WO2016063293A1

WO2016063293A1 - Novel 2-substituted imidazole compound and use thereof

Info

Publication number: WO2016063293A1
Application number: PCT/IN2015/000391
Authority: WO
Inventors: Tetsuya Imai; Surendra Kumar KUMAWAT; Manish Kumar SINGH; Ram Kishore; Dhuni Lal YADAV; Srinivas VENUVENKA
Original assignee: Oat & Iil India Laboratories Private Limited
Priority date: 2014-10-21
Filing date: 2015-10-16
Publication date: 2016-04-28
Also published as: TW201617322A

Abstract

An object of the present invention is to provide novel 2-substituted imidazole compounds or salts thereof that have pesticidal activity. The present invention provides a 2-substituted imidazole compounds represented by Formula (1) : or a salt thereof, wherein R¹, R², and R³are identical or different and each represent hydrogen, or C₁-C₄-haloalkyl; R⁴represents (1) hydrogen or a substituent as defined herein, R⁵represents C_1-12alkyl or other substituents as defined herein, A represents NR⁶, O or S(O)_m, m = 0, 1 or 2, W, X, Y, and Z are identical or different and each represent CR⁴or N, R6 is C_1-12 alkyl or a substituent as defined herein, and n is an integer of 1 to 4.

Description

NOVEL 2 -SUBSTITUTED IMIDAZOLE COMPOUND AND USE THEREOF

Technical Field

The present invention relates to a novel 2-substituted imidazole compound and use thereof.

Background Art

To achieve high crop efficiency, it is very important to control mites and plant diseases caused by fungal plant pathogens. To grow agricultural products, therefore, agricultural chemicals, such as fungicides and miticides, have been used.

However, as a result of long-term use of fungicides or miticides, recent years have seen the emergence of fungi

resistant to chemicals or mites resistant to miticides. It has thus become difficult to accomplish control by use of known fungicides or miticides.

Under such circumstances, there is a demand for the development of new types of pest-controlling agents, including a fungicide and a miticide, which are expected to achieve

fungicidal or miticidal activity not only against chemical- sensitive fungi or mites, but also against chemical-resistant fungi or mites.

Thus far, as an imidazole compound, for example, German patent publication No. 3621265 (Patent Literature (PTL) 1) discloses a compound that is represented by Formula (A) and that has trifluoromethyl at position 2 of the imidazole ring:

PTL 1 also discloses that this compound has fungicidal activity.

However, PTL 1 nowhere discloses the miticidal activity of the compound represented by Formula (A) . Further, WO 2012/062749 (Patent Literature (PTL) 2 ) discloses 2 ( 1H) -benzimidazolone derivatives represented by

Formula ( B ) :

(B),

wherein R₂ is halogen and R₂ is alkyl. PTL 2 also discloses that this compound has fungicidal activity.

However, PTL 2 nowhere discloses the miticidal activity of the compound represented by Formula (B) . Summary of Invention

Technical Problem

An object of the present invention is to provide a novel 2-substituted imidazole compound or a salt thereof that controls a pest.

Another object of the present invention is to provide a method for preparing the 2-substituted imidazole compound or a salt thereof.

Solution to Problem

[0006]

The present inventors conducted extensive research to achieve the above objects, and succeeded in synthesizing a compound represented by the following Formula (1) or a salt thereof that has fungicidal and/or miticidal activity. The present inventors have conducted further research based on the above findings. The present invention has thereby been

accomplished.

More specifically, the present invention includes the following embodiments: Item 1: A 2-substituted imidazole compound represented b Formula (1) :

or a salt thereof,

wherein R¹, R², and R³ are identical or different and each represent hydrogen, halogen, or C₁_₄ haloalkyl,

R⁴ represents

(1) hydrogen,

(2) nitro,

(3) cyano,

(4) halogen,

(5) C₁_₄ alkyl,

(6) C₁_₄ haloalkyl,

(7) C₁_₄ alkoxy,

(8) C₁_₄ haloalkoxy,

(9) benzyloxy,

(10) benzylthio,

(11) C₂ -4 alkenyloxy,

(12) C₂ -4 alkynyloxy,

(13) cyano C₁_₄ alkoxy,

(14) C_3-8 cycloalkyl,

(15) C_3-8 cycloalkyl C₁_₄ alkoxy,

(16) C₁_₄ alkylsulfonyloxy,

(17) C₁_₄ alkylsulfinyloxy,

(18) arylsulfonyloxy,

(19) arylsulfinyloxy,

(20) C₁_₄ alkylthio,

(21) C₁_₄ haloalkylthio,

(22) aryl, or

(23) heterocyclic group, two R⁴ groups, taken together, may form a ring, via or not via at least one heteroatom,

the groups (1) to (23) represented by R⁴ may optionally be further substituted,

R⁵ represents

(1) C_1-12 alkyl,

(2) C_1-12 haloalkyl,

(3) C₁_₄ alkoxy C₁_₄ alkyl,

(4) C₁_₄ haloalkoxy C₁_₄ alkyl,

(5) C₂-₄ alkenyl,

(6) C₂-₄ alkynyl,

(7) C_3-8 cycloalkyl,

(8) C_3-8 cycloalkyl C₁_₄ alkyl,

(9) C₁_₄ alkyl-carbonyl,

(10) cyano C₁_₈ alkyl,

(11) C₁_₄ alkylsulfonyl,

(12) C₁_₄ alkylsulfinyl,

(13) arylsulfonyl,

(14) arylsulfinyl,

(15) aryl,

(16) heterocyclic group, or

(17) heterocyclic-substituted C₁_₄ alkyl,

the groups (1) to (17) represented by R⁵ may optionally be further substituted,

A represents O, S(O)_m, or NR⁶,

wherein R⁶ represents

(1) C₁-₁₂ alkyl,

(2) C_1-12 haloalkyl,

(3) C₁_₄ alkoxy C₁_₄ alkyl,

(4) C₁_₄ haloalkoxy C₁_₄ alkyl,

(5)C₂-₄ alkenyl,

(6)C₂-₄ alkynyl,

(7) C_3-8 cycloalkyl,

(8) C_3-8 cycloalkyl C₁_₄ alkyl,

(9) C₁_₄ alkyl-carbonyl, (10) cyano C₁_₈ alkyl,

(11) C₁_₄ alkylsulfonyl,

(12) C₁_₄ alkylsulfinyl,

(13) arylsulfonyl,

(14) arylsulfinyl ,

(15) aryl,

(16) heterocyclic group, or

(17) heterocyclic-substituted C₁_₄ alkyl,

the groups (1) to (17) represented by R⁶ may optionally be further substituted, and

wherein when A is NR⁶, R⁵ and R⁶, taken together with the nitrogen, may form a 3- to 7-membered ring, via or not via at least one heteroatom,

m represents 0, 1, or 2,

W, X, Y, and Z are identical or different and each represent CR⁴ or N, and

n is an integer of 1 to 4.

Item 2: The 2-substituted imidazole compound or a salt thereof according to Item 1, wherein A is O or S(O)_ra.

Item 3: The 2-substituted imidazole compound or a salt thereof according to Item 1, wherein A is O. Item 4: The 2-substituted imidazole compound or a salt thereof according to Item 1, wherein A is S(O)_m.

Item 5: The 2-substituted imidazole compound or a salt thereof according to Item 1, wherein R¹, R², and R³ each represent halogen .

Item 6: The 2-substituted imidazole compound or a salt thereof according to Item 1, wherein R⁴ is any one of the groups (1) to (13) and (16) to (23) defined as R⁴ in Item 1. Item 7: A pest-controlling agent containing the 2- substituted imidazole compound or a salt thereof of any one of

Items 1 to 6.

Item 8: A plant pest-controlling agent containing the 2-substituted imidazole compound or a salt thereof of any one of

Items 1 to 6.

Item 9: A fungicide containing the 2-substituted imidazole compound or a salt thereof of any one of Items 1 to 6.

Item 10: A miticide containing the 2-substituted imidazole compound or a salt thereof of any one of Items 1 to 6.

Advantageous Effects of Invention

The 2-substituted imidazole compound or a salt thereof of the present invention has an effect on pests at a low dose.

In particular, the compound of the present invention has an excellent effect of controlling fungal plant pathogens and mites .

Description of Embodiments

2-Substituted imidazole compound or a salt thereof

The present invention is directed to a compound represented by

Formula 1)

or a salt thereof (hereinafter sometimes referred to as "the compound (1) of the present invention" or a "compound of the invention") , wherein R¹, R², R³, R⁴, R⁵, A, W, X, Y, Z, and n are as defined above .

The following shows specific examples of the groups represented by R¹, R², R³, R⁴, R⁵, A, W, X, Y, Z, and n in Formula (1) above.

Examples of halogen include fluorine, chlorine, bromine, iodine, and the like.

Examples of C₁_₄ alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and like C₁_₄ straight-chain or branched-chain alkyl.

Examples of C₁_₄ haloalkyl include fluoromethyl, chloromethyl, bromomethyl, iodomethyl, difluoromethyl,

trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2, 2, 2-trifluoroethyl, pentafluoroethyl, 1-fluoropropyl, 2- chloropropyl, 3-fluoropropyl, 3-chloropropyl, 3,3,3- trifluoropropyl, 1-fluorobutyl, 1-chlorobutyl, 4-fluorobutyl, 4 , 4 , 4-trifluorobutyl, and like C₁_₄ straight-chain or branched- chain alkyl substituted with 1 to 9, and preferably 1 to 5, halogen atoms .

Examples of C₁_₄ alkoxy include methoxy, ethoxy, n- propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, and like C₁_₄ straight-chain or branched-chain alkoxy.

Examples of C₁_₄ haloalkoxy include fluoromethoxy, bromomethoxy, iodomethoxy, difluoromethoxy, trifluoromethoxy, 2- fluoroethoxy, 2-chloroethoxy, 1-fluoroethoxy, pentafluoroethoxy,

1-fluoropropoxy, 2-chloropropoxy, 3-fluoropropoxy, 3- chloropropoxy, 1-fluorobutoxy, 1-chlorobutoxy, 4-fluorobutoxy, and like C₁_₄ straight-chain or branched-chain alkoxy substituted with 1 to 9 halogen atoms.

Examples of C_2-4 alkenyloxy include vinyloxy, allyloxy,

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

Examples of C_2-4 alkynyloxy include ethynyloxy, 1- propynyloxy, l-methyl-2-propynyloxy, 1-butynyloxy, 2-butynyloxy,

3-butynyloxy, and the like.

Examples of cyano C₁_₄ alkoxy include cyanomethoxy, cyanoethoxy, cyano-n-propoxy, cyano-iso-propoxy, cyano-n-butoxy, cyano-iso-butoxy, cyano-sec-butoxy, cyano- tert-butoxy, and like C₁_₄ straight-chain or branched-chain alkoxy substituted with a cyano group.

Examples of C₃_₈ cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like.

Examples of C_3-8 cycloalkyl C₁_₄ alkyl include cyclopropylmethyl, cyclobutylethyl, cyclopentyl-n-propyl,

cyclohexyl-n-butyl, cyclooctylmethyl, and the like.

Examples of C₁_₄ alkylsulfonyloxy include

methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy,

isopropylsulfonyloxy, n-butylsulfonyloxy, isobutylsulfonyloxy, sec-butylsulfonyloxy, tert-butylsulfonyloxy, and like

alkylsulfonyloxy groups whose alkyl moiety is C₁_₄ straight-chain or branched-chain alkyl.

Examples of C₁_₄ alkylsulfinyloxy include

methylsulfinyloxy, ethylsulfinyloxy, n-propylsulfinyloxy,

isopropylsulfinyloxy, n-butylsulfinyloxy, isobutylsulfinyloxy, sec-butylsulfinyloxy, tert-butylsulfinyloxy, and like

alkylsulfinyloxy groups whose alkyl moiety is C₁_₄ straight-chain or branched-chain alkyl.

Examples of arylsulfonyloxy include phenylsulfonyloxy, 1-naphthylsulfonyloxy, 2-naphthylsulfonyloxy, and the like.

Examples of arylsulfinyloxy include phenylsulfinyloxy,

1-naphthylsulfinyloxy, 2-naphthylsulfinyloxy, and the like.

Examples of C₁_₄ alkylthio include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec- butylthio, tert-butylthio, and like C₁_₄ straight-chain or

branched-chain alkylthio.

Examples of C₁_₄ haloalkylthio include fluoromethylthio, chloromethylthio, bromomethylthio, iodomethylthio,

difluoromethylthio, trifluoromethylthio, 2-fluoroethylthio, 2- chloroethylthio, 1-fluoroethylthio, pentafluoroethylthio, 1- fluoro-n-propylthio, 2-chloro-n-propylthio, 3-fluoro-n-propylthio, 3-chloro-n-propylthio, 1-fluoro-n-butylthio, l-chloro-n-butylthio,

4-fluoro-n-butylthio, and like C₁_₄ straight-chain or branched- chain alkylthio substituted with 1 to 9 halogen atoms.

Examples of aryl include phenyl, naphthyl, and the like. Examples of heterocyclic group include 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 substitutable position with an oxo or thioketone group. These heterocyclic groups further include those optionally substituted at any substitutable position with 1 to 5 (preferably 1 to 3) substituents, such as halogen atoms, C₁_₄ alkyl groups, C₁_₄ haloalkyl groups, or substituted heterocyclic groups (e.g., 3- chloropyridin-2-yl, 5-trifluoromethylpyridin-2-yl, and 4-methyl- 1, 3-thiazole) .

In addition to the groups listed above as examples of C₁_₄ alkyl, examples of C_1-12 alkyl include n-heptyl, isoheptyl, n- octyl, isooctyl, n-nonyl, isononyl, n-decyl, isodecyl, n-undecyl, isoundecyl, ri-dodecyl, isododecyl, and like C_1-12 straight-chain or branched-chain alkyl.

In addition to the groups listed above as examples of C₁_₄ haloalkyl, examples of C₁_₁₂ haloalkyl include

3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-tridecafluorooctyl, and like C₁_₁₂ straight-chain or branched-chain alkyl substituted with 1 to 20 halogen atoms.

Examples of C₁_₄ alkoxy C₁_₄ alkyl include methoxymethyl, ethoxymethyl, n-propoxymethyl, isopropoxymethyl, n-butoxymethyl, sec-butoxymethyl, methoxyethyl, methoxy-n-propoxy,

methoxyisopropyl, methoxy-n-butyl, and like alkoxyalkyl in which C₁_₄ straight-chain or branched-chain alkyl is substituted with C₁- 4 straight-chain or branched-chain alkoxy.

Examples of C₁_₄ haloalkoxy C₁_₄ alkyl include fluoromethoxymethyl, chloromethoxymethyl, bromomethoxymethyl, iodomethoxymethyl, difluoromethoxymethyl, trifluoromethoxymethyl,

2-fluoroethoxymethyl, 2-chloroethoxyisopropyl, 1-fluoroethoxy-.n- butyl, 2, 2, 2-trifluoroethoxy-tert-butyl, pentafluoroethoxymethyl, 1-fluoropropoxyethyl, 2-chloropropoxy-sec-butyl, 3- fluoropropoxymethyl, 3-chloropropoxymethyl, 1-fluorobutoxy-.n- propyl, 1-chlorobutoxyethyl, 4-fluorobutoxymethyl, and like straight-chain or branched-chain alkoxyalkyl substituted with 1 to 9 halogen atoms.

Examples of C₂_₄ alkenyl include vinyl, allyl, 2-butenyl,

3-butenyl, 1-methylallyl, and the like.

Examples ofC₂-₄ alkynyl include ethynyl, 1-propynyl, 1- methyl-2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, and the like.

Examples of C₁_₄ alkyl-carbonyl include methylcarbonyl (acetyl), ethylcarbonyl (propionyl) , n-propylcarbonyl (butyryl) , isopropylcarbonyl (isobutyryl) , n-butylcarbonyl (valeryl) ,

isobutylcarbonyl (isovaleryl) , sec-butylcarbonyl, tert- butylcarbonyl, and like C₁_₄ straight-chain or branched-chain alkylcarbonyl groups.

Examples of cyano C₁_₈ alkyl include cyanomethyl, cyanoethyl, cyano-n-propyl, cyano-isopropyl, cyano-n-butyl, cyano-isobutyl, cyano-sec-butyl, cyano-tert-pentyl, cyano-n-hexyl, cyano-n-heptyl, cyano-n-octyl, and like C₁_₈ straight-chain or branched-chain alkyl substituted with a cyano group.

Examples of C₁_₄ alkylsulfonyl include methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n- butylsulfonyl, isobutylsulfonyl , see-butylsulfonyl, tert- butylsulfonyl, and like alkylsulfonyl groups whose alkyl moiety is C₁_₄ straight-chain or branched-chain alkyl.

Examples of C₁_₄ alkylsulfinyl include methylsulfinyl, ethylsulfinyl, Ji-propylsulfinyl, isopropylsulfinyl, n- butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert- butylsulfinyl, and like alkylsulfinyl groups whose alkyl moiety is C₁_₄ straight-chain or branched-chain alkyl.

Examples of arylsulfonyl include phenylsulfonyl, 1- naphthylsulfonyl, 2-naphthylsulfonyl, and the like.

Examples of arylsulfinyl include phenylsulfinyl, 1- naphthylsulfinyl, 2-naphthylsulfinyl, and the like.

Examples of heterocyclic C₁_₄ alkyl include

pyridylmethyl, pyridylethyl, pyridyl-n-propyl, benzothiazolyl- isopropyl, 1, 2, 4-triazol-l-yl-n-butyl, 2-thienyl-isobutyl,

pyrazinyl-sec-butyl, pyridazinyl-tert-butyl, 2- benzothiazolylethyl, oxazolylisopropyl, isoxazoyl-sec-butyl, thiazolylisobutyl, 8-quinolylmethyl, oxadiazolyl-n-propyl, and the like.

The groups (1) to (23) represented by R⁴ may optionally be further substituted. The groups (1) to (17) represented by R⁵ W may optionally be further substituted. The groups (1) to (17) represented by R⁶ may optionally be further substituted. Examples of the substituents for the groups (1) to (23) represented by R⁴, the groups (1) to (17) represented by R⁵, and the groups (1) to (17) represented by R⁶ include nitro and cyano, as well as the above-mentioned halogen, C₁_₄ alkyl, C₁_₄ haloalkyl, C₁_₄ alkoxy, C₁_₄ haloalkoxy, C₂-₄ alkenyloxy, C_2-4 alkynyloxy, cyano C₁_₄ alkoxy, C_3-8 cycloalkyl, C_3-8 cycloalkyl C₁_₄ alkyl, C₁_₄ alkylsulfonyloxy, C₁_₄ alkylsulfinyloxy, arylsulfonyloxy, arylsulfinyloxy,

C₁_₄ alkylthio, C₁_₄ haloalkylthio, aryl, heterocyclic group, Ci-12 alkyl, C₁_₄ alkoxy C₁_₄ alkyl, C₁_₄ haloalkoxy C₁_₄ alkyl, C_2-4 alkenyl,C₂-₄ alkynyl, C₁_₄ alkyl-carbonyl, cyano C₁_₈ alkyl, C₁_₄

alkylsulfonyl, C₁_₄ alkylsulfinyl, arylsulfonyl, arylsulfinyloxy, heterocyclic C₁_₄ alkyl, and the like. Of these, preferable substituents are halogen, C₁_₄ alkyl, C1-.4 haloalkyl, C₁_₄ alkoxy, C₁_₄ haloalkoxy, and C₁_₄ alkylthio, and more preferable

substituents are chlorine, fluorine, trifluoromethyl,

trifluoromethoxy, and methylthio.

For example, aryl or heterocyclic group represented by R⁴, R⁵, and R⁶ may have 1 to 5 above substituents. Preferable substituted aryl groups are halogen-substituted aryl, C₁_₄ alkyl- substituted aryl, C₁_₄ haloalkyl-substituted aryl, C_:_4 alkoxy- substituted aryl, C₁_₄ haloalkoxy-substituted aryl, and Ci-4 alkylthio-substituted aryl. More preferable substituted aryl groups are chlorine-substituted aryl, fluorine-substituted aryl, trifluoromethyl-substituted aryl, trifluoromethoxy-substituted aryl, and methylthio-substituted aryl.

Preferable substituted heterocyclic groups are halogen- substituted heterocyclic group, C₁_₄ alkyl-substituted

heterocyclic group, C₁_₄ haloalkyl-substituted heterocyclic group, C₁_₄ alkoxy-substituted heterocyclic group, C₁_₄ haloalkoxy- substituted heterocyclic group, and heterocyclic-substituted C_:-₄ alkylthio .

The aryl or heterocyclic group of arylsulfonyl,

arylsulfinyl, or alkyl-substituted heterocyclic group represented by R⁴, R⁵, and R⁶ may also optionally have 1 to 5 substituents above.

The salts of the compounds represented by Formula (1) may be any type of salts as long as they are agriculturally acceptable. Examples of the salts include hydrochloride salt, sulfate salt, nitrate salt, and like inorganic acid salts;

acetate salt, methanesulfonic acid salt, and like organic acid salts; sodium salt, potassium salt, and like alkali metal salts; magnesium salt, calcium salt, and like alkaline earth metal salts; dimethylammonium, triethylammonium, and like quaternary ammonium salts; and the like.

R¹, R², and R³ of the formula representing the compound

(1) of the present invention may be identical or different and each represent hydrogen, halogen, or C₁_₄ haloalkyl. R¹, R², and R³ each preferably represent halogen. R¹ more preferably represents fluorine or chlorine, and R² and R³ each more preferably represent chlorine. R¹, R², and R³ each particularly preferably represent chlorine .

A of the formula representing the compound (1) of the present invention represents O, S(O)_m, or NR⁶, and A preferably represents O or S(O)_m.

R⁴ of the formula representing the compound (1) of the present invention is any one of the groups (1) to (23) defined as

R⁴ in Claim 1. R⁴ is preferably any one of the groups (1) to (13) and (16) to (23) above. R⁴ is more preferably any one of the groups (1) to (8), (10), (11), (13), (17), (20), and (22).

The groups (1) to (17) represented by R⁴ of the formula representing the compound (1) of the present invention may

further optionally be substituted.

Two R⁴ groups, taken together, may form a ring, via or not via at least one heteroatom. Examples of the ring include C_3-8 cycloalkyl, aryl, heterocyclic group, and the like. These C_3-8 cycloalkyl, aryl, and heterocyclic groups are as defined above.

Of these rings, aryl is preferable, and phenyl is more preferable. In this specification, a heteroatom refers to at least one atom selected from the group consisting of oxygen, sulfur, and

nitrogen .

R⁵ of the formula representing the compound of the present invention is any one of (1) to (17) defined as R⁵ in Claim 1. R⁵ is preferably any one of (1) to (3), (5) to (10), and (15).

The groups (1) to (17) represented by R⁵ of the formula representing the compound (1) of the present invention may

further optionally be substituted.

R⁶ of the formula representing compound (1) of the present invention is any one of (1) to (17) defined as R⁶ in Claim 1. R⁶ is preferably any one of (1) to (3), (5) to (10), and (15).

The groups (1) to (17) represented by R⁶ of the formula representing the compound (1) of the present invention may

further optionally be substituted.

When A is NR⁶, R⁵ and R⁶, taken together with the nitrogen, may form a 3- to 7-membered ring, via or not via at least one heteroatom. The 3- to 7-membered ring refers to a hetero ring having at least one nitrogen atom. Examples thereof include aziridine, morpholine, azetidine, pyrrolidine, piperidine, and like saturated hetero rings; pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, and like heteroaryl groups; and the like.

W, X, Y, and Z may be identical or different, and each represent CR⁴ or N. It is preferable that at least one of W, X, Y, and Z represents N, and the rest represent CR⁴, or that W, X, Y, and Z each represent CR⁴. It is more preferable that W, X, Y, Z each represent CR⁴.

Of the compound (1) of the present invention, a preferable compound is a 2-substituted imidazole compound or a salt thereof in which

R¹, R², and R³ each represent halogen,

R⁴ is any one of the groups (1) to (13) and (16) to (23),

two R⁴ groups, taken together, may form a ring, via or not via at least one heteroatom,

the group represented by R⁴ above may further optionally be substituted, R⁵ is any one of (1) to (3), (5) to (10), and (15), the group represented by R⁵ above may further optionally be substituted,

A represents O or S(O)_m,

m represents 0, 1, or 2, and

W, X, Y, and Z are identical or different and each represent CR⁴ or N.

A more preferable compound is a 2-substituted imidazole compound or a salt thereof in which

R¹ is fluorine or chlorine,

R² and R³ each represent chlorine,

R⁴ is any one of the groups (1) to (8), (10), (11), (13), (17), (20), and (22),

the group represented by R⁴ above may further optionally be substituted,

R⁵ is any one of (1) to (3), (5) to (10), and (15),

the group represented by R⁵ above may further optionally be substituted,

A represents O, and

W, X, Y, and Z are identical or different and each represent CR⁴ or N; or

a 2-substituted imidazole compound or a salt thereof in which R¹ represents fluorine or chlorine,

R⁴ and R³ each represent chlorine,

the group represented by R⁴ above may further optionally be substituted,

R⁵ is any one of (1) to (3), (5) to (10), and (15),

the group represented by R⁵ above may further optionally be substituted, A represents S(O)_m,

m is 0, 1, or 2, and

W, X, Y, and Z are identical or different and each represent CR⁴ or N.

When the compound (1) has isomers such as optical isomers, stereoisomers, regioisomers, and the like,

any of the isomers and mixtures thereof are included within the scope of the compound (1) . For example, when the compound (1) has optical isomers, the optical isomer separated from a racemic mixture is also included within the scope of the compound (1) .

Each of such isomers may be obtained as a single compound by known synthesis and separation means (e.g., concentration,

solvent extraction, column chromatography, and recrystallization) .

Method for preparing a 2-substituted imidazole compound or a salt thereof

The compound (1) of the present invention is produced in accordance with the process described in the following

Reaction Scheme 1.

Reaction Scheme 1

wherein R¹, R², R³, R⁴, R⁵, A, W, X, Y, Z, and n are as defined above, and R⁷ represents a leaving group.

As shown in Reaction Scheme 1 above, the compound (1) of the present invention is prepared by reacting a compound represented by Formula (2) with a compound represented by Formula (3) .

Examples of the leaving group represented by R⁷ include chlorine, bromine, iodine, and like halogen atoms, and alkyl sulfonate, aryl sulfonate, and the like.

In the reaction of the compound represented by Formula (2) and the compound represented by Formula (3), the proportions of these compounds used are not particularly limited, and may be suitably selected from a wide range. The latter is usually used in an amount of about 1 to 5 moles, preferably about 1 mole, per mole of the former.

The above reaction is preferably carried out in the presence of a base. As the base, a wide variety of known bases may be used. Examples include sodium carbonate, potassium

carbonate, sodium bicarbonate, potassium bicarbonate, and like alkali metal carbonates; sodium hydroxide, potassium hydroxide, and like alkali metal hydroxides; sodium hydride, potassium hydride, and like alkali metal hydrides; sodium methoxide, sodium ethoxide, potassium tert-butoxide, and like alkali metal

alkoxides; and triethylamine, pyridine, and like organic bases. These bases may be used alone, or in a combination of two or more.

The base may be used in a stoichiometric amount or more than the stoichiometric amount, with respect to the compound represented by Formula (2) . The base is preferably used about 1 to 5 times the stoichiometric amount. When triethylamine,

pyridine, or like an organic base is used, it can be used in large excess to serve also as a reaction solvent.

The above reaction may be carried out in a suitable solvent or in the absence of solvent. When the reaction is carried out in a solvent, usable solvents for the reaction are not limited insofar as they are inert to the reaction. Examples of solvents include n-hexane, cyclohexane, n-heptane, and like aliphatic or alicyclic hydrocarbons; benzene, chlorobenzene, toluene, xylene, and like aromatic hydrocarbons; methylene

chloride, 1, 2-dichloroethane, chloroform, carbon tetrachloride, and like halogenated hydrocarbons; diethyl ether, tetrahydrofuran (THF) , 1,4-dioxane, and like ethers; N, W-dimethylformamide (DMF), and like amides; dimethylsulfoxide, and like sulfoxides; and the like. These solvents may be used alone or in a combination of two or more, as required.

The reaction temperature of the above reaction, although not limited, is in the range of -20°C to the boiling point of the solvent used, and is preferably 0 to 25°C. The reaction time varies according to, for example, the reaction temperature. The reaction is usually completed in about 0.5 to about 24 hours.

The compound represented by Formula (2) and the compound represented by Formula (3) used as starting materials in

Reaction Scheme 1 above are known compounds or compounds easily prepared by a known method.

The compound of the present invention represented by

Formula (1) or a salt thereof prepared according to the process shown in Reaction Scheme 1 above may be easily isolated from the reaction mixture and purified by known isolation and purification techniques such as filtration, solvent extraction, distillation, recrystallization, and column chromatography.

When the compound (1) has regioisomers, each regioisomer may be separated by a usual separation step such as silica gel chromatography.

Pest-Controlling Agent

The compound (1) of the present invention may be used as an active ingredient of a pest-controlling agent. Examples of pest-controlling agents include agents (fungicides or virucides) for controlling plant diseases that cause problems in the

agricultural and horticultural fields; agents (agricultural and horticultural insecticide, miticides, nematicides, or soil

insecticides) for controlling pests, mites, nematode, or soil pests that all cause problems in the agricultural and

horticultural fields, animal ectoparasite-controlling agent (e.g., pulicide, ixodicide, and pedivulicideon) , and the like.

For use as an active ingredient of a pest-controlling agent, it is possible to use the compound (1) of the present invention as is with no additional components. However, it is usually preferable to use the compound by combining with a solid carrier, liquid carrier, or gaseous carrier (propellant) , and optionally with a surfactant and other adjuvants for

pharmaceutical preparation, and formulating the resulting mixture into various forms such as oil solutions, emulsiion, wettable powders, flowable preparations, granules, dusts, aerosols,

fumigants, or the like, according to known preparation methods.

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

Examples of solid carriers usable in the formulations include solid carriers in a fine powder or granular form, such as clays (e.g., kaolin clay, diatomaceous earth, synthetic hydrated silicon dioxide, bentonite, Fubasami clay, and acid clay) , talcs, ceramics, other inorganic minerals (e.g., celite, quartz, sulfur, active carbon, calcium carbonate, and hydrated silica) , and chemical fertilizers (e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and ammonium chloride); and the like.

Examples of liquid carriers include water, alcohols (e.g., methanol and ethanol) , ketones (e.g., acetone and

methylethylketone) , aromatic hydrocarbons (e.g., benzene, toluene, xylene, ethylbenzene, and methylnaphthalene) , aliphatic

hydrocarbons (e.g., hexane, cyclohexane, kerosene, and light oil), esters (e.g., ethyl acetate and butyl acetate), nitriles (e.g., acetonitrile and isobutyronitrile) , ethers (e.g., diisopropyl ether and dioxane) , acid amides (e.g., N, iV-dimethylformamide and N, W-dimethylacetamide) , halogenated hydrocarbons (e.g.,

dichloromethane, trichloroethane, and carbon tetrachloride) , dimethylsulfoxide, soybean oil, cottonseed oil, and like

vegetable oils, and the like.

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

Examples of surfactants include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl aryl ethers, polyoxyethylene adducts thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives, and the like.

Examples of adjuvants for pharmaceutical preparation include fixing agents, dispersants, stabilizers, and the like.

Examples of the fixing agents and dispersants include casein, gelatin, polysaccharides (e.g., starch, gum arabic, cellulose derivatives, and alginic acid) , lignin derivatives, bentonite, sugars, and water-soluble synthetic polymers (e.g., polyvinyl alcohol, polyvinyl pyrrolidone, and polyacrylic acids) .

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

For the pest-controlling agent of the present invention, it is preferable to use the compound (1) as is, or by diluting it with water or the like. The pest-controlling agent of the present invention may be used by mixing with, for example, other pest- controlling agents, such as known insecticides, nematicides, acaricides, fungicides, herbicides, plant-growth-controlling agents, synergists, soil conditioners, animal feeds, and the like, or may be used simultaneously with these agents without mixing.

The amount of the pest-controlling agent of the invention is not limited, and may be suitably selected from a wide range according to various conditions such as the

concentration of active ingredient, the form of preparation, type of disease or pest to be treated, type of plant, severity of disease, 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 type of fertilizer, etc.

When used as a fungicide, the compound (1) of the present invention is usually used in an amount of 0.01 to 500 g/100 m², and preferably 1 to 200 g/100 m². When used as a miticide, the compound (1) of the present invention is usually used in an amount of 0.1 to 500 g/100 m², and preferably 1 to 200 g/100 m².

When the emulsion, wettable powder, flowable preparation, or the like is used by diluting with water, the concentration is 0.1 to 1,000 ppm, and preferably 1 to 500 ppm. The granules, dusts, or the like can be used as is without

dilution.

The amount or concentration of application of the compound may be suitably increased or decreased according to the type of formulation, time of application, place of application, method of application, type of insect, severity of damage, and the like.

The compound (1) of the present invention is characterized by having a particularly excellent fungicidal activity and a broad spectrum of activity. The compound may be used for controlling plant diseases ascribed to various fungal pathogens or resistant fungal pathogens. Examples of such fungal pathogens include those that cause cucumber gray mold, rice plant blast, rice plant sheath blight, 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, strawberry

powdery mildew, tobacco powdery mildew, and the like.

The compound (1) of the present invention is effectively used as an agricultural and horticultural insecticide, miticide, nematicide, or a soil insecticide. Specifically, the compound (1) of the present invention is effective for

controlling

pests, such as green peach aphid, cotton aphid, and like aphids; diamondback moth, cabbage armyworm, common cutworm, codling moth, bollworm, tobacco budworm, gypsy moth, rice leafroller, smaller tea tortrix, Colorado potato beetle, cucurbit leaf beetle, boll weevil, planthoppers, leafhoppers, scales, bugs, whiteflies, thrips, grasshoppers, anthomyiid flies, scarabs, black cutworm, cutworm, ants, and agricultural pest insects; slugs, snails, and like gastropods; rat mite, cockroaches, housefly, house mosquito, and like hygienic insect pests; Angoumois grain moth, adzuki bean weevil, red flour beetle, mealworms, and like stored grain

insects; casemaking clothes moth, black carpet beetles,

subterranean termites, and like clothes insect pests and house and household insect pests; and the like,

mites, such as two-spotted spider mites, carmine spider mites, citrus red mites, Kanzawa spider mites, European red mites, broad mites, pink citrus rust mites, bulb mites, and like plant- parasitic mites; Tyrophagus putrescentiae, Dermatophagoides farinae, Chelacaropsis moorei, and like house dust mites; and the like, and

soil pests, such as root-knot nematodes, cyst nematodes, root- lesion nematodes, white-tip nematode, strawberry bud nematode, pine wood nematode, and like plant parasitic nematodes; pill bugs, sow bugs, and like isopods; and the like.

The pest-controlling agent of the present invention is also effective for controlling various pests resistant to

chemicals such as organophosphorus agents, carbamate agents, synthetic pyrethroid agents, and neonicotinoid agent.

Examples

The present invention is described in more detail with reference to the following Examples; however, the present

invention is not limited to these Examples.

All of the compounds shown in Examples 1 to 4 and

Tables 1 and 2 are separated by silica gel chromatography using ethyl acetate and n-hexane as developing solvents. TLC plates (silica gel 60F₂₅4, produced by Merck & Co., Inc.) were used, and those having a higher Rf value are considered to be compound A while those having a lower Rf value are considered to be compound Production Example 1: Production of 5-chloro-lH-benzimidazole- 2 (3H) -thione

Pyridine (20 ml) was added to 4-chlorobenzene-l, 2- diamine (5.0 g, 35.2 mmol, 1 equiv. ) and carbon disulfide (5.0 g, 176 mmol, 5 equiv.). Under nitrogen atmosphere, the mixture was then heated at 65°C and stirred for 10 hours. The resulting mixture was cooled to room temperature and poured into ice water, and the pH of the mixture was made acidic with acetic acid. The precipitate was collected by filtration, washed with distilled water, and recrystallized from ethanol to give the title compound as a white solid (6.0 g) .

¹H NMR (DMSO) : δ 12.63 (d, J = 10.0 Hz, 2H) , 7.15-7.10 (m, 3H) .

Production Example 2: Production of 5-chloro-2- (methylthio) -1H- benzimidazole and 6-chloro-2- (methylthio) -lH-benzimidazole

THF (10 ml) and K₂CO₃ (1.12 g, 8.116 mmol, 1.5 equiv.) were added to the 5-chloro-lH-benzimidazole-2 (3H) -thione (1.0 g, 5.415 mmol, 1 equiv.) obtained in Production Example 1, and then methyl iodide (0.768 g, 5.415 mmol, 1 equiv.) was added thereto under nitrogen atmosphere. The mixture was stirred at room temperature for 4 hours. The resulting mixture was poured into ice water, and extracted with ethyl acetate. The combined organic layer was washed with distilled water, and dried over sodium sulfate. After filtration, the filtrate was concentrated under reduced pressure to give a crude product. The residue thus obtained was purified by silica gel chromatography (with a mixed solution of ethyl acetate and n-hexane) to give the title

compounds as two regioisomers in the form of white solids (0.850 g) ·

'H NMR (DMSO): δ 12.68 (bs, 1H) , 7.47 (s, 1H) , 7.41 (d, J = 8.4 Hz, 1H), 7.13-7.10 (dd, J = 2.0, 8.4 Hz, 1H) , 2.68 (s, 3H) . MS m/z: 199.08 (M+H) .

Production Example 3: Production of 5-chloro-2- (methylsulfonyl ) - lH-benzimidazole and 6-chloro-2- (methylsulfonyl ) -lH-benzimidazole Chloroform (20 ml) was added to a mixture of 5-chloro- 2- (methylthio) -lH-benzimidazole and 6-chloro-2- (methylthio) -1H- benzimidazole (0.500 g, 2.525 mmol, 1 equiv.), and then 3- chloroperbenzoic acid (0.958 g, 5.555 mmol, 2.2 equiv.) was added thereto at room temperature. The mixture was stirred at room temperature for 3 hours. The resulting mixture was quenched into an aqueous NaHCO₃ solution, and extracted with methylene chloride. The combined organic layer was washed with distilled water and brine, and dried over sodium sulfate. After filtration, the filtrate was concentrated under reduced pressure to give a crude product. The residue thus obtained was purified by silica gel chromatography (with a mixed solution of ethyl acetate and n- hexane) to give the title compounds as two regioisomers in the form of white solids (0.200 g) .

¹H NMR (DMSO) : δ 12.64 (s, 1H) , 7.47 (s, 1H) , 7.40 (d, J = 8.4 Hz, 1H) , 7.12-7.10 (m, 1H) , 2.67 (s, 3H) . MS mlz: 228.9 (M-H) .

Example 1: Production of 5-chloro-2- (methylsulfonyl) -1- (trichloromethylthio) -lH-benzimidazole or 6-chloro-2- (methylsulfonyl) -1- (trichloromethylthio) -lH-benzimidazole (4A or 4B)

THF (5 ml) was added to a mixture of 5-chloro-2- (methylsulfonyl) -lH-benzimidazole and 6-chloro-2-

(methylsulfonyl) -lH-benzimidazole (0.100 g, 0.433 mmol, 1 equiv.), and then portion-wise sodium hydride (0.021 g, 0.520 mmol, 1.2 equiv.) was added thereto at 0°C. Trichloromethanesulfenyl chloride (0.124 g, 0.650 mmol, 1.5 equiv.) was added dropwise to the mixture, followed by stirring at 0°C. and the mixture was stirred at room temperature for 4 hours. The resulting mixture was poured into ice water, and extracted with ethyl acetate. The combined organic layer was washed with distilled water and brine, and dried over sodium sulfate. After filtration, the filtrate was concentrated under reduced pressure to give a crude product. The residue thus obtained was purified by silica gel chromatography (with a mixed solution of ethyl acetate and n-hexane) to give the title compounds as two regioisomers in the form of white solids (0.200 g of regioisomer 4A and 0.012 g of regioisomer 4B) .

1H NMR (DMSO) : (4A) δ 7.90-7.65 (m, 2H) , 7.42 (bs, 1H) , 3.49 (s, 3H) ; (4B) δ 7.66-7.70 (m, 2H) , 7.32 (d, J = 8.0 Hz, 1H) , 3.08 (s, 3H) .

Example 2: Production of 5, 6-dichloro-2- (methylthio) -1- (trichloromethylthio) -lH-benzimidazole (19)

Sodium hydride (0.052 g, 1.287 mmol, 1.5 equiv. ) was portion-wise added to 5, 6-dichloro-2- (methylthio) -1H- benzimidazole (0.200 g, 0.858 mmol, 1 equiv.) in THF (10 ml) at 0°C. Trichloromethanesulfenyl chloride (0.159 g, 0.858 mmol, 1.0 equiv.) was added dropwise to the mixture, followed by stirring at 0°C. and the mixture was stirred at room temperature for 4 hours. The resulting mixture was poured into ice water, and extracted with ethyl acetate. The combined organic layer was washed with distilled water and brine, and dried over sodium sulfate. After filtration, the filtrate was concentrated under reduced pressure to give a crude product. The residue thus obtained was purified by silica gel chromatography (with_^ a mixed solution of ethyl acetate and n-hexane) to give the title compound as a white solid (0.150g).

¹H NMR DMSO-d₆: δ 7.98 (d, J = 4.0 Hz, 1H) , 7.84 (s, 1H) , 2.73 (s, 3H) .

Production Example 4: Production of 5-bromo-2-ethoxy-lH- benzimidazole and 6-bromo-2-ethoxy-lH-benzimidazole

4-bromobenzene-l, 2-diamine (1.0 g, 5.346 mmol, 1 equiv.) and tetraethoxymethane (5 ml) were stirred with heating under nitrogen atmosphere at 70°C for 10 hours. The mixture was cooled to room temperature, and the entire solvent was evaporated with a rotary evaporator. The residue thus obtained was purified by silica gel chromatography (with a mixed solution of ethyl acetate and n-hexane) to give the title compounds as a mixture of two regioisomers in the form of white solid (0.7 g) . ¹H NMR (DMSO) : δ 12.02 (bs, 1H) , 7.53-7.17 (m, 3H) , 4.50-4.44 (q, J = 7.2 Hz, 2H), 1.37 (t, J = 7.2 Hz, 3H) .

Example 3: Production of 5-bromo-2-ethoxy-l- (trichloromethylthio) -lH-benzimidazole or 6-bromo-2-ethoxy-l- (trichloromethylthio) -lH-benzimidazole (331A or 331B)

THF (30 ml) was added to a mixture of 5-bromo-2-ethoxy- 1H-benzimidazole and 6-bromo-2-ethoxy-lH-benzimidazole (0.60 g, 2.488 mmol, 1.0 equiv. ) , and then portion-wise sodium hydride (0.089 g, 3.732 mmol, 1.5 equiv.) was added thereto at 0°C.

Trichloromethanesulfenyl chloride (0.462 g, 2.488 mmol, 1.0 equiv.) was added dropwise to the reaction mixture, followed by stirring at 0°C. The thus-obtained mixture was stirred at room temperature for 4 hours. The resulting mixture was poured into ice water, and extracted with ethyl acetate. The combined organic layer was washed with distilled water and brine, and dried over sodium sulfate. After filtration, the filtrate was concentrated under reduced pressure to give a crude product. The residue thus obtained was purified by silica gel chromatography (with a mixed solution of ethyl acetate and n-hexane) to give the title

compounds as two regioisomers in the form of white solids (0.315 g of regioisomer 331A and 0.260 g of regioisomer 331B) .

¾ NMR (DMSO): (331A) 5 7.66 (d, J = 1.6 Hz, 1H) , 7.42 (d, J = 8.4 Hz, 1H) , 7.33-7.31 (m, 1H) , 4.71-4.63 (m, 2H) , 1.56-1.49 (m, 3H) ; (331B) δ 7.69 (d, J = 0.8 Hz, 1H) , 7.40-7.35 (m, 2H) , 4.70-4.62 (m, 2H) , 1.56-1.49 (m, 3H) .

Example 4: Production of 2-ethoxy-3- (trichloromethylthio) -3H- benzo [d] imidazole-5-carbonitrile or 2-ethoxy-3- (trichloromethylthio) -3H-benzo [d] imidazole-6-carbonitrile (328A or 328B)

THF (30 ml) was added to a mixture of 2-ethoxy-3H- benzo [d] imidazole-5-carbonitrile and 2-ethoxy-3H- benzo [d] imidazole-6-carbonitrile (0.42 g, 2.243 mmol, 1.0 equiv.), and then portion-wise sodium hydride (0.080 g, 3.364 mmol, 1.5 equiv.) was added thereto at 0°C. Trichloromethanesulfenyl chloride (0.417 g, 2.243 mraol, 1.0 equiv.) was added dropwise to the mixture, followed by stirring at 0°C. The thus-obtained mixture was stirred at room temperature for 4 hours. The reaction mixture was poured into ice water, and extracted with ethyl acetate. The combined organic layer was washed with distilled water and brine, and dried over sodium sulfate. After filtration, the filtrate was concentrated under reduced pressure to give a crude product. The residue thus obtained was purified by silica gel chromatography (with a mixed solution of ethyl acetate and n- hexane) to give the title compounds as two regioisomers in the form of white solids (0.060 g of regioisomer 328A and 0.062 g of regioisomer 328B) .

¹H NMR (CDC1₃) : (328A) δ 7.81 (s, 1H) , 7.64-7.62 (m, 2H) , 4.73- 4.68 (m, 2H) , 1.55-1.51 (m, 3H) ; (328B) δ 7.84 (s, 1H) , 7.59-7.54 (m, 2H) , 4.74-4.70 (m, 2H) , 1.58-1.51 (m, 3H) .

Tables 1 and 2 show the thus-obtained compounds represented by Formula (1-1) and (1-2), respectively, and the melting point and ¹H-NMR data of each compound.

Example 5

Each of the compounds shown in Tables 1 and 2 other than the compounds obtained in Example 1 (4A and 4B) , the

compound obtained in Example 2 (19), the compounds obtained in Example 3 (331A and 331B) , and the compounds obtained in Example 4 (328A and 328B) was produced by a method similar to any of the methods described in Examples 1 to 4. The abbreviations in Tables 1 and 2 are as indicated below.

F: fluoro

CI: chloro

Br: bromo

Me: methyl Et: ethyl

Pr: propyl

Bu: butyl

Ph: phenyl

CF₃: trifluoromethyl

CF₃0: trifluoromethoxy

MeO: methoxy

EtO: ethoxy

CN : cyano

N0₂: nitro

S: sulfur atom

0: oxygen atom

n-: norma1- i-: iso- t-: tertiary-

Cy: cyclo

&: a mixture of regioisomers, the case where the regioisomers could not be isolated

or: the case where both regioisomers could be isolated, but the substituent positions of the isomers could not be determined M. Pt . :melting point

MSrmass spectrometry

No.: compound number Table 1

201

The terms "A" and "B" in Tables 1 and 2 mean that, considering compound 1A and compound IB, for example, when compound 1A is a compound in which R⁴ is 5-chloro, compound IB is a compound in which R⁴ is 6-chloro, and when compound 1A is a compound in which R⁴ is 6-chloro, compound IB is a compound in which R⁴ is 5-chloro.

Below are Preparation Examples in which the "parts refers to "parts by weight."

Preparation Example 1 (Emulsions)

10 parts of each compound of the invention was

dissolved in 45 parts of Solvesso 150 and 35 parts of N- methylpyrrolidone . 10 parts of an emulsifier (trade name: Sorpol 3005X, produced by Toho Chemical Industry Co., Ltd.) was added thereto. The mixtures were mixed by stirring to give 10%

emulsions .

Preparation Example 2 (Wettable powders)

20 parts of each compound of the invention was added to a mixture of 2 parts of sodium lauryl sulfate, 4 parts of sodium lignin sulfonate, 20 parts of fine powder of synthetic hydrated silicon dioxide, and 54 parts of clay. The mixtures were mixed by stirring by a juice mixer to give 20% wettable powders.

Preparation Example 3 (Granules)

2 parts of sodium dodecylbenzenesulfonate, 10 parts bentonite, and 83 parts of clay were added to 5 parts of each compound of the invention, and each mixture was sufficiently mixed by stirring. An appropriate amount of water was added thereto. The resulting mixtures were further stirred and granulated by a granulator. The granules were air-dried to give 5% granules.

Preparation Example 4 (Dusts)

1 part of each compound of the invention was dissolved in an appropriate amount of acetone. 5 parts of fine powder of synthetic hydrated silicon dioxide, 0.3 parts of acidic isopropyl phosphate (PAP), and 93.7 parts of clay were added thereto. The mixtures were mixed by stirring by a juice mixer, and acetone was removed by evaporation to give 1% dusts.

Preparation Example 5 (Flowable preparations)

20 parts of each compound of the invention was mixed with 20 parts of water containing 3 parts of polyoxyethylene tristyrylphenyl ether phosphoric acid ester triethanolamine and 0.2 parts of Rhodorsil 426R. The mixtures were subjected to wet pulverization by DYNO-Mill, and mixed with 60 parts of water containing 8 parts of propylene glycol and 0.32 parts of xanthan gum to give 20% suspensions in water.

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

Test Example 1 (Fungicidal test on cucumber gray mold)

A small amount of mycelia of Botrytis cinerea was collected from a culture tube, and aseptically transferred to a potato dextrose agar (PDA) plate. The plate on which Botrytis cinerea was seeded was maintained for five days in the dark, then for four days under blacklight-blue (BLB) irradiation, and finally for four days in the dark at 20°C.

Meanwhile, 100 ml of a YG (0.2% yeast extract + 1% glucose) solution was prepared using distilled water. 20 ml of the YG solution was poured into the culture plate, and the surface was scraped with a brush. The obtained suspension was filtered through tissue paper. The filtrate thus obtained was diluted with the YG solution to 1 x 10⁶ cfu of spores per ml.

A solution of each compound of the invention (500 ppm) was sprayed on fresh and excised cucumbers at least at the three- leaf stage. A cotyledon of the treated plant was cut and placed on moist tissue paper on a plastic tray. 50 μΐ of the spore suspension (YG solution) was dropped on the middle of the

cotyledon using a micropipette. A small piece of absorbent cotton was then placed on the spore suspension drop, and 50 μΐ of the YG solution was again dropped on the absorbent cotton. The plastic tray containing the cotyledon was placed in a box containing water at the bottom, and maintained at room temperature (20°C) .

Five days after inoculation, the radial growth of the fungus was measured, and the activity of each compound was calculated as a preventive value according to the following equation .

Equation

Preventive value = {1- (average radius of lesions in treated plant/average radius of lesions in untreated plant) }^χ100

The compounds that exhibited a percent disease control value of 50% or more at 500 ppm are as follows:

Compound Nos . : 7, 50, 53, 81A, 81B, 84B, 86A, 87A, 87B, 89B, 91A, 95, 108A, 109A, 109B, 112, 114, 116A, 117B, 120, 128, 129, 133A, 133B, 134, 139, 145, 146, 147, 190B, 193, 200A, 204, 231B, 238, 241, 242, 245, 247, 254, 259, 267, 272, 273, 291, 305, 325A, 327, 331, 332, 334 and 335.

Test Example 2 (Fungicidal test on cucumber powdery mildew)

An aqueous solution of Sorpol 355 (produced by Toho

Chemical Industry Co., Ltd.) (100 ppm) was added to a methanol solution of each test compound to give sample solutions (500 ppm) Each sample solution was spread on cucumbers (14 days after seeding) planted in a pot (7.5 cm in diameter), and air-dried. A suspension containing spores of cucumber powdery mildew (1.0 * 10⁵ cells/ml) was sprayed on the plant using a spray gun. After air- drying, the plant was left to stand in an acrylic resin

greenhouse and, after 10 days, was checked for the severity of disease. The preventive value was calculated, compared with the severity of disease in untreated plant.

The preventive value was calculated by the following equation, compared with the severity of disease in untreated plant .

Equation

The compounds that exhibited a percent disease control value of 80% or more at 500 ppm are as follows:

Compound Nos . : 14B, 19, 20, 31, 49, 55, 57, 62, 63, 65, 70, 71, 72, 81A, 88, 92B, 93A, 93B, 94, 96, HOB, 111A, 127, 132, 145,

151, 152A, 152B, 153, 157B, 158B, 200A, 200B, 215A, 220, 233, 245.

Test Example 3 (Miticidal test on two-spotted spider mites)

A piece of non-woven fabric (4.5 * 5.5 cm) was suspended inside a plastic cup through an incision made in the lid of the plastic cup. After tap water was poured into the cup, the cup was covered with the lid. A kidney bean leaf specimen (about 3.5 x 4.5 cm) was then placed on the sufficiently soaked, non-woven fabric. Another kidney bean leaf specimen with two- spotted spider mites (about 30 mite samples) was placed on top of the first leaf, and the fabric and leaves were left to stand in a thermostatic chamber having a temperature of 25±2°C and a humidity of 40%. An aqueous solution of Sorpol 355 (produced by Toho

Chemical Industry Co., Ltd.) (100 ppm) was added to a methanol solution of each compound of the invention to give a sample solution of each compound of the invention (500 ppm) . Each sample solution was then sprayed on the leaves, and the leaves were air- dried and left to stand in a thermostatic chamber (25±2°C,

humidity of 50%) . The mortality rate of the two-spotted spider mites was investigated two days after treatment.

The compounds that exhibited a mortality of 50% or more at 500 ppm are as follows:

Compound Nos: 20, 32, 33, 44, 47, 48, 61B, 62, 63, 64, 65, 71, 72, 73B, 75, 77, 78, 84A, 84B, 105, 194, 288B.

Claims

We claim:

1. A 2-substituted imidazole compound represented by Formula ( 1 )

or a salt thereof,

wherein R¹, R², and R³ are identical or different and

represent hydrogen, halogen, or C₁_₄ haloalkyl,

R⁴ represents

(1 hydrogen,

(2 nitro,

(3 cyano,

(4 halogen,

(5 C₁_₄ alkyl,

(6 C₁_₄ haloalkyl,

(7 C₁_₄ alkoxy,

(8 C₁_₄ haloalkoxy,

(9 benzyloxy,

(10 benzylthio,

(11C₂-₄ alkenyloxy,

(12 C_2-4 alkynyloxy,

(13 cyano C₁_₄ alkoxy,

(14 C_3-8 cycloalkyl,

(15 C_3-8 cycloalkyl C₁_₄ alkoxy,

(16 C₁_₄ alkylsulfonyloxy,

(17 C₁_₄ alkylsulfinyloxy,

(18 arylsulfonyloxy,

(19 arylsulfinyloxy,

(20 C₁_₄ alkylthio, 2016/063293

(21) C₁_₄ haloalkylthio,

(22) aryl, or

(23) heterocyclic group,

R⁵ represents

(1) C_1-12 alkyl,

(2) C_1-12 haloalkyl,

(3) C₁_₄ alkoxy C₁_₄ alkyl,

(4) C₁_₄ haloalkoxy C₁_₄ alkyl,

(5)C₂-₄ alkenyl,

(6)C₂-₄ alkynyl,

(7) C_3-8 cycloalkyl,

(8) C_3-8 cycloalkyl C₁_₄ alkyl,

(9) C₁_₄ alkyl-carbonyl,

(10 cyano C₁-₈ alkyl,

(11 C₁_₄ alkylsulfonyl,

(12 C₁_₄ alkylsulfinyl,

(13 arylsulfonyl,

(14 arylsulfinyl,

(15 aryl,

(16, heterocyclic group, or

(17 heterocyclic-substituted

A represents 0, S(O)_m, or NR⁶,

wherein R⁶ represents

(1) C_1-12 alkyl,

(2) d-12 haloalkyl,

(3) C₁_₄ alkoxy C₁_₄ alkyl,

(4) C₁_₄ haloalkoxy C₁_₄ alkyl,

(5)C₂-₄ alkenyl,

(6) C_2-4 alkynyl, 2016/063293

(7) C₃_8 cycloalkyl,

(8) C_3-8 cycloalkyl C₁_₄ alkyl,

(9) C₁_₄ alkyl-carbonyl,

(10) cyano C₁_₈ alkyl,

(11) C₁_₄ alkylsulfonyl,

(12) C₁_₄ alkylsulfinyl,

(13) arylsulfonyl,

(14) arylsulfinyl,

(15) aryl,

(16) heterocyclic group, or

(17) heterocyclic-substituted C₁_₄ alkyl,

m represents 0, 1, or 2,

W, X, Y, and Z are identical or different and each represent CR⁴ or N, and

n is an integer of 1 to 4.

2. The 2-substituted imidazole compound or a salt thereof according to claim 1, wherein A is 0 or S(O)_m.

3. The 2-substituted imidazole compound or a salt thereof according to claim 1, wherein A is 0.

4. The 2-substituted imidazole compound or a salt thereof according to claim 1, wherein A is S(O)_m.

5. The 2-substituted imidazole compound or a salt thereof according to claim 1, wherein R¹, R², and R³ each

represent halogen.

6. The 2-substituted imidazole compound or a salt thereof according to claim 1, wherein R⁴ is any one of the groups (1) to (13) and (16) to (23) defined as R⁴ in claim 1.

7. A pest-controlling agent containing the 2- substituted imidazole compound or a salt thereof of any one of claims 1 to 6.

8. A fungicide containing the 2-substituted imidazole compound or a salt thereof of any one of claims 1 to 6.

9. A miticide containing the 2-substituted imidazole compound or a salt thereof of any one of claims 1 to 6.