WO2016063293A1 - Nouveau composé imidazole 2-substitué et son utilisation - Google Patents

Nouveau composé imidazole 2-substitué et son utilisation Download PDF

Info

Publication number
WO2016063293A1
WO2016063293A1 PCT/IN2015/000391 IN2015000391W WO2016063293A1 WO 2016063293 A1 WO2016063293 A1 WO 2016063293A1 IN 2015000391 W IN2015000391 W IN 2015000391W WO 2016063293 A1 WO2016063293 A1 WO 2016063293A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
compound
substituted
salt
groups
Prior art date
Application number
PCT/IN2015/000391
Other languages
English (en)
Inventor
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 (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Oat & Iil India Laboratories Private Limited filed Critical Oat & Iil India Laboratories Private Limited
Publication of WO2016063293A1 publication Critical patent/WO2016063293A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D235/26—Oxygen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A01N43/52—1,3-Diazoles; Hydrogenated 1,3-diazoles condensed with carbocyclic rings, e.g. benzimidazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D235/28—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D235/30—Nitrogen atoms not forming part of a nitro radical

Definitions

  • the present invention relates to a novel 2-substituted imidazole compound and use thereof.
  • fungicidal or miticidal activity not only against chemical- sensitive fungi or mites, but also against chemical-resistant fungi or mites.
  • 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.
  • PTL 1 nowhere discloses the miticidal activity of the compound represented by Formula (A) .
  • WO 2012/062749 Patent Literature (PTL) 2 ) discloses 2 ( 1H) -benzimidazolone derivatives represented by
  • R 2 is halogen and R 2 is alkyl.
  • PTL 2 also discloses that this compound has fungicidal activity.
  • 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.
  • 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
  • Item 1 A 2-substituted imidazole compound represented b Formula (1) :
  • R 1 , R 2 , and R 3 are identical or different and each represent hydrogen, halogen, or C 1 _ 4 haloalkyl
  • R 4 represents
  • (23) heterocyclic group two R 4 groups, taken together, may form a ring, via or not via at least one heteroatom,
  • R 5 represents
  • A represents O, S(O) m , or NR 6 ,
  • R 6 represents
  • R 5 and R 6 taken together with the nitrogen, may form a 3- to 7-membered ring, via or not via at least one heteroatom
  • n 0, 1, or 2
  • W, X, Y, and Z are identical or different and each represent CR 4 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 R 1 , R 2 , and R 3 each represent halogen .
  • Item 6 The 2-substituted imidazole compound or a salt thereof according to Item 1, wherein R 4 is any one of the groups (1) to (13) and (16) to (23) defined as R 4 in Item 1.
  • Item 7 A pest-controlling agent containing the 2- substituted imidazole compound or a salt thereof of any one of
  • Item 8 A plant pest-controlling agent containing the 2-substituted imidazole compound or a salt thereof of any one of
  • 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.
  • the 2-substituted imidazole compound or a salt thereof of the present invention has an effect on pests at a low dose.
  • the compound of the present invention has an excellent effect of controlling fungal plant pathogens and mites .
  • the present invention is directed to a compound represented by
  • the compound (1) of the present invention or a salt thereof (hereinafter sometimes referred to as "the compound (1) of the present invention” or a “compound of the invention”) , wherein R 1 , R 2 , R 3 , R 4 , R 5 , A, W, X, Y, Z, and n are as defined above .
  • halogen examples include fluorine, chlorine, bromine, iodine, and the like.
  • C 1 _ 4 alkyl examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and like C 1 _ 4 straight-chain or branched-chain alkyl.
  • C 1 _ 4 haloalkyl examples include fluoromethyl, chloromethyl, bromomethyl, iodomethyl, difluoromethyl,
  • C 1 _ 4 alkoxy examples include methoxy, ethoxy, n- propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, and like C 1 _ 4 straight-chain or branched-chain alkoxy.
  • C 1 _ 4 haloalkoxy examples include fluoromethoxy, bromomethoxy, iodomethoxy, difluoromethoxy, trifluoromethoxy, 2- fluoroethoxy, 2-chloroethoxy, 1-fluoroethoxy, pentafluoroethoxy,
  • C 2-4 alkenyloxy examples include vinyloxy, allyloxy,
  • C 2-4 alkynyloxy examples include ethynyloxy, 1- propynyloxy, l-methyl-2-propynyloxy, 1-butynyloxy, 2-butynyloxy,
  • cyano C 1 _ 4 alkoxy examples include cyanomethoxy, cyanoethoxy, cyano-n-propoxy, cyano-iso-propoxy, cyano-n-butoxy, cyano-iso-butoxy, cyano-sec-butoxy, cyano- tert-butoxy, and like C 1 _ 4 straight-chain or branched-chain alkoxy substituted with a cyano group.
  • C 3 _ 8 cycloalkyl examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like.
  • C 3-8 cycloalkyl C 1 _ 4 alkyl examples include cyclopropylmethyl, cyclobutylethyl, cyclopentyl-n-propyl,
  • C 1 _ 4 alkylsulfonyloxy examples include
  • alkylsulfonyloxy groups whose alkyl moiety is C 1 _ 4 straight-chain or branched-chain alkyl.
  • C 1 _ 4 alkylsulfinyloxy examples include
  • alkylsulfinyloxy groups whose alkyl moiety is C 1 _ 4 straight-chain or branched-chain alkyl.
  • arylsulfonyloxy examples include phenylsulfonyloxy, 1-naphthylsulfonyloxy, 2-naphthylsulfonyloxy, and the like.
  • arylsulfinyloxy examples include phenylsulfinyloxy,
  • C 1 _ 4 alkylthio examples include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec- butylthio, tert-butylthio, and like C 1 _ 4 straight-chain or
  • C 1 _ 4 haloalkylthio examples 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,
  • aryl examples include phenyl, naphthyl, and the like.
  • heterocyclic group examples include thienyl, furyl, tetrahydrofuryl, dioxolanyl, dioxanyl, pyrrolyl, pyrrolinyl, pyrrolidinyl, oxazolyl, isoxazolyl, oxazolinyl, oxazolidinyl, isoxazolinyl, thiazolyl, isothiazolyl, thiazolinyl, thiazolidinyl, isothiazolinyl, pyrazolyl, pyrazolidinyl, imidazolyl,
  • thiadiazolinyl triazolyl, triazolinyl, triazolidinyl, tetrazolyl, tetrazolinyl, pyridyl, dihydropyridyl, tetrahydropyridyl,
  • tetrahydropyrazinyl piperazinyl, triazinyl, dihydrotriazinyl, tetrahydrotriazinyl, hexahydrotriazinyl, tetrazinyl,
  • 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, C 1 _ 4 alkyl groups, C 1 _ 4 haloalkyl groups, or substituted heterocyclic groups (e.g., 3- chloropyridin-2-yl, 5-trifluoromethylpyridin-2-yl, and 4-methyl- 1, 3-thiazole) .
  • 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.
  • examples of C 1 _ 12 haloalkyl include
  • C 1 _ 4 alkoxy C 1 _ 4 alkyl examples include methoxymethyl, ethoxymethyl, n-propoxymethyl, isopropoxymethyl, n-butoxymethyl, sec-butoxymethyl, methoxyethyl, methoxy-n-propoxy,
  • C 1 _ 4 haloalkoxy C 1 _ 4 alkyl examples include fluoromethoxymethyl, chloromethoxymethyl, bromomethoxymethyl, iodomethoxymethyl, difluoromethoxymethyl, trifluoromethoxymethyl,
  • C 2 _ 4 alkenyl examples include vinyl, allyl, 2-butenyl,
  • C 2 - 4 alkynyl examples include ethynyl, 1-propynyl, 1- methyl-2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, and the like.
  • C 1 _ 4 alkyl-carbonyl examples include methylcarbonyl (acetyl), ethylcarbonyl (propionyl) , n-propylcarbonyl (butyryl) , isopropylcarbonyl (isobutyryl) , n-butylcarbonyl (valeryl) ,
  • isobutylcarbonyl (isovaleryl) , sec-butylcarbonyl, tert- butylcarbonyl, and like C 1 _ 4 straight-chain or branched-chain alkylcarbonyl groups.
  • cyano C 1 _ 8 alkyl examples 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 C 1 _ 8 straight-chain or branched-chain alkyl substituted with a cyano group.
  • C 1 _ 4 alkylsulfonyl examples include methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n- butylsulfonyl, isobutylsulfonyl , see-butylsulfonyl, tert- butylsulfonyl, and like alkylsulfonyl groups whose alkyl moiety is C 1 _ 4 straight-chain or branched-chain alkyl.
  • C 1 _ 4 alkylsulfinyl examples include methylsulfinyl, ethylsulfinyl, Ji-propylsulfinyl, isopropylsulfinyl, n- butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert- butylsulfinyl, and like alkylsulfinyl groups whose alkyl moiety is C 1 _ 4 straight-chain or branched-chain alkyl.
  • arylsulfonyl examples include phenylsulfonyl, 1- naphthylsulfonyl, 2-naphthylsulfonyl, and the like.
  • arylsulfinyl examples include phenylsulfinyl, 1- naphthylsulfinyl, 2-naphthylsulfinyl, and the like.
  • heterocyclic C 1 _ 4 alkyl examples include
  • pyridylmethyl pyridylethyl
  • pyridyl-n-propyl benzothiazolyl- isopropyl, 1, 2, 4-triazol-l-yl-n-butyl, 2-thienyl-isobutyl,
  • the groups (1) to (23) represented by R 4 may optionally be further substituted.
  • the groups (1) to (17) represented by R 5 W may optionally be further substituted.
  • the groups (1) to (17) represented by R 6 may optionally be further substituted.
  • Examples of the substituents for the groups (1) to (23) represented by R 4 , the groups (1) to (17) represented by R 5 , and the groups (1) to (17) represented by R 6 include nitro and cyano, as well as the above-mentioned halogen, C 1 _ 4 alkyl, C 1 _ 4 haloalkyl, C 1 _ 4 alkoxy, C 1 _ 4 haloalkoxy, C 2 - 4 alkenyloxy, C 2-4 alkynyloxy, cyano C 1 _ 4 alkoxy, C 3-8 cycloalkyl, C 3-8 cycloalkyl C 1 _ 4 alkyl, C 1 _ 4 alkylsulfonyloxy, C 1 _ 4 alkylsul
  • alkylsulfonyl C 1 _ 4 alkylsulfinyl, arylsulfonyl, arylsulfinyloxy, heterocyclic C 1 _ 4 alkyl, and the like.
  • preferable substituents are halogen, C 1 _ 4 alkyl, C1-.4 haloalkyl, C 1 _ 4 alkoxy, C 1 _ 4 haloalkoxy, and C 1 _ 4 alkylthio, and more preferable
  • substituents are chlorine, fluorine, trifluoromethyl,
  • aryl or heterocyclic group represented by R 4 , R 5 , and R 6 may have 1 to 5 above substituents.
  • Preferable substituted aryl groups are halogen-substituted aryl, C 1 _ 4 alkyl- substituted aryl, C 1 _ 4 haloalkyl-substituted aryl, C : _4 alkoxy- substituted aryl, C 1 _ 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.
  • substituted heterocyclic groups are halogen- substituted heterocyclic group, C 1 _ 4 alkyl-substituted
  • heterocyclic group C 1 _ 4 haloalkyl-substituted heterocyclic group, C 1 _ 4 alkoxy-substituted heterocyclic group, C 1 _ 4 haloalkoxy- substituted heterocyclic group, and heterocyclic-substituted C : - 4 alkylthio .
  • arylsulfinyl, or alkyl-substituted heterocyclic group represented by R 4 , R 5 , and R 6 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.
  • (1) of the present invention may be identical or different and each represent hydrogen, halogen, or C 1 _ 4 haloalkyl.
  • R 1 , R 2 , and R 3 each preferably represent halogen.
  • R 2 and R 3 each more preferably represent chlorine.
  • R 1 , R 2 , and R 3 each particularly preferably represent chlorine .
  • a of the formula representing the compound (1) of the present invention represents O, S(O) m , or NR 6 , and A preferably represents O or S(O) m .
  • R 4 of the formula representing the compound (1) of the present invention is any one of the groups (1) to (23) defined as
  • R 4 in Claim 1 is preferably any one of the groups (1) to (13) and (16) to (23) above.
  • R 4 is more preferably any one of the groups (1) to (8), (10), (11), (13), (17), (20), and (22).
  • Two R 4 groups, taken together, may form a ring, via or not via at least one heteroatom.
  • 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.
  • aryl is preferable, and phenyl is more preferable.
  • a heteroatom refers to at least one atom selected from the group consisting of oxygen, sulfur, and
  • R 5 of the formula representing the compound of the present invention is any one of (1) to (17) defined as R 5 in Claim 1.
  • R 5 is preferably any one of (1) to (3), (5) to (10), and (15).
  • R 6 of the formula representing compound (1) of the present invention is any one of (1) to (17) defined as R 6 in Claim 1.
  • R 6 is preferably any one of (1) to (3), (5) to (10), and (15).
  • R 5 and R 6 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 CR 4 or N. It is preferable that at least one of W, X, Y, and Z represents N, and the rest represent CR 4 , or that W, X, Y, and Z each represent CR 4 . It is more preferable that W, X, Y, Z each represent CR 4 .
  • a preferable compound is a 2-substituted imidazole compound or a salt thereof in which
  • R 1 , R 2 , and R 3 each represent halogen
  • R 4 is any one of the groups (1) to (13) and (16) to (23),
  • two R 4 groups, taken together, may form a ring, via or not via at least one heteroatom
  • R 5 is any one of (1) to (3), (5) to (10), and (15), the group represented by R 5 above may further optionally be substituted,
  • A represents O or S(O) m
  • n 0, 1, or 2
  • W, X, Y, and Z are identical or different and each represent CR 4 or N.
  • a more preferable compound is a 2-substituted imidazole compound or a salt thereof in which
  • R 1 is fluorine or chlorine
  • R 2 and R 3 each represent chlorine
  • R 4 is any one of the groups (1) to (8), (10), (11), (13), (17), (20), and (22),
  • two R 4 groups, taken together, may form a ring, via or not via at least one heteroatom
  • R 5 is any one of (1) to (3), (5) to (10), and (15),
  • A represents O
  • W, X, Y, and Z are identical or different and each represent CR 4 or N; or
  • R 4 and R 3 each represent chlorine
  • R 4 is any one of the groups (1) to (8), (10), (11), (13), (17), (20), and (22),
  • two R 4 groups, taken together, may form a ring, via or not via at least one heteroatom
  • R 5 is any one of (1) to (3), (5) to (10), and (15),
  • n 0, 1, or 2
  • W, X, Y, and Z are identical or different and each represent CR 4 or N.
  • 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) .
  • 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,
  • the compound (1) of the present invention is produced in accordance with the process described in the following
  • R 1 , R 2 , R 3 , R 4 , R 5 , A, W, X, Y, Z, and n are as defined above, and R 7 represents a leaving group.
  • 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 R 7 include chlorine, bromine, iodine, and like halogen atoms, and alkyl sulfonate, aryl sulfonate, and the like.
  • 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.
  • a base a wide variety of known bases may be used. Examples include sodium carbonate, potassium
  • 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.
  • 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.
  • usable solvents for the reaction are not limited insofar as they are inert to the reaction.
  • solvents include n-hexane, cyclohexane, n-heptane, and like aliphatic or alicyclic hydrocarbons; benzene, chlorobenzene, toluene, xylene, and like aromatic hydrocarbons; methylene
  • 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.
  • Reaction Scheme 1 above are known compounds or compounds easily prepared by a known method.
  • 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.
  • each regioisomer may be separated by a usual separation step such as silica gel chromatography.
  • the compound (1) of the present invention may be used as an active ingredient of a pest-controlling agent.
  • pest-controlling agents include agents (fungicides or virucides) for controlling plant diseases that cause problems in the
  • 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
  • animal ectoparasite-controlling agent e.g., pulicide, ixodicide, and pedivulicideon
  • animal ectoparasite-controlling agent e.g., pulicide, ixodicide, and pedivulicideon
  • the compound (1) of the present invention 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
  • 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%.
  • 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.
  • 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
  • chemical fertilizers e.g., ammonium sul
  • liquid carriers examples include water, alcohols (e.g., methanol and ethanol) , ketones (e.g., acetone and
  • aromatic hydrocarbons e.g., benzene, toluene, xylene, ethylbenzene, and methylnaphthalene
  • aromatic hydrocarbons e.g., benzene, toluene, xylene, ethylbenzene, and methylnaphthalene
  • 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
  • gaseous carriers examples include butane gas, LPG (liquefied petroleum gas) , dimethyl ether, carbon dioxide gas, and the like.
  • 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.
  • adjuvants for pharmaceutical preparation include fixing agents, dispersants, stabilizers, and the like.
  • fixing agents and dispersants examples 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) .
  • stabilizers examples 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.
  • 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.
  • 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.
  • the compound (1) of the present invention 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 m 2 , and preferably 1 to 200 g/100 m 2 . 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 m 2 , and preferably 1 to 200 g/100 m 2 .
  • 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
  • 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
  • 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
  • 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
  • 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.
  • organophosphorus agents such as organophosphorus agents, carbamate agents, synthetic pyrethroid agents, and neonicotinoid agent.
  • Tables 1 and 2 are separated by silica gel chromatography using ethyl acetate and n-hexane as developing solvents. TLC plates (silica gel 60F 25 4, 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
  • Production Example 2 Production of 5-chloro-2- (methylthio) -1H- benzimidazole and 6-chloro-2- (methylthio) -lH-benzimidazole
  • 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.
  • Example 1 Production of 5-chloro-2- (methylsulfonyl) -1- (trichloromethylthio) -lH-benzimidazole or 6-chloro-2- (methylsulfonyl) -1- (trichloromethylthio) -lH-benzimidazole (4A or 4B)
  • Production Example 4 Production of 5-bromo-2-ethoxy-lH- benzimidazole and 6-bromo-2-ethoxy-lH-benzimidazole
  • Example 3 Production of 5-bromo-2-ethoxy-l- (trichloromethylthio) -lH-benzimidazole or 6-bromo-2-ethoxy-l- (trichloromethylthio) -lH-benzimidazole (331A or 331B)
  • Tables 1 and 2 show the thus-obtained compounds represented by Formula (1-1) and (1-2), respectively, and the melting point and 1 H-NMR data of each compound.
  • 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.
  • 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.
  • 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.
  • a small amount of mycelia of Botrytis cinerea was collected from a culture tube, and aseptically transferred to a potato dextrose agar (PDA) plate.
  • PDA potato dextrose agar
  • 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.
  • BLB blacklight-blue
  • 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 10 6 cfu of spores per ml.
  • Preventive value ⁇ 1- (average radius of lesions in treated plant/average radius of lesions in untreated plant) ⁇ ⁇ 100
  • the compounds that exhibited a percent disease control value of 50% or more at 500 ppm are as follows:
  • the preventive value was calculated by the following equation, compared with the severity of disease in untreated plant .
  • Preventive value ⁇ 1- (average radius of lesions in treated plant/average radius of lesions in untreated plant) ⁇ ⁇ 100
  • the compounds that exhibited a percent disease control value of 80% or more at 500 ppm are as follows:
  • 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
  • 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:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

La présente invention vise à fournir de nouveaux composés imidazole 2-substitués ou des sels de ces derniers qui présentent une activité pesticide. La présente invention concerne des composés imidazole 2-substitués représentés par la formule (1) : ou un sel de ces derniers, dans laquelle R1, R2 et R3 sont identiques ou différents et représentent chacun un atome d'hydrogène, ou un halogénoalkyle en C1-C4; R4 représente (1) un hydrogène ou un substituant tel que défini dans la description, R5 représente un alkyle en C1-12 ou d'autres substituants tels que définis dans la description, A représente NR6, O ou S(O)m, m = 0, 1 ou 2, W, X, Y et Z sont identiques ou différents et représentent chacun CR4 ou N, R6 est un alkyle en C1-12 ou un substituant tel que défini dans la description, et n est un nombre entier de 1 à 4.
PCT/IN2015/000391 2014-10-21 2015-10-16 Nouveau composé imidazole 2-substitué et son utilisation WO2016063293A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
IN2997/DEL/2014 2014-10-21
IN2997DE2014 2014-10-21
IN688/DEL/2015 2015-03-13
IN688DE2015 2015-03-13

Publications (1)

Publication Number Publication Date
WO2016063293A1 true WO2016063293A1 (fr) 2016-04-28

Family

ID=54783985

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IN2015/000391 WO2016063293A1 (fr) 2014-10-21 2015-10-16 Nouveau composé imidazole 2-substitué et son utilisation

Country Status (2)

Country Link
TW (1) TW201617322A (fr)
WO (1) WO2016063293A1 (fr)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1492948A (fr) * 1966-05-18 1967-08-25 Sulfénylbenzazoles
FR1508322A (fr) * 1966-11-23 1968-01-05 Dérivés des benzylthiobenzimidazoles
FR1565347A (fr) * 1967-09-08 1969-05-02
GB1173149A (en) * 1965-12-06 1969-12-03 Dynachim Sarl Halogeno-Alkane-Sulphenyl Heterocyclics
FR2046114A5 (en) * 1970-01-30 1971-03-05 Dynachim Sarl Benzimidazole derivs anthelmintic, antifung - al bactericidal, aericidal, insecticidal, nema
FR2061874A5 (en) * 1969-09-18 1971-06-25 Aries Robert N-(1-perhaloalkanesulphenyl-2-benzimidazolyl
FR2104637A1 (en) * 1969-10-29 1972-04-21 Aries Robert Benzimidazoles as fungicides - esp 1-polyhaloalkyl sulphenyl 2-(aminoalkoxycarbonylamino)benzimidazoles
DE3621265A1 (de) 1986-06-25 1988-01-07 Bayer Ag N-sulfenylierte 2-trifluormethyl-benzimidazole
WO2012062749A1 (fr) 2010-11-12 2012-05-18 Bayer Cropscience Ag Benzimidazolidinones utilisables comme fongicides

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1173149A (en) * 1965-12-06 1969-12-03 Dynachim Sarl Halogeno-Alkane-Sulphenyl Heterocyclics
FR1492948A (fr) * 1966-05-18 1967-08-25 Sulfénylbenzazoles
FR1508322A (fr) * 1966-11-23 1968-01-05 Dérivés des benzylthiobenzimidazoles
FR1565347A (fr) * 1967-09-08 1969-05-02
FR2061874A5 (en) * 1969-09-18 1971-06-25 Aries Robert N-(1-perhaloalkanesulphenyl-2-benzimidazolyl
FR2104637A1 (en) * 1969-10-29 1972-04-21 Aries Robert Benzimidazoles as fungicides - esp 1-polyhaloalkyl sulphenyl 2-(aminoalkoxycarbonylamino)benzimidazoles
FR2046114A5 (en) * 1970-01-30 1971-03-05 Dynachim Sarl Benzimidazole derivs anthelmintic, antifung - al bactericidal, aericidal, insecticidal, nema
DE3621265A1 (de) 1986-06-25 1988-01-07 Bayer Ag N-sulfenylierte 2-trifluormethyl-benzimidazole
WO2012062749A1 (fr) 2010-11-12 2012-05-18 Bayer Cropscience Ag Benzimidazolidinones utilisables comme fongicides

Also Published As

Publication number Publication date
TW201617322A (zh) 2016-05-16

Similar Documents

Publication Publication Date Title
JP5269609B2 (ja) 害虫防除剤
NO172435B (no) Imidazolforbindelser, biocide preparater som inneholder disse imidazolforbindelser, samt forbindelser egnet som utgangsforbindelser for fremstilling av de nevnte imidazolforbindelser
WO2006013896A1 (fr) Dérivé de quinoline et insecticide contenant celui-ci comme constituant actif
CN109206397B (zh) 一种胡椒酸衍生物及其制备和应用
KR20170058388A (ko) 3-(3-클로로-1h-피라졸-1-일)피리딘의 제조 방법
CN109803956B (zh) 新颖的苯甲酰胺化合物、其制备方法及杀螨剂
WO2018051252A2 (fr) Nouveau composé amide, son procédé de production et miticide
JP4726373B2 (ja) オキシムｏ−エーテル化合物および農園芸用殺菌剤
WO2016092559A1 (fr) Dérivés de pyrazole substitués ayant une activité fongicide
CN110452167B (zh) 喹啉类衍生物及其制备方法和用途
WO2016063293A1 (fr) Nouveau composé imidazole 2-substitué et son utilisation
CN113549053B (zh) 一种吡唑喹（唑）啉醚类化合物及其应用
CA2394720C (fr) Composes de cyanomethylene et compositions fongicides
WO2016114165A1 (fr) Composé carbamate et utilisation associée
CN105777640B (zh) 一种吡唑环己二醇醚类化合物及其应用
JP2000319270A (ja) シアノメチレン化合物及び農園芸用殺菌剤
KR20050110237A (ko) 4-퀴놀린온 유도체를 포함하는 농원예용 살균제 조성물
CN110724136B (zh) 酰胺类化合物及其制备方法和应用
JP4565286B2 (ja) ６−ハロアルキル−３−（置換アミノ）−１，２，４−トリアジン−５−オン誘導体、これを有効成分とする農薬、及びその製造中間体
WO2020003219A1 (fr) Dérivés de pyrazole substitués à titre d'insecticides et de fongicides
CA2165318C (fr) Derives de la 4-amino-2-quinoleinone
JP2020203883A (ja) ２，４−ジオキソ−１，４−ジヒドロチエノピリミジン化合物及び農園芸用殺菌剤
CN115160305A (zh) 含4,5-二氢异恶唑的酰胺类化合物及其盐、制备方法和用途
CN116924952A (zh) 一种含硫酰胺类化合物及其制备方法和应用
CN115340495A (zh) 邻硝基苯类化合物及其制备方法和用途

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15805321

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15805321

Country of ref document: EP

Kind code of ref document: A1