of the present invention is to provide a carbamate compound or a salt thereof that controls diseases. The present invention provides a carbamate compound represented by Formula (1), or a salt thereof, wherein R₁, R₃ and R₆ are identical or different and each represents hydrogen, or the like; R₂ represents hydrogen, halogen, or C_1-6 alkyl; R₄ and R₅ are identical or different and each represents hydrogen, or the like; R₇ represents hydrogen, or the like; R₈ represents hydrogen, or C_1-6 alkyl; X and Χ₁ independently represent oxygen, or sulfur; Y represents oxygen, or sulfur; Z represents oxygen/ or sulfur; l is an integer of 0 to 2; m is an integer of 0 to 3; n is an integer of 0 to 4; and when l, m or n is more than one, the l, m or n may be the same or different.

Description

DESCRIPTION

Title of Invention:

NOVEL FUNGICIDAL CARBAMATE COMPOUNDS Technical Field

The present invention relates to novel carbamate

compounds and a process for preparing the same. The invention further provides an agricultural and horticultural fungicide composition comprising the said compounds.

Background Art

In recent years, the control of drug resistant fungi could not be accomplished by the use of known fungicides. The development of resistance in various fungi is mainly due to the long term and heavy use of known fungicides. Consequently, there is a demand for development of new types of compounds having a fungicidal activity against drug resistant fungi.

WO 2015/147314 (Patent Literature (PTL) 1) and WO

2015/147336 (Patent Literature (PTL) 2) disclose the compounds represented by the formula (A) which has a pyrazole moiety in the molecule. These publications also mentioned that the compound represented by the formula (A) is useful as fungicide to control plant diseases.

Wherein, Ri is halogen, C1-C4 alkyl group; R2 is hydrogen, halogen, C1-C4 alkyl group; R3 is hydrogen, halogen, C₁-C3 alkyl group, C1-C3 alkoxy group, C₃-C₄ cycloalkyl group; Z is halogen C1-C3 alkyl group, C1-C3 alkoxy group; Q is represented by Qi, Q₂ and Q₃ as shown below:

Qi Q₂ Q₃

Wherein, R₄ is C₁-C3 alkyl group; R₅ is hydrogen, hydroxy, methyl; R₆ is hydrogen, hydroxy, methyl, methoxy; X_x is oxygen, sulfur; X2 is oxygen, sulfur, NR₇ or a direct bond; R₇ is hydrogen, C₁-C3 alkyl group. However, these publications do not deal with the compounds of the present invention.

Citation List

Patent Literature

PTL 1: WO 2015/147314

PTL 2: WO 2015/147336

Summary of Invention

Solution to Problem

The present invention provides novel carbamate compounds which exhibit excellent fungicidal activity against drug resistant fungi as well as drug sensitive fungi.

The present invention also provides a process for

preparing the said carbamate compounds.

The present invention further provides a new type of fungicide for agriculture and horticulture which exhibits a remarkable fungicidal effect against chemical-resistant fungi as well as chemical-sensitive fungi. Specifically, the present inventors conducted extensive research and succeeded in synthesizing 'a compound represented by the following Formula (1) or a salt thereof that has fungicidal activity. The present inventors have conducted further research based on the above findings.

The present invention has thereby been accomplished.

More specifically, the present invention includes the following embodiments:

Item 1 : A carbamate compound is represented by the formula (1) :

or a salt thereof,

wherein R_x, R3 and R₆ are identical or different and each represents hydrogen, halogen, nitro, cyano, hydroxyl, formyl, carboxy, optionally substituted amino, Ci-6 alkyl, Ci_₆

haloalkyl, Ci_₆ alkoxy, Ci_₆ haloalkoxy, Ci_₆ alkoxy Ci_₆ alkyl, Ci_6 haloalkoxy Ci-6 alkyl, Ci_₆ alkoxycarbonyl , Ci_₅

haloalkoxycarbonyl, cyano Ci_₆ alkyl, cyano Ci_₆ alkoxy, C₂-6 alkenyl, C₂_₆ haloalkenyl , cyano C₂_₆ alkenyl, C₂_₆ alkynyl, C₂-6 haloalkynyl, cyano C₂_₆ alkynyl, C₃-₈ cycloalkyl, C₃_₈ cycloalkyl Ci-6 alkyl, Ci_₆ alkylthio, Ci_₆ haloalkylthio, C₃_₈

cycloalkylthio, C₃-₈ cycloalkyl Ci_₆ alkylthio, Ci_₆ alkoxy Ci_₆ alkylthio, Ci_₆ alkylsulfonyl, Ci_₆ alkylsulfinyl , Ci_₆

haloalkylsulfonyl , Ci_₆ haloalkylsulfinyl, C₃_₈

cycloalkylsulfonyl, C₃_₈ cycloalkylsulfinyl, C₃_₈ cycloalkyl Ci-₆ alkylsulfonyl, C₃_₈ cycloalkyl Ci_₆ alkylsulfinyl, C₂-6

alkenyloxy, C₂_₆ alkynyloxy, C₂_₆ haloalkenyloxy, C₂-6

haloalkynyloxy, Ci-₆ alkylsulfonyloxy, Ci_₆ alkylsulfinyloxy, Ci-6 alkylcarbonyl, Ci_₆ haloalkylcarbonyl , OCN, SCN, SF₅, optionally substituted aryloxy, optionally substituted aryl Ci-6 alkyloxy, optionally substituted arylthio, optionally substituted aryl Ci-₆ alkylthio, optionally substituted

arylsulfonyl, optionally substituted arylsulfinyl , optionally substituted heteroaryloxy, optionally substituted

arylsulfonyloxy, optionally substituted arylsulfinyloxy, optionally substituted aryl, or optionally substituted

heteroaryl ;

R₂ represents hydrogen, halogen, or Ci_₆ alkyl;

R₄ and R₅ are identical or different and each represents hydrogen, halogen, or Ci-e alkyl;

R₇ represents hydrogen, hydroxyl, formyl, cyano, Ci_₆ alkyl, Ci_₆ haloalkyl, Ci_₆ alkoxy, Ci_₆ haloalkoxy, Ci_₆ alkoxy Ci-6 alkyl, Ci_₆ haloalkoxy Ci-₆ alkyl, C₃-₈ cycloalkyl, C₃-₈ cycloalkyl Ci-₆ alkyl, Ci_₆ alkylcarbonyl , Ci_6 haloalkylcarbonyl, Ci-6 alkoxycarbonyl , C₂-₆ haloalkoxycarbonyl, C₂-₆ alkenyl, C₂-₆ haloalkenyl, C₂-e cyanoalkenyl, C₂-6 alkynyl, C₂-6 haloalkynyl, C₂_6 cyanoalkynyl, Ci_₆ alkylsulfonyl , Ci_₆ alkylsulfinyl, Ci_₆ haloalkylsulfonyl, Ci_₆ haloalkylsulfinyl, C₃_₈

cycloalkylsulfonyl, C₃-₈ cycloalkylsulfinyl , C₃_₈ cycloalkyl Ci_₆ alkylsulfonyl, C₃_₈ cycloalkyl Ci-₆ alkylsulfinyl , optionally substituted arylsulfonyl, optionally substituted arylsulfinyl , or optionally substituted aryl;

R₈ represents hydrogen, or Ci-6 alkyl;

X and Xi independently represent oxygen, or sulfur;

Y represents oxygen, or sulfur;

Z represents oxygen, or sulfur;

1 is an integer of 0 to 2;

m is an integer of 0 to 3;

n is an integer of 0 to 4; and

when 1, m or n is more than one, the 1, m or n may be the same or different.

Item 2 : The carbamate compound or a salt thereof according to Item 1, wherein each Ri is independently hydrogen, halogen, nitro, Ci_₆ alkyl, Ci_₆ haloalkyl, Ci_₆ alkoxycarbonyl, cyano Ci-6 alkyl, optionally substituted aryl.

Item 3: The carbamate compound or a salt thereof according to any one of the preceding items, wherein R₂ is hydrogen or Ci-6 alkyl . Item 4 : The carbamate compound or a salt thereof according to any one of the preceding items, wherein each R₃ is

independently hydrogen, halogen or Ci_₆ alkyl.

Item 5: The carbamate compound or a salt thereof according to any one of the preceding items, wherein R₄ and R₅ each

represent hydrogen or Ci-₆ alkyl. Item 6: The carbamate compound or a salt thereof according to any one of the preceding items, wherein each R₆ is

independently hydrogen, halogen, Ci-₆ alkyl or Ci-6 alkoxy.

Item 7 : The carbamate compound or a salt thereof according to any one of the preceding items, wherein R₇ is hydrogen, Ci-6 alkyl or Ci_₆ alkylcarbonyl .

Item 8: The carbamate compound or a salt thereof according to any one of the preceding items, wherein R₈ is Ci-6 alkyl.

Item 9: The carbamate compound or a salt thereof according to any one of the preceding items, wherein X and Xi are oxygen.

Item 10: The carbamate compound or a salt thereof according to any one of the preceding items, wherein Y is oxygen.

Item 11: The carbamate compound or a salt thereof according to any one of the preceding items, wherein Z is sulfur and the 1,3-thiazole ring containing Z is selected from the group consisting of:

and the * is the point of attachment to the parent compound. Item 12: The carbamate compound or a salt thereof according to any one of the preceding items, wherein each Ri is

independently hydrogen, halogen, Ci_₆ alkyl or Ci_₆ haloalkyl.

Item 13: The carbamate compound or a salt thereof according to any one of the preceding items, wherein R₂ is Ci_₆ alkyl.

Item 14 : The carbamate compound or a salt thereof according to any one of the preceding items, wherein R₂ is methyl. Item 15: The carbamate compound or a salt thereof according to any one of the preceding items, wherein each R₃ is hydrogen.

Item 16: The carbamate compound or a salt thereof according to any one of the preceding items, wherein R and R5 each

represent hydrogen.

Item 17: The carbamate compound or a salt thereof according to any one of the preceding items, wherein R₆ is hydrogen, halogen or Ci-6 alkyl.

Item 18: The carbamate compound or a salt thereof according to any one of the preceding items, wherein R₇ is hydrogen or 0χ_₆ alkylcarbonyl . Item 19: The carbamate compound or a salt thereof according to any one of the preceding items, wherein R₈ is methyl or ethyl.

Item 20: The carbamate compound or a salt thereof according to any one of the preceding items, wherein Rg is methyl.

Item 21: The carbamate compound or a salt thereof according to any one of the preceding items, wherein the 1,3-thiazole ring is :

and the * is the point of attachment to the parent compound.

Item 22: The carbamate compound or a salt thereof according to any one of the preceding items, wherein the carbamate compound is represented by the formula (1A) :

Item 23: The carbamate compound or a salt thereof according to any one of the preceding items, wherein the 1 , 3-thiazole ring is :

and the * is the point of attachment to the parent compound.

Item 24: The carbamate compound or a salt thereof according to any one of the preceding items, wherein the 1, 3-thiazole ring is :

and the * is the point of attachment to the parent compound. Item 25: A carbamate compound selected from the group

consisting of compounds lA-1, 1A-2, 1A-3, 1A-4, 1A-5, 1A-6, 1A-9, lA-10, 1A-12, 1A-13, 1A-14, 1A-15, 1A-16, lA-17," 1A-18, 1A-22, 1A-25, 1A-28, 1A-29, 1A-30, 1A-31, 1A-32, 1A-33, 1A-34, 1A-35, 1A-36, 1A-37, 1A-38, 1A-39, 1A-40, 1A-41, 1A-42, 1A-43, 1A-44, 1A-45, 1A-46, 1A-47, 1A-48, 1A-49, 1A-50, 1A-51, lB-1, 1B-2, lC-1, and lC-2, or a salt thereof.

Item 26: A carbamate compound selected from the group

consisting of compounds lA-1, 1A-2, 1A-3, 1A-4, 1A-5, 1A-6, 1A-9, lA-10, 1A-12, 1A-13, 1A-14, 1A-15, 1A-16, 1A-17, 1A-18, 1A-22, 1A-23, 1A-25, 1A-29, 1A-30, 1A-33, 1A-34, 1A-37, 1A-38, 1A-39, 1A-40, 1A-41, 1A-42, 1A-46, 1A-47, 1A-48, 1A-49, 1A-50, 1A-51, lB-1, 1B-2, lC-1, and lC-2, or a salt thereof. Item 27: A carbamate compound selected from the group

consisting of compounds lA-1, 1A-2, 1A-3, 1A-4, 1A-5, 1A-6, 1A-9, lA-10, 1A-12, 1A-13, 1A-14, 1A-15, 1A-17, 1A-18, 1A-25, 1A-29, 1A-30, 1A-33, 1A-37, 1A-38, 1A-39, 1A-40, 1A-41, 1A-47, 1A-48, 1A-49, 1A-50, 1A-51, lB-1, 1B-2, lC-1, and lC-2, or a salt thereof.

Item 28: A carbamate compound selected from the group

consisting of compounds 1A-4, 1A-5, 1A-12, 1A-15, 1A-17, 1A-29, 1A-35, 1A-36, 1A-37, 1A-40, 1A-49, lC-1, and lC-2, or a salt thereof.

Item 29: A carbamate compound selected from the group

consisting of compounds lA-1, 1A-2, 1A-3, 1A-4, 1A-5, 1A-6, 1A-7, 1A-9, lA-10, lA-11, 1A-12, 1A-13, 1A-14, 1A-15, 1A-17, 1A-18, 1A-19, 1A-20, 1A-22, 1A-23, 1A-25, 1A-26, 1A-29, 1A-30, 1A-33, 1A-35, 1A-36, 1A-37, 1A-38, 1A-39, 1A-40, 1A-41, 1A-42, 1A-43, 1A-44, 1A-45, 1A-46, 1A-47, 1A-48, 1A-49, 1A-50, 1A-51, lB-1, 1B-2, lC-1, and lC-2, or a salt thereof. Item 30: A plant disease-controlling agent containing the carbamate compound or a salt thereof according to any one of Items 1 to 29.

Item 31: A fungicide containing the carbamate compound or a salt thereof according to any one of Items 1 to 29.

Advantageous Effects of Invention

A carbamate compound or a salt thereof according to the present invention achieves an excellent fungicidal effect on fungal plant pathogens. Additionally, the heterocyclic

compound or a salt thereof according to the present invention is useful as a new type of fungicide that exhibits excellent fungicidal activity not only against chemical-sensitive fungi, but also against chemical-resistant fungi.

Description of Embodiments

Hereinafter, the present invention will be described in more detail with reference to examples, but the technical scope of the present invention is not limited to these

examples. Throughout the entire specification, a singular expression should be understood as encompassing the concept thereof in the plural form, unless specifically noted

otherwise. Thus, singular articles (e.g., "a", "an", "the" and the like in case of English) should also be understood as encompassing the concept thereof in the plural form unless specifically noted otherwise. Further, the terms used herein should be understood as being used in the meaning that is commonly used in the art, unless specifically noted otherwise. Thus, unless defined otherwise, all terminologies and

scientific technical terms that are used herein have the same meaning as the terms commonly understood by those skilled in the art to which the present invention pertains. In case of a contradiction, the present specification (including the definitions) takes precedence.

A carbamate compound or a salt thereof

The invention provides a carbamate compound or a salt thereof represented by the formula (1) for use in agriculture and horticulture.

Wherein Ri, R₂, R3, Rs_> Re, F , Re, X, i, Y, Z, 1, m and n are as defined above.

Next, the terms in the present specification are

described below.

In the present specification, the number of substituents of a group defined by "optionally substituted" or "substituted" is not particularly limited if it is substitutable, and is one or plural. In addition, unless otherwise indicated, the

description for each group is also applied when the group is one part of or a substituent on other groups.

"Ci-6 alkyl" means a linear or branched, saturated

hydrocarbon group having one to six carbon atoms.

"C₂-6 alkenyl" means a linear or branched, unsaturated hydrocarbon group having two to six carbon atoms and

containing one to three double bonds.

"C2-6 alkynyl" means a linear or branched, unsaturated hydrocarbon group having two to six carbon atoms and

containing one triple bond.

"C3-8 cycloalkyl" means a cyclic alkyl having three to eight carbon atoms, and includes those cyclic alkyl having a partially bridged structure.

"Ci-6 alkoxy" refers to a "Ci-6 alkyloxy group", and the "Ci-6 alkyl" moiety is defined the same as the above-described "Ci-6 alkyl" .

"Aryl" means a monocyclic or polycyclic aromatic

hydrocarbon .

"Heterocyclic" means a saturated, unsaturated, or

aromatic heterocyclic group which has at least one of nitrogen, oxygen, phosphorus and/or sulfur atoms in the ring and may be bonded at any substitutable position.

"Heteroaryl" means an aromatic heterocyclic group which has at least one of nitrogen, oxygen, and/or sulfur atoms in the ring and may be bonded at any substitutable position, wherein the ring member atoms of the heteroaryl include

'besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from N, 0 and S.

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

Examples of halogen include, but are not particularly limited to, fluorine, chlorine, bromine, iodine, and the like.

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

Examples of Ci-6 haloalkyl include, but are not

particularly limited to Ci_₆ straight-chain or branched-chain alkyl substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethyl , chloromethyl , bromomethyl,

iodomethyl, difluoromethyl , 2 , 2-difluoroethyl , trifluoromethyl , 2 , 2 , 2-trifluoroethyl , pentafluoroethyl , 3 , 3 , 3-trifluoropropyl , 4 , 4 , 4-trifluorobutyl, heptafluoroisobutyl , and the like.

Examples of Ci-₆ alkoxy include, but are not particularly limited to Ci_₆ straight-chain or branched-chain alkoxy, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, and the like.

Examples of Ci-e haloalkoxy include, but are not

particularly limited to Ci-₆ straight-chain or branched-chain alkoxy 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, heptafluoroisobutoxy, and the like.

Examples of Ci-e alkoxy Ci-6 alkyl include, but are not particularly limited to alkoxyalkyl in which Ci-6 straight- chain or branched-chain alkyl is substituted with Ci-₆

straight-chain or branched-chain alkoxy, such as methoxymethyl , ethoxymethyl , n-propoxymethyl , isopropoxymethyl , n- butoxymethyl , isobutoxymethyl , sec-butoxymethyl , tert- butoxymethyl , methoxyethyl , ethoxyethyl, methoxy-n-propyl , methoxy-n-butyl , and the like.

Examples of Ci-6 haloalkoxy Ci_₆ alkyl include, but are not particularly limited to straight-chain or branched-chain alkoxyalkyl substituted with 1 to 9, preferably 1 to 5,

halogen atoms, such as fluoromethoxymethyl ,

chloromethoxymethyl , bromomethoxymethyl , iodomethoxymethyl , difluoromethoxymethyl , trifluoromethoxymethyl, 2,2,2- tri fluoroethoxymethyl , and the like.

Examples of C₃~₈ cycloalkyl include, but are not

particularly limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like.

Examples of C3-8 cycloalkyl C\-₆ alkyl include, but are not particularly limited to, cyclopropylmethyl , cyclobutylethyl , cyclopentylmethyl , cyclohexylmethyl and the like.

Examples of Ci_₆ alkylcarbonyl include, but are not

particularly limited to Ci_₆ straight-chain or branched-chain alkylcarbonyl groups, such as methylcarbonyl (acetyl),

ethylcarbonyl (propionyl), n-propylcarbonyl (butyryl),

isopropylcarbonyl ( isobutyryl ) , n-butylcarbonyl (valeryl) , isobutylcarbonyl ( isovaleryl ) , sec-butylcarbonyl , tert- butylcarbonyl , and the like.

Examples of Ci_₆ haloalkylcarbonyl include, but are not particularly limited to Ci_₆ straight-chain or branched-chain alkylcarbonyl substituted with 1 to 9, and preferably 1 to 5, halogen atoms, such as fluoromethylcarbonyl ,

chloromethylcarbonyl , bromomethylcarbonyl , iodomethylcarbonyl , dichloromethylcarbonyl , t ichloromethylcarbonyl ,

difluoromethylcarbonyl , trifluoromethylcarbonyl ,

chlorodifluoromethylcarbonyl , bromodifluoromethylcarbonyl , dichlorofluoromethylcarbonyl , 2,2, 2-trichloroethylcarbonyl ,

2 , 2 , 2-trifluoroethylcarbonyl, pentafluoroethylcarbonyl , and the like.

Examples of Ci_₆ alkoxycarbonyl include, but are not particularly limited to Ci_₆ straight-chain or branched-chain alkoxycarbonyl groups, such as methoxycarbonyl , ethoxycarbonyl , n-propoxycarbonyl , isopropoxycarbonyl, n-butoxycarbonyl , isobutoxycarbonyl , sec-butoxycarbonyl, tert-butoxycarbonyl , and the like.

Examples of 0ι__δ haloalkoxycarbonyl include, but are not particularly limited to Ci_₆ straight-chain or branched-chain alkoxycarbonyl substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethoxycarbonyl ,

chloromethoxycarbonyl , bromomethoxycarbonyl ,

iodomethoxycarbonyl , dichloromethoxycarbonyl ,

trichloromethoxycarbonyl , difluoromethoxycarbonyl ,

trifluoromethoxycarbonyl , 2,2, 2-trifluoroethoxymethy1 ,

pentafluoroethoxycarbonyl , 3, 3, 3-trifluoropropoxycarbonyl , 4,4, 4 -trifluorobutoxycarbonyl , heptafluoroisopropoxycarbonyl , and the like.

Examples of cyano Ci- 6 alkyl include, but are not particularly limited to Ci_₆ straight-chain or branched-chain alkyl substituted with a cyano group, such as cyanomethyl, cyanoethyl, cyano-n-propyl , cyano-isopropyl , cyano-n-butyl , cyano-isobutyl , cyano-sec-butyl , cyano-tert-butyl , cyano-n- hexyl, and the like.

Examples of cyano Ci-6 alkoxy include Cx-₆ straight-chain or branched-chain alkoxy substituted with a cyano group, such as cyanomethoxy, cyanoethoxy, cyano-n-propoxy, cyano- isopropoxy, cyano-n-butoxy , cyano-iso-butoxy , cyano-sec-butoxy , cyano-tert-butoxy, cyano-hexyloxy , and the like.

Examples of C₂-6 alkenyl include, but are not particularly limited to, vinyl, allyl, 2-butenyl, 3-butenyl, 1-methylallyl , and the like.

Examples of C2-6 haloalkenyl include, but are not

particularly limited to, 2 , 2-dichlorovinyl , 2 , 2-dibromovinyl , 2 , 2-difluorovinyl, 3, 3-difluoro-2-allyl , 4 , -difluoro-3- butenyl, , 4 , 4-trifluoro-2-butenyl, and the like.

Examples of C₂-e alkynyl include, but are not particularly limited to, ethynyl, 2-propynyl (propargyl) , l-methyl-2- propynyl, 1-butynyl, 2-butynyl, 3-butynyl, and the like.

Examples of C₂-6 haloalkynyl include, but are not

particularly limited to, fluoroethynyl , bromoethynyl ,

chloroethynyl , iodoethynyl, 3, 3, 3-trifluoro-l-propynyl, and the like.

Examples of cyano C2-6 alkenyl include, but are not

particularly limited to, 2-cyanovinyl , 2, 2-dicyanovinyl, 3- cyano-2-allyl , 3 , 3-dicyano-2-allyl , 4 -cyano-3-butenyl , 4,4- dicyano-3-butenyl, 4 , 4 , 4-tricyano-2-butenyl, and the like.

Examples of cyano C2-6 alkynyl include, but are not

particularly limited to, cyanoethynyl , 3-cyano-l-propynyl and the like.

Examples of Ci-6 alkylsulfonyl include, but are not

particularly limited to Ci-₆ straight-chain or branched-chain alkylsulfonyl groups, such as methylsulfonyl , ethylsulfonyl , n-propylsulfonyl, isopropylsulfonyl , n-butylsulfonyl ,

isobutylsulfonyl , sec-butylsulfonyl , tert-butylsulfonyl , and the like.

Examples of Ci_₆ haloalkylsulfonyl include, but are not particularly limited to, fluoromethylsulfonyl ,

chloromethylsulfonyl , bromomethylsulfonyl, iodomethylsulfonyl , dichloromethylsulfonyl , trichloromethylsulfonyl ,

difluoromethylsulfonyl , t ifluoromethylsulfonyl ,

chlorodifluoromethylsulfonyl , bromodifluoromethylsulfonyl , dichlorofluoromethylsulfonyl, 2,2, 2-trichloroethylsulfonyl, 2, 2, 2-trifluoroethylsulfonyl, pentafluoroethylsulfonyl , and like Ci-6 straight-chain or branched-chain alkylsulfonyl substituted with 1 to 9, and preferably 1 to 5, halogen atoms.

Examples of Ci-6 alkylsulfinyl include, but are not particularly limited to Ci-6 straight-chain or branched-chain alkylsulfinyl groups, such as methylsulfinyl , ethylsulfinyl, n-propylsulfinyl , isopropylsulfinyl , n-butylsulfinyl ,

isobutylsulfinyl , sec-butylsulfinyl , tert-butylsulfinyl , and the like.

Examples of Ci_₆ haloalkylsulfinyl include, but are not particularly limited to Ci_6 straight-chain or branched-chain alkylsulfinyl substituted with 1 to 9, and preferably 1 to 5, halogen atoms, such as fluoromethylsulfinyl ,

chloromethylsulfinyl , bromomethylsulfinyl, iodomethylsulfinyl , dichloromethylsulfinyl , trichloromethylsulfinyl ,

difluoromethylsulfinyl , trifluoromethylsulfinyl ,

chlorodifluoromethylsulfinyl , bromodifluoromethylsulfinyl , dichlorofluoromethylsulfinyl , 2,2,2-trichloroethylsulfinyl, 2,2,2-trifluoroethylsulfinyl, pentafluoroethylsulfinyl , and the like.

Examples of Ci-6 alkylthio include, but are not

particularly limited to Ci-₆ straight-chain or branched-chain alkylthio, such as methylthio, ethylthio, n-propylthio , isopropylthio , n-butylthio, isobutylthio, sec-butylthio, tert- butylthio, and the like.

Examples of 0χ_₆ haloalkylthio include, but are not particularly limited to Ci_₆ straight-chain or branched-chain alkylthio substituted with 1 to 9, and 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 , pentafluoroethylthio, and the like.

Examples of C₃-₈ cycloalkylsulfonyl include, but are not particularly limited to, cyclopropylsulfonyl ,

cyclobutylsulfonyl , cyclopentylsulfonyl , cyclohexylsulfonyl, and the like.

Examples of C₃_₈ cycloalkylsulfinyl include, but are not particularly limited to, cyclopropylsulfinyl,

cyclobutylsulfinyl, cyclopentylsulfinyl, cyclohexylsulfinyl , and the like.

Examples of C₃-₈ cycloalkylthio include, but are not particularly limited to, cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, and the like.

Examples of C3-8 cycloalkyl Ci-6 alkylsulfonyl include, but are not particularly limited to, cyclopropylmethylsulfonyl, 2- cyclopropylethylsulfonyl , 3-cyclopropylpropylsulfonyl ,

cyclohexylmethylsulfonyl , and the like.

Examples of C3-8 cycloalkyl Ci-6 alkylsulfinyl include, but are not particularly limited to, cyclopropylmethylsulfinyl , 2- cyclopropylethylsulfinyl, 3-cyclopropylpropylsulfinyl ,

cyclohexylmethylsulfinyl , and the like.

Examples of C3-8 cycloalkyl Ci-₆ alkylthio include, but are not particularly limited to, cyclopropylmethylthio, 2- cyclopropylethylthio, 3-cyclopropylpropylthio,

cyclohexylmethylthio, and the like.

Examples of Ci_6 alkoxy Ci-6 alkylthio include, but are not particularly limited to alkoxyalkylthio in which Ci_₆ straight- chain or branched-chain alkylthio is substituted with Ci_~e straight-chain or branched-chain alkoxy, such as

methoxymethylthio, ethoxymethylthio, n-propoxymethylthio, isopropoxymethylthio, n-butoxymethylthio, sec-butoxymethylthio, tert-butoxymethylthio, 2-methoxyethylthio, and the like.

Examples of C₂-e alkenyloxy include, but are not

particularly limited to, vinyloxy, 1-propenyloxy,

isopropenyloxy , allyloxy, 2-butenyloxy, 3-butenyloxy, 1- methylallyloxy, and the like.

Examples of C2-6 haloalkenyloxy include, but are not particularly limited to, 2 , 2-dichlorovinyloxy, 2,2- dibromovinyloxy, 2 , 2-difluorovinyloxy, 3 , 3-difluoro-2-allyloxy 4 , 4-difluoro-3-butenyloxy, 4 , 4 , 4-trifluoro-2-butenyloxy, and the like.

Examples of C₂~6 alkynyloxy include, but are not

particularly limited to, ethynyloxy, 2-propynyloxy, 1-methyl- 2-propynyloxy, 1 , l-dimethyl-2-propynyloxy, 1-butynyloxy, 2- butynyloxy, 3-butynyloxy, and the like.

Examples of C₂-e haloalkynyloxy include, but are not particularly limited to, fluoroethynyloxy, bromoethynyloxy, chloroethynyloxy, iodoethynyloxy, 3 , 3 , 3-trifluoro-1- propynyloxy, and the like.

Examples of Ci_₆ alkylsulfonyloxy include, but are not particularly limited to Ci_₆ straight-chain or branched-chain alkylsulfonyl groups, such as methylsulfonyloxy,

ethylsulfonyloxy, n-propylsulfonyloxy, isopropylsulfonyloxy, n-butylsulfonyloxy, isobutylsulfonyloxy, sec-butylsulfonyloxy, tert-butylsulfonyloxy, and the like.

Examples of Ci_₆ alkylsulfinyloxy include, but are not particularly limited to Ci_₆ straight-chain or branched-chain alkylsulfinyloxy groups, such as methylsulfinyloxy,

ethylsulfinyloxy, n-propylsulfinyloxy, isopropylsulfinyloxy, n-butylsulfinyloxy, isobutylsulfinyloxy, sec-butylsulfinyloxy, tert-butylsulfinyloxy, and the like.

Examples of substituted or unsubstituted amino include, but are not particularly limited to, amino, monoalkylamino, dialkylamino, monoacylamino, and the like.

Examples of the alkyl include Ci-₆ alkyl mentioned above, and the like.

Examples of the acyl include Ci_₆ alkoxycarbonyl ,

haloalkoxycarbonyl , arylcarbonyl mentioned above, and the like

Examples of aryl include, but are not particularly limited to, phenyl, 1-naphthyl, 2-naphthyl, and the like.

Examples of aryl Ci_₆ alkyl include, but are not

particularly limited to, benzyl, phenylethyl, phenyl-n-propyl and the like. These aryl Ci-6 alkyl can be further substituted at both the parts alkyl as well as aryl.

Examples of aryloxy include, but are not particularly limited to, phenoxy, 1-naphthyloxy, 2-naphthyloxy, and the like.

Examples of aryl Ci_₆ alkoxy include, but are not

particularly limited to, benzyloxy, phenylethoxy , phenyl-n- propoxy, phenyl-n-butoxy , 1-naphthylmethoxy, 2-naphthylmethoxy, and like.

Examples of heteroaryloxy include, but are not

particularly limited to, pyridinyloxy , pyrimidinyloxy ,

pyrazolyloxy , and the like.

Examples of heteroaryl Ci-₆ alkoxy include, but are not particularly limited to, pyridinylmethoxy, pyridinylethoxy, pyrimidinylethoxy , pyrazolylmethoxy , and like.

Examples of arylsulfonyl include, but are not

particularly limited to, phenylsulfonyl , 1-naphthylsulfonyl , 2-naphthylsulfonyl , and the like.

Examples of arylsulfinyl include, but are not

particularly limited to, phenylsulfinyl , 1-naphthylsulfinyl , 2-naphthylsulfinyl, and the like.

Examples of arylthio include, but are not particularly limited to, phenylthio, 1-naphthylthio, 2-naphthylthio, and the like.

Examples of arylsulfonyloxy include, but are not

particularly limited to, phenylsulfonyloxy, 1- naphthylsulfonyloxy, 2-naphthylsulfonyloxy, and the like.

Examples of arylsulfinyloxy include, but are not

particularly limited to, phenylsulfinyloxy, 1- naphthylsulfinyloxy, 2-naphthylsulfinyloxy, and the like.

Examples of aryl Ci-₆ alkylthio include, but are not particularly limited to, benzylthio, phenylethylthio, phenyl- n-propylthio, phenyl-n-butylthio, 1-naphthylmethylthio, 2- naphthylmethylthio, and the like.

Examples of heteroaryl include, but are not particularly limited to, thienyl, furyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl , pyrazolyl, imidazolyl, oxadiazolyl, thiadiazolyl , triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl,

isoindolyl, indazolyl, quinazolinyl , carbazolyl, benzoxazolyl , benzisoxa zolyl , benzothiazolyl , benzisothiazolyl ,

benzimidazolyl , quinolinyl, isoquinolinyl , pyridoindolyl , cinnolinyl, phthalazinyl , quinoxalinyl , purinyl,

phenothiazinylfuranyl , benzofuranyl , chromanyl, benzothienyl , and the like.

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

Examples of a heterocyclic group include, but are not particularly limited to, thienyl, furyl, tetrahydrofuryl , dioxolanyl, dioxanyl, pyrrolyl, pyrrolinyl, pyrrolidinyl , oxazolyl, isoxazolyl, oxazolinyl, oxazolidinyl , isoxazolinyl , thiazolyl, isothiazolyl ,^■ thiazolinyl , thiazolidinyl ,

isothiazolinyl , pyrazolyl, pyrazolidinyl , imidazolyl,

imidazolinyl , imidazolidinyl , oxadiazolyl, oxadiazolinyl , thiadiazolinyl, triazolyl, triazolinyl, triazolidinyl , tetrazolyl, tetrazolinyl , pyridyl, dihydropyridyl ,

tetrahydropyridyl , piperidyl, oxazinyl, dihydroxazinyl , morpholino, thiazinyl, dihydrothiazinyl , thiamorpholino, pyridazinyl, dihydropyridazinyl , tetrahydropyridazinyl , hexahydropyridazinyl , oxadiazinyl, dihydrooxadiazinyl , tetrahydrooxadiazinyl , thiadiazolyl , thiadiazinyl ,

dihydrothiadiazinyl , tetrahydrothiadiazinyl , pyrimidinyl, dihydropyrimidinyl , tetrahydropyrimidinyl ,

hexahydropyrimidinyl , pyrazinyl, dihydropyrazinyl ,

tetrahydropyrazinyl , piperazinyl, triazinyl, dihydrotriazinyl , tetrahydrotriazinyl, hexahydrotriazinyl , tetrazinyl,

dihydrotetrazinyl, indolyl, indolinyl, isoindolyl, indazolyl, quinazolinyl, dihydroquinazolyl , tetrahydroquinazolyl , carbazolyl, benzoxazolyl , benzoxazolinyl , benzisoxazolyl , benzisoxazolinyl, benzothiazolyl , benzisothiazolyl ,

benzisothiazolinyl , benzimidazolyl , indazolinyl, quinolinyl, dihydroquinolinyl , tetrahydroquinolinyl, isoquinolinyl , dihydroisoquinolinyl, tetrahydroisoquinolinyl , pyridoindolyl , dihydrobenzoxazinyl , cinnolinyl, dihydrocinnolinyl ,

tetrahydrocinnolinyl , phthalazinyl, dihydrophthalazinyl , tetrahydrophthalazinyl , quinoxalinyl, dihydroquinoxalinyl , tetrahydroquinoxalinyl , purinyl, dihydrobenzotriazinyl, dihydrobenzotetrazinyl , phenothiazinylfuranyl , benzofuranyl , chromanyl, benzothienyl , and the like.

These heterocyclic groups include those substituted at any subst itutable position with an oxo or thioketone group.

All the heterocyclics mentioned above may optionally be further substituted. Examples of the number of substituents include, but are not particularly limited to, 1 to 20

(preferably 1 to 10, and more preferably 1 to 5) .

Examples of "substituted" or "substituents" include: but are not particularly limited to, the halogen, nitro, cyano, hydroxyl, formyl, Ci-6 alkyl, Ci-6 haloalkyl, Ci-₆ alkoxy, Ci_₆ haloalkoxy, Ci_6 alkoxy Ci-₆ alkyl, Ci-₆ haloalkoxy Ci-6 alkyl, C₃_ 8 cycloalkyl, C₃-s cycloalkyl Ci-6 alkyl, Ci_₆ alkylcarbonyl , Ci_6 haloal kylcarbonyl , arylcarbonyl , aryloxycarbonyl , C₁-₆

alkoxycarbonyl , C\- e haloalkoxycarbonyl , Ci-₆ cyanoalkyl, Ci_6 cyanoalkoxy, C₂-6 alkenyl, C2-6 haloalkenyl, C₂-6 alkynyl, C₂- e haloalkynyl, Ci-₆ alkylsulfonyl, Ci_₆ haloalkylsulfonyl, Ci_₆ alkylsulfinyl, Ci-₆ haloalkylsulfinyl, Ci_₆ alkylthio, Ci-6 haloalkylthio, C₃_₈ cycloalkylsulfonyl , C₃_₈ cycloalkylsulfinyl , C₃_8 cycloalkylthio, C₃-₈ cycloalkyl Ci_₆ alkylsulfonyl, C₃_₈ cycloalkyl Ci-6 alkylsulfinyl , C₃-₈ cycloalkyl Ci-6 alkylthio, Ci_ 6 alkoxy Ci_₆ alkylsulfonyl , Ci^₆ alkoxy Ci-₆ alkylsulfinyl, Ci-6 alkoxy Ci-₆ alkylthio, C₂-6 alkenyloxy, C₂_₆ haloalkenyloxy, C₂_₆ alkynyloxy, C₂-6 haloalkynyloxy , Ci_₆ alkylsulfonyloxy, Ci_6 haloalkylsulfonyloxy, Ci_₆ alkylsulfinyloxy, Ci_6

haloalkylsulfinyloxy, OCN, SCN, SF₅, substituted or

unsubst ituted amino, aryl, aryl Ci_₆ alkyl, aryloxy, aryl Ci_6 alkoxy, arylsulfonyl , arylsulfinyl , arylthio, aryl Ci_₆

alkylsulfonyl, aryl Ci-₆ alkylsulfinyl, aryl Ci-6 alkylthio, heterocyclic, heterocyclic Ci-g alkyl, heterocyclic oxy, and the like. Of these, preferable substituents are¹ halogen, nitro, cyano, Ci_₆ alkyl, Ci-6 haloalkyl, Ci_₆ alkoxy, Ci-₆ haloalkoxy, Ci_6 alkylsulfonyl , Ci-6 haloalkylsulfonyl, Ci_₆ alkylsulfinyl , Ci_₆ haloalkylsulfinyl, Ci-₆ alkylthio, Ci-₆ haloalkylthio, substituted or unsubst ituted amino, aryl, and heterocyclic, and more preferable substituents are fluorine, chlorine, nitro, methyl, ethyl, trifluoromethyl , methoxy, and trifluoromethoxy .

Preferable substituted aryl groups are halogen- substituted aryl, Ci_₆ alkyl-substituted aryl, Ci_₆ haloalkyl- substituted aryl, halogen and Ci_6 haloalkyl-substituted aryl, Ci-6 alkoxy-subst ituted aryl, Ci_6 haloalkoxy-substituted aryl, and Ci-6 al kylthio-substituted aryl. More preferable

substituted aryl groups are chlorine-substituted aryl,

fluorine-substituted aryl, trifluoromethyl-subst ituted aryl, chlorine- and trifluoromethyl-subst ituted aryl,

trifluoromethoxy-subst ituted aryl, and methoxy-subst ituted aryl, and methylthio-subst ituted aryl.

Preferable substituted heteroaryl groups are halogen- substituted heteroaryl, Ci-e alkyl-substituted heteroaryl, C ₆ haloalkyl-substituted heteroaryl, halogen and Ci-6 haloalkyl- substituted heteroaryl, Ci-6 alkoxy-substituted heteroaryl, Ci-₆ haloalkoxy-substituted heteroaryl, and Ci_6 alkylthio- substituted heteroaryl. More preferable substituted heteroaryl groups are chlorine-substituted heteroaryl, fluorine- substituted heteroaryl, trifluoromethyl-substituted heteroaryl, chlorine- and trifluoromethyl-subst ituted heteroaryl,

trifluoromethoxy-substituted heteroaryl, and methoxy- substituted heteroaryl, and methylthio-substituted heteroaryl.

Preferable substituted heterocyclic groups are halogen- substituted heterocyclic, Ci-6 alkyl-substituted heterocyclic, Ci-6 haloalkyl-substituted heterocyclic, Ci_₆ alkoxy-substituted heterocyclic, Ci-6 haloalkoxy-substituted heterocyclic, and Ci-6 alkylthio-subst ituted heterocyclic. More preferable

substituted heterocyclic groups are chlorine-substituted heterocyclic, fluorine-substituted heterocyclic,

trifluoromethyl-subst ituted heterocyclic, trifluoromethoxy- substituted heterocyclic, methoxy-subst ituted heterocyclic, and methylthio-substituted heterocyclic.

The salts of the compoun'ds represented by Formula (1) may be any type of salts as long as they are agriculturally

acceptable. Examples of the salts include inorganic acid salts, such as a hydrochloride salt, a sulfate salt, a nitrate salt, and the like; organic acid salts such as an acetate salt, a methanesulfonic acid salt, and the like; alkali metal salts such as a sodium salt, a potassium salt, and the like;

alkaline earth metal salts such as a magnesium salt, a calcium salt, and the like; quaternary ammonium salts such as dimethylammonium, triethylammonium, and the like; and the like In an embodiment, X and Xi represents oxygen or sulfur; Y represents oxygen, or sulfur;

Z represents oxygen, or sulfur;

1 is an integer 0 to 2;

m is an integer 0 to 3; and

n is an integer 0 to 4.

Among compounds (1) of the present invention, a

preferable compound is a compound in which R_x is hydrogen, halogen, nitro, Ci-₆ alkyl, Ci_₆ haloalkyl, Ci_₆ alkylcarbonyl , cyano Ci-6 alkyl, optionally substituted aryl and a more preferable compound (1) is a compound in which Ri is hydrogen, chlorine, bromine, methyl, chloromethyl , trifluoromethyl , methoxycarbonyl , ethoxycarbonyl , or cyanomethyl .

Among compounds (1) of the present invention, a

preferable compound is a compound in which R2 is hydrogen, or Ci-6 alkyl and a more preferable compound (1) is a compound in which R₂ is methyl.

Among compounds (1) of the present invention, a

preferable compound is a compound in which R3 is hydrogen, halogen, or Ci_6 alkyl and a more preferable compound (1) is a compound in which R₃ is hydrogen.

Among compounds (1) of the present invention, a

preferable compound is a compound in which R₄ is hydrogen, or Ci-6 alkyl and a more preferable compound (1) is a compound in which R₄ is hydrogen.

Among compounds (1) of the present invention, a

preferable compound is a compound in which R5 is hydrogen, or Ci-6 alkyl and a more preferable compound (1) is a compound in which R₅ is hydrogen.

Among compounds (1) of the present invention, a

preferable compound is a compound in which Rg is hydrogen, halogen, Ci-e alkyl or Ci_₆ alkoxy and a more preferable

compound (1) is a compound in which R is hydrogen, chlorine, methyl, or methoxy.

Among compounds (1) of the present invention, a

preferable compound is a compound in which R₇ is hydrogen, Ci_₆ alkyl or Ci_6 alkylcarbonyl and a more preferable compound (1) is a compound in which R₇ is hydrogen, methyl, ethyl,

isopropyl, acetyl, propionyl, or isobutyryl.

Among compounds (1) of the present invention, a

preferable compound is a compound in which R₈ is Ci_₆ alkyl and a more preferable compound (1) is a compound in which R₈ is methyl .

Among compounds (1) of the present invention, a

preferable compound is a compound in which X is oxygen, or sulfur and a more preferable compound (1) is a compound in which X is oxygen.

Among compounds (1) of the present invention, a

preferable compound is a compound in which Xi is oxygen, or sulfur and a more preferable compound (1) is a compound in which Xi is oxygen.

Among compounds (1) of the present invention, a

preferable compound is a compound in which Y is oxygen, or sulfur and a more preferable compound (1) is a compound in which Y is oxygen.

Among compounds (1) of the present invention, a

preferable compound is a compound in which Z is oxygen, or sulfur and a more preferable compound (1) is a compound in which Z is sulfur.

Of these, a more preferable compound of the present invention is a compound or a salt thereof in which

Ri is hydrogen, halogen, nitro, Ci-6 alkyl, Ci_₆ haloalkyl, Ci_₆ alkylcarbonyl, or cyano Ci_₆ alkyl;

R₂ is hydrogen or Ci-6 alkyl;

R₃ is hydrogen, halogen, or Ci_₆ alkyl;

R is hydrogen or Ci-6 alkyl;

R5 is hydrogen or Ci-6 alkyl;

R₆ is hydrogen, halogen, Ci_₆ alkyl or Ci_₆ alkoxy;

R₇ is hydrogen, Ci-6 alkyl or Ci_₆ alkylcarbonyl;

R₈ is Ci-6 alkyl;

X and Xi independently represent oxygen, or sulfur;

Y represents oxygen or sulfur;

Z represents oxygen or sulfur;

1 is an integer of 0 to 2; m is an integer of 0 to 3; and

n is an integer of 0 to 4.

A more particularly preferable compound of the present invention is a compound or a salt thereof in which

Ri is hydrogen, halogen, Ci-e alkyl, or Ci-g haloalkyl;

R2 is hydrogen or methyl;

R3 is hydrogen;

R₄ is hydrogen;

R₅ is hydrogen;

R₆ is hydrogen, chlorine, methyl or methoxy;

R₇ is hydrogen, methyl, ethyl, isopropyl, acetyl, propionyl or isobutyryl ;

R₈ is methyl;

X and Xi independently represent oxygen;

Y represents oxygen;

Z represents oxygen;

1 is an integer of 0 to 2;

m is an integer of 0 to 3; and

n is an integer of 0 to 4.

The invention also provides a process for preparing a carbamate or a salt thereof represented by the formula (1)

Wherein Ri, R₂, R3, R , RS_A

R7, X, Xi, Y, Z, 1, m and n are as defined above.

The carbamate compound represented by Formula (1) can be readily prepared according to following reaction scheme 1 to scheme 4, but is not limited to these methods.

The carbamate compound represented by Formula (ID) can be prepared by the reaction of a 2-substituted five-membered heterocycle compound (2a) with a boron compound (3) in the presence of a catalyst, a base and a solvent as mentioned in reaction scheme 1:

Reaction scheme 1

Wherein, Ri, R₂, R3, R4, R5, Re, Rs/ X, Xi, Y, Z, 1, m and n are as defined above.

A represents halogen, methanesulfonyloxy, p- toluenesulfonyloxy or trifluoromethanesulfonyloxy .

R₉ represents hydrogen, Ci-6 alkyl (the substituent may form -CH₂CH2-, -C (CH₃) 2-C (CH₃) 2- or -CH₂-CH₂-CH₂- with two adjacent Rg) .

The aforementioned reaction can be performed in the presence of a transition metal catalyst. As the transition metal catalyst, a conventionally known transition metal catalyst can widely be used, and examples of the transition metal catalyst include palladium compounds such as palladium acetate (II), tet akis ( triphenylphosphine ) palladium ( 0 ) , bis ( triphenylphosphine ) palladium ( I I ) dichloride,

tris (dibenzylideneacetone ) dipalladium, and [1,1'- bis (diphenylphosphino) ferrocene] dichloropalladium ( II ) complex with dichloromethane ; and the like, preferably

tetrakis (triphenylphosphine) palladium (0) .

The amount of the palladium catalyst to be used is usually 0.01 to 1.0 mol, preferably 0.05 to 0.1 mol, per 1 mol of the compound (3) .

The amount of the compound (2a) to be used is usually 0.5 to 5 mol, preferably 1.0 to 2.0 mol, per 1 mol of the compound (3) .

The aforementioned reaction can be performed in the absence or presence of a base. Among the above, the reaction is performed preferably in the presence of the base. As the base, a conventionally known base can widely be used, and examples of the bases include: alkali metal carbonates such as sodium carbonate, potassium carbonate, cesium carbonate, potassium bicarbonate, sodium bicarbonate, and the like;

alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and the like; inorganic bases such as alkali metal hydrides such as sodium hydride and potassium hydride, and the like; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide , and the like; organic bases such as pyridine, triethylamine, diethylamine, dimethylamine, methylamine, imidazole, benzimidazole , diisopropylethylamine , 4-dimethylamine pyridine, piperidine, and the like; and the like, preferably sodium carbonate, potassium carbonate, cesium carbonate, potassium bicarbonate, sodium bicarbonate, and sodium hydride. Any one of these bases or a combination of two or more types thereof is used.

The amount of the base to be used is usually 1.0 to 5.0 mol, preferably 1.0 to 2.0 mol, per 1 mol of the compound (3) .

The aforementioned reaction is performed in an

appropriate solvent or without any solvent. When the

aforementioned reaction is carried out in the solvent, no limitations are placed on the solvent as long as the solvent is inactive with respect to the aforementioned reaction.

Examples of such a solvent include: fatty acid or

alicyclic hydrocarbon-based solvents such as n-hexane,

cyclohexane, n-heptane, and the like; aromatic hydrocarbon- based solvents such as benzene, chlorobenzene , toluene, xylene, and the like; halogenated hydrocarbon-based solvents such as methylene chloride, 1 , 2-dichloroethane , chloroform, and carbon tetrachloride, and the like; ether-based solvents such as diethyl ether, tetrahydrofuran (THF) , 1,4-dioxane, dimethoxyethane, and the like; esters solvents such as methyl acetate, ethyl acetate, and the like; acetonitrile ; amide- based solvents such as N, N-dimethylformamide (DMF), N,N- dimethylacetamide, N-methyl-2-pyrolidone and the like; and sulfoxide-based solvents such as dimethyl sulfoxide, sulfolane and the like; H₂0; acetic acid, preferably, dimethoxyethane and a mixed solvent of ethanol-H₂0 and toluene-H₂0. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.

The amount of the solvent to be used is usually 1.0 to 20 liters, preferably 1.0 to 10 liters, per 1 mol of the compound (3) .

Reaction temperature for the aforementioned reaction is not particularly limited, and is typically within a range between -10°C and a boiling point of the solvent used and preferably 0 to 120°C.

Reaction time varies depending on, for example, the reaction temperature, and the reaction typically ends in approximately 0.5 to 24 hours.

The carbamate compound represented by Formula (IE) can be prepared by the reaction of a 5-substituted five-membered heterocycle compound (2b) with a boron compound (3) in the presence of a catalyst, a base and a solvent as mentioned in reaction scheme 2:

Reaction scheme 2

(2b) (3) (1 E)

Wherein, Ri, R₂, R₃, ^, Rs, R-6_A X, Xi, Y, Z, 1, m and n are as defined above.

R_g represents hydrogen, Ci_₆ alkyl (the substituent may form -CH₂CH₂-, -C (CH₃) ₂-C (CH₃) ₂- or -CH₂-CH₂-CH₂- with two adj acent R₉) .

The aforementioned reaction can be performed in the presence of a transition metal catalyst. As the transition metal catalyst, a conventionally known transition metal catalyst can widely be used, and examples of the transition metal catalyst include palladium compounds such as palladium acetate (II), tetrakis ( triphenylphosphine )palladium(0) , bis ( triphenylphosphine ) palladium ( I I ) dichloride,

tris (dibenzylideneacetone) dipalladium, and [Ι,ΐ' - bis (diphenylphosphino ) ferrocene] dichloropalladium ( II ) complex with dichloromethane ; and the like, preferably

tetrakis ( triphenylphosphine ) palladium ( 0 ) .

The amount of the compound (2b) to be used is usually 0.5 to 5 mol, preferably 1.0 to 2.0 mol, per 1 mol of the compound (3) .

alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and the like; inorganic bases such as alkali metal hydrides such as sodium hydride and potassium hydride, and the like; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, and the like; organic bases such as pyridine, triethylamine, diethylamine, dimethylamine, methylamine, imidazole, benzimidazole, diisopropylethylamine, 4-dimethylamine pyridine, piperidine, and the like; and the like, preferably sodium carbonate, potassium carbonate, cesium carbonate, potassium bicarbonate, sodium bicarbonate, and sodium Hydride. Any one of these bases or a combination of two or more types thereof is used.

The aforementioned reaction is performed in an

appropriate solvent or without any solvent. When the

Examples of such a solvent include: fatty acid or alicyclic hydrocarbon-based solvents such as n-hexane, cyclohexane, n-heptane, and the like; aromatic hydrocarbon- based solvents such as benzene, chlorobenzene , toluene, xylene, and the like; halogenated hydrocarbon-based solvents such as methylene chloride, 1 , 2-dichloroethane, chloroform, and carbon tetrachloride, and the like; ether-based solvents such as diethyl ether, tetrahydrofuran (THF) , 1,4-dioxane, dimethoxyethane, and the like; esters solvents such as methyl acetate, ethyl acetate, and the like; acetonitrile ; amide- based solvents such as N , N-dimethylformamide (DMF), N,N- dimethylacetamide , N-methyl-2-pyrolidone and the like; and sulfoxide-based solvents such as dimethyl sulfoxide, sulfolane and the like; H₂0; acetic acid, preferably, dimethoxyethane and a mixed solvent of ethanol-H₂0 and toluene-H₂0. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.

The carbamate compound represented by Formula (IF) can be prepared by the reaction of a 4 -substituted five-membered heterocycle compound (2c) with a boron compound (3) in the presence of a catalyst, a base and a solvent as mentioned in reaction scheme 3: Reaction scheme 3

Wherein, R_l7 R₂, R₃, R₄, Rs, Re, Re, X, i, Y, Z, 1, m and n are as defined above.

A represents halogen, methanesulfonyloxy , p- toluenesulfonyloxy or trifluoromethanesulfonyloxy .

Rg represents hydrogen, Ci_6 alkyl (the substituent may form -CH₂CH₂-, -C (CH₃) ₂-C (CH₃) ₂- or -CH₂-CH₂-CH₂- with two adj acent Rg) .

The aforementioned reaction can be performed in the presence of a transition metal catalyst. As the transition metal catalyst, a conventionally known transition metal catalyst can widely be used, and examples of the transition metal catalyst include palladium compounds such as palladium acetate (II) , tetrakis (triphenylphosphine) palladium ( 0 ) , bis (triphenylphosphine) palladium ( II ) dichloride,

tris (dibenzylideneacetone) dipalladium, and [Ι,ΐ' - bis (diphenylphosphino )ferrocene]dichloropalladium(II) complex with dichloromethane ; and the like, preferably

tetrakis ( triphenylphosphine ) palladium ( 0 ) .

The amount of the compound (2c) to be used is usually 0.5 to 5 mol, preferably 1.0 to 2.0 mol, per 1 mol of the compound (3) .

The aforementioned reaction can be performed in the absence or presence of a base. Among the above, the reaction is performed preferably in the presence of the base. As the base, a conventionally known base can widely be used, and examples of the bases include: alkali metal carbonates such as sodium carbonate, potassium carbonate, cesium carbonate, potassium bicarbonate, sodium bicarbonate, and the like; alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and the like; inorganic bases such as alkali metal hydrides such as sodium hydride and potassium hydride, and the like; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide , and the like; organic bases such as pyridine, t riethylamine , diethylamine , dimethylamine , methylamine, imidazole, benzimidazole, diisopropylethylamine , 4-dimethylamine pyridine, piperidine, and the like; and the like, preferably sodium carbonate, potassium carbonate, cesium carbonate, potassium bicarbonate, sodium bicarbonate, and sodium hydride. Any one of these bases or a combination of two or more types thereof is used.

The aforementioned reaction is performed in an

appropriate solvent or without any solvent. When the

Examples of such a solvent include: fatty acid or

alicyclic hydrocarbon-based solvents such as n-hexane,

cyclohexane, n-heptane, and the like; aromatic hydrocarbon- based solvents such as benzene, chlorobenzene, toluene, xylene, and the like; halogenated hydrocarbon-based solvents such as methylene chloride, 1 , 2-dichloroethane , chloroform, and carbon tetrachloride, and the like; ether-based solvents such as diethyl ether, tetrahydrofuran (THF) , 1,4-dioxane, dimethoxyethane , and the like; esters solvents such as methyl acetate, ethyl acetate, and the like; acetonitrile ; amide- based solvents such as , N-dimethylformamide (DMF), N,N- dimethylacetamide , N-methyl-2-pyrolidone and the like; and sulfoxide-based solvents such as dimethyl sulfoxide, sulfolane and the like; H₂O; acetic acid, preferably, dimethoxyethane and a mixed solvent of ethanol-R^O and toluene-H₂0. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary. The amount of the solvent to be used is usually 1.0 to 20 liters, preferably 1.0 to 10 liters, per 1 mol of the compound (3) .

The compound (3) used in this step can be produced according to a known method (for example, the method described in WO2016/114165, WO2016/11 164 , O2016/114162 and

WO2016/114161) .

The carbamate compound represented by Formula (1) can be prepared by the reaction of a reagent (4) with a compound (1G) in the presence of a catalyst, a base and a solvent as

mentioned in reaction scheme :

Reaction scheme 4

(1 G)

Wherein, R_lf R₂, R₃, R₄, R₅, Re, R₇, R^'e, , Xi, Y, Z, 1, m and n are as defined above, and G represents a leaving group.

The ratio between the compound (1G) and a reagent (4) used in the reaction is not particularly limited and can appropriately be selected from a wide range. The amount of a reagent (4) to be used is usually 1.0 to 5.0 mol, preferably 1.0 to 2.0 mol, per 1 mol of the compound (1G) . The aforementioned reaction can be performed in the absence or presence of a base. Among the above, the reaction is performed preferably in the presence of the base. As the base, a conventionally known base can widely be used, and examples of the base include: alkali metal carbonates such as sodium carbonate, potassium carbonate, cesium carbonate, potassium bicarbonate, sodium bicarbonate, and the like;

alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and the like; inorganic bases such as alkali metal hydrides such as sodium hydride and potassium hydride, and the like; alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide , and the like; organic bases such as pyridine, triethylamine , diethylamine, dimethylamine, methylamine, imidazole, benzimidazole, diisopropylethylamine, 4 -dimethylamine pyridine, piperidine, and the like; and the like, preferably alkali metal carbonates and alkali metal hydrides, more preferably sodium carbonate, potassium

carbonate, potassium bicarbonate, sodium bicarbonate and sodium hydride. Any separate one of these bases or a

combination of two or more types thereof is used.

The amount of the base to be used is usually 1.0 to 5.0 mol, preferably 1.0 to 3.0 mol, per 1 mol of the compound (1G).

The aforementioned reaction can be performed by further adding a radical initiator. Examples of the radical initiator include, but are not particularly limited to sulfurous acid adducts, such as sulfurous acid, a sulfurous acid salt,

Rongalite (compound name, sodium formaldehydesulfoxylate ) , and the like. The base and' the radical initiator can be used in combination .

When the radical initiator is used, as an additive amount thereof, the amount of the radical initiator to be used is usually 0.1 to 10.0 mol, preferably 0.1 to 5.0 mol, per 1 mol of the compound (1G) .

The aforementioned reaction is performed in an

appropriate solvent. Examples of the solvent include: fatty acid or alicyclic hydrocarbon-based solvents such as n-hexane, cyclohexane n-heptane, and the like; aromatic hydrocarbon- based solvents such as benzene, chlorobenzene , toluene, xylene, and the like; halogenated hydrocarbon-based solvents such as methylene chloride, 1 , 2-dichloroethane , chloroform, carbon tetrachloride, and the like; ether-based solvents such as diethyl ether, THF, 1,4-dioxane, and the like; ester-based solvents such as methyl acetate, ethyl acetate, and the like; amide-based solvents such as acetonit rile ; DMF, N,N- dimethylacetamide , N-methyl-2-pyrrolidone , and the like;

dimethyl sulfoxide and the like sulfoxide-based solvents;

polar solvents such as alcohol-based solvents such as

sulfolane, methanol, ethanol, isopropyl alcohol, and the like; water; and the like. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.

The amount of the solvent to be used is usually 1.0 to 20 liters, preferably 1.0 to 10 liters, per 1 mol of the compound (1G) .

The reaction temperature varies depending on the starting compound, the reagent, the solvent and the like, but it is usually from -40°C to the reflux temperature in the reaction system, preferably from 0 to 100°C.

The reaction time varies depending on the compound, the reagent, the solvent and the reaction temperature and the like, but is usually from 5 minutes to 48 hours, preferably from 10 minutes to 24 hours.

The compound represented by Formula (1) obtained by the method shown in Schemes from 1 to 4 is easily isolated from a reaction mixture and can be purified by use of typical

isolation means and purification means, for example,

filtration, solvent extraction, distillation,

recrystallization, column chromatography, etc.

Although a form used for the present compound may be the present compound as itself, the present compound is usually prepared by mixing the present compound with solid carriers, liquid carriers, gas carriers, surfactants and the others, and if necessary, adding stickers, dispersers and stabilizers, to formulate into wettable powders, water dispersible granules, flowables, granules, dry flowables, emulsifiable concentrates, aqueous solutions, oil solutions, smoking agents, aerosols, microcapsules and the others, In these formulations, the present compound is contained in a range of usually 0.1 to 99%, preferably 0.2 to 90% by weight.

Examples of the solid carrier include clays (for example, kaolin, diatomaceous earth, synthetic hydrated silicon dioxide, Fubasami clay, bentonite and acid clay) , talcs or the other inorganic minerals (for example, sericite, quartz powder, sulfur powder, activated charcoal, calcium carbonate and hydrated silica) in the form of fine powders or particulates, and examples of the liquid carries include water, alcohols (for example, methanol and ethanol), ketones (for example, acetone and methyl ethyl ketone), aromatic hydrocarbons (for example, benzene, toluene, xylene, ethylbenzene and methyl naphthalene), aliphatic hydrocarbons (for example, n-hexane, cyclohexane and kerosene), esters (for example, ethyl acetate and butyl acetate) , nitriles (for example, acetonitrile and isobutyronitrile) , ethers (for example, dioxane and

diisopropyl ether), acid amides (for example, N,N-dimethyl formamide (DMF) and dimethylacetamide ) , halogenated

hydrocarbons (for example, dichloroethane trichloroethylene and carbon tetrachloride) and the others.

Examples of the surfactants include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenated compounds thereof, polyethylene glycol ethers, polyol esters and sugar alcohol derivatives.

Examples of other auxiliary agents for formulation

include stickers, dispersers and stabilizers, specifically casein, gelatin, polysaccharides (for example, starch, gum arabic, cellulose derivatives and alginic acid) , lignin

derivatives, bentonite, sugars, water-soluble synthetic

polymers (for example, polyvinyl alcohol, polyvinyl

pyrrolidone and polyacrylic acids) , PAP (acidic isopropyl phosphate) , BHT (2, 6-di-tert-butyl-4-methylphenol) , BHA (a mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4- methoxyphenol ) , vegetable oils, mineral oils, fatty acids or fatty acid esters thereof and the others.

The method for applying the present compound is not particularly limited, as far as the applying form is a form by which the present compound may be applied substantially, and includes, for example, an application to plants such as a foliage application; an application to area for cultivating plants such as a submerged treatment; and an application to soil such as seed disinfection.

The application dose varies depending on weather

conditions, dosage forms, timing of application, methods of application, areas to be applied, target diseases and target crops etc., but is in the range of usually from 1 to 500 g, and preferably from 2 to 200 g per 1,000 m² of the area to be applied. The emulsifiable concentrate, the wettable powder or the suspension concentrate, etc., is usually applied by diluting it with water. In this case, the concentration of the present compound after dilution is in the range of usually 0.0005 to 2% by weight, and preferably 0.005 to 1% by weight. The dust formulation or the granular formulation etc., is usually applied, as itself without diluting it. In the

application to seeds, the amount of the present compound is in the range of usually from 0.001 to 100 g, and preferably from 0.01 to 50 g per 1 kg of the seeds.

Herein, examples of the place where the pests live include paddy fields, fields, tea gardens, orchards, non- agricultural lands, houses, nursery trays, nursery boxes, nursery soils and nursery bed.

Also, in another embodiment, for example, the present compound can be administered to the inside (inside of the body) or the outside (body surface) of the below-mentioned vertebrate to exterminate systemically or unsystemically living things or parasites which are parasitic on the

vertebrate. Examples of a method of the internal medication include an oral administration, an anal administration, atransplantation, an administration via injection

subcutaneously, intramuscularly or intravenously. Examples of a method of outside medication include a transdermal administration. Also, the present compound can be ingested to a livestock animal so as to exterminate sanitary insects which occur in the excrement of the animal.

When the present compound is applied to the animals such as the livestock animal and pets on which pests are parasitic, the dose varies depending on the administration method etc., but it is desirable in general to administer the present compound so that a dose of the active ingredient (the present compound or salts thereof) is in the range of generally from 0.1 mg to 2,000 mg and preferably 0.5 mg to 1,000 mg per 1 kg of body weight of the animal .

The present compound can be used as an agent for

controlling plant disease in agricultural lands such as fields, paddy fields, lawns, orchards. The compound of the present invention can control diseases occurred in the agricultural lands or the others for cultivating the following ' 'plant' ' .

Crops: corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean, peanut, buckwheat, beet, rapeseed, sunflower, sugar cane, tobacco, and the others; Vegetables: solanaceous vegetables (for example, eggplant, tomato, pimento, pepper and potato), cucurbitaceous vegetables (for example, cucumber, pumpkin, zucchini, water melon and melon), cruciferous

vegetables (for example, Japanese radish, white turnip,

horseradish, kohlrabi, Chinese cabbage, cabbage, leaf mustard, broccoli, cauliflower), asteraceous vegetables (for example, burdock, crown daisy, artichoke and lettuce) , liliaceous vegetables (for example, green onion, onion, garlic and

asparagus), ammiaceous vegetables (for example, carrot,

parsley, celery and parsnip), chenopodiaceous vegetables (for example, spinach and Swiss chard), lamiaceous vegetable's (for example, Perilla frutescens, mint and basil), strawberry, sweet potato, Dioscorea japonica, colocasia and the others;

Flowers: Ornamental foliage plants: Fruits: pomaceous fruits (for example, apple, pear, Japanese pear, Chinese quince and quince), stone fruits (for example, peach, plum, nectarine, Prunus mume, cherry fruit, apricot and prune), citrus fruits (for example, Citrus unshiu, orange, lemon, lime and

grapefruit), nuts (for example, chestnut, walnuts, hazelnuts, almond, pistachio, cashew nuts and macadamia nuts), berry fruits (for example, blueberry, cranberry, blackberry and raspberry) , grape, kaki persimmon, olive, Japanese plum, banana, coffee, date palm, coconuts, and the others; Trees other than fruit trees: tea, mulberry, flowering plant, roadside trees (for example, ash, birch, dogwood, Eucalyptus, Ginkgo biloba, lilac, maple, Quercus, poplar, Judas tree, Liquidambar formosana, plane tree, zelkova, Japanese

arborvitae, fir wood, hemlock, juniper, Pinus, Picea, and Taxus cuspidata) ; and the others.

The above-mentioned ''plant'' includes genetically modified crops.

The pests on which the present compound has a control efficacy include plant pathogens such as filamentous fungus, as well as harmful arthropods such as harmful insects and harmful mites, and nemathelminth such as nematodes, and specifically include the following examples, but are not limited thereto.

Rice diseases: blast (Magnaporthe grisea) , brown spot (Cochliobolus miyabeanus), sheath blight (Rhizoctonia solani), bakanae disease (Gibberella fujikuroi), and downy mildew

( Sclerophthora macrospora ) ;

Wheat diseases: powdery mildew (Erysiphe graminis), fusarium blight (Fusarium graminearum, F. avenaceum, F.

culmorum, Microdochium nivale) , rust (Puccinia striiformis, P. graminis, P. recondita), snow mould (Micronectriella nivale), typhulasnow blight (Typhula sp.), loose smut (Ustilago

tritici) , stinking smut (Tilletia caries, T. controversa ) , eyespot (Pseudocercosporella herpotrichoides ) , leaf blotch (Septoria tritici), glume blotch ( Sta'gonospora nodorum) , tan spot (Pyrenophora tritici-repentis ) , rhizoctonia seeding blight (Rhizoctonia solani), and take all disease

(Gaeumannomyces graminis);

Barley diseases: powdery mildew (Erysiphe graminis), fusarium blight (Fusarium graminearum, F. avenaceum, F.

culmorum, Microdochium nivale), rust (Puccinia striiformis, P. graminis, P. hordei), loose smut (Ustilago nuda) , scald

(Rhynchosporium secalis), net blotch (Pyrenophora teres), spot blotch (Cochliobolus sativus), leaf stripe (Pyrenophora

graminea) , Ramularia disease (Ramularia collo-cygni) , and rhizoctonia seeding blight (Rhizoctonia solani);

Corn diseases: rust (Puccinia sorghi), southern rust

(Puccinia polysora) , northern leaf blight ( Setosphaeria

turcica), southern leaf blight (Cochliobolus heterostrophus ) , anthracnose (Colletotrichum graminicola) , gray leaf spot

(Cercospora zeae-maydis ) , eyespot (Kabatiella zeae) , and phaeosphaeria leaf spot ( Phaeosphaeria maydis);

Cotton diseases: anthracnose (Colletotrichum gossypii) , grey mildew (Ramularia areola), alternaria leaf spot

(Alternaria macrospora, A. gossypii);

Coffee diseases: rust (Hemileia vastatrix) ;

Rape seed diseases: sclerotinia rot (Sclerotinia

sclerotiorum) , black spot (Alternaria brassicae) , and black leg (Phoma lingam) ;

Citrus diseases: melanose (Diaporthe citri), scab

(Elsinoe fawcettii), and fruit rot (Penicillium digitatum, P. italicum) ;

Apple diseases: blossom blight (Monilinia mali), canker

(Valsa ceratosperma) , powdery mildew (Podosphaera leucotricha) , alternaria leaf spot (Alternaria alternata apple pathotype) , scab (Venturia inaequalis), and bitter rot (Colletotrichum acutatum) ;

Pear diseases: scab (Venturia nashicola, V. pirina) , black spot (Alternaria alternata Japanese pear pathotype) and rust (Gymnosporangium haraeanum) ;

Peach diseases: brown rot (Monilinia fructicola) , scab (Cladosporium carpophilum) and Phomopsis rot (Phomopsis sp.);

Grapes disease's: anthracnose (Elsinoe ampelina) , ripe rot

(Glomerella cingulata) , powdery mildew (Uncinula necator) , rust (Phakopsora ampelopsidis ) , black rot (Guignardia

bidwellii), and downy mildew (Plasmopara viticola);

Diseases of Japanese persimmon: anthracnose (Gloeosporium kaki) and leaf spot (Cercospora kaki, Mycosphaerella nawae) ;

Diseases of gourd family: anthracnose (Colletotrichum lagenarium) , powdery mildew ( Sphaerotheca fuliginea) , gummy stem blight (Didymella bryoniae) , target spot (Corynespora cassiicola) , fusarium wilt (Fusarium oxysporum) , downy mildew ( Pseudoperonospora cubensis), phytophthora rot ( Phytophthora sp.) and damping-off (Pythium sp.)

Tomato diseases: early blight (Alternaria solani), leaf mold (Cladosporium fulvum) , leaf mold ( Pseudocercospora fuligena) , and late blight (Phytophthora infestans);

Eggplant disease: brown spot (Phomopsis vexans) and powdery mildew (Erysiphe cichoracearum) ;

Diseases of Cruciferous Vegetables: alternaria leaf spot (Alternaria japonica) , white spot (Cercosporella brassicae) , clubroot (Plasmodxophora parasitica), downy mildew

(Peronospora parasitica);

Welsh onion diseases: rust (Puccinia allii);

Soybean diseases: purple stain (Cercospora kikuchii), sphaceloma scad (Elsinoe glycines), pod and stem blight

(Diaporthe phaseolorum var. sojae), rust (phakopsora

pachyrhizi), target spot (Corynespora cassiicola), anthracnose (Colletotrichum glycines, C. truncatum) , Rhizoctonia aerial blight (Rhizoctonia solani), septoria brown spot (Septoria glycines) and frog eye leaf spot (Cercospora sojina);

Kidney bean diseases: anthracnose (Colletotrichum

lindemuthianum) ;

Peanut diseases: early leaf spot (Cercospora personata) , late leaf spot (Cercospora arachidicola ) and southern blight (Sclerotium rolfsii) ;

Garden pea diseases: powdery mildew (Erysiphe pisi);

Potato diseases: early blight (Alternaria solani), late blight (Phytophthora infestans), and verticillium wilt

( erticillium albo-atrum, V. dahliae, V. nigrescens);

' Strawberry diseases: powdery mildew ( Sphaerotheca

humuli ) ;

Tea diseases: net blister blight (Exobasidium

reticulatum) , white scab (Elsinoe leucospila) , gray blight ( Pestalotiopsis sp.) and anthracnose (Colletotrichum theae- sinensis) ;

Tobacco diseases: brown spot (Alternaria longipes), powdery mildew (Erysiphe cichoracearum) , anthracnose

(Colletotrichum tabacum) , downy mildew (Peronospora tabacina) , and black shank ( Phytophthora nicotianae) ;

Sugar beet diseases: cercospora leaf spot (Cercospora beticola) , leaf blight (Thanatephorus cucumeris), root rot (Thanatephorus cucumeris) and aphanomyces root rot

(Aphanomyces cochlioides ) ;

Rose diseases: black spot (Diplocarpon rosae) and powdery mildew ( Sphaerotheca pannosa);

Diseases of Chrysanthemum: leaf blight (Septoria

chrysanthemi-indici ) and white rust (Puccinia horiana) ;

Onion diseases: botrytis leaf blight (Botrytis cinerea, B. byssoidea, B. squamosa), gray-mold neck rot (Botrytis allii), and small sclerotial rot (Botrytis squamosa) ;

Various crops diseases: gray mold (Botrytis cinerea), and sclerotinia rot (Sclerotinia sclerotiorum) ;

Diseases of Japanese radish: alternaria leaf spot

(Alternaria brassicicola) ;

Turfgrass diseases: dollar spot (Sclerotinia homoeocarpa) , brown patch and large patch (Rhizoctonia solani); and

Banana diseases: Sigatoka disease (Mycosphaerella

fijiensis, Mycosphaerella musicola) .

Hemiptera: Delphacidae (for example, Laodelphax

striatellus, Nilaparvata lugens, or Sogatella furcifera) ;

Deltocephalinae (for example, Nephotettix cincticeps, or

Nephotettix virescens) ; Aphididae (for example, Aphis gossypii, Myzus persicae, Brevicoryne brassicae, Macrosiphum euphorbiae, Aulacorthum solani, Rhopalosiphum padi, Toxoptera citricidus ) ; Pentatomidae (for example, Nezara antennata, Riptortus

clavatus, Leptocorisa chinensis, Eysarcoris parvus,

Halyomorpha mista, or Lygus lineolaris ) ; Aleyrodidae (for example, Trialeurodes vaporariorum, or Bemisia argentifolii ) ; Coccoidea (for example, Aonidiella aurantii, Comstockaspis perniciosa, Unaspis citri, Ceroplastes rubens, or Icerya purchasi); Tingidae, Psyllidae; Bed bugs (Cimex lectularius) and the others .

Lepidoptera: Pyralidae (for example, Chilo suppressalis ,

Tryporyza incertulas, Cnaphalocrocis medinalis, Notarcha derogata, Plodia interpunctella , Ostrinia furnacalis, Hellula undalis, Pediasia teterrellus ) , Noctuidae (for example, Spodoptera litura, Spodoptera exigua, Pseudaletia separata, Mamestra brassicae, Agrotis ipsilon, Plusia nigrisigna,

Trichoplusia spp., Heliothis spp., or Helicoverpa spp.;

Pieridae (for example, Pieris rapae) , Tortricidae (for example, Adoxophyes spp., Grapholita molesta, Cydia pomonella,

Leguminivora glycinivorella , Matsumuraeses azukivora,

Adoxophyes orana fasciata, Adoxophyes sp . , Homona magnanima, Archips fuscocupreanus , Cydia pomonella); Gracillariidae (for example, Caloptilia theivora, Phyllonorycter ringoniella) ;

Carposinidae (for example, Carposina niponensis ) ; Lyonetiidae (for example, Lyonetia spp.); Lymantriidae (for example,

Lymantria spp., or Euproctis spp.); Yponomeutidae (for example, Plutella xylostella); Gelechiidae (for example, Pectinophora gossypiella or Phthorimaea operculella); Arctiidae (for

example, Hyphantria cunea) ; Tineidae (for example, Tinea translucens, or Tineola bisselliella) ; and the others;

Thysanoptera : Thysanoptera (for example, Frankliniella occidentalis , Thrips palmi, Scirtothrips dorsalis, Thrips tabaci, Frankliniella intonsa, Frankliniella fusca) ;

Diptera: Musca domestica, Culex pipiens pallens, Tabanus trigonus, Hylemya antiqua, Hylemya platura, Anopheles sinensis, Agromyza oryzae, Hydrellia griseola, Chlorops oryzae, Dacus cucurbitae, Ceratitis capitata, Liriomyza trifolii, and the others ;

Coleoptera: Epilachna vigintioctopunctata, Aulacophora femoralis, Phyllotreta striolata, Oulema oryzae, Echinocnemus squameus, Lissorhoptrus oryzophilus, Anthonomus grandis,

Callosobruchus chinensis, Sphenophorus venatus, Popillia japonica, Anomala cuprea, Diabrotica spp., Leptinotarsa

decemlineata , Agriotes spp., Lasioderma serricorne, Anthrenus verbasci, Tribolium castaneum, Lyctus brunneus, Anoplophora malasiaca, Tomicus piniperda) , and the others;

Orthoptera: Locusta migratoria, Gryllotalpa africana, Oxya yezoensis, Oxya japonica, and the others ;

Hymenoptera: Athalia rosae, Acromyrmex spp., Solenopsis spp., and the others;

Nematodes: Aphelenchoides besseyi, Nothotylenchus acris, Heterodera glycines, Meloidogyne incognita, Pratylenchus , Nacobbus aberrans, and the others;

Blattariae: Blattella germanica, Periplaneta fuliginosa, Periplaneta americana, Periplaneta brunnea, Blatta orientalis, and the others;

Acarina: Tetranychidae (for example, Tetranychus urticae,

Panonychus citri, or Oligonychus spp . ) ; Eriophyidae (for example, Aculops pelekassi); Tarsonemidae (for example,

Polyphagotarsonemus latus); Tenuipalpidae ; Tuckerellidae

Acaridae (for example, Tyrophagus putrescentiae ) ;

Pyroglyphidae (for example, Dermatophagoides farinae, or

Dermatophagoides pteronyssinus ) ; Cheyletidae (for example, Cheyletus eruditus, Cheyletus malaccensis, or Cheyletus

moorei); Dermanyssidae ; and the others.

The formulation comprising the present compound or salts thereof can also be used in the field relating to a treatment of livestock diseases or livestock industry, and for example, can exterminate the living things or parasites which are parasitic on the inside and/or the outside of a vertebrate such as human being, cow, sheep, pig, poultry, dog, cat and fish, so as to maintain public health.

Examples of the pests include Ixodes spp. (for example, Ixodes scapularis), Boophilus spp. (for example, Boophilus microplus), Amblyomma spp., Hyalomma spp., Rhipicephalus spp. (for example, Rhipicephalus sanguineus), Haemaphysalis spp.

(for example, Haemaphysalis longicornis ) , dermacentor spp., Ornithodoros spp. (for example, Ornithodoros moubata) ,

Dermanyssus gallinae, Ornithonyssus sylviarum, Sarcoptes spp. (for example, Sarcoptes scabiei), Psoroptes spp., Chorioptes spp., Demodex spp., Eutrombicula spp., Ades spp. (for example, Aedes albopictus), Anopheles spp., Culex spp., Culi'coides spp., Musca spp., Hypoderma spp., Gasterophilus spp., Haematobia spp., Tabanus spp., Simulium spp., Triatoma spp., Phthiraptera (for example, Damalinia spp.), Linognathus spp., Haematopinus spp., Ctenocephalides spp. (for example, Ctenocephalides felis) Xenopsylla spp., monomorium pharaonis and nematodes, hairworm (for example, Nippostrongylus brasiliensis ,

Trichostrongylus axei, Trichostrongylus colubriformis ) ,

Trichinella spp. (for example, Trichinella spiralis), Haemonchus contortus, Nematodirus spp. (for example,

Nematodirus battus) , Ostertagia circumcincta , Cooperia spp., Hymenolepis nana, and the others. The carbamate (1) of the invention is used, for example, as active ingredient for a fungicide.

The carbamate (1) of the invention can be used by being made into the desirable form such as an oil, emulsion, wettable powder, flowable preparation, granules, powder, aerosol, fumigant or the like. In this case, the content of the carbamate (1) of the invention is not limited and can be suitably selected from a wide range according to various conditions such as the form of preparation, kind of disease to be treated, kind of plant, severity of disease, place of application, time of application, method of application, chemicals to be used in combination (insecticide, nematicide, acaricide, fungicide, herbicide, plant growth control agent, synergist, soil conditioner, etc.) , amount and kind of fertilizer and so on. The content is usually about 0.01 to about 95% by weight, based on the total amount of the

fungicidal preparation.

A fungicidal preparation containing the carbamate (1) of the invention as the active ingredient can be produced

according to known processes. For example, the carbamate (1) of the invention may be mixed with a carrier such as a solid carrier, a liquid carrier, a gaseous carrier or the like.

Optionally a surfactant and other adjuvants for

preparation may be added.

Useful carriers can be any of known ones which are usually used in this field.

Examples of useful solid carriers are fine or granules of clays (kaolin clay, diatomaceous earth, synthetic hydrated silicon dioxide, bentonite, fubasami clay, acid clay and the like) , talcs, ceramics, other inorganic minerals 8cerite, quartz, sulfur, activated carbon, calcium carbonate, hydrated silica, etc.) , and so on.

Useful liquid carriers are, for example, water, alcohols (such as methanol, ethanol, etc.) , ketones (such as acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (such as benzene, toluene, xylene, ethylbenzene , methylnaphthalene, etc.), aliphatic hydrocarbons (such as hexane, cyclohexane, kerosene, light oil, etc.), esters (such as ethyl acetate, butyl acetate, etc.), nitriles (such as acetonitrile ,

isobutyronitrile, etc.), ethers (such as diisopropyl ether, dioxane, etc.), acid amides (such as N, N-dimethylformamide, N, -dimethylacetamide, etc.) , halogenated hydrocarbon (such as dichloromethane , trichloroethane , carbon tetrachloride, etc.), dimethylsulfoxide , soybean oil, cotton seed oil, vegetable oils and so on.

Examples of useful gaseous carriers (propellants ) are butane gas, LPG (liquefied petroleum gas) , dimethyl ether, carbon dioxide, etc.

Examples of useful surfactants are alkyl ester sulfates, alkyl sulfonates, alkylarylsulfonates , alkyl aryl ethers, polyoxyethylenated products thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol compounds, etc .

Examples of useful adjuvants for preparation are fixing agents such as casein, gelatin, polysaccharides (starch powder, gum Arabic, cellulose compound, alginic acid, etc.), lignin compounds, bentonite, saccharides, synthetic water-soluble polymers (polyvinyl alcohol, polyvinyl pyrrolidone,

polyacrylic acid, etc.) and the like; stabilizers such as PAP (acidic isopropyl phosphate), BBH (2 , 6-di-tert-butyl-4- methylphenol ) , BRA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl- -methoxyphenol ) , vegetable oils, mineral oils, fatty acids, esters thereof and the like.

The fungicidal preparation of the invention thus obtained can be used as it is or as diluted with water. The preparation may be prepared by being mixed with any of insecticides, nematicides, acaricides, fungicides, herbicides, plant growth control agents, synergists, soil conditioners, etc. The

preparation of the invention may be applied simultaneously with other preparations.

When the preparation of the invention is used as a

fungicide for use in agriculture and horticulture, the amount of the preparation of the invention is not limited and can be suitably selected from a wide range according to various conditions such as the concentration of active ingredient, the form of preparation, kind of disease to be treated, kind of plant, severity of disease or mite, time for application, method of application, chemicals to be used in combination (insecticide, nematicide, miticide, fungicide, herbicide, plant growth control agent, synergist, soil conditioner, etc.), amount and kind of a fertilizer and so on. The amount is usually about 0.001 to about 100 g per 100 m² of the area.

When an emulsion, wettable powder, flowable preparation or the like diluted with water is used, the concentration of the fungicidal or miticidal preparation is about 0.1 to about 1000 ppm, preferably about 1 to 500 ppm. The granules, particles or the like are applied as such without dilution.

The compound of the invention is characterized by having an excellent fungicidal activity and a broad spectrum of activity. The compound can be used for control of plant

diseases ascribed to pathogenic fungi and resistant pathogenic fungi. Examples of such pathogenic fungi include those that cause or are resistant to fungicides to treat rice plant blast, rice plant sheath blight, grey mould on tomato and the like, apple powdery mildew, apple alternaria blotch, persimmon powdery mildew, grape powdery mildew, barley powdery mildew, wheat powdery mildew, cucumber powdery mildew, cucumber gray mold, tomato late blight, potato blight and the like.

EXAMPLES

The invention will be described in more details with reference to Preparation examples, Formulation examples and Test examples.

The present invention describes in more details with reference to the following Reference examples production examples, Formulation example and Test examples. However, the present invention is not limited to these examples. In

addition, alterations can be made within the scope that does not depart from the scope of the present invention. Preparation example 1

Preparation of methyl (2- ( (2-methyl-4- (4-

( trifluoromethyl) thiazol-2-yl) phenoxy) methyl ) phenyl ) carbamate (Compound lA-1)

(1) 1- ( 2-Nitrobenzyloxy ) -4 -bromo-2-methylbenzene

To a cooled solution of 4-bromo-2-methylphenol (0.93 g, 5.0 mmol) and ( 2-nitrophenyl ) methanol (1.0 g, 6.5 mmol) in dry THF (10 ml) was added triphenylphosphine (1.9 g, 7.5 mmol) followed by slow addition of diethylazodicarboxylate (0.78 g, 7.5 mmol) under nitrogen atmosphere. The resulting mixture was then stirred at room temperature for 12h. The reaction mixture was then poured into cold distilled water and extracted with ethyl acetate (3 x 70 mL) . The combined organic layer was washed with distilled water, dried over sodium sulfate,

filtered and concentrated under reduced pressure to get crude residue. The residue was then purified by column

chromatography (ethyl acetate : n-hexane = 1:9) to afford the title compound.

XH NMR (CDC1₃) : δ 8.18 (d, J = 8.0 Hz, 1H) , 7.88 (d, J = 7.6 Hz, 1H), 7.70 (t, J = 8.4 Hz, 1H) , 7.51 (t, J = 7.6 Hz, 1H) , 7.31- 7.30 (m, 1H), 7.27-7.24 (m, 1H) , 6.74 (d, J = 8.4 Hz, 1H) , 5.46 (s, 2H) , 2.30 (s, 3H) . (2) 2- (( 4 -Bromo-2-methylphenoxy) methyl ) aniline

Cuprous chloride (0.74 g, 7.5 mmol) was added to a cooled solution of 1- ( 2-nitrobenzyloxy ) -4-bromo-2-methylbenzene (1.2 g, 3.7 mmol) in methanol (10 ml) . To this mixture, sodium borohydride (0.69 g, 18.7 mmol) was then portion-wise added. The resulting mixture was then stirred at room temperature for 2h. The reaction mixture was then quenched by saturated

ammonium chloride solution and diluted with ethyl acetate (100 mL) . The organic layer was washed with distilled water, dried over sodium sulfate, filtered and concentrated under reduced pressure to get the title compound as a light yellow solid

(0.90 g, crude) . It was then used in the next step without further purification. ^XH NMR (DMSO-dg) : δ 7.33-7.30 (m, 2H) , 7.18-7.17 (m, 1H) , 7.04- 7.00 (m, 2H) , 6.68-6.66 (m, 1H) , 6.55 (t, J = 7.2 Hz, 1H) , 5.06 (bs, 2H) , 4.95 (s, 2H) , 2.16 (s, 3H) . (3) Methyl 2- ( ( 4 -bromo-2-methylphenoxy ) methyl ) phenylcarbamate

To a cooled solution of 2- ( ( -Bromo-2- methylphenoxy) methyl ) aniline (0.90 g, 3.1 mmol) in chloroform (10 ml) was added pyridine (0.74 g, 9.3 mmol) . To this mixture, methyl chloroformate (0.43 g, 4.6 mmol) was then slowly added. The resulting mixture was then stirred at room temperature for 12h. The reaction mixture was then poured into cold water and extracted with dichloromethane (3 x 80 mL) . The combined

organic layer was washed with distilled water, dried over sodium sulfate, filtered and concentrated under reduced

pressure to get crude product. The crude was then purified by column chromatography (ethyl acetate : n-hexane = 1:4) to afford the title compound as a white solid (0.75 g, Yield: 69%) .

¾ NMR (DMSO-d₆) : δ 9.01 (bs, 1H) , 7.49-7.45 (m, 2H) , 7.36-7.30 (m, 3H) , 7.18 (t, J = 7.6 Hz, 1H) , 6.93 (d, J = 8.4 Hz, 1H) , 5.12 (s, 2H) , 3.65 (s, 3H) , 2.17 (s, 3H) .

(4) Methyl 2- ( ( 2-methyl-4- ( , 4 , 5 , 5-tetramethyl-l , 3 , 2- dioxaborolan-2-yl ) phenoxy) methyl ) phenylcarbamate

To a mixture of methyl 2- ( ( -bromo-2-methyl

phenoxy ) methyl ) phenylcarbamate (0.75 g, 2.1 mmol) and

potassium acetate (0.42 g, 4.3 mmol) in 1,4-dioxane (5.0 ml) was added [1,1'- bis ( diphenylphosphino ) ferrocene ] dichloropalladium (II) complex with dichloromethane (0.09 g, 0.10 mmol) followed by

bis (pinacolato) diboron (0.81 g, 3.2 mmol) under nitrogen

atmosphere. The resulting mixture was then refluxed for 3h.

The reaction mixture was then diluted with ethyl acetate. The organic layer was then washed with distilled water, dried over sodium sulfate, filtered and concentrated under reduced

pressure to get title compound as a light yellow residue (0.4 g, crude) . It was then used in the next step without any

further purification. H NMR (CDCI₃) : δ 8.01 (bs, 1H) , 7.66-7.59 (m, 3H) , 7.39-7.35 (m, 1H), 7.30-7.29 (m, 1H) , 7.10-7.06 (m, 1H) , 6.96 (d, J =

8.0 Hz, 1H) , 5.11 (s, 2H) , 3.74 (s, 3H) , 2.25 (s, 3H) , 1.33 (s,

12H) .

(5) Methyl (2- ( ( 2-methyl-4- ( - ( trifluoromethyl ) thiazol-2- yl ) phenoxy) methyl ) phenyl ) carbamate (Compound lA-1)

To a mixture of 2-bromo-4- (trifluoromethyl) thiazole

(0.058 g, 0.25 mmol) and potassium carbonate (0.070 g, 0.5 mmol) in 1,4-dioxane (5 ml) was added

tetrakis ( triphenylphosphine ) palladium ( 0 ) (0.014 g, 0.01 mmol) followed by methyl 2- ( ( 2-methyl - - ( , 4 , 5 , 5-tetramethyl-1 , 3 , 2- dioxaborolan-2-yl ) phenoxy) methyl ) phenylcarbamate (0.1 g, 0.25 mmol) under nitrogen atmosphere. The resulting mixture was then refluxed for 3h. The reaction mixture was then diluted with ethyl acetate (50 mL) . The organic layer was then washed with distilled water, dried over sodium sulfate, filtered and concentrated under reduced pressure to get crude. The crude was then purified by column chromatography (ethyl acetate:: n- hexane = 1:3) to afford the title compound as a white solid (0.060 g, Yield: 47%) .

¹ti NMR (CDCI₃) : δ 8.00 (bs, 1H) , 7.81-7.77 (m, 2H) , 7.66 (s, 1H), 7.51 (bs, 1H), 7.39 (t, J = 7.2 Hz, 1H), 7.33 (d, J = 7.6 Hz, 1H) , 7.11 (t, J = 7.6 Hz, 1H) , 7.00 (d, J = 8.8 Hz, 1H) , 5.16 (s, 2H) , 3.77 (s, 3H), 2.31 (s, 3H) .

Preparation example 2

Preparation of methyl 2- ( ( 4- (4-chlorothiazol-2-yl) -2- methylphenoxy) methyl ) phenylcarbamate (1A-2) ;

To a mixture of 2 , 4-dichlorothiazole (0.06 g, 0.39 mmol) and potassium carbonate (0.11 g, 0.78 mmol) in 1,4-dioxane

(5.0 ml) was added tetrakis ( triphenylphosphine ) palladium ( 0 ) (22 mg, 0.02 mmol) followed by methyl 2- ( (2-methyl-4- (4, 4, 5, 5- tetramethyl-1 , 3, 2-dioxaborolan-2- yl ) phenoxy ) methyl ) phenylcarbamate (0.15 g, 0.39 mmol) under nitrogen atmosphere. The resulting mixture was then refluxed for 3h. The reaction mixture was then diluted with ethyl acetate (50 mL) . The organic layer was then washed with

distilled water, dried over sodium sulfate, filtered and concentrated under reduced pressure to get crude. The crude was then purified by column chromatography (ethyl acetate : n- hexane = 1:3) to afford methyl 2- ( ( 4 - ( 4 -chlorothiazol-2-yl ) -2- methylphenoxy) methyl ) phenylcarbamate as a white solid (0.050 g, Yield: 33%) .

^XH NJ R (CDC1₃) : δ 7.99 (bs, 1H) , 7.77 (s, 1H) , 7.75-7.72 (m, 1H) , 7.53 (bs, 1H) , 7.41-7.37 (m, 1H) , 7.32 (d, J = 7.6 Hz, 1H) , 7.11 (t, J = 7.6 Hz, 1H) , 7.01-6.98 (m, 2H) , 5.14 (s, 2H) , 3.77 (s, 3H) , 2.30 (s, 3H) .

Preparation example 3

Preparation of methyl (3-chloro-2- ( (2-methyl-4- (4- methylthiazol-2-yl ) phenoxy) methyl ) phenyl ) carbamate (compound

1A-39)

(1) 2- (4-Methoxy-3-methylphenyl) -4 -methylthiazole

To a solution of 2-bromo-4-methylthiazole (1.0 g, 5.6 mmol) in DMF:H₂0 (10:1, 3.0 ml) was added sodium carbonate

(1.19 g, 0.0112 mole) followed addition of 1,1'- bis ( diphenylphosphino) ferrocene-palladium ( II ) di chloride

dichloromethane (0.457 g, 5.6 mmol) under nitrogen atmosphere. 4-Methoxy-3-methylphenylboronic acid (1.38 g, 8.41 mmol) was added to the reaction mixture and then it was stirred at 100°C for 12h. The reaction mixture was diluted with ethyl acetate (50 mL) and washed with water (3 x 50 mL) , dried over sodium sulfate and evaporated to dryness. The crude was purified by column chromatography to afford 2- ( 4-methoxy-3-methylphenyl ) - 4-methylthiazoleas as a yellow viscous oil (0.80 g, Yield:

65%) .

¹R NMR (CDCI₃) : δ 7.73-7.71 (m, 2H) , 6.84 (d, J = 9.2 Hz, 1H) , 6.79-6.78 (m, 1H) , 3.87 (s, 3H) , 2.48 (s, 3H) , 2.26 (s, 3H) .

(2) 2 -Methyl- 4- ( 4 -methylthiazol-2-yl ) phenol

A solution of 2- ( 4-methoxy-3-methylphenyl ) -4- methylthiazole (0.8 g, 3.6 mmol) in aq. HBr (10 ml) and acetic acid (5.0 ml) was refluxed at 120°C for 24h. After completion of the reaction, the reaction mixture was treated with sat. sodium bicarbonate solution till the pH became -10. It was extracted with ethyl acetate (3 x 50 mL) , washed with water (3 x 50 mL) , dried over sodium sulfate and evaporated to dryness to afford the title compound as light yellow solid (0.70 g, Yield 93%) . It was then used in the next step as such without any further purification.

^XH NMR (CDC1₃) : δ 7.73 (s, 1H) , 7.64-7.62 (m, 1H) , 6.80-6.78 (m, 2H) , 5.07 (bs, 1H) , 2.48 (s, 3H) , 2.29 (s, 3H) . (3) 2- (Bromomethyl ) -l-chloro-3-nitrobenzene

To a solution of l-chloro-2-methyl-3-nitrobenzene (1.0 g, 5.8 mmol)) in carbon tetrachloride (30 ml) was added N- bromosuccinimide (1.03 g, 5.8 mmol) followed by benzoyl

peroxide (0.071 g, 0.29 mmol) . The reaction mixture was

refluxed at 80°C for 6h. Then the reaction mixture was cooled to room temperature and filtered. The reaction mixture was diluted with dichloromethane (50 mL) and washed with water (3 x 50 mL) , dried over sodium sulfate and evaporated to dryness. The crude compound was purified by column chromatography to afford 2- (bromomethyl ) -l-chloro-3-nitrobenzene as a yellow viscous oil (0.60 g, Yield: 41%) .

¾ NMR (CDCI₃) : δ 7.87-7.85 (m, 1H) , 7.70-7.68 (m, 1H) , 7.43 (t, J = 8.0 Hz, 1H) , 4.87 (s, 2H) . (4) 2- ( 4- ( (2-Chloro-6-nitrobenzyloxy) -3-methylphenyl ) -4- methylthiazole

To a solution of 2-methyl-4- (4-methylthiazol-2-yl) phenol (0.7 g, 3.4 mmol) in acetonitrile (10 ml) was added potassium carbonate (0.7 g, 5.1 mmol) followed by 2- (bromomethyl ) -1- chloro-3-nit'robenzene (0.85 g, 3.4 mol) and the reaction mixture was refluxed at 80°C for 3h. The reaction mixture was diluted with ethyl acetate (70 mL) and washed with water (3 x 100 mL) , dried over sodium sulfate and evaporated to dryness. The crude compound was purified by column chromatography to afford 2- ( 4 -( 2-chloro- 6-nitrobenzyloxy ) -3-methylphenyl ) -4 - methylthiazole as a yellow solid (0.80 g, Yield: 62%) .

1H MR (CDCI₃) : δ 7.75-7.72 (m, 3H) , 7.70-7.67 (m, 1H) , 7.47 (t, J = 8.0 Hz, 1H) , 6.93 (d, J = 9.2 Hz, 111) , 6.79-6.78 (m, 1H) , 5.49 (s, 2H), 2.48 (s, 3H) , 2.17 (s, 3H)

(5) 3-Chloro-2- ( (2-methyl-4- ( -methylthiazol-2-yl ) phenoxy ) methyl) aniline

To a solution of 2- ( 4- (2-chloro-6-nitrobenzyloxy) -3- methylphenyl ) -4 -methylthiazole (0.80 g, 2.1 mmol) in methanol (20 ml) was added cuprous chloride (0.63 g, 6.3 mmol) followed by sodium borohydride (0.24 g, 6.4 mmol) at 0°C. The reaction mixture was stirred at room temperature for 3h. Then the reaction mixture was filtered and diluted with ethyl acetate (100 mL) and washed with water (3 x 60 mL) , dried over sodium sulfate and evaporated to dryness under reduced pressure to afford the title compound as a light yellow solid (0.60 g, crude) . It was used as such in the next step without any further purification.

^XH NMR (CDC1₃) : δ 7.75-7.71 (m, 2H) , 7.09-7.04 (m, 2H), 6.83- 6.79 (m, 2H) , 6.61 (d, J = 8.0 Hz, 1H) , 5.34 (s, 2H) , 4.27 (bs, 2H) , 2.48 (s, 3H) , 2.16 (s, 3H) . (6) Methyl (3-chloro-2- ( (2-methyl-4- (4-methylthiazol-2- yl ) phenoxy ) methyl ) phenyl ) carbamate (Compound 1A-39)

To a solution of 3-chloro-2- ( (2-methyl-4- (4- methylthiazol-2-yl ) phenoxy ) methyl ) aniline (0.60 g, 1.7 mmol) in dichloromethane (10 ml) was added pyridine (0.20 g, 2.5 mmol) followed by methyl chloroformate (0.20 g, 2.1 mmol) . The reaction mixture was stirred at room temperature for 3h. The reaction mixture was diluted with dichloromethane (70 mL) and washed with water (3 x 50 mL) , dried over sodium sulfate and evaporated to dryness under reduced pressure. The crude

compound was purified by column chromatography to afford methyl 3-chloro-2- ( (2-methyl-4- ( 4 -methylthiazol-2- yl ) phenoxy ) methyl ) phenyl carbamate as a yellow solid (0.50 g, Yield: 71%) .

¹ti NMR (CDCI₃) : δ 7.96 (d, J = 8.0 Hz, 1H) , 7.90 (bs, 1H) , 7.77 (s, 1H) , 7.74-7.71 (m, 1H) , 7.29 (t, J = 8.4 Hz, 1H) , 7.16- 7.14 (m, 1H) , 7.05 (d, J = 8.8 Hz, 1H) , 6.80 (d, J = 1.2 Hz, 1H) , 5.40 (s, 2H), 3.77 (s, 3H) , 2.49 (s, 3H) , 2.30 (s, 3H) . Preparation example 4

Preparation of methyl 3-chloro-2- ( ( 2-methyl-4 - ( 4- methylthiazol-2-yl) phenoxy) methyl ) phenyl (methyl ) carbamate

(Compound 1A- 4 3 )

To a solution of methyl ( 3-chloro-2- ( (2-methyl-4- ( - methylthiazol-2-yl ) phenoxy) methyl ) phenylcarbamate (70 mg, 0.17 mmol) in dichloromethane (2.0 ml) was added sodium hydride (6.0 mg, 0.26 mmol) at 0°C. After 10 minutes, methyl iodide (37 mg, 0.26 mmol) was added to the reaction mixture. The reaction mixture was stirred at room temperature for 3h. The reaction mixture was diluted with ethyl acetate (40 mL) and washed with water (3 x 20 mL) , dried over sodium sulfate and evaporated to dryness under reduced pressure. The crude

compound was purified by column chromatography to afford methyl 3-chloro-2- ( (2-methyl-4- ( 4-methylthiazol-2- yl ) phenoxy) methyl ) phenyl (methyl ) carbamate as a yellow viscous oil (40 mg, Yield: 55%) .

¾ NMR (CDC1₃) : δ 7.75-7.73 (m, 2H) , 7.45-7.43 (m, 1H) , 7.36 (t, J = 8.0 Hz, 1H) , 7.15-7.11 (m, 1H) , 6.98 (d, J = 9.2 Hz, 1H) , 6.79 (d, J = 1.2 Hz, 1H) , 5.12 (d, J = 10.0 Hz, 1H) , 5.03 (d,

J= 10.0 Hz, 1H) , 3.76-3.22 (m, 6H) , 2.49 (s, 3H) , 2.20 (s, 3H) .

Preparation example 5

Preparation of methyl acetyl ( 3-chloro-2- (( 2-methyl-4 -( 4 - methylthiazol-2-yl ) phenoxy) methyl ) phenyl ) carbamate (Compound 1A- 4 6 )

To a solution of methyl 3-chloro-2- ( (2-methyl-4- (4- methylthiazol-2-yl ) phenoxy) methyl ) phenylcarbamate (90 mg, 0.22 mmol) in DMF (5.0 ml) was added sodium hydride (8 mg, 0.33 mmol) at 0°C. After 10 minutes, acetyl chloride (22 mg, 0.30 mmol) was added to the reaction mixture and then it was

stirred at room temperature for 3h. The reaction mixture was diluted with ethyl acetate (30 mL) and washed with water (3 x 20 mL) , dried over sodium sulfate and evaporated to dryness under reduced pressure. The crude compound was purified by column chromatography to afford methyl acetyl ( 3-chloro-2- ( (2- methyl-4- ( 4-methylthiazol-2-yl ) phenoxy) methyl ) phenyl ) carbamate as a yellow viscous oil (50 mg, Yield: 50%) . H NMR (CDCI₃) : δ 7.75-7.74 (m, 1H) , 7.71-7.69 (m, 1H) , 7.50 (d, J = 7.6 Hz, 1H) , 7.38 (t, J = 8.0 Hz, 1H) , 7.06 (d, J = 8.0 Hz, 1H) , 6.90 (d, J = 8.4 Hz, 1H) , 6.79 (s, 1H) , 3.53 (s, 3H) , 2.61 (s, 3H) , 2.48 (s, 3H), 2.20 (s, 3H) .

Preparation example 6

Preparation of methyl 2- ( (2-methyl-4- (thiazol-5- yl ) phenoxy ) methyl ) phenylcarbamate (Compound lB-1)

To a solution of 5-bromothiazole (0.15 g, 0.91 mmol) in 1 , 4 -dioxane : H₂O (5:1, 6.0 mL) was added potassium phosphate (0.38 g, 1.8 mmol) followed by

Tetrakis (triphenylphosphine) palladium (50 mg, 0.04 mmol) under nitrogen atmosphere. Methyl 2- ( ( 2-methyl-4 - ( , 4 , 5 , 5- tetramethyl-1 , 3 , 2-dioxaborolan-2-yl ) phenoxy ) methyl )

phenylcarbamate (0.65 g, 1.6 mmol) was added to the reaction mixture and then it was stirred at 100°C for 12h. The reaction mixture was diluted with ethyl acetate (50 mL) and washed with water (3 x 40 mL) , dried over sodium sulfate and evaporated to dryness under reduced pressure. The crude compound was

purified by column chromatography to afford methyl 2-((2- methyl-4- (thiazol-5-yl) phenoxy) methyl) phenylcarbamate as a yellow viscous oil (0.20 g, Yield: 62%) .

¹ti NMR (DMSO-d₆) : δ 8.70 (s, 1H) , 8.01-7.96 (m, 2H) , 7.62 (bs, 1H) , 7.41-7.37 (m, 3H) , 7.32 (d, J = 7.2 Hz, 1H) , 7.12 (t, J = 7.2 Hz, 1H) , 6.99-6.96 (m, 1H), 5.13 (s, 2H) , 2.99 (s, 3H) , 2.30 (s, 3H) .

Preparation example 7

Preparation of methyl 2- ( (2-methyl-4- (thiazol-4- yl ) phenoxy ) methyl ) phenylcarbamate (Compound lC-1) ' To a solution of 4 -bromothiazole (0.1 g, 0.61 mmol) in 1 , -dioxane : H₂O (5:1, 6 mL) was added potassium phosphate

(0.26 g, 1.2 mmol) followed by

Tetrakis (triphenylphosphine) palladium (35 mg, 0.031 mmol) under nitrogen atmosphere. Methyl 2- ( ( 2-methyl-4 - ( 4 , 4 , 5 , 5- tetramethyl-1 , 3, 2-dioxaborolan-2- yl ) phenoxy ) methyl ) phenylcarbamate (0.38 g, 0.97 mmol) was added to the reaction mixture and then it was stirred at 100°C for 12h. The reaction mixture was diluted with ethyl acetate (50 mL) and washed with water (3 x 25 mL) , dried over sodium sulfate and evaporated to dryness under reduced pressure. The crude compound was purified by column chromatography to afford methyl 2- ( (2-methyl-4- (thiazol-4- yl ) phenoxy ) methyl ) phenylcarbamate as a yellow viscous oil

(0.15 g, Yield: 69%) .

^XH NMR (DMSO-d₆) : δ 9.14 (s, 1H) , 9.03 (bs, 1H) , 7.97 (s, 1H) , 7.80-7.77 (m, 1H) , 7.50 (d, J = 8.0 Hz, 2H) , 7.41-7.30 (m, 2H) , 7.20-7.17 (m, 1H) , 7.04 (d, J = 8.4 Hz, 1H) , 5.18 (s, 2H) , 3.66 (s, 3H) , 2.24 (s, 3H) .

Preparation example 8

Preparation of methyl 2- ( (2-methyl-4- ( 4-methylthiazol-2- yl ) phenoxy ) methyl ) -3-methoxyphenylcarbamate (Compound 1A-38)

(1) 2- (Bromomethyl ) -l-methoxy-3-nitrobenzene

To a solution of l-methoxy-2-methyl-3-nitrobenzene (2 g, 12.0 mmol)) in carbon tetrachloride (20 ml) was added N- bromosuccinimide (2.56 g, 14.4 mmol) followed by benzoyl peroxide (0.14 g, 0.6 mmol) . The reaction mixture was refluxed at 80°C for 6h. The reaction mixture was the cooled to room temperature and filtered. The filtrate was diluted with

dichloromethane (80 mL) and washed with water (3 x 30 mL) , dried over sodium sulfate and evaporated to dryness. The crude was purified by column chromatography to afford 2-

(bromomethyl ) -l-methoxy-3-nit robenzene as a yellow viscous oil (1.6 g, Yield: 83%) .

¾ NMR (CDC1₃) : δ 7.74-7.72 (m, 1H) , 7.61-7.58 (m, 1H) , 7.12 (t, J = 8.0 Hz, 1H), 4.91 (s, 2H) , 4.01 (s, 3H) . ;

(2) 1- (2-Methoxy-6-nitrobenzyloxy) -4-bromo-2-methylbenzene

To a solution of 4-bromo-2-methylphenol (1.0 g, 5.3 mmol) in acetonitrile (10 ml) was added potassium carbonate (1.1 g, 6.4 mmol) followed by 2- (bromomethyl ) -l-methoxy-3-nitrobenzene (1.58 g, 6.4 mmol) and the reaction mixture was refluxed at 80°C for 3h. The reaction mixture was diluted with ethyl acetate and washed with water, dried over sodium sulfate and evaporated to dryness under reduced pressure. The crude was purified by column chromatography to afford 1- (2-methoxy-6- nitrobenzyloxy ) -4-bromo-2-methylbenzene as a yellow solid (1.2 g, Yield: 83.8%) .

1H NMR (CDC1₃) : δ 7.47-7.39 (m, 2H), 7.24-7.21 (m, 2H) , 7.16- 7.14 (m, 1H) , 6.79 (d, J = 9.2 Hz, 1H) , 5.34 (s, 2H) , 3.93 (s, 3H) , 2.07 (s, 3H) .

( 3 ) 2- ( ( 4-Bromo-2-methylphenoxy ) methyl ) -3-methoxyaniline To a solution of 1- (2-methoxy-6-nitrobenzyloxy) -4-bromo-

2-methylbenzene (0.5 g, 1.4 mmol) in methanol (10 ml) was added cuprous chloride (0.21 g, 2.1 mmol) followed by sodium borohydride (0.18 g, 5.0 mmol) at 0°C and the reaction mixture was stirred at room temperature for 3h. The reaction mixture was diluted with ethyl acetate (50 mL) and washed with water (3 x 30 mL) , dried over sodium sulfate and evaporated to dryness under reduced pressure to afford the title compound (0.2 g, crude) . It was used as such in the next step without any further purification.

2H NMR (CDCI₃) : δ 7.24-7.22 (m, 2H) , 7.09 (t, J = 8.4 Hz, 1H) , 6.95 (d, J = 9.2 Hz, 1H) , 6.35-6.33 (m, 2H) , 5.20 (s, 2H) , 4.13 (bs, 2H), 3.83 (s, 3H) , 2.17 (s, 3H) .

(4) Methyl 2- ( ( 4 -bromo-2-methylphenoxy ) methyl ) -3- methoxyphenylcarbamate

To a solution of 2- ( ( 4 -bromo-2-methylphenoxy ) methyl ) -3- methoxyaniline (0.2 g, 0.62 mmol) in dichloromethane (5.0 ml) was added pyridine (98 mg, 1.2 mmol) followed by methyl chloroformate (70 mg, 0.74 mmol) . The reaction mixture was stirred at room temperature for 3h. The reaction mixture was diluted with dichloromethane (30 mL) and washed with water (3 x 20 mL) , dried over sodium sulfate and evaporated to dryness under reduced pressure. The crude was purified by column chromatography to afford methyl 2- ( ( 4-bromo-2- methylphenoxy) methyl ) -3-methoxyphenylcarbamate as a yellow solid (0.14 g, Yield: 59%) .

¹ti NMR (CDCI₃) : δ 7.82 (bs, 1H) , 7.64 (d, J = 8.4 Hz, 1H) , 7.29 (t, J = 8.4 Hz, 1H) , 7.27-7.22 (m, 2H) , 6.91 (d, J = 8.4 Hz, 1H) , 6.65 (d, J = 8.4 Hz, 1H) , 5.28 (s, 2H) , 3.86 (s, 3H) , 3.76 (s, 3H) , 2.21 (s, 3H) . (5) Methyl 2- ( ( 2-methyl- - ( 4 , 4 , 5 , 5-tetramethyl-l , 3 , 2- dioxaborolan-2-yl ) phenoxy ) methyl ) -3 -methoxyphenyl carbamate

To a mixture of methyl 2- ( ( 4-bromo-2- methylphenoxy) methyl ) -3-methoxyphenylcarbamate (0.15 g, 0.4 mmol) and potassium acetate (77 mg, 0.8 mraol) in 1,4- dioxane:H₂0 (5:1, 6 ml), was added

tetrakis (triphenylphosphine) palladium (45 mg, 0.04 mmol) followed by bis (pinacolato) diboron (0.15 g, 0.6 mmol) under nitrogen atmosphere. The reaction was then refluxed at 85°C for 12h. After cooled to room temperature, the reaction mixture was diluted with ethyl acetate (70 mL) and washed with water (3 x 50 mL) , dried over sodium sulfate and evaporated to dryness under reduced pressure. The crude compound was purified by column chromatography to afford methyl 2-( (2- methyl-4- (4,4,5, 5-tetramethyl-l, 3, 2-dioxaborolan-2-yl ) phenoxy ) methyl ) -3-methoxyphenylcarbamate as a yellow viscous oil (0.09 g, Yield: 53%) .

^XH NMR (CDC1₃) : δ 7.88 (bs, 1H) , 7.64-7.60 (m, 3H) , 7.28 (t, J = 8.4 Hz, 1H) , 7.06 (d, J = 8.4 Hz, 1H) , 6.64 (d, J = 8.0 Hz, 1H) , 5.30 (s, 2H) , 3.86 (s, 3H) , 3.74 (s, 3H) , 2.24 (s, 3H) , 1.26 (s, 9H) .

(6) Methyl 2- ( ( 2-methyl-4- ( 4-methylthiazol-2- yl ) phenoxy ) methyl ) -3-methoxyphenylcarbamate (Compound 1A-38)

To a solution of 2-bromo-4-methylthiazole (0.041 g, 0.23 mmol) in 1 , 4-dioxane : ¾0 (4:1, 6 ml) were sequentially added sodium carbonate (50 mg, 0.50 mmol), 1,1'- bis (diphenylphosphino ) ferrocene-palladium (II)dichloride dichloromethane complex (19 mg, 0.02 mmol) and methyl 2-( (2- methyl-4- (4, 4, 5, 5-tetramethyl-l , 3 , 2-dioxaborolan-2- yl ) phenoxy ) methyl ) -3-methoxyphenylcarbamate (0.10 g, 0.2 mmol) under nitrogen atmosphere. The reaction was stirred at 100°C for 12h. The reaction mixture was diluted with ethyl acetate (50 mL) and washed with water (3 x 20 rtiL) , dried over sodium sulfate and evaporated to dryness under reduced pressure. The crude compound was purified by column chromatography to afford methyl 2- ( ( 2 -methy1-4 - ( 4-methylthiazol-2-yl ) phenoxy) methyl ) -3- methoxyphenylcarbamate as an off-white solid (49 mg, Yield:

53.4%) .

^XH NMR (CDC1₃) : δ 7.85 (bs, 1H) , 7.73 (s, 1H) , 7.71-7.68 (m, 1H), 7.65 (d, J= 8.0 Hz, 1H) , 7.30 (t, J = 8.0 Hz, 1H) , 7.08 (d, J = 8.4 Hz, 1H) , 6.79 (d, J = 1.2 Hz, 1H) , 6.66 (d, J =

8.0 Hz, 1H) , 5.33 (s, 2H) , 3.88 (s, 3H) , 3.76 (s, 3H), 2.48 (s, 3H) , 2.29 (s, 3H) .

Preparation example 9

Preparation of methyl (3-methyl-2- ( (2-methyl-4- (4- methylthiazol-2-yl) phenoxy) methyl ) phenyl ) carbamate (Compound 1A-15)

( 1 ) ( 2 -Methyl- 6-nitrophenyl ) methanol

To a solution of 2-methyl-6-nitrobenzoic acid (2.0 g, 12.0 mmol)) in dichloromethane (20 ml) was added oxalyl

chloride (3.47 g, 30.0 mmol) dropwise at 0°C followed by

addition of dimethylformamide (0.2 mL) . The reaction mixture was stirred at room temperature for lh. The reaction mixture was evaporated to dryness under reduced pressure. Dry THF was added to it make a clear solution followed by addition of sodium borohydride (1.2 g, 36.0 mmol) at 0°C. The reaction mixture was stirred at room temperature for lh. It was

quenched with water and extracted with ethyl acetate (3 x 50 mL) , washed with NH₄C1 solution (3 x 30 mM) , dried over sodium sulfate and evaporated to dryness under reduced pressure to afford 2-methyl-6-nitrophenyl ) methanol as an off-white solid (1.65 g, crude) . It was used as such in the next step without any further purification.

¹ti NMR (CDCI₃) : δ 7.69 (d, J = 8.0 Hz 1H) , 7.45 (d, J = 7.60 Hz 1H 1H) , 7.34 (t, J = 8.0 Hz, 1H) , 4.69 (d, J = 7.2 Hz, 2H) , 2.64 (t, J = 7.6 Hz 1H) , 2.55 (s, 3H) ( 2 ) ( 2-Amino-6-methylphenyl ) methanol

To a solution of 2-methyl- 6-nitrophenyl ) methanol (1.0 g, 5.0 mmol) in methanol (10 ml) were sequentially added cuprous chloride (1.7 g, 15.0 mmol) and sodium borohydride (1.8 g, 40.0 mmol) at 0°C. The reaction mixture was stirred at 0°C for lh. The reaction mixture was diluted with ethyl acetate (60 mL) and washed with water (3 x 30 mL) , dried over sodium sulfate and evaporated to dryness under reduced pressure to afford ( 2-amino-6-methylphenyl ) methanol as a brownish solid (0.70 g, crude) . It was used as such in the next step without any further purification.

^XH NMR (CDCla) : δ 7.01 (t, J = 7.6 Hz, 1H) , 6.58 (t, J = 7.6 Hz 2H) , 4.76 (s, 2H) , 233 (s, 3H) . (3) Methyl ( 2 -( hydroxymethyl ) -3-methylphenyl ) carbamate

To a solution of 2-amino-6-methylphenyl) methanol (0.70 g, 0.62 mmol) in dichloromethane (5.0 ml) were sequentially added pyridine (20 mg, 0.32 mmol) and methyl chloroformate (48 mg, 0.32 mmol) . The reaction mixture was stirred at room

temperature for lh. The reaction mixture was diluted with dichloromethane (30 mL) and washed IN HC1 (3 x 20 mL) , dried over sodium sulfate and evaporated to dryness under reduced pressure to afford methyl ( 2- (hydroxymethyl ) -3- methylphenyl ) carbamate as a white solid (0.50 g, crude) . It was used as such in the next step without any further

purification .

¹ti NMR (CDCI₃) : δ 7.59 (s, 1H) , 7.56 (d, J = 8.4 Hz, 1H) , 7.20 (t, J = 8 Hz, 1H) , 6.96 (d, J = 7.6 Hz, 1H) , 4.74 (d, J = 5.2 Hz, 2H), 3.78 (s, 3H) , 2.40 (s, 3H) .

(4) Methyl (2- (bromomethyl) -3-methylphenyl) carbamate

To a solution of methyl (2- (hydroxymethyl) -3- methylphenyl ) carbamate (0.50 g, 0.62 mmol ) in dichloromethane (5 ml) was added phosphorous tribromide (1.0 g, 0.95 mmol) at 0°C. The reaction mixture was stirred at 0°C for lh. The reaction mixture was diluted with dichloromethane (30 mL) and washed with sodium thiosulfate solution (3 x 20 mL) , dried over sodium sulfate and evaporated to dryness under reduced pressure to afford methyl ( 2- (bromomethyl ) -3- methylphenyl ) carbamate a white solid (0.55 g, crude) . It was used as such in the next step without any further purification. Η NMR (CDC1₃) : δ 7.57 (bs, 1H) , 7.22 (d, J = 8 Hz, 1H) , 6.99 (d, J = 7.6 Hz, 1H) , 6.68 (s, 1H) , 4.54 (s, 2H) , 3.80 (s, 3H) , 2.41 (s, 3H) .

(5) Methyl (2- ( ( 4-bromo-2-methylphenoxy ) methyl) -3- methylphenyl ) carbamate

To a solution of -bromo-2-methylphenol (0.40 g, 5.3 mmol) in acetonitrile (10 ml) were sequentially added

potassium carbonate (0.59 g, 10.6 mmol) and methyl (2-

(bromomethyl ) -3-methylphenyl ) carbamate (0.55 g, 5.3 mmol) at 0°C. The reaction mixture was refluxed at 80°C for 3h. After cooling at room temperature, the reaction mixture was diluted with ethyl acetate (50 mL) and washed with water (3 x 30 mL) , dried over sodium sulfate and evaporated to dryness under reduced pressure to afford methyl (2- ( ( 4-bromo-2- methylphenoxy) methyl ) -3-methylphenyl ) carbamate as an off-white solid (0.54 g, crude) . It was used as such in the next step without any further purification.

2H NMR (CDCI₃) : δ 7.75 (bs, 1H) , 7.39 (bs, 1H) , 7.30-7.26 (m, 3H) , 7.03-6.97 (m, 1H) , 6.85 (t, J = 4.8, 1H) , 5.06 (s, 2H) , 3.74 (s, 3H) , 2.38 (s, 3H) , 2.18 (s, 3H) .

(6) Methyl ( 3-methyl-2- ( ( 2-methyl- - ( , 4 , 5 , 5-tetramethyl- ; 1,3, 2-dioxaborolan-2-yl ) phenoxy) methyl) phenyl) carbamate

To a mixture of methyl (2- ( (4-bromo-2- methylphenoxy) methyl ) -3-methylphenyl ) carbamate (0.150 g, 0.4 mmol) and potassium acetate (77 mg, 0.8 mmol) in 1,4- dioxane:H₂0 (5:1, 6 ml, was added

tetrakis ( triphenylphosphine ) palladium (45 mg, 0.04 mmol) followed by bis (pinacolato) diboron (0.15 g, 0.6 mrnol) under nitrogen atmosphere. The reaction was then refluxed at 85°C for 12h. After cooled to room temperature, the reaction

mixture was diluted with ethyl acetate (70 mL) and washed with water (3 x 50 mL) , dried over sodium sulfate and evaporated to dryness under reduced pressure. The crude compound was

purified by column chromatography to afford methyl (3-methyl- 2- ( (2 -methyl- - (4,4,5, 5-tetramethyl-l, 3, 2-dioxaborolan-2- yl ) phenoxy) methyl ) phenyl ) carbamate as an off-white solid (0.09 g, Yield: 53%) . ¹R NMR (CDC1₃) : δ 7.76 (d, J = 5.6 Hz 1H) , 7.68 (d, J = 8.4 Hz 1H) , 7.64 (s, 1H) , 7.47 (bs, 1H) , 7.28-7.24 (m, 1H) , 6.99 (t, J = 8.4 Hz, 2H) , 5.11 (s, 2H) , 3.72 (s, 3H) , 2.39 (s, 3H) , 2.21 (s, 3H) , 1.34 (s, 12H) . (7) Methyl ( 3-methyl-2 - ( ( 2 -methyl-4 - ( 4 -methylthiazol-2 - yl ) phenoxy) methyl ) phenyl ) carbamate (Compound 1A-15)

To a solution of 2-bromo-4-methylthiazole (0.041 g, 0.23 mmol) in 1, -dioxane : H₂0 (4:1, 6 ml) were sequentially added sodium carbonate (50 mg, 0.50 mmol), 1,1'- bis (diphenylphosphino) ferrocene-palladium ( II ) dichloride

dichloromethane complex (19 mg, 0.02 mmol) and methyl (3- methy1-2- ( ( 2 -methyl- 4 - (4,4,5, 5-tetramethyl-l , 3 , 2-dioxaborolan- 2-yl ) phenoxy ) methyl ) phenyl ) carbamate (0.10 g, 0.20 mmol) under nitrogen atmosphere. The reaction was stirred at 100°C for 12h. The reaction mixture was diluted with ethyl acetate (50 mL) and washed with water (3 x 20 mL) , dried over sodium sulfate and evaporated to dryness under reduced pressure. The crude compound was purified by column chromatography to afford methyl 2- ( ( 2 -methyl- 4 - ( 4 -methylthiazol-2-yl ) henoxy) methyl ) -3- methoxyphenylcarbamate as an off-white solid (49 mg, Yield:

53.4%) .

¹ti NMR (CDCI₃) : δ 7.77-7.74 (m, 3H) , 7.44 (bs, 1H) , 7.28 (t, J = 8.2 Hz 1H) , 7.02-6.98 (m, 2H) , 6.81 (d, J = 8.0 Hz 1H) , 5.13 (s, 2H) , 3.74 (s, 3H), 2.48 (s, 3H) , 2.41 (s, 3H) , 2.26 (s, 3H) . Representative compounds of the present invention are exemplified in the following Tables 1 to 3, but the present invention is not limited to these compounds.

The compounds shown in Tables 1 to 3, other than the compounds obtained in Preparation Examples 1 to 9, were

produced by methods similar to the methods described in

Preparation examples 1 to 9 or methods described in the

description .

The abbreviations in Tables 1 to 3 are as indicated below.

F: fluoro, CI: chloro, Br: bromo, Me: methyl, Et : ethyl, iPr: isopropyl, t-Bu: tert-butyl, CF₃: trifluoromethyl , Ph :

phenyl, N0₂ : nitro, CN : cyano, OMe : methoxy.

Table 1: Detail and ¹H NMR of the compounds synthesized

belonging to the formula (1A) :

CDCI₃/TMS: 8.01 (bs, IH) , 7.82-

7.67 (m, 2H) , 7.59 (s, IH) , 7.39

(t, J = 7.6 Hz, IH) , 7.32 (d, J

= 7.2 Hz, IH) , 7.27-7.26 (m,A- 3 H 0 H H

2H) , 7.11 (t, J = 7.2 Hz, IH) , 7.00 (d, J = 8.4 Hz, IH) , 5.16 (s, 2H), 3.77 (s, 3H) , 2.31 (s, 3H) .

CDCI₃/TMS: 7.82-7.80 (m, 3H) ,

7.77 (bs, IH) , 7.42 (s, IH) ,A- 4 H 0 Me H 7.30-7.27 (m, 2H) , 7.05-6.99 (m,

2H) , 5.15 (s, 2H) , 3.75 (s, 3H) , 2.42 (s, 3H) , 2.27 (s, 3H) .

DMSO-c¾: 9.04 (bs, IH) , 7.72 (s,

IH) , 7.70 (s, IH) , 7.50 (d, J =

8.0 Hz, 2H) , 7.33 (t, J = 7.6A- 5 4 -Me 1 H H Hz, IH), 7.20-7.17 (m, 2H) , 7.07

(d, J = 8.0 Hz, IH) , 5.19 (s, 2H) , 3.65 (s, 3H) , 2.39 (s, 3H) , 2.24 (s, 3H) .

DMSO-d₆: 9.04 (bs, IH) , 7.67 (s,

IH) , 7.65-7.64 (m, IH) , 7.50-

7.47 (m, 3H) , 7.32 (t, J = 7.2A- 6 5-Me 1 H H Hz, IH) , 7.19 (t, J = 7.2 Hz,

IH) , 7.06 (d, J = 8.4 Hz, IH) , 5.19 (s, 2H) , 3.65 (s, 3H) , 2.46 (s, 3H) , 2.23 (s, 3H) .

DMSO-dg: 9.06 (bs, IH) , 8.50 (s,

IH) , 7.80-7.78 (m, 2H) , 7.50 (d,

J = 7.6 Hz, 2H) , 7.33 (t, J =A- 7 4-C0₂Me 1 H H 7.2 Hz, IH) , (t, J = 7.2 Hz,

IH) , 7.12 (d, J = 9.2 Hz, IH) , 5.22 (s, 2H) , 3.85 (s, 3H) , 3.66 (s, 3H) , 2.26 (s, 3H) .

CDCI₃/TMS: 8.00 (bs, IH), 7.80-

7.77 (m, 2H), 7.52 (s, IH) , 7.39

(t, J = 7.6 Hz, IH) , 7.33 (d, J

= 7.2 Hz, IH) , 7.11 (t, J = 7.6

.4 -Me,

A- 8 2 H H Hz, IH) , 7.12 (d, J =8.4 Hz, '5-C0₂Et

IH) , 5.15 (s, 2H) , 4.37 (q, J =7.2 Hz, 2H) , 3.77 (s, 3H) , 2.76 (s, 3H) , 2.30 (s, 3H) , 1.38 (t, J = 7.2 Hz, 3H) . DMSO-d₆: 9.06 (bs, IH) , 8.47 (s,

IH), 7.80-7.78 (m, 2H) , 7.50 (d,

J = .6 Hz, 2H) , 7.33 (t, J =

7.6 Hz, IH) , 7.19 (t, J = 7.6A-9 4-C0₂Et 1 H H Hz, IH) , 7.12 (d, J = 9.2 Hz,

IH) , 5.24 (s, 2H) , 4.33 (q, J =7.2 Hz, 2H) , 3.66 (s, 3H) , 2.26 (s, 3H) , 1.34 (t, J = 7.2 Hz, 3H) .

DMSO-dij: 9.06 (bs, IH) , 7.78 (s,

IH), 7.75-7.73 (m, 2H) , 7.50 (d,

J = 7.6 Hz, 2H) , 7.33 (t, J =A-

4-Br 1 H H 7.6 Hz, IH) , 7.19 (t, J = 7.60

Hz, IH), 7.10-7.08 (m, IH) , 5.21 (s, 2H) , 3.65 (s, 3H) , 2.24 (s, 3H) .

CDCI₃/TMS: 8.12 (bs, IH) , 7.86-

7.73 (m, 2H) , 7.75 (bs, IH) ,A- 7.30 (d, J = 8.4 Hz, 2H) , 7.04-

4-C0₂Me 1 Me H

1 6.99 (m, 2H) , 5.15 (s, 2H) , 3.98

(s, 3H) , 3.75 (s, 3H) , 2.42 (s, 3H) , 2.26 (s, 3H) .

CDCI₃/TMS: 7.77-7.76 (m, 3H) ,

7.35-7.26 (m, 2H) , 7.15 (s, IH) ,A-

4-Cl 1 Me H 7.03-6.99 (t, J = 7.6 Hz , 2H) ,2 5.15 (s, 2H) , 3.75 (s, 3H) , 2.41

(s, 3H) , 2.26 (s, 3H) .

CDCI₃/TMS: 7.78-7.75 (m, 3H) ,A- 7.35-7.26 (m, 2H) , 7.04-6.99 (m,

4-Br 1 Me H

3 3H) , 5.15 (s, 2H) , 3.75 (s, 3H) ,

2.41 (s, 3H) , 2.26 (s, 3H) .

CDCI₃/TMS: 8.10 (s, IH) , 7.86-

7.83 (m, 2H) , 7.76 (d, J = 6.0

Hz, IH), 7.37 (bs, IH) , 7.30-A- 7.26 (m, IH) , 7.06-6.99 (m, 2H) ,

4-C0₂Et 1 Me H

4 5.15 (s, 2H) , 4.44 (q, J = 7.2

Hz, 2H), 3.74 (s, 3H) , 2.41 (s, 3H) , 2.26 (s, 3H) , 1.43 (t, J = 7.2 Hz, 3H) .

CDCI₃/TMS: 7.77-7.74 (m, 3H) ,

7.44 (bs, IH) , 7.28 (t, J = 8.2A- Hz, IH), 7.02-6.98 (m, 2H) , 6.81

4 -Me 1 Me H

5 (d, J = 8.0 Hz, IH) , 5.13 (s,

2H), 3.74 (s, 3H) , 2.48 (s, 3H) , 2.41 (s, 3H) , 2.26 (s, 3H) . CDCI₃/TMS: 7.81 (d, J = 6 Hz,

2H) , 7.75 (bs, IH) , 7.28 (t, J =

8 Hz, 2H) , 7.04-6.99 (m, 2H) ,A- 4 -Me,

2 Me H 5.15 (s, 2H) , 4.37 (q, J = 7.26 5 -C0₂Et

Hz, 2H), 3.74 (s, 3H), 2.77 (s, 3H) , 2.41 (s, 3H) , 2.26 (s, 3H) , 1.38 (t, J = 7.2 Hz, 3H) .

CDCI₃/TMS: 7.77-7.70 (m, 3H) ,

7.45 (m, 2H) , 7.28 (t, J = 7.6A-

5 -Me 1 Me H Hz, IH) , 7.06-6.98 (m, 2H) , 5.137

(s, 2H) , 3.74 (s, 3H) , 2.49 (s, 3H) , 2.41 (s, 3H) , 2.25 (s, 3H) .

CDCI₃/TMS: 7.81 (d, J = 5.6 Hz,

2H) , 7.76 (bs, IH) , 7.67 (s,A- IH), 7.36 (bs, IH) , 7.31-7.26

4 -CF₃ 1 Me H

8 (m, IH) , 7.05-7.00 (m, 2H) , 5.16

(s, 2H) , 3.75 (s, 3H) , 2.42 (s, 3H) , 2.27 (s, 3H) .

CDCI₃/TMS: 9.07 (bs, IH) , 8.42

(s, IH) , 7.86 (bs, 2H) , 7.50 (d,

J = 8.0 Hz, 2H) , 7.35-7.31 (m,A- IH) , 7.21 (t, J = 7.6 Hz, IH) ,

5 -C0₂Et 1 H H

9 7.12-7.10 (m, IH) , 5.23 (s, 2H) ,

4.35 (q, J = 7.2 Hz, 2H) , 3.65 (s, 3H) , 2.25 (s, 3H), 1.33 (t, J = 6.8 Hz, 3H) .

CDCI₃/TMS: 8.37 (s, IH) , 7.84 (d,

J = 8 Hz, 2H) , 7.76 (bs, IH) ,

7.31 (t, J = 7.6 Hz, 2H) , 7.06-A-

5 -C0₂Et 1 Me H 7.00 (m, 2H) , 5.16 (s, 2H) , 4.370

(q, J = 7.2 Hz, 2H) , 3.75 (s, 3H) , 2.42 (s, 3H) , 2.31 (s, 3H) , 1.42 (t, J = 7.2 Hz, 3H) .

CDCI₃/TMS: 7.88 (s, IH) , 7.81 (d,

J = 6.8 Hz, 2H) , 7.44-7.42 (m,A- 2H) , 7.31 (d, J = 8 Hz, IH) ,

5 -Br 1 Me H

1 7.06-6.99 (m, 2H) , 5.15 (s, 2H) ,

3.75 (s, 3H) , 2.42 (s, 3H) , 2.26 (s, 3H) .

CDCI₃/TMS: 8.38 (s, IH), 7.85-

7.80 (m, 2H) , 7.76 (bs, IH) ,A- 7.38 (s, IH) , 7.29 (s, IH) ,

5 -C0₂Me 1 Me H

2 7.07-6.96 (m, 2H) , 5.16 (s, 2H) ,

3.92 (s, 3H) , 3.75 (s, 3H) , 2.42 (s, 3H) , 2.28 (s, 3H) .

DMSO-dg: 7.78 (s, IH) , 7.70-7.38

(m, IH), 7.28-7.25 (m, 2H) , 7.04 (d, J = 8.4 Hz, 2H) , 6.98 (d, JA-

5-CH₂Cl 1 Me H = 7.6 Hz, IH) , 6.94 (d, J = 8.00 Hz, IH) , 5.12 (s, 2H) , 4.00 (s,

2H) , 3.74 (s, 3H) , 2.42 (s, 3H) , 2.21 (s, 3H) .

DMSO-d₆: 8.98 (s, IH) , 7.47-7.45 (m, 3H) , 7.32 (t, J = 7.6 Hz, IH) , 7.19 (t, J = 7.2 Hz, IH) ,A-

5-CH₂CI 1 H H 7.05-7.03 (m, 2H) , 6.91 (d, J =1 8.0 Hz, IH) , 5.09 (s, 2H) , 4.04

(s, 2H), 3.64 (s, 3H) , 2.18 (s, 3H) .

CDCI₃/TMS: 8.01-7.94 (m, 3H) , 7.86-7.82 (m, 2H) , 7.59 (bs,A- 4- (4- IH) , 7.41-7.37 (m, IH) , 7.34-

1 H H

2 F-Ph) 7.32 (m, 2H) , 7.15-7.09 (m, 3H) ,

7.02-6.99 (m, IH) , 5.16 (s, 2H) , 3.77 (s, 3H) , 2.33 (s, 3H) .

CDCI₃/TMS: 9.05 (s, IH) , 7.73- 7.72 (m, 3H) , 7.50 (d, J = 7.6 Hz, 2H) , 7.34-7.31 (m, IH) , 7.21A-

5-CH₂CN 1 H ' H (t = 7.6 Hz, IH) , 7.09 (d, J =3 8.4 Hz, IH) , 5.21 (s, 2H) , 4.37

(s, 2H) , 3.66 (s, 3H) , 2.24 (s, 3H) .

CDCI₃/TMS: 8.17 (bs, IH) , 7.90- 7.74 (m, 4H) , 7.48-7.41 (m, 3H) ,A- 4-(3- 7.32 (d, J = 7.2 Hz, 2H) , 7.06-

1 Me H

4 Br-Ph) 6.99 (m, 2H) , 5.16 (s, 2H) , 3.75

(s, 3H) , 2.43 (s, 3H), 2.30 (s, 3H) .

CDCI₃/TMS: 8.01-8.00 (m, IH) , 7.72 (bs, IH) , 7.39-7.35 (m, IH) , 7.31-7.27 (m, IH) , 7.09-A-

4-CH₂CN 1 H H 7.05 (m, 3H) , 6.90 (d, J = 8.85 Hz, IH), 6.69 (s, IH) , 5.11 (s,

2H) , 3.9i7 (s, 2H), 3.76 (s, 3H) , 2.23 (s, 3H) .

CDCI₃/TMS: 7.79 (s, IH) , 7.57 (bs, IH) , 7.28-7.26 (m, IH) ,A- 7.10 (d, J = 8.4 Hz, 2H) , 6.98-

4-CH₂Cl 1 Me H

6 6.92 (m, 2H) , 6.71 (s, IH) , 5.07

(s, 2H), 3.98 (s, 2H) , 3.74 (s, 3H) , 2.39 (s, 3H) , 2.20 (s, 3H) . CDCI₃/TMS: 7.75 (s, 3H) , 7.69 (s,

IH) , 7.29 (s, 2H) , 7.05-6.99 (m,A-

5-CH₂CN 1 Me H 2H) , 5.15 (s, 2H) , 3.95 (s, 2H) ,7

3.75 (s, 3H) , 2.42 (s, 3H) , 2.26 (s, 3H) .

CDCI₃/TMS: 7.85 (bs, IH) , 7.73

(s, IH), 7.71-7.68 (m, IH) , 7.65

(d, J= 8.0 Hz, IH) , 7.30 (t, J =

8.0 Hz, IH) , 7.08 (d, J = 8.4A-

4 -Me 1 OMe H Hz, IH) , 6.79 (d, J = 1.2 Hz,8

IH) , 6.66 (d, J = 8.0 Hz, IH) , 5.33 (s, 2H) , 3.88 (s, 3H) , 3.76 (s, 3H) , 2.48 (s, 3H) , 2.29 (s, 3H) .

CDCI₃/TMS: 7.96 (d, J = 8.0 Hz,

IH) , 7.90 (bs, IH) , 7.77 (s,

IH) , 7.74-7.71 (m, IH), 7.29 (t,A- J = 8.4 Hz, IH) , 7.16-7.14 (m,

4 -Me 1 CI H

9 IH) , 7.05 (d, J = 8.8 Hz, IH) ,

6.80 (d, J = 1.2 Hz, IH) , 5.40 (s, 2H), 3.77 (s, 3H) , 2.49 (s, 3H) , 2.30 (s, 3H) .

CDCI₃/TMS: 7.73-7.71 (m, IH) ,

7.68-7.65 (m, IH) , 7.39 (t, J =

8.4 Hz, IH) , 6.99 (d, J = 8.4

Hz, IH) , 6.95 (d, J = 8.4 Hz,A- IH) , 6.77 (d, J = 1.2 Hz, IH) ,

4 -Me 1 OMe COMe

0 6.75 (d, J = 7.6 Hz, IH) , 5.17

(d, J = 11.2 Hz, IH) , 4.90 (d, J= 11.2 Hz, IH) , 3.90 (s, 3H) , 3.50 (s, 3H) , 2.59 (s, 3H) , 2.48 (s, 3H) , 2.19 (s, 3H) .

CDCI₃/TMS: 7.73-7.72 (m, 2H) ,

7.37 (t, J = 8.0 Hz, IH) , 7.01

(d, J = 8.8 Hz, IH) , 6.94 (d, J

= 8.0 Hz, IH) , 6.81-6.78 (m,A-

4-Me 1 OMe Et 2H) , 5.10 (d, J = 10.4 Hz, IH) ,1

4.89 (d, J= 10.4 Hz, IH) , 3.85 (s, 3H), 3.74-3.42 (m, 5H) , 2.49 (s, 3H), 2.17 (s, 3H) , 1.13 (t, J = 7.2 Hz, 3H) . CDCI₃/TMS: 7.75-7.73 (m, IH) ,

7.68-7.65 (m, IH) , 7.38 (t, J =

8.4 Hz, IH), 6.99 (d, J = 8.0Hz,

IH) , 6.95 (d, J = 8.4 Hz, IH) ,A- 6.77-6.73 (m, 2H) , 5.16 (d, J =

4-Me 1 OMe COEt

2 11.6 Hz, IH) , .87 (d, J= 11.6

Hz, IH), 3.90 (s, 3H) , 3.50 (s, 3H) , 2.97 (q, J = 7.2 Hz, 2H) , 2.48 (s, 3H) , 2.18 (s, 3H) , 1.14 (t, J = 7.2 Hz, 3H) .

CDCI₃/TMS: 7.75-7.73 (m, 2H) ,

7.45-7.43 (m, IH) , 7.36 (t, J =

8.0 Hz, IH) , 7.15-7.11 (m, IH) ,A- 6.98 (d, J = 9.2 Hz, IH) , 6.79

4 -Me 1 CI Me

3 (d, J = 1.2 Hz, IH) , 5.12 (d, J

= 10.0 Hz, IH) , 5.03 (d, J= 10.0 Hz, IH), 3.76-3.22 (m, 6H) , 2.49 (s, 3H) , 2.20 (s, 3H) .

CDCI₃/TMS: 7.75-7.74 (m, 2H) ,

7.46-7.44 (m, 1H),7.36 (t, J =

8.0 Hz, IH) , 7.15-7.11 (m, IH) ,

6.98 (d, J = 9.6 Hz , IH) , 6.79A-

4-Me 1 CI Et (d, J = 1.2 Hz, IH) , 5.08 (d, J4

= 10.0 Hz, IH) , 4.99 (d, J= 10.0 Hz, IH), 3.83-3.46 (m, 7H) , 2.49 (s, 3H) , 2.19 (s, 3H) , 1.13 (t, J = 7.2 Hz, 3H) .

CDCI₃/TMS: 7.75-7.74 (m, 2H) ,

7.48-7.45 (m, 1H),7.35 (t, J =

8.0 Hz, IH) , 7.10 (d, J = 8.0

Hz, IH) , 6.97 (d, J = 9.2 Hz,A- IH) , 6.79 (d, J = 1.2 Hz, IH) ,

4-Me 1 CI iPr

5 5.04 (d, J = 9.6 Hz, IH) , 4.94

(d, J= 9.6 Hz, IH) , 4.37-4.36 (m, IH), 3.62 (s, 3H) , 2.49 (s, 3H) , 2.19 (s, 3H) , 1.29-1.21 (m, 6H) .

CDCI₃/TMS : 7.75-7.74 (m, IH) ,

7.71-7.69 (m, IH) , 7.50 (d, J =

7.6 Hz, IH) , 7.38 (t, J = 8.0A- Hz, IH) , 7.06 (d, J = 8.0 Hz ,

4-Me 1 CI COMe

6 IH) , 6.90 (d, J = 8.4 Hz, IH) ,

6.79 (s, IH) , 3.53 (s, 3H) , 2.61 (s, 3H), 2.48 (s, 3H) , 2.20 (s, 3H) . CDCI₃/TMS: 7.77-7.76 (m, IH) ,

7.70-7.67 (m, IH) , 7.62-7.57 (m,

IH) , 7.39-7.35 (m, 2H) , 7.22-

1A- 7.19 (m, IH) , 6.84 (d, J = 8.4

4 -Me 1 H Me

47 Hz, IH) , 6.79 (d, J = 1.2 Hz,

IH) , 5.10-5.00 (m, 2H) , 3.66 (s, 3H) , 3.27 (s, 3H) , 2.48 (s, 3H) , 2.32 (s, 3H) .

CDCI₃/TMS: 7.78-7.77 (m, IH) ,

7.70-7.67 (m, IH) , 7.62-7.61 (m,

IH) , 7.40-7.33 (m, 2H) , 7.14 (d,

J = 6.8 Hz, IH) , 6.85 (d, J =

1A- 8.4 Hz, IH) , 6.79 (d, J = 1.2

4 -Me 1 H iPr

48 Hz, IH), 5.08-4.98 (m, 2H) ,

4.45-4.43 (m, IH) , 3.65 (s, 3H) , 2.49 (s, 3H) , 2.32 (s, 3H) , 1.33 (d, J = 6.8 Hz, 3H) , 1.05 (d, J = 6.8 Hz, 3H) .

CDCI₃/TMS: 7.77-7.76 (m, IH) ,

7.69-7.67 (m, IH) , 7.61-7.59 (m,

IH) , 7.38-7.35 (m, 2H) , 7.22-

7.17 (m, IH) , 6.84 (d, J = 8.4

1A-

4 -Me 1 H Et Hz, IH) , 6.79 (d, J = 1.2 Hz, 49

IH) , 5.09-4.99 (m, 2H) , 3.91- 3.50 (m, 5H) , 2.49 (s, 3H) , 2.32 (s, 3H) , 1.18 (t, J = 6.8 Hz, 3H) .

CDCI₃/TMS: 7.76-7.75 (m, IH) ,

7.66-7.63 (m, IH) , 7.56-7.54 (m,

IH) , 7.43-7.37 (m, 2H) , 7.10-

7.08 (m, IH) , 6.80-6.76 (m, 2H) ,

1A-

4-Me 1 H COiPr 4.99 (d, J = 12.8 Hz, IH) , 4.90

50

(d, J= 12.4 Hz, IH) , 3.87-3.76 (m, IH), 3.66 (s, 3H) , 2.48 (s, 3H) , 2.30 (s, 3H) , 1.25-1.20 (m, 6H) .

CDCI₃/TMS: 7.76-7.75 (m, IH) ,

7.66-7.63 (m, IH) , 7.57-7.55 (m,

IH) , 7.44-7.38 (m, 2H) , 7.12-

1A- 7.10 (m, IH) , 6.80-6.78 (m, 2H) ,

4 -Me 1 H COMe

51 5.01 (d, J = 12.8 Hz, IH) , 4.94

(d, J= 12.8 Hz, IH) , 3.65 (s, 3H) , 2.64 (s, 3H) , 2.48 (s, 3H) , 2.26 (s, 3H) .

Table 2: Detail and H NMR of the compounds synthesized belonging to the formula (IB) :

Table 3: Detail and H NMR of the compounds synthesized belonging to the formula (1C) :

Given below are Formulation examples in which the parts refer to parts by weight.

Formulation example 1 ( Emulsifiable concentrate) 10 parts of each compound of the invention was dissolved in 45 parts of Solvesso^® 150 and 35 parts of N- methylpyrrolidone . 10 parts of emulsifier (trade name: Sorpol^® 3005X, manufactured by Toho Kagaku Co., Ltd.) was added

thereto. These ingredients were mixed while stirring, thereby producing a 10% emulsifiable concentrate.

Formulation example 2 (Wettable powder)

20 parts of each compound of the invention was added to the mixture of 2 parts of sodium lauryl sulfate, 4 parts of sodium lignin sulfonate, 20 parts of fine powders of water- containing synthetic silicon oxide and 54 parts of clay. These ingredients were mixed while stirring by a juice mixer,

thereby producing 20% wettable powders.

Formulation example 3 (Granule)

5 parts of each compound of the invention was mixed with 2 parts of sodium dodecylbenzenesulfonate, 10 parts of

bentonite and 83 parts of clay, followed by thorough agitation. A suitable amount of water was added, and the mixture was further stirred. The mixture was granulated by a granulator and air-dried, producing 5% granules.

Formulation example 4 (Dust)

1 part of each compound of the invention was dissolved in a suitable amount of acetone. To the solution were added 5 parts of the fine powders of water-containing synthetic

silicon oxide, 0.3 parts of acidic isopropyl phosphate (PAP) and 93.7 parts of clay, followed by mixing and stirring by a juice mixer. Acetone was removed therefrom by evapora'tion, producing a 1% powder formulation.

Formulation example 5 (Flowable preparation)

20 parts of each compound of the invention was mixed with 20 parts of water-containing 3 parts of

polyoxyethylenetristyrylphenyl ether phosphoric acid and

triethanolamine and 0.2 parts of Rhodorsil^® 426R (manufactured by RhodiaChimie) . The mixture was pulverized by a mill (trade name: DYNO-Mill, and manufactured by Willy A. Bachofen AG) using a wet method, and further mixed with 60 parts of water- containing 8 parts of propylene glycol and 0.32 parts of xanthan gum, thereby producing a 20% suspension in water.

Test example is given below to demonstrate that the compound of the invention is useful as active ingredients of a

fungicide .

Test Examples are given below to demonstrate that the compounds of the invention are useful as an active ingredient for fungicides.

Test example 1 (Fungicidal test on Sphaerotheca fuliginea, cucumber )

The solution of the compound of the invention (500 ppm) was sprayed on fresh healthy two week old cucumber plants. The plants were air-dried and inoculated with freshly prepared spore suspension (l><10⁶cfu spore per ml) . The inoculated

plants were then placed in green house (25°C, a humidity of 60% and 16L8D) .

The disease area rate after 12 days of inoculation was measured and the activity of the compound was shown as

preventive value calculated according to the following

eguation. Preventive value = {1- (disease area rate on treated) / (disease area rate on control) } x 100.

The compounds that exhibited the preventive value of 50% or more are as follows:

Compound nos . : lA-1, 1A-2, 1A-3, 1A-4, 1A-5, 1A-6, 1A-9, lA-10, 1A-12, 1A-13, 1A-14, 1A-15, 1A-16, 1A-17, 1A-18, 1A-22, 1A-25, 1A-28, 1A-29, 1A-30, 1A-31, 1A-32, ΊΑ-33, 1A-34, 1A-35, 1A-36, 1A-37, 1A-38, 1A-39, 1A-40, 1A-41, 1A-42, 1A-43, 1A-44, 1A-45, 1A-46, 1A-47, 1A-48, 1A-49, 1A-50, 1A-51, lB-1, 1B-2, lC-1, lC-2. Test example 2 (Fungicidal test on Botrytis cinerea)

The solution of the compound of the invention (500 ppm and 200 ppm) was sprayed on fresh healthy cucumber plant at least three leaf stage. The cotyledon of the treated plant was cut, and its leaf was put on moist tissue paper on plastic tray. 50μ1 of spore suspension (lxl0⁶cfu spore per ml) was dropped on the middle of the leaf using micropipette . And then a small disc of absorbent cotton was put on the spore drop, and again the 50μ1 of spore suspension was dropped on the disc. Leaves were kept at room temperature (20°C) .

The radial growth of fungus after five day of inoculation was measured and the activity of the compound was shown as preventive value calculated according to the following

equation. Preventive value = {1- (radial growth on treated) / (radial growth on control) } x 100

The compounds that exhibited the preventive value of 50% or more at a treatment concentration of 500 ppm are as

follows :

Compound nos.: lA-1, 1A-2, 1A-3, 1A-4, 1A-5, 1A-6, 1A-9, lA-10, 1A-12, 1A-13, 1A-14, 1A-15, 1A-16, 1A-17, 1A-18, 1A-22, 1A-23, 1A-25, 1A-29, 1A-30, 1A-33, 1A-34, 1A-37, 1A-38, 1A-39, 1A-40, 1A-41, 1A-42, 1A-46, 1A-47, 1A-48, 1A-49, 1A-50, 1A-51, lB-1, 1B-2, lC-1, lC-2.

The compounds that exhibited the preventive value of 50% or more at a treatment concentration of 200 ppm are as

follows :

Compound nos.: lA-1, 1A-2, 1A-3, 1A-4, 1A-5, 1A-6, 1A-9, lA-10, 1A-12, 1A-13, 1A-14, 1A-15, 1A-17, 1A-18, 1A-25, 1A-29, 1A-30, 1A-33, 1A-37, 1A-38, 1A-39, 1A-40, 1A-41, 1A-47, 1A-48, 1A-49, 1A-50, 1A-51, lB-1, 1B-2, lC-1, lC-2.

Test example 3 (Fungicidal test on Phytophthora infestans)

The solution of the compound of the invention (500 ppm) was sprayed on fr'esh healthy tomato plant at least at the three leaf stage. The plants were air-dried and inoculated with freshly prepared sporangia suspension (l><10⁶cfu zoospore per ml) . The inoculated plants were then placed in a dew

chamber (20°C and a humidity of 100%). One day after

inoculation the plants were shifted to thermostatic chamber (20°C, a humidity of 80%, and 16L8D) .

The disease area rate after 5 days of inoculation was measured and the activity of the compound was shown as preventive value calculated according to the following

equation. Preventive value = {1- (disease area rate on treated) / (disease area rate on control) } x 100.

Compound nos. : 1A-4, 1A-5, 1A-12, 1A-15, 1A-17, 1A-29, 1A-35, 1A-36, 1A-37, 1A-40, 1A-49, lC-1, lC-2.

Test example 4 (Fungicidal test on Pyricularia grisea)

The solution of the compound of the invention (500 ppm) was sprayed on fresh healthy two week old millet plants. The plants were air-dried and inoculated with freshly prepared spore suspension (lxl0⁶cfu spore per ml) . The inoculated plants were then placed in a dew chamber (25°C and a humidity of 100%) . One day after inoculation the plants were shifted to thermostatic chamber (25°C, a humidity of 80%, and 16L8D) .

The disease area rate after 5-7 days of inoculation was measured and the activity of the compound was shown as

preventive value calculated according to the following

Compound nos. : lA-1, 1A-2, 1A-3, 1A-4, 1A-5, 1A-6, 1A-7, 1A-9, lA-10, lA-11, 1A-12, 1A-13, 1A-14, 1A-15, 1A-17, 1A-18, 1A-19, 1A-20, 1A-22, 1A-23, 1A-25, 1A-26, 1A-29, 1A-30, 1A-33, 1A-35, 1A-36, 1A-37, 1A-38, 1A-39, 1A-40, 1A-41, 1A-42, 1A-43, 1A-44, 1A-45, 1A-46, 1A-47, 1A-48, 1A-49, 1A-50, 1A-51, lB-1, 1B-2, lC-1, lC-2.

(Note)

As described above, the present invention is illustrated by preferable embodiments of the present invention. However, it will be understood that the scope of the present invention should be interpreted only by the claims. It is understood that patents, patent applications and literatures cited herein are incorporated herein by reference, as if the contents thereof are specifically described herein. The present application claims priority to Indian Patent Application No. 201711003382 filed on January 30, 2017 with the Indian Patent Office (Intellectual Property India), the entire content of which is incorporated herein by reference.

Industrial Applicability

The carbamate compound of the present invention has a controlling effect against plant diseases and is useful as an active ingredient of a plant control agent.

Claims

Claim 1:

A carbamate compound is represented by the formula (1) :

or a salt thereof,

wherein Ri, R3 and R₆ are identical or different and each represents hydrogen, halogen, nitro, cyano, hydroxyl, formyl, carboxy, optionally substituted amino, Ci-6 alkyl, Ci-₆

haloalkyl, Ci-6 alkoxy, Ci_₆ haloalkoxy, Ci_₆ alkoxy Ci-6 alkyl, Ci-6 haloalkoxy Ci_₆ alkyl, Ci_₆ alkoxycarbonyl , Ci-₆

haloalkoxycarbonyl , cyano Ci-₆ alkyl, cyano Ci_₆ alkoxy, C₂-6 alkenyl, C₂-6 haloalkenyl, cyano C2-6 alkenyl, C₂-6 alkynyl, C₂-6 haloalkynyl, cyano C₂-6 alkynyl, C₃_₈ cycloalkyl, C₃~₈ cycloalkyl Ci-6 alkyl, Ci_₆ alkylthio, Ci_₆ haloalkylthio , C₃_₈

cycloalkylthio, C₃_₈ cycloalkyl Ci_₆ alkylthio, Ci_₆ alkoxy Ci_₆ alkylthio, Ci_₆ alkylsulfonyl, Ci_₆ alkylsulf inyl , Ci_₆

haloalkylsulfonyl, Ci-6 haloalkylsulfinyl, C₃_₈

cycloalkylsulfonyl , C₃_₈ cycloalkylsulfinyl , C₃_₈ cycloalkyl Ci-₆ alkylsulfonyl, C₃-₈ cycloalkyl Ci_₆ alkylsulf inyl , C₂-6

alkenyloxy, C₂-6 alkynyloxy, C₂-6 haloalkenyloxy, C₂~6

haloalkynyloxy , Ci-6 alkylsulfonyloxy, Ci-6 alkylsulfinyloxy, Ci-6 alkylcarbonyl, Ci_₆ haloalkylcarbonyl , OCN, SCN, SF₅, optionally substituted aryloxy, optionally substituted aryl Ci-6 alkyloxy, optionally substituted arylthio, optionally substituted aryl Ci-6 alkylthio, optionally substituted

arylsulfonyl , optionally substituted arylsulfinyl , optionally substituted heteroaryloxy , optionally substituted

heteroaryl ;

R₂ represents hydrogen, halogen, or Ci-6 alkyl;

R₄ and R5 are identical or different and each represents hydrogen, halogen, or Ci-6 alkyl;

R₇ represents hydrogen, hydroxyl, formyl, cyano, Ci_6 alkyl, Ci_₆ haloalkyl, Ci_₆ alkoxy, Ci-₆ haloalkoxy, Ci_₆ alkoxy Ci_6 alkyl, Ci-6 haloalkoxy Ci_₆ alkyl, C3-8 cycloalkyl, C₃_₈ cycloalkyl Ci_₆ alkyl, Ci_₆ alkylcarbonyl , Ci-₆ haloalkylcarbonyl , Ci-6 alkoxycarbonyl, C₂_₆ haloal koxycarbonyl , C₂_₆ alkenyl, C₂_₆ haloalkenyl, C₂-6 cyanoalkenyl , C₂_₆ alkynyl, C₂_₆ haloalkynyl, C₂-6 cyanoalkynyl, Ci_₆ alkylsulfonyl, Ci_₆ alkylsulfinyl, Ci_₆ haloalkylsulfonyl, Ci_₆ haloalkylsulfinyl , C₃-₈

cycloalkylsulfonyl , C₃-₈ cycloal kylsulfinyl , C₃_₈ cycloalkyl Ci_6 alkylsulfonyl , C₃_₈ cycloalkyl Ci_₆ alkylsulfinyl , optionally substituted arylsulfonyl , optionally substituted arylsulfinyl , or optionally substituted aryl;

R₈ represents hydrogen, or Ci-₆ alkyl;

X and Xi independently represent oxygen, or sulfur;

Y represents oxygen, or sulfur;

Z represents oxygen, or sulfur;

1 is an integer of 0 to 2;

m is an integer of 0 to 3;

n is an integer of 0 to 4; and

when 1, m or n is more than one, the 1, m or n may be the same or different.

Claim 2 : The carbamate compound or a salt thereof according to claim 1, wherein R_x is hydrogen, halogen, nitro, Ci-₆ alkyl, Ci_ 6 haloalkyl, Ci_₆ alkoxycarbonyl, cyano Ci_₆ alkyl, optionally substituted aryl.

Claim 3: The carbamate compound or a salt thereof according to claim 1 or 2, wherein R₂ is hydrogen or Ci_₆ alkyl.

Claim 4 : The carbamate compound or a salt thereof according to any one of claims 1 to 3, wherein R₃ is hydrogen, halogen or Ci-6 alkyl.

Claim 5: The carbamate compound or a salt thereof according to any one of claims 1 to 4, wherein R₄ and R₅ each represent hydrogen or Ci_ 6 alkyl.

Claim 6: The carbamate compound or a salt thereof according to any one of claims 1 to 5, wherein R₆ is hydrogen, halogen, Ci_₆ alkyl or Ci-₆ alkoxy.

Claim 7 : The carbamate compound or a salt thereof according to any one of claims 1 to 6, wherein R₇ is hydrogen, Ci-₆ alkyl or Ci- 6 alkylcarbonyl .

Claim 8 : The carbamate compound or a salt thereof according to any one of claims 1 to 7, wherein R₈ is Ci_₆ alkyl.

Claim 9: A plant disease-controlling agent containing the carbamate compound or a salt thereof according to any one of claims 1 to 8.

Claim 10: A fungicide containing the carbamate compound or a salt thereof according to any one of claims 1 to 8.