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WO2012004326A1 - Pesticidal pyrroline derivatives - Google Patents

Pesticidal pyrroline derivatives Download PDF

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Publication number
WO2012004326A1
WO2012004326A1 PCT/EP2011/061451 EP2011061451W WO2012004326A1 WO 2012004326 A1 WO2012004326 A1 WO 2012004326A1 EP 2011061451 W EP2011061451 W EP 2011061451W WO 2012004326 A1 WO2012004326 A1 WO 2012004326A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
carbonyl
spp
methyl
trifluoromethyl
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PCT/EP2011/061451
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French (fr)
Inventor
Tetsuya Murata
Koichi Araki
Hidetoshi Kishikawa
Hidekazu Watanabe
Norio Sasaki
Eiichi Shimojo
Teruyuki Ichihara
Katsuhiko Shibuya
Ulrich Görgens
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Bayer Cropscience Ag
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Publication of WO2012004326A1 publication Critical patent/WO2012004326A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/20—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member 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 to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention relates to novel pesticidal pyrroline derivatives and the use thereof as pesticides.
  • Patent Documents 1 to 5 describe that pesticidal pyrroline compounds are useful as pest controlling agents. However, they have not described the pesticidal pyrroline derivatives of the present invention.
  • Patent Document 1 WO2009/022746
  • Patent Document 2 WO2009/072621
  • Patent Document 3 WO2009/097992
  • Patent Document 4 WO2009/1 12275
  • Patent Document 5 WO2010/020521).
  • R 1 and R 2 are as defined below, or
  • R 2 is as defined below, preferably is hydroxy-carbonyl, Ci.n-alkoxy-carbonyl or cyano; or mixtures of the positional isomers; T is selecte
  • B represents N or C-X 3 ;
  • X 1 , X 2 , X 3 , X 4 and X 5 each independently represent hydrogen, halogen, C1 2 alkyl, Ci.n haloalkyl, nitro, Ci-12 alkoxy, CM2 haloalkoxy, cyano, Cu 2 alkylsulfenyl, Cu 2 alkylsulfinyl, Cu 2 alkylsulfonyl, Cu 2 haloalkylsulfenyl, C 1 . 12 haloalkylsulfinyl, C1 2 haloalkylsulfonyl, hydroxy, mercapto, amino, C 1 .
  • Y 1 , Y 2 , Y 3 , Y 4 and Y 5 each independently represent hydrogen, halogen, C1 2 alkyl, Ci.n haloalkyl, nitro, C3. 8 cycloalkyl, C3. 8 cyclohaloalkyl, C1 2 alkoxy, C1 2 haloalkoxy, cyano, C1 2 alkylsulfenyl, C 1 . 12 alkylsulfinyl, C1 2 alkylsulfonyl, C 1 .
  • G represents any one of the following formulae Gl to G9:
  • Z represents hydrogen, C1 2 haloalkyl, nitro, C1.12 alkoxy, cyano, C1 2 haloalkoxy, C1.12 alkylsulfenyl, Ci-12 alkylsulfinyl, C1.12 alkylsulfonyl, C1 2 haloalkylsulfenyl, C1.12 haloalkylsulfinyl, C1.12 haloalkylsulfonyl, hydroxy or thiol; k represents 0, 1, 2, 3 or 4;
  • R represents C1.12 alkyl or C1 2 haloalkyl
  • R 1 and R 2 are absent, or each independently represent hydrogen, halogen, cyano, amino, azido, hydroxy, mercapto, hydroxy-carbonyl, C1.12 alkylamino-carbonyl, C1 2 alkoxy-carbonyl, C1 2 alkoxy, C1 2 alkyl, C2-12 alkenyl, C2-12 alkynyl, C1 2 alkylthio, C1 2 alkylsulfinyl or C1 2 alkylsulfonyl, provided that R 1 and R 2 are not simultaneously absent, and provided that R 1 and R 2 are not simultaneously hydrogen;
  • R 3 represents hydrogen, amino, hydroxy, cyano, R 8 -CH 2 -, R 8 -CO-, R 8 -CS-, C1 2 alkyl, C1 2 haloalkyl, Ci-12 alkoxy, C1 2 haloalkoxy, C2-12 alkenyl, C2-12 alkynyl, C1.12 alkyl-carbonyl or C1.12 alkyl-carbonylamino
  • R 4 represents hydrogen, cyano, carbonyl, thiocarbonyl, R 8 -CO-, R 8 -CS-, C1 2 alkyl-carbonyl, C1 2 alkyl-thiocarbonyl, C1 2 haloalkyl-carbonyl, C1 2 haloalkyl-thiocarbonyl, C1 2 alkylamino-carbonyl, Ci-12 alkylamino-thiocarbonyl, di(Ci_i2 alkyl)amino-carbonyl, di(Ci_i2 al
  • R 3 and R 4 may form a 3-, 4-, 5- or 6-membered, saturated or unsaturated heterocyclic ring together with the nitrogen atom to which they are bound, wherein the heterocyclic ring may be substituted with oxo, thioxo or nitro;
  • R 5 represents hydrogen, cyano, C1.12 alkyl or C1 2 haloalkyl
  • R 6 represents hydrogen, Cu2 alkyl, alkylcarbonyl or Ci.n alkoxycarbonyl
  • R 7 represents hydrogen or Cu2 alkyl
  • R 8 represents phenyl or a 3-, 4-, 5- or 6-membered, saturated or unsaturated heterocyclic ring
  • R 9 and R 10 each independently represent hydrogen, halogen, Cu2 alkyl or C1.12 haloalkyl
  • R 11 represents hydrogen, cyano, nitro, C1.12 alkyl, C1 2 haloalkyl, C3.8 cycloalkyl-Ci.12 alkyl, C1.12 alkyl-carbonyl, C1 2 haloalkyl-carbonyl, C1 2 alkoxy-carbonyl, C1.12 haloalkoxy-carbonyl, C1 2 alkylsulfonyl, haloalkylsulfonyl, aryl-Ci.12 alkyl, the aryl moiety of which may be substituted with 1, 2 or 3 times the group R 12 , or heterocyclic ring-Ci.12 alkyl, the heterocyclic ring moiety of which may be substituted with 1 , 2 or 3 times the group R 12 ;
  • R 12 represents hydrogen, halogen, cyano, nitro, C1 2 alkyl, C1 2 haloalkyl, Ci.n alkoxy, Ci.n haloalkoxy or Ci-12 alkoxy-carbonyl; m represents 1 or 2; whereas the groups defined above may be further substituted with at least one substituent selected from halogen, C1.12 alkyl, C1 2 haloalkyl, nitro, alkoxy, cyano, Ci.n haloalkoxy, C1 2 alkylsulfenyl, C1.12 alkylsulfinyl, C1 2 alkylsulfonyl, C1.12 haloalkylsulfenyl, C1 2 haloalkylsulfinyl, C1 2 haloalkylsulfonyl, hydroxy and mercapto.
  • ⁇ represents ⁇ or C-X 3 ;
  • X 1 , X 2 , X 3 , X 4 and X 5 each independently represent hydrogen, halogen, Ci_6 alkyl, nitro, Ci_6 alkoxy, Ci_6 haloalkoxy, cyano, Ci_6 alkylsulfenyl, Ci_6 alkylsulfinyl, Ci_6 alkylsulfonyl, Ci_6 haloalkylsulfenyl, Ci_6 haloalkylsulfinyl, Ci_6 haloalkylsulfonyl, hydroxy, mercapto, amino, Ci_6 acylamino, Ci_6 alkoxy-carbonylamino, Ci_6 haloalkoxy-carbonylamino, Ci_6 alkoxy- imino, Ci_6 haloalkoxy- imino, alkylsulfonylamino or sulfur pentafluoride;
  • Y 1 , Y 2 , Y 3 , Y 4 and Y 5 each independently represent hydrogen, halogen, Ci_6 alkyl, nitro, C3.7 cycloalkyl, C3.7 cyclohaloalkyl, Ci_6 alkoxy, Ci_6 haloalkoxy, cyano, Ci_6 alkylsulfenyl, Ci_6 alkylsulfinyl, Ci_6 alkylsulfonyl, Ci_6 haloalkylsulfenyl, Ci_6 haloalkylsulfinyl, Ci_6 haloalkylsulfonyl, Ci_6 alkylsulfonyloxy, Ci_6 alkylaminosulfonyl, Ci_6 haloalkylaminosulfonyl, di(Ci_6 alkyl)aminosulfonyl, di(Ci_6 haloalkyl)aminosulfonyl,
  • Z represents hydrogen, haloalkyl, nitro, Ci_6 alkoxy, cyano, Ci_6 haloalkoxy, Ci_6 alkylsulfenyl, Ci_6 alkylsulfinyl, Ci_6 alkylsulfonyl, Ci_6 haloalkylsulfenyl, Ci_6 haloalkylsulfinyl, Ci_6 haloalkylsulfonyl, hydroxy or thiol; k represents 0, 1, 2, 3 or 4; R represents Ci_6 alkyl or
  • R 1 and R 2 are absent, or each independently represent hydrogen, halogen, cyano, amino, azido, hydroxy, mercapto, hydroxy-carbonyl, Ci_ 6 alkylamino-carbonyl, lkoxy-carbonyl, alkoxy, Ci_6 alkyl, C 2 -6 alkenyl, C 2 _ 6 alkynyl, alkylthio, alkylsulfinyl or alkylsulfonyl, provided that R 1 and R 2 are not simultaneously absent, and provided that R 1 and R 2 are not simultaneously hydrogen;
  • R 3 represents hydrogen, amino, hydroxy, cyano, R 8 -CH 2 -, R 8 -CO-, R 8 -CS-, Ci_ 6 alkyl, Ci_ 6 haloalkyl, Ci_ 6 alkoxy, C 2 -6 alkenyl, C 2 _ 6 alkynyl, Ci_6 alkyl-carbonyl or alkyl-carbonylamino,
  • R 4 represents hydrogen, cyano, carbonyl, thiocarbonyl, R 8 -CO-, R 8 -CS-, Ci_6 alkyl-carbonyl, Ci_6 alkyl-thiocarbonyl, Ci_6 haloalkyl-carbonyl, Ci_6 haloalkyl-thiocarbonyl, Ci_6 alkylamino-carbonyl, Ci_6 alkylamino-thiocarbonyl, di(Ci_6 alkyl)amino-carbonyl, di(Ci_6 alkyl)amino-thio
  • R 3 and R 4 may form a 3-, 4-, 5- or 6-membered, saturated or unsaturated heterocyclic ring together with the nitrogen atom to which they are bonded, wherein the heterocyclic ring may be substituted with oxo, thioxo or nitro;
  • R 5 represents hydrogen, cyano
  • R 6 represents hydrogen, alkylcarbonyl or alkoxycarbonyl
  • R 7 represents hydrogen or Ci_6 alkyl
  • R 8 represents phenyl or a 3-, 4-, 5- or 6-membered, saturated or unsaturated heterocyclic ring
  • R 9 and R 10 each independently represent hydrogen, halogen, Ci_6 alkyl or
  • R 11 represents hydrogen, cyano, nitro, Ci_6 alkyl, Ci_6 haloalkyl, C 3 .7 cycloalkyl-Ci.6 alkyl, Ci_6 alkyl-carb onyl, C e haloalkyl-carbonyl, C e alkoxy-carbonyl, C e haloalkoxy-carbonyl, C e alkylsulfonyl, aryl-Ci_6 alkyl, the aryl moiety of which may be substituted with 1 , 2 or 3 times the group R 12 , or heterocyclic ring-Ci.6 alkyl, the heterocyclic ring moiety of which may be substituted with 1 , 2 or 3 times the group R 12 ;
  • R 12 represents hydrogen, halogen, cyano, nitro, Ci_6 alkyl, or Ci-6 alkoxy-carbonyl;
  • m represents 1 or 2; and the groups defined above may be further substituted with at least one
  • novel pyrroline derivatives are preferably those given in the following embodiments , and such embodiments should be understood in any case as subgroups of the compounds represented by Formula (I) described above.
  • Embodiment 1 Compounds of Formula ( ⁇ ):
  • X 1 , X 2 , X 4 , X 5 , R, B and T have the same definition as described above, respectively, and Hal represents fluorine, chlorine, bromine or iodine.
  • X 1 , X 2 , X 4 , X 5 , R, B and T have the same definition as described above, respectively and R represents hydrogen or Ci_6 alkyl.
  • X 1 , X 2 , X 4 , X 5 , R, B and T have the same definition as described above, respectively and R represents hydrogen or Ci_6 alkyl.
  • T is a group Tl , wherein Y 2 or Y 3 is cyano and wherein G is G4, G5 or G6, and wherein all other substituents and groups are as defined before for Formula (I).
  • T is a group T2, wherein Y 2 or Y 3 is cyano and wherein G is G4, G5 or G6, and wherein all other substituents and groups are as defined before for Formula (I).
  • alkyl in the present specification represents linear or branched Ci_i 2 alkyl such as methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl, preferably Ci_6 alkyl, and more preferably CM alkyl.
  • haloalkyl represents, for example, CH 2 F, CHF 2 , CF 3 , CF 2 C1, CFCI 2 , CF 2 Br, CF 2 CF 3 , CFHCF 3 , CH 2 CF 3 , CFC1CF 3 , CC1 2 CF 3 , CF 2 CH 3 , CF 2 CH 2 F, CF 2 CHF 2 , CF 2 CF 2 C1, CF 2 CF 2 Br, CFHCH 3 , CFHCHF 2 , CFHCHF 2 , CHFCF 3 , CHFCF 2 C1, CHFCF 2 Br, CFC1CF 3 , CC1 2 CF 3 , CF 2 CF 2 CF 3 , CH 2 CF 2 CF 3 , CF 2 CH 2 CF 3 , CF 2 CH 2 CF 3
  • alkoxy represents, for example, methoxy, ethoxy, n-propoxy, i-propoxy, n-, iso-, sec- or tert-butoxy, pentyloxy or hexyloxy, and represents linear or branched Ci_i 2 , preferably Ci_6, and more preferably CM alkoxy. The alkoxy may be further substituted with any substituent.
  • halogen and each halogen moiety included in each halogen-substituted group represent fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.
  • cycloalkyl represents C3.8 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, and preferably represents C3.7 cycloalkyl, more preferably C3.6 cycloalkyl.
  • cycloalkyl moiety included in each group that has the cycloalkyl as a constituent those which are the same as “cycloalkyl” described above can be exemplified.
  • cyclohaloalkyl represents, for example, fluorocyclopropyl, chlorocyclopropyl, difluorocyclopropyl, dichlorocyclopropyl or undecafluorocyclohexyl.
  • alkenyl represents C2-12 alkenyl, preferably C2-6 alkenyl such as vinyl, allyl, 1-propenyl, 1- (or 2-, or 3-) butenyl and 1-pentenyl, more preferably C2-5 alkenyl, and further preferably C2-4 alkenyl.
  • alkynyl represents C2-12 alkynyl, preferably C2-6 alkynyl such as ethynyl, propargyl, 1-propynyl, butan-3-ynyl and pentan-4-ynyl, more preferably C2-5 alkynyl, and further preferably C2-4 alkynyl.
  • aryl represents a C & n aromatic hydrocarbon group, for example, phenyl, naphthyl, biphenyl, preferably a Ce-io aromatic hydrocarbon group, more preferably a Ce aromatic hydrocarbon group, phenyl.
  • heterocyclic ring may represent a 5-membered or 6-membered heterocyclic group containing at least one N, O or S as a heteroatom, or the ring may represent a fused heterocyclic group that may be benzo-fused, and further the carbon atom on the ring may be substituted with oxo or thioxo.
  • heterocyclic ring examples include pyrrolidinyl, piperidinyl, morpholinyl and thiomorpholinyl (examples of those saturated), dihydropyrrolyl, dihydroisoxazolyl, dihydropyrazolyl, dihydroxazolyl and dihydrothiazolyl (examples of those partially saturated), furyl, thienyl, pyrrolyl, isoxazolyl, pyrazolyl, oxazolyl, isothiazolyl, thiazolyl, imidazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, benzoxazolyl, benzothiazolyl, quinolyl and the like, wherein the heterocyclic ring may be substituted
  • substituent in the expression of "may be substituted with any substituent” represents, for example, amino, hydroxy, oxo, thioxo, halogen, nitro, cyano, isocyano, mercapto, isothiocyanate, carboxy, carbamide, SF 5 , aminosulfonyl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, monoalkylamino, dialkylamino, N-alkylcarbonyl-amino, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, cycloalkenyloxy, alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryloxycarbonyl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, arylcarbonyl, alkylcarbonyl, alkenylcarbonyl,
  • the terms “combating”, “controlling” or “expelling” are used synonymously refers to the biological capability of the active compound which results in the killing, in the inhibition of the growth, or in the inhibition of the proliferation of the targeted organism.
  • the compounds of Formulae (I), ( ⁇ ), (I-Ia) or (I-b) of the present invention can be obtained by, for example, the preparation methods (a), (b) or (c) described below.
  • X 1 , X 2 , X 4 , X 5 , R, B and T are defined herein, are reacted with a halogenating agent in the presence of a suitable diluent if necessary.
  • X 1 , X 2 , X 4 , X 5 , R, B, T and R 20 are as defined herein.
  • R represents hydroxy-carbonyl or Ci_6 alkoxy-carbonyl and T represents T-l :
  • X 1 , X 2 , X 4 , X 5 , Y 1 , Y 2 , Y 3 , Y 4 , R, B and R 20 are as defined herein or a mixture of compounds (I-IIa) and (I-IIb),
  • H represents hydrogen and G represents any one of Gl to G9 as described above, in the presence of a suitable diluent and/or suitable base if necessary.
  • the preparation method (a) may be conducted according to conventional organic synthesis.
  • the halogenating agent in the preparation method (a) includes, for example, chlorine, bromine, iodine, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, l,3-dichloro-5,5-hydantoin, l,3-dibromo-5,5-dimethylhydantoin, benzyltrimethylammonium tetrachloroiodinate, sodium hypochlorite and the like.
  • the reaction of the preparation method (a) may be performed in a suitable diluent and examples of the diluent used at this time include aliphatic hydrocarbons (hexane, cyclohexane, heptane, and the like), aliphatic halogenated hydrocarbons (dichloromethane, chloroform, carbon tetrachloride, dichloroethane, and the like), aromatic hydrocarbons (benzene, toluene, xylene, chlorobenzene, and the like), ethers (diethyl ether, dibutyl ether, dimethoxyethane (DME), tetrahydrofuran, dioxane, and the like), esters (ethyl acetate, ethyl propionate, and the like) , acid amides (dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, and the like), nitriles
  • the preparation method (a) may be performed in a substantially wide temperature range. Generally, the preparation method (a) may be performed at about -78 °C to about 200 °C, preferably at about -10 °C to about 100 °C. In addition, the reaction is desirably conducted at normal pressures, but may be also handled under elevated or reduced pressure. The reaction time is 0.1 to 72 hours, preferably 1 to 24 hours.
  • the step (b-1) in the preparation method (b) may be conducted according to the methods described in, for example, EP1538138 (Al) or WO2009-097992 (Al).
  • the reaction of the step (b-1) in the preparation method (b) may be performed in a suitable diluent, and examples of the diluent used at this time are the same as the examples of the diluent in the preparation method (a).
  • the suitable copper reagent in the step (b-1) in the preparation method (b) includes copper oxide (I), copper oxide (II), copper acetylacetonate (II), copper acetate (II), copper cyanide (I) and the like.
  • the step (b-1) in the preparation method (b) may be performed in a substantially wide temperature range.
  • the step (b-1) may be performed at about 20 °C to about 200 °C, preferably at about 40 °C to about 150 °C.
  • the reaction is desirably conducted at normal pressures, but may be also handled under elevated or reduced pressure.
  • the reaction time is 0.1 to 72 hours, preferably 1 to 24 hours.
  • step (b-1) in the preparation method (b) for example, 1 mole of the compound of Formula (III) is reacted with 0.5 mole to 2 moles of the compound of Formula (IV) and 0.1 mole to 2 mole of a copper reagent, for example, copper oxide (I) in a diluent, for example, toluene, whereby obtaining the corresponding compound of Formula (V).
  • a copper reagent for example, copper oxide (I) in a diluent, for example, toluene
  • the compounds of Formula (III), which are the starting materials in the step (b-1) in the preparation metho d (b ) , are novel, and representative examples there o f inc lude methyl 3-(3,5-dichlorophenyl)-4,4,4-trifluorobuten-2-enoate, methyl 4,4,4-trifluoro-3-(3,4,5-trichloro- phenyl)-buten-2-enoate, ethyl 4,4,4-trifluoro-3-(3,4,5-trichlorophenyl)-buten-2-enoate, isopropyl 4,4,4-trifluoro-3-(3,4,5-trichlorophenyl)-buten-2-enoate, tert-butyl 4,4,4-trifluoro-3-(3,4,5-trichloro- phenyl)-buten-2-enoate, benzyl 4,4,4-trifluoro-3-(3,4,5-trichlorophenyl)-
  • Examples of the compounds of Formula (IV), which are the starting materials in the step (b-1) in the preparation method (b), include those known, and representative examples thereof include 3-bromo-4-fluorobenzylisocyanide, 2-fluoro-5-(isocyanomethyl)benzonitrile and 5-(isocyano- methyl)-2-(lH-l,2,4-triazol-l-yl)benzonitrile.
  • the compounds may be prepared by the methods described in the documents, e.g., Tetrahedron Letters 29(27) (1988) pp. 3343-3346; Heterocycles 31 (1990) pp. 1855-1860; Journal of Organic Chemistry 70 (2005) pp. 3542-3553; or Organic & Biomolecular Chemistry 1(9) (2003) pp. 1475-1479.
  • the step (b-2) in the preparation method (b) may be performed according to the methods described in JP-ANo. 2007-91708, or Chem. Lett. (1985) pp. 1601-1604.
  • the reaction of the step (b-2) in the preparation method (b) may be performed in a suitable diluent, and examples of the diluent used at this time are the same as the examples of the diluent in the preparation method (a).
  • the suitable base of the step (b-2) in the preparation method (b) includes alkaline metal bases such as sodium carbonate, potassium carbonate, sodium hydrocarbonate, potassium hydrocarbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide and potassium-tert-butoxide, and organic bases such as triethylamine, diisopropylethylamine, tributylamine, N-methylmorpholine, N,N-dimethylaniline, ⁇ , ⁇ -diethylaniline, 4-tert-butyl-N,N-dimethylaniline, pyridine, picoline, lutidine, diazabicycloundecene, diazabicyclooctane and imidazole, and the like.
  • alkaline metal bases such as sodium carbonate, potassium carbonate, sodium hydrocarbonate, potassium hydrocarbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide and potassium-tert-butoxide
  • the reaction of the step (b-2) in the preparation method (b) may be performed in a substantially wide temperature range. Generally, the reaction may be performed at about -78 °C to about 200 °C, preferably at about -10 °C to about 100 °C. In addition, the reaction is desirably conducted at normal pressures, but may be also handled under elevated or reduced pressure.
  • the reaction time is 0.1 to 72 hours, preferably 1 to 24 hours.
  • step (b-2) in the preparation method (b) for example, 1 mole of the compound of Formula (V) is reacted with 1 to 0.1 mole of a base such as diazabicycloundecene in a diluent, for example, pyridine, whereby obtaining the objective compound of Formulae (I-Ia) and/or (I-Ib), which is encompassed by Formula (I) of the present invention.
  • a base such as diazabicycloundecene in a diluent, for example, pyridine
  • Representative examples of the compounds of Formula (V) in the step (b-2) in the preparation method ( b ) include methyl 2-(3-bromo-4-fluoro- phenyl)-4-(3,5-dichlorophenyl)-4-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-3-c arb o x y l at e , m e thy l 2-(3-bromo-4-fluorophenyl)-4-(3,4,5-trichlorophenyl)-4-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-3-carb o x y l a t e , e t h y l 2-(3-bromo-4-fluorophenyl)-4-(3,4,5
  • the preparation method (c) may be conducted according to the method described in WO2009-097992 (Al).
  • the reaction of the preparation method (c) may be performed in a suitable diluent, and examples of the diluent used at this time are the same as the examples of the diluent in the preparation method (a).
  • the reaction of the preparation method (c) may be performed using, as a base, an alkaline metal base such as lithium hydride, sodium hydride, potassium hydride, lithium amide, sodium amide, lithium diisopropylamide, butyl lithium, tert-butyl lithium, trimethylsilyl lithium, lithium hexamethyldisilazide, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide and potassium-tert-butoxide, an organic base such as triethylamine, diisopropylethylamine, tri b uty l ami n e , N-methyl morpholine, ⁇ , ⁇ -dimethylaniline, N,N-diethylaniline,
  • an alkaline metal base such as lithium hydride, sodium hydride, potassium hydride, lithium amide, sodium amide, lithium diisopropylamide, butyl lithium, tert-
  • the preparation method (c) may be performed in a substantially wide temperature range. Generally, the preparation method (c) may be performed at about -78 °C to about 200 °C, preferably at about -10 °C to about 200 °C. In addition, the reaction is desirably conducted at normal pressures, but may be also handled under elevated or reduced pressure. The reaction time is 0.1 to 72 hours, preferably 0.1 to 48 hours.
  • 1 mole of the compound of Formulae (I-IIa) and/or (I-IIb) is reacted with 1 mole to 3 moles of H-G, for example, H-G6 in a diluent, for example, DMF in the presence of 1 mole to 3 moles of a base such as potassium carbonate, whereby obtaining the corresponding compound of Formula (I) of the present invention.
  • a diluent for example, DMF
  • a base such as potassium carbonate
  • the compounds of Formulae (I-IIa-Br) and/or (I-IIb-Br) and Formulae (I-IIa-CN) and/or (I-IIb-CN), which are encompassed by Formulae (I-IIa) and/or (I-IIb) that is a starting material in the preparation method (c), may be prepared by the method described in the scheme 1 :
  • Step c-1 and Step c-2 may be conducted according to the preparation method (b); in Step c-3, the compounds of Formula (I-IIa-Br) are reacted with a cyano reagent and/or a catalyst in the presence of a suitable diluent if necessary, whereby obtaining the compounds of Formula (I-IIa-CN); the reaction of Step c-3 may be performed in a suitable diluent, and examples of the diluent used at this time are the same as the examples of the diluent in the preparation method (a), desirably dimethylformamide (DMF); the reaction of Step c-3 may be performed in the presence of a suitable catalyst, and examples of the catalyst used at this time include a transitional metal such as Pd(PPh 3 )
  • Step c-3 may be performed at about 0 °C to about 200 °C, preferably at about 30 °C to about 180 °C.
  • the reaction is desirably conducted at normal pressures, but may be also handled under elevated or reduced pressure.
  • the reaction time is 0.1 to 72 hours, preferably 0.1 to 24 hours; and in performing Step c-3, for example, 1 mole of the compound of Formula (I-IIa-Br) is reacted with 0.5 mole to 3 moles of the cyanating agent, for example, zinc cyanide in a diluent, for example, DMF, in the presence of catalytic amount of Pd(PPh 3 ) 4 , whereby obtaining the compound of Formula (I-IIa-CN), which is encompassed by the compounds of Formula (I-IIa) of the present invention.
  • the cyanating agent for example, zinc cyanide in a diluent, for example, DMF
  • H-G As the compounds of Formula (H-G) which are the starting materials in the preparation method (c), there are many known compounds represented by H-G2, H-G3, H-G4, H-G5, H-G6, H-G8 or H-G9, and the specific examples thereof include
  • the compounds according to the invention may have one or more asymmetrical carbons, and accordingly, the compounds of the present invention encompass the optical isomers thereof.
  • the compounds according to the invention may be used in combination with suitable synergists or other active compounds, such as for example insecticides, acaricides, nematicides, fungicides, biological control agents, and bacterizides.
  • suitable synergists or other active compounds such as for example insecticides, acaricides, nematicides, fungicides, biological control agents, and bacterizides.
  • Such combinations can also result in a synergistic effect, i.e. the biological activity of such a combination is synergistically increased.
  • Such combinations may called mixtures.
  • combination partners are the following insecticides, acaricides, nematicides:
  • the active ingredients specified herein by their "common name” are known and described, for example, in the Pesticide Manual ("The Pesticide Manual", 14th Ed., British Crop Protection Council 2006) or can be searched in the internet (e.g. http://www.alanwood.net/pesticides).
  • Acetylcholinesterase (AChE) inhibitors for example carbamates, e.g. Alanycarb, Aldicarb, Bendiocarb, Benfuracarb, Butocarboxim, Butoxycarboxim, Carbaryl, Carbofuran, Carbosulfan, Ethiofencarb, Fenobucarb, Formetanate, Furathiocarb, Isoprocarb, Methiocarb, Methomyl, Metolcarb, Oxamyl, Pirimicarb, Propoxur, Thiodicarb, Thiofanox, Triazamate, Trimethacarb, XMC, and Xylylcarb; or organophosphates, e.g.
  • AChE Acetylcholinesterase
  • GABA-gated chloride channel antagonists for example cyclodiene organochlorines, e.g. Chlordane and Endosulfan; or phenylpyrazoles (fiproles), e.g. Ethiprole and Fipronil.
  • Sodium channel modulators / voltage-dependent sodium channel blockers for example pyrethroids, e.g. Acrinathrin, Allethrin, d-cis-trans Allethrin, d-trans Allethrin, Bifenthrin, Bioallethrin, Bioallethrin S-cyclopentenyl isomer, Bioresmethrin, Cycloprothrin, Cyfluthrin, beta-Cyfluthrin, Cyhalothrin, lambda-Cyhalothrin, gamma-Cyhalothrin, Cypermethrin, alpha-Cypermethrin, beta-Cypermethrin, theta-Cypermethrin, zeta-Cypermethrin, Cyphenothrin [(lR)-trans isomers], Deltamethrin, Empenthrin [(EZ)-(IR) isomers), Esfenvalerate,
  • Nicotinic acetylcholine receptor (nAChR) agonists for example neonicotinoids, e.g. Acetamiprid, Clothianidin, Dinotefuran, Imidacloprid, Nitenpyram, Thiacloprid, and Thiamethoxam; or
  • Nicotinic acetylcholine receptor (nAChR) allosteric activators for example spinosyns, e.g. Spinetoram and Spinosad.
  • Chloride channel activators for example avermectins/milbemycins, e.g. Abamectin, Emamectin benzoate, Lepimectin, and Milbemectin.
  • Juvenile hormone mimics for example juvenile hormon analogues, e.g. Hydroprene, Kinoprene, and Methoprene; or Fenoxycarb; or Pyriproxyfen.
  • Miscellaneous non-specific (multi-site) inhibitors for example alkyl halides, e.g. Methyl bromide and other alkyl halides; or Chloropicrin; or Sulfuryl fluoride; or Borax; or Tartar emetic.
  • alkyl halides e.g. Methyl bromide and other alkyl halides; or Chloropicrin; or Sulfuryl fluoride; or Borax; or Tartar emetic.
  • Microbial disruptors of insect midgut membranes e.g. Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis, and BT crop proteins: CrylAb, CrylAc, CrylFa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34/35Abl .
  • Inhibitors of mitochondrial ATP synthase for example Diafenthiuron; or organotin miticides, e.g. Azocyclotin, Cyhexatin, and Fenbutatin oxide; or Propargite; or Tetradifon.
  • Uncouplers of oxidative phoshorylation via disruption of the proton gradient for example Chlorfenapyr, DNOC, and Sulfluramid.
  • Nicotinic acetylcholine receptor (nAChR) channel blockers for example Bensultap, Cartap hydrochloride, Thiocyclam, and Thiosultap-sodium.
  • Inhibitors of chitin biosynthesis type 0, for example Bistrifluron, Chlorfluazuron, Diflubenzuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Lufenuron, Novaluron, Noviflumuron, Teflubenzuron, and Triflumuron.
  • Inhibitors of chitin biosynthesis type 1, for example Buprofezin.
  • Moulting disruptors for example Cyromazine.
  • Ecdysone receptor agonists for example Chromafenozide, Halofenozide, Methoxyfenozide, and Tebufenozide.
  • Octopamine receptor agonists for example Amitraz.
  • Mitochondrial complex III electron transport inhibitors for example Hydramethylnon; or Acequinocyl; or Fluacrypyrim.
  • Mitochondrial complex I electron transport inhibitors for example METI acaricides, e.g. Fenazaquin, Fenpyroximate, Pyrimidifen, Pyridaben, Tebufenpyrad, and Tolfenpyrad; or
  • Rotenone (Derris). (22) Voltage-dependent sodium channel blockers, e.g. Indoxacarb; or Metaflumizone.
  • Inhibitors of acetyl CoA carboxylase for example tetronic and tetramic acid derivatives, e.g. Spirodiclofen, Spiromesifen, and Spirotetramat.
  • Mitochondrial complex IV electron transport inhibitors for example phosphines, e.g. Aluminium phosphide, Calcium phosphide, Phosphine, and Zinc phosphide; or Cyanide.
  • Ryanodine receptor modulators for example diamides, e.g. Chlorantraniliprole and Flubendiamide.
  • Further active ingredients with unknown or uncertain mode of action for example Amidoflumet, Azadirachtin, Benclothiaz, Benzoximate, Bifenazate, Bromopropylate, Chinomethionat, Cryolite, Cyantraniliprole (Cyazypyr), Cyflumetofen, Dicofol, Diflovidazin, Fluensulfone, Flufenerim, Flufiprole, Fluopyram, Fufenozide, Imidaclothiz, Iprodione, Meperfluthrin, Pyridalyl, Pyrifluquinazon, Tetramethylfluthrin, and iodomethane; furthermore products based on Bacillus firmus (including but not limited to strain CNCM 1-1582, such as, for example,VOTiVOTM, BioNem
  • Inhibitors of the ergosterol biosynthesis for example aldimorph, azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, diniconazole-M, dodemorph, dodemorph acetate, epoxiconazole, etaconazole, fenarimol, fenbuconazole, fenhexamid, fenpropidin, fenpropimorph, fluquinconazole, flurprimidol, flusilazole, flutriafol, furconazole, furconazole-cis, hexaconazole, imazalil, imazalil sulfate, imibenconazole, ipconazole, metconazole, myclobutanil, naftifme, nuarimol, oxpoconazole, paclo
  • inhibitors of the respiratory chain at complex I or II for example bixafen, boscalid, carboxin, diflumetorim, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, furmecyclox, isopyrazam (mixture of syn-epimeric racemate 1RS,4SR,9RS and anti-epimeric racemate I RS, 4SR,9SR), isopyrazam (anti-epimeric racemate 1RS,4SR,9SR), isopyrazam (anti-epimeric enantiomer 1R,4S,9S), isopyrazam (anti-epimeric enantiomer 1 S,4R,9R), isopyrazam (syn epimeric racemate 1RS,4SR,9RS), isopyrazam (syn-epimeric enantiomer 1R,4S,9R), isopyrazam (syn-epimeric en
  • inhibitors of the respiratory chain at complex III for example ametoctradin, amisulbrom, azoxystrobin, cyazofamid, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, famoxadone, fenamidone, fenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, triclopyricarb, trifloxystrobin, (2E)-2-(2- ⁇ [6-(3-chloro-2-methylphenoxy)-5-fluoropyrimidin-4-yl]oxy ⁇ phenyl)-2-(methoxyimino)-N-m ethylethanamide,
  • Inhibitors of the mitosis and cell division for example benomyl, carbendazim, chlorfenazole, diethofencarb, ethaboxam, fluopicolide, fuberidazole, pencycuron, thiabendazole, thiophanate-methyl,t h i o p h a n a t e , z o x a m i d e ,
  • Compounds capable to induce a host defence for example acibenzolar-S-methyl, isotianil, probenazole and tiadinil.
  • Inhibitors of the amino acid and/or protein biosynthesis for example andoprim, blasticidin-S, cyprodinil, kasugamycin, kasugamycin hydrochloride hydrate, mepanipyrim, pyrimethanil and 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-l-yl)quinoline.
  • Inhibitors of the ATP production for example fentin acetate, fentin chloride, fentin hydroxide and silthiofam.
  • Inhibitors of the cell wall synthesis for example benthiavalicarb, dimethomorph, flumorph, iprovalicarb, mandipropamid, polyoxins, polyoxorim, validamycin A and valifenalate.
  • Inhibitors of the lipid and membrane synthesis for example biphenyl, chloroneb, dicloran, edifenphos, etridiazole, iodocarb, iprobenfos, isoprothiolane, propamocarb, propamocarb hydrochloride, prothiocarb, pyrazophos, quintozene, tecnazene and tolclofos-methyl.
  • Inhibitors of the melanine biosynthesis for example carpropamid, diclocymet, fenoxanil, phthalide, p y r o q u i l o n , t r i c y c l a z o l e a n d 2 , 2 , 2-trifluoroethyl ⁇ 3-methyl-l-[(4-methylbenzoyl)amino]butan-2-yl ⁇ carbamate.
  • Inhibitors of the nucleic acid synthesis for example benalaxyl, benalaxyl-M (kiralaxyl), bupirimate, clozylacon, dimethirimol, ethirimol, furalaxyl, hymexazol, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl and oxolinic acid.
  • Inhibitors of the signal transduction for example chlozolinate, fenpiclonil, fludioxonil, iprodione, procymidone, quinoxyfen and vinclozolin.
  • All named fungicide mixing partners of the classes (1) to (16) can, if their functional groups enable this, optionally form salts with suitable bases or acids.
  • Herbicidal compounds which can be used in combination with the active compounds according to the invention in mixed formulations or in tank mix are, for example, known active compounds as they are described in, for example, Weed Research 26, 441-445 (1986), or "The Pesticide Manual", 15th edition, The British Crop Protection Council and the Royal Soc.
  • active compounds which may be mentioned as herbicides or plant growth regulators which are known from the literature and which can be combined with the compounds according to the invention are the following (compounds are either described by "common name” in accordance with the International Organization for Standardization (ISO) or by chemical name or by a customary code number), and always comprise all applicable forms such as acids, salts, ester, or modifications such as isomers, like stereoisomers and optical isomers.
  • ISO International Organization for Standardization
  • acetochlor acibenzolar, acibenzolar-S-methyl, acifluorfen, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim-sodium, ametryn, amicarbazone, amidochlor, amidosulfuron, aminocyclopyrachlor, aminocyclopyrachlor-methyl, aminocyclopyrachlor-potassium, aminopyralid, amitrole, ammoniumsulfamat, ancymidol, anilofos, asulam, atrazine, azafenidin, azimsulfuron, aziprotryn, beflubutamid, benazolin, benazolin-ethyl, bencarbazone, benfluralin, benfuresate, bensulide, bensulfuron, bensulfuron-methyl, bent
  • the compounds and mixtures according to the invention show strong pesticidal actions, and accordingly, can be used as pesticides. Furthermore, the compounds or the mixtures according to the invention do not have harmful drug-adverse action on cultivated plants, and show strong expelling effects against harmful insects. Accordingly, the compounds or mixtures according to the invention can be used to combat harmful insects which occure in the agriculture, in particular on plants, such as harmful sucking plant insects, chewing plant insects and other plant-parasitic pests, stored-product insects, sanitarily harmful organisms and the like, and can be applied for the purpose of suh combatting.
  • the harmful / organisms insects are for example:
  • Coleoptera for example, Callosobruchus chinensis, Sitophilus zeamais, Tribolium castaneum, Epilachna vigintioctomaculata, Agriotes fuscicollis, Anomala rufocuprea, Leptinotarsa decemlineata, Diabrotica spp., Monochamus alternatus, Lissorhoptrus oryzophilus, Lyctus bruneus and Aulacophora femoralis; Lepidoptera, for example, Lymantria dispar, Malacosoma neustria, Pieris rapae, Spodoptera litura, Mamestra brassicae, Chilo suppressalis, Pyrausta nubilalis, Ephestia cautella, Adoxophyes orana, Carpocapsa pomonella, Agrotisfucosa, Galleria mellonella, Plutella maculipennis, Heliothis virescens and
  • Nematoda such as Meloidogyne incognita, Bursaphelenchus lignicolus Mamiya et Kiyohara, Aphelenchoides besseyi, Heterodera glycines and Pratylenchus spp.
  • the compounds of the present invention show excellent plant tolerability and a desirable toxicity profile for warm-blooded animals, and are well tolerable by the environment, and accordingly, suitable in protecting plants and parts of plants.
  • the application of the compounds of the present invention can lead to the increase of the harvested amount, and the improvement of the quality of harvested materials.
  • the above-described compounds are suitable in protecting preserved products and materials, in the sanitary field, in the agriculture, gardening or veterinary field, and in expelling harmful pests, particularly insects, acari, helminthes, nematoda and mollusks encountered in the forest, garden or recreational facilities.
  • the compounds of the present invention can be used preferably as plant-protecting agents.
  • the compounds of the present invention have activity to normally sensitive and resistant species in all or some of the growth steps thereof.
  • the above-described harmful insects include those described below:
  • Anoplura for example, there are Damalinia spp., Haematopinus, Linognathus spp., Pediculus spp. and Trichodectes spp.
  • Arachnida there are Acarus siro, Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Chorioptes spp., Dermanyssus gallinae, Eotetranychus spp., Epitrimerus pyri, Eutetranyctus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans, Metatetranychus spp., Oligonychus spp., Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus la
  • Chilopoda for example, there are Geophilus spp. and Scutigera spp.
  • Coleoptera for example, there are Acanthoscelides obtectus, Adoretus spp., Agelastica alni, Agriotes spp., Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp., Anthrenus spp., Apogonia spp., Atomaria spp., Attagenus spp., Bruchidius obtectus, Bruchus spp., Ceuthorhynchus spp., Cleonus mendicus, Conoderus spp., Cosmopolites spp., Costelytra zeal andica, Curculio spp., Cryptorhynchus lapathi, Dermestes spp., Diabrotica spp., Epilachna spp., Faustinus cubae, Gibbium psylloides, Heteronych
  • Diplopoda there is Blaniulus guttulatus.
  • Diptera for example, there are Aedes spp., Anopheles spp., Bibio hortulanus, Calliphora erythrocephala, Ceratitis capitata, Chrysomyia spp., Cochliomyia spp., Cordylobia anthropophaga, Culex spp., Cuterebra spp., Dacus oleae, Dermatobia hominis, Drosophila spp., Fannia spp., Gastrophilus spp., Hylemyia spp., Hyppobosca spp., Hypoderma spp., Liriomyza spp., Lucilia spp., Musca spp., Nezara spp., Oestrus spp., Oscinella frit, Pegomyia hyo
  • Gastropoda for example, there are Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp. and Succinea spp.
  • Helminths for example, there are Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp., Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medeinensis, Echinococcus granulosus, Echinococcus multiocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa loa, Nemat
  • Protozoa such as Eimeria can be expelled by the compounds of the present invention.
  • Heteroptera there are Anasa tristis, Antestiopsis spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus,spp., Euschistus spp., Eurygaster spp., Heliopeltis spp., Horchias nobiellus, Leptocorisa spp., Leptoglossus phyllopus, Lygus spp., Macropes excavatus, Miridae, Nezara spp., Oebalus spp., Pentomidae, Piesma quadrata, Piezodorus spp., Psallus seriatus, P
  • Homoptera for example, there are Acyrthosipon spp., Aeneolamia spp., Agonoscena spp., Aleurodes spp., Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anuraphis cardui, Aonidiella spp., Aphanostigma piri, Aphis spp., Arboridia apicalis, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp., Brachycaudus helichrysii, Brachycolus spp., Brevicoryne brassicae, Calligypona marginata, Carneocephala fulgida, Ceratovacuna lanigera, Cercopidae, Cer
  • Isopoda for example, there are Armadillidium vulgare, Oniscus asellus and Porcellio scaber.
  • Isoptera for example, there are Reticulitermes spp. and Odontotermes spp.
  • Lepidoptera for example, there are Acronicta major, Aedia leucomelas, Agrotis spp., Alabama argillacea, Anticarsia spp., Barathra brassicae, Bucculatrix thurberiella, Bupalus piniarius, Cacoecia podana, Capua reticulana, Carpocapsa pomonella, Cheimatobia brumata, Chilo spp., Choristoneura fumiferana, Clysia ambiguella, Cnaphalocerus spp., Earias insulana, Ephestia kuehniella, Euproctis chrysorrhoea, Euxoa spp., Feltia spp., Galleria mellonella, Helicoverpa
  • Orthoptera for example, there are Acheta domesticus, Blatta orientalis, Blattella germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta Americana and Schistocerca gregaria.
  • Siphonaptera for example, there are Ceratophyllus spp. and Xenopsylla cheopis.
  • Symphyla for example, there is Scutigerella immaculata.
  • Thynsanoptera for example, there are Balothrips biformis, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni and Thrips spp.
  • Thysanura for example, there is Lepisma saccharina.
  • Examples of the plant-parasitic Nematoda include Anguina spp., Aphelenchoides spp., Belonoaimus spp., Bursaphelenchus spp., Ditylenchus dipsaci, Globodera spp., Heliocotylenchus spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus similis, Rotylenchus spp., Trichodorus spp., Tylenchorhynchus spp., Tylenchulus spp., Thlenchulus semipenetrans and Xiphinema spp.
  • all plants and parts of plants can be treated.
  • the plant refer to all plants and plant populations including desirable and undesirable wild plants or genetically modified plants (including naturally occurring genetically modified plants).
  • the genetically modified plants may be plants that can be obtained by conventional improvement of plant variety and optimization or biotechnology and genetic engineering, or a combination method thereof.
  • Transgenic plants, and plant varieties that can be protected or non-protected by the plant breeders, are included in the term "genetically modified plant” or "genetically modified plants”.
  • the parts of plants should be understood to refer to all the parts or organs of plants existing above and under the ground such as a bud, leaf, flower and root and the like.
  • the examples include a leaf, needle-like leaf (needle), stalk, stem, flower, fruiting body, fruit, seed, root, tuber and stalk under the ground.
  • the parts of plants also include harvested materials, and materials propagating sexually or asexually, for example, a cuttage, tuber, stalk under the ground, lateral branch and seed.
  • the treatment of plants or parts of plants with the active compounds or mixtures according to the present invention is performed directly, or by conventional treatments, for example, immersion, spray, evaporation, atomization, scattering, coating or injection.
  • the treatment is performed by coating it with one or more compounds so that the compounds are applied to the surroundings, the inhabitant environment or preservation place.
  • the compounds of the present invention have a systemic activity, which means that the compounds can permeate into a plant and move from the underground part to the above-ground part of the plant.
  • plants and parts of plants can be treated according to the present invention.
  • wild plant species and plant variants, or those obtained by traditional plant breeding methods such as crossbreeding or protoplast fusion and the like, and parts thereof are treated.
  • transgenic plants and plant varieties (genetically modified organisms), which are obtained by combination of genetic engineering and suitable conventional methods, and parts thereof are treated.
  • the terms "parts,” “parts of plants,” and “plant parts” are as explained above.
  • plants of plant varieties commercially available or used are treated according to the present invention.
  • the plant varieties are understood to refer to plants that have new characteristic ("trail") obtained by conventional breed improvement, mutation introduction or recombination DNA technology. They may be plant varieties, biotypes or genotypes.
  • the treatment according to the present invention may have ultra-additive ("synergic") effects depending on plant species or plant varieties, their habitat and proliferation conditions (soil, weather, growth period, nutrition). Accordingly, beyond the effects practically expected, it is possible to obtain, for example, reduction of application rate and/or expansion of activity spectrum and/or increase of the activity of the substances and the compositions that can be used according to the present invention, improvement of plant growth, increase of tolerability for high or low temperature, increase of tolerability for drought or moisture or salts contained in the soil, improvement of flowering ability, simplification of harvest, acceleration of maturation, increase of harvest yield, improvement of quality of harvest products and/or increase of the nutrition value and improvement of preservation stability and/or processability of harvested products.
  • the desirable transgenic plants or plant varieties (obtained by genetic engineering) treated according to the present invention include all plants having genetic substances that can provide the plants with very advantageous and useful traits based on genetic modification.
  • traits include improvement of plant growth, increase of tolerability for high or low temperature, increase of tolerability for drought or moisture or salts contained in the soil, improvement of flowering ability, simplification of harvest, acceleration of maturation, increase of harvest yield, improvement of quality of harvested products and/or increase of the nutrition value and improvement of preservation stability and/or prosessability of harvested products.
  • Examples where such traits are particularly emphasized include improvement of the protection of plants against harmful pests and harmful microorganisms such as insect, tick, plant pathogenic fungus, bacteria and/or virus, and increase of tolerability of plants against compounds having certain type of herbicidal activities.
  • Examples of the transgenic plant include important cereal plants such as cereals (barley, rice), corn, soybean, potato, sugar beet, tomato, bean and other plant variants, important cereal plants such as cotton, tobacco or rape and fruit plants (fruits like an apple, a pear or a citrus fruits and fruit-bearing plants like a grape), particularly importantly, corn, soybean, potato, cotton, tobacco and rape.
  • the trait considered to be important is the increase of protection of plants against insects, acari, nematodes, slugs and snails by a toxin formed in the plant, particularly by a toxin formed in the plant particularly by genetic substances derived from Bacillus thuringiensis (for example, genes CrylA(a), CrylA(b), CrylA(c), CryllA, CrylllA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CrylF and combinations thereof).
  • Bacillus thuringiensis for example, genes CrylA(a), CrylA(b), CrylA(c), CryllA, CrylllA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CrylF and combinations thereof.
  • Bt plant Such a plant is hereinafter called as "Bt plant.”
  • SB plant Such a plant is hereinafter called as "Bt plant.”
  • SAR systemic acquired resistance
  • PTA phosphinotricine
  • Bt plant examples include corn variants, cotton variants, soybean variants and potato variants marketed under the trade name of YIELD GARD (R) (for example, corn, cotton, soybean), KnockOut (R) (for example, corn), StarLink (R) (for example, corn), Bollgard (R) (cotton), Nucotn (R) (cotton) and NewLeaf ⁇ (potato).
  • R YIELD GARD
  • R for example, corn, cotton, soybean
  • KnockOut for example, corn
  • StarLink for example, corn
  • Bollgard (R) cotton
  • Nucotn (R) cotton
  • NewLeaf ⁇ potato
  • Examples of the herbicide-resistant plants include corn variants, cotton variants and soybean variants marketed under the trade name of Roundup Ready (R) (resistant for glyphosate, for example, corn, cotton, soybean), Lib ertyLink (R) (resistant for phosphinotricine, for example, rape), IMI (R) (resistant for imidazolinones) and STS (R) (resistant for sulfonyl urea, for example, corn).
  • R Roundup Ready
  • R resistant for glyphosate
  • corn cotton, soybean
  • Lib ertyLink resistant for phosphinotricine, for example, rape
  • IMI resistant for imidazolinones
  • STS R
  • the herbicide-resistant plants i.e., the plant obtained by conventional breeding methods to have resistance to herbicides
  • the novel compounds of the present invention can be effectively used for various harmful parasitic pests (endo- and ecto-parasitic pests), for example, insects and helminthes.
  • harmful parasitic pests include harmful organisms described below.
  • insects include Gasterophilus spp., Stomoxys spp., Trichodectes spp., Rhodonius spp., Ctenocephalides canis, Cimx lecturius, Ctenocephalides felis, Lucilia cuprina and the like.
  • Examples of Acari include Ornithodoros spp., Ixodes spp., Boophilus spp. and the like.
  • the active compounds of the present invention are active against parasitic pests, in particularly, endo-parasitic pests or ecto-parasitic pests.
  • the term of the endo-parasitic pests includes particularly helminthes such as cestode, Nematoda or fluke, Protozoa such as coccidia and the like.
  • the ecto-parasitic pests include typically and preferably arthropod pests, particularly, insects such as fly (bite fly and licking fly), larvae of parasitic fly, louse, public lice, bird louse and flea, or acari such as mites, e.g., hard tick or soft tick, or itch mite, trombiculid mite and Ornithonyssus sylviarum (bird mite).
  • the parasitic pests which can be expelled by the active compound according to the invention are the following:
  • Haematopinus spp. there are Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.
  • Specific examples thereof include Linognathus setosus, Linognathus vituli, Linognathus ovillus, Linognathus oviformis, Linognathus pedalis, Linognathus stenopsis, Haematopinus asini macrocephalus, Haematopinus eurysternus, Haematopinus suis, Pediculus humanus capitis, Pediculus humanus corporis, Phylloera vastatrix, Phthirus pubis and Solenopotes capillatus.
  • Trimenopon spp. Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp.
  • Specific examples thereof include Bovicola bovis, Bovicola ovis, Bovicola limbata, Damalina bovis, Trichodectes canis, Felicola subrostratus, Bovicola caprae, Lepikentron ovis and Werneckiella equi.
  • Nematocerina and Brachycerina there are Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Odagmia spp., Wilhelmia spp., Hybomitora spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia
  • Tipula spp Specific examples thereof include Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles gambiae, Anopheles maculipennis, Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Fannia canicularis, Sarcophaga carnaria, Stomoxys calcitrans, Tipula paludos, Lucilia cuprina, Lucilia sericata, Simulium reptans, Phlebotomus papatasi, Phlebotomus longipalpis, Odagmia ornata, Wilhelmia equina, Boophthora erythrocephala, Tabanus bromius, Tabanus spodopterus, Tabanus atratus, Tabanus
  • From Siphonaptrida for example, there are Pulex spp., Ctenocephalides spp., Tunga spp., Xenopsylla spp. and Ceratophyllus spp. Specific examples thereof include Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans and Xenopsylla cheopsis.
  • From Heteropterida for example, there are Cimex spp., Triatoma spp., Rhodnius spp. and Panstrongylus spp.
  • From Blattarida for example, there are Blatta orientalis, Periplaneta americana, Blattela germanica and Supella spp. (for example, Supella longipalpa).
  • Argas spp. Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Rhipicephalus (Boophilus) spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Dermanyssus spp., Rhipicephalus spp.
  • Argas persicus Argas reflexus, Ornithodorus moubata, Otobius megnini, Rhipicephalus (Boophilus) microplus, Rhipicephalus (Boophilus) decoloratus, Rhipicephalus (Boophilus) annulatus, Rhipicephalus (Boophilus) calceratus, Hyalomma annatolicum, Hyalomma aegypticum, Hyalomma marginatum, Hyalomma transiens, Rhipicephalus evertsi, Ixodes ricinus, Ixodes hexagonus, Ixodes canisuga, Ixodes pilosus, Ixodes rubicundus, Ixodes scapularis, Ixodes holocyclus, Haemaphysalis concinna, Haemaphysalis punctata, Haemaphysalis cinnabarina, Ha
  • the active compounds of the present invention are also suitable in expelling arthropodal pests, helminthes and protozoa attacking animals (in particular vertebrates).
  • the animals include agricultural domestic animals such as a cow, a sheep, a goat, a horse, a pig, a donkey, a camel, a buffalo, a rabbit, a chicken, a turkey, a duck, a goose, a nursery fish and a honeybee.
  • the term "animals” in this context also include companion animals such as a dog, a cat, a caged bird, an aquarium fish and the like, and animals known as experimental animals such as a hamster, a guinea pig, a rat and a mouse.
  • the term "expelling" used in the present specification with respect to the veterinary field means that the active compounds are effective in reducing occurrence of parasitic organisms in each animal infected by such parasitic organisms to harmless level. More specifically, the term “expelling” used in the present specification means that the active compounds are effective in killing each parasitic pest, inhibiting the growth thereof, or inhibiting the proliferation thereof.
  • the compounds of the present invention can be directly applied in the treatment of animals.
  • the compounds of the present invention are applied as pharmaceutical compositions that may include pharmaceutically acceptable excipients and/or adjuvants known in this field.
  • the active compounds may be prepared as shampoo, an appropriate formulation usable in aerosol, or as an no-pressure spray, for example, a pump spray and aerosol spray.
  • the active compounds of the present invention can be applied directly or after dilution (for example, 100 to 10,000 fold dilution) as a formulation containing 1 % to 80 % by weight amount of the active compounds (for example, powders, wettable powders ("WP”), emulsion, emulsifiable concentrate (“EC”), flowable formulation (flowable), uniform solution and suspendable concentrate (“SC”), or can be used as a chemical bath.
  • WP wettable powders
  • EC emulsion
  • SC uniform solution and suspendable concentrate
  • the active compounds of the present invention may be used in combination with appropriate synergic agents such as acaricides, pesticides, helminthicides or protozoacides, etc., or with other active compounds.
  • appropriate synergic agents such as acaricides, pesticides, helminthicides or protozoacides, etc.
  • other active compounds such as acaricides, pesticides, helminthicides or protozoacides, etc.
  • pesticides substances that have a pesticidal activity for harmful organisms encompassing all of the above are called pesticides.
  • the active compounds of the present invention When used as pesticides, they can be prepared in conventional formulation forms.
  • the formulation form include solution, emulsion, wettable powders, water-dispersible granules, suspension, powders, foam, paste, tablet, granules, aerosol, and natural and synthetic substances to which the active compounds are impregnated, microcapsule, seed coating agents, formulation used with a combustion device (for example, a fumatory and fuming cartridge, can, coil and the like as a combustion device) or ULV (cold mist, warm mist) and the like.
  • a combustion device for example, a fumatory and fuming cartridge, can, coil and the like as a combustion device
  • ULV cold mist, warm mist
  • the formulations can be prepared by mixing the active compounds with a spreading agent, i.e., liquid diluent or carrier, liquefied gas diluent or carrier, or solid diluent or carrier, and optionally with a surfactant, i.e., emulsifier and/or dispersant and/or foaming agent.
  • a spreading agent i.e., liquid diluent or carrier, liquefied gas diluent or carrier, or solid diluent or carrier
  • a surfactant i.e., emulsifier and/or dispersant and/or foaming agent.
  • organic solvents can be also used as auxiliary solvents.
  • liquid diluent or carrier examples include aromatic hydrocarbons (for example, xylene, toluene, alkyl naphthalene), chlorinated aromatic, or chlorinated aliphatic hydrocarbons (for example, chlorobenzene, ethylene chloride or methylene chloride), aliphatic hydrocarbons (for example, cyclohexane), paraffins (for example, mineral oil fraction), alcohols (for example, butanol or glycol, and ethers or esters thereof and the like), ketones (for example, acetone, methylethyl ketone, methylisobutyl ketone, cyclohexanone and the like), strong polar solvents (for example, dimethylformamide, dimethylsulfoxide and the like), water and the like.
  • aromatic hydrocarbons for example, xylene, toluene, alkyl naphthalene
  • chlorinated aromatic for example, chlorobenzene, ethylene chloride or m
  • the liquefied gas diluent or carrier may be gas at normal temperature and pressure such as butane, propane, nitrogen gas, carbon dioxide and aerosol propellents such as halogenated hydrocarbon.
  • solid diluent examples include pulverized natural minerals (kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatom earth and the like), pulverized synthetic minerals (for example, highly dispersed silicic acid, alumina, silicate and the like) and the like.
  • solid carrier for granules examples include pulverized and sieved rocks (for example, calcite, marble, pumice, meerschaum, dolomite and the like), synthetic granules of inorganic and organic powders, particulates of an organic material (for example, sawdust, coconut shells, corn cob and tobacco stalk and the like) and the like.
  • emulsifier and/or the foaming agent examples include non-ionic and anionic emulsifiers (for example, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid alcohol ether (for example, alkylarylpolyglycol ether), alkylsulfonate, alkylsulfate, arylsulfonate and the like), albumin hydrolysate and the like.
  • non-ionic and anionic emulsifiers for example, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid alcohol ether (for example, alkylarylpolyglycol ether), alkylsulfonate, alkylsulfate, arylsulfonate and the like
  • albumin hydrolysate for example, albumin hydrolysate and the like.
  • dispersant examples include lignin-sulfite waste liquor and methyl cellulose.
  • Anchoring agents can be also used in the formulation (powders, granules or emulsion), and examples of the anchoring agents include carboxymethylcellulose, natural and synthetic polymers (for example, gum arabic, polyvinyl alcohol, polyvinyl acetate and the like) and the like.
  • Colorants can be also used, and examples of the colorants include inorganic pigments (for example, iron oxide, titanium oxide, Prussian blue and the like), organic dyes (alizarin dye, azoic dye or metal phthalocyanine dye and the like), and further trace elements such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • inorganic pigments for example, iron oxide, titanium oxide, Prussian blue and the like
  • organic dyes alizarin dye, azoic dye or metal phthalocyanine dye and the like
  • further trace elements such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • the above-described formulations may contain the active ingredients in an amount range of generally 0.1 % to 95 % by weight, preferably 0.5 % to 90 % by weight.
  • the compounds of the present invention may also exist as a mixture with other active compounds, for example, pesticides, poison baits, bactericides, acaricides, nematodacides, fungicides, growth control substances, herbicides and the like in a form of commercially useful formulation and an application form adjusted from the formulation thereof.
  • active compounds for example, pesticides, poison baits, bactericides, acaricides, nematodacides, fungicides, growth control substances, herbicides and the like in a form of commercially useful formulation and an application form adjusted from the formulation thereof.
  • the content of the compounds of the present invention in the commercially useful applicatiion form may vary in a broad range.
  • concentration of the active compounds of the present invention in a practical use may be in a range of, for example, 0.0000001 % to 100 % by weight, preferably 0.00001 % to 1 % by weight.
  • the compounds of the present invention can be used according to any conventional methods suitable for each application form.
  • the compounds of the present invention have stability that is effective for alkaline substances present on lime materials when the compounds are used against hygienic pests and other stored product pests. In addition, they exhibit excellent residual effectiveness in woods and soils.
  • the active compounds of the present invention have low toxicity for warm-blooded animals, and thus can be used safely.
  • Step 3-2 Synthesis of l-(4- ⁇ 3-[3,5-bis(trifluoromethyl)phenyl]-4-chloro-3-(trifluoromethyl)-3,4-di- hydro-2H-pyrrol-5-yl ⁇ -2-bromophenyl)methaneamine
  • Step 4-1 Synthesis of 4- ⁇ 3-[3,5-bis(trifluoromethyl)phenyl]-4-bromo-3-(trifluoromethyl)-3,4-di- hydro-2H-p
  • Step 4-2 Synthesis of 4- ⁇ 3-[3,5-bis(trifluoromethyl)phenyl]-4-bromo-3-(trifluoromethyl)-3,4-di- hydro-2H-p
  • reaction mixture was diluted with tert-butylmethyl ether, and then washed with 2N hydrochloric acid, water and brine.
  • the organic layer was dried over anhydrous magnesium sulfate, filtered, and then concentrated under reduced pressure.
  • the obtained residue was purified with silica-gel column chromatography to obtain the desired product (30 mg).
  • the solvent was distilled under reduced pressure, and the remaining acetic acid was removed by distillation in presence of toluene to obtain 30 g of a crude product.
  • the crude product was recrystallized from hexane to obtain the titled compound in 17.9 g and 85.5 % yield.
  • the mother liquor was distilled under reduced pressure and treated in the same manner to obtain 2.6 g of the titled compound as a second crystal.
  • Step 5-2 Synthesis of methyl (2E)-4,4,4-trifluoro-3-(3,4,5-trichlorophenyl)buta-2-enoate
  • Step 5-4 Synthesis of methyl 5-(3-bromo-4-fluorophenyl)-3-(3,4,5-trichlorophenyl)-3-(trifluoro- methyl)-3,4-dihydro-2H-pyrrol-4-carboxylate
  • Step 6-1 Synthesis of methyl 2-(3-cyano-4-fluorophenyl)-4-(3,4,5-trichlorophenyl)-4-(trifluoro-
  • N-(3-cyano-4-fluorobenzyl)formamide 550 mg, 3.09 mmol
  • N,N-diisopropylethylamine (1.80 g, 13.9 mmol) were stirred with dichloromethane (20 ml) in ice-cold water bath, and the solution of phosphorus oxychloride (710 mg, 4.63 mmol) in dichloromethane (10 ml) was added dropwise thereto. After the complete addition, the reaction mixture was stirred for 0.5 hour, and further stirred for 2 hours at room temperature. The reaction mixture was poured into dichloromethane, and then washed with water, an aqueous solution of sodium hydrogen carbonate and brine.
  • N-(3-bromo-4-fluorobenzyl)formamide (280 mg, 1.21 mmol), and N,N-diisopropylethylamine (702 mg, 5.43 mmol) were stirred in dichloromethane (10 ml) under ice-cooling.
  • test solutions were prepared as described below unless otherwise mentioned.
  • Emulsifier 1 part by weight of Polyoxyethylene alkylphenyl ether To prepare a suitable concoction of the active compound, 1 part by weight of the active compound was mixed with the above amount of the solvent containing the above amount of the emulsifier, and the resulting mixture was diluted with water to a predetermined concentration.
  • Biological test example 1 Test on Spodoptera litura larvae Leaves of sweet potato were immersed in the test solution at the appropriate concentration, and the leaves were dried in air. The leaves were then placed in a petri dish having a diameter of 9 cm, and ten Spodoptera litura at third instar larvae were released therein. The petri dishes were placed in a temperature-controlled chamber at 25 °C. After 2 days and 4 days more sweet potato leaves were added. After 7 days, the number of dead larvae was counted to calculate the insecticidal activity. An insecticidal activity of 100 % means that all larvae were killed, whereas an insecticidal activity of 0 % means that no larva was killed. In the current test, the results of two petri dishes for each treatment were averaged.
  • the compound Nos. 5-2, 5-3, 5-4, 5-6, 6-2, 6-3, 6-4, 7-1 , 7-2, 7-3, 7-4, 7-5, 7-6 and 7-7 showed an insecticidal activity of 100 % at an active compound concentration of 100 ppm.
  • Biological test example 2 Test on Tetranychus urticae 50 to 100 adult mites of Tetranychus urticae were inoculated to leaves of kidney bean at two-leaf stage planted in a pot of 6 cm in diameter. After one day, test solution at the appropriate concentration was sprayed thereon in a sufficient amount using a spray gun. After the spraying, the plant pot was placed inside a greenhouse, and after 7 days, the acaricidal activity was calculated. An acaricidal activity of 100 % means that all mites were killed, whereas an acaricidal activity of 0 % means that no mite was killed.
  • the compound Nos. 5-2, 5-3, 5-6, 6-4, 7-1 , 7-2, 7-3, 7-4, 7-5, 7-6 and 7-7 showed an acaricidal activity of 100 % at an active compound concentration of 100 ppm.
  • Leaves of cucumber were immersed in the test solution at the appropriate concentration, and the leaves were dried in air. The leaves were then put in a plastic cup containing sterilized black soil and five Aulacophora femoralis at second instar larvae were released in the cup. The cups were placed in a temperature-controlled chamber at 25 °C. After 7 days, the number of dead larvae was counted, and thus the insecticidal activity was calculated. An insecticidal activity of 100 % means that all larvae were killed, whereas an insecticidal activity of 0 % means that no larva was killed.
  • the compound Nos. 5-2, 5-3, 5-6, 6-4, 7-1 , 7-2, 7-3, 7-4, 7-5, 7-6 and 7-7 showed an insecticidal activity of 100 % at an active compound concentration of 100 ppm.
  • active compound 10 mg are dissolved in 0.5 ml solvent, and the concentrate is diluted with cattle blood to the desired concentration.
  • Approximately 20 adult unfed (Ctenocepahlides felis) are placed in flea chambers.
  • the blood chamber, sealed with parafilm on the bottom, are filled with cattle blood supplied with compound solution and placed on top of the flea chamber, so that the fleas are able to suck the blood.
  • the blood chamber is heated to 37 °C whereas the flea chamber is kept at room temperature. After 2 days mortality in % is determined. 100 % means that all the fleas have been killed; 0 % means that none of the fleas have been killed.
  • Biological test example 6 Test on Musca domestica Solvent: Dimethyl sulfoxide To produce a suitable preparation of active compound, 10 mg of active compound are dissolved in 0.5 ml solvent, and the concentrate is diluted with water to the desired concentration. Prior to the assay, a piece of kitchen sponge is soaked with a mixture of sugar and compound solution and placed into a container. 10 adults (Musca domestica) are placed into the container and closed with a perforated lid. After 2 days mortality in % is determined. 100 % means that all the flies have been killed; 0 % means that none of the flies have been killed.
  • active compound 10 mg of active compound are dissolved in 0.5 ml solvent, and the concentrate is diluted with water to the desired concentration.
  • Eight to ten adult engorged female Boophilus microplus ticks are placed in perforated plastic beakers and immersed in aqueous compound solution for one minute. Ticks are transferred to a filter paper in a plastic tray. Egg deposition of fertile eggs is monitored after. After 7 days mortality in % is determined. 100 % means that all the ticks have been killed; 0 % means that none of the ticks have been killed.
  • active compound 10 mg of active compound are dissolved in 0.5 ml solvent, and the concentrate is diluted with solvent to the desired concentration.
  • Five adult engorged female ticks (Boophilus microplus) are injected with 1 ⁇ compound solution into the abdomen. Ticks are transferred into replica plates and incubated in a climate chamber for a period of time. Egg deposition of fertile eggs is monitored. After 7 days, mortality in % is determined. 100 % means that all eggs are infertile; 0 % means that all eggs are fertile.
  • active compound 10 mg of active compound are dissolved in 0.5 ml solvent, and the concentrate is diluted with water to the desired concentration.
  • Nymphs of the tick Amblyomma hebraeum are placed in perforated plastic beakers and immersed in aqueous compound solution for one minute. Ticks are transferred to a filter paper in a petridish and incubated in a climate chamber for 42 days. After 42 days, mortality in % is determined. 100 % means that all the ticks have been killed; 0 % means that none of the ticks have been killed.

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  • Pyrrole Compounds (AREA)

Abstract

Pyrroline derivatives represented by Formula (I) below and the use thereof as pesticide and animal parasite-controling agent. wherein each substituent is as defined in the specification.

Description

Pesticidal pyrroline derivatives
The present invention relates to novel pesticidal pyrroline derivatives and the use thereof as pesticides.
Patent Documents 1 to 5 describe that pesticidal pyrroline compounds are useful as pest controlling agents. However, they have not described the pesticidal pyrroline derivatives of the present invention. (Patent Document 1= WO2009/022746, Patent Document 2 = WO2009/072621, Patent Document 3 = WO2009/097992, Patent Document 4 = WO2009/1 12275, Patent Document 5 = WO2010/020521).
Inventors of the present invention extensively studied to develop novel compounds which are highly active as pesticides and have a broad spectrum use. As a result, the inventors have found this time novel pyrroline derivatives that show a wide spectrum with high activity, and further are quickly degraded in nature to be highly safe to the environment.
Thus, the invention is directe e following Formula (I):
Figure imgf000002_0001
wherein, the chemical moiety represented by the followin
stands for the following chemical moiety (a):
Figure imgf000002_0003
wherein R1 and R2 are as defined below, or
stands for one of the foll onal isomers:
Figure imgf000002_0004
wherein R2 is as defined below, preferably is hydroxy-carbonyl, Ci.n-alkoxy-carbonyl or cyano; or mixtures of the positional isomers; T is selecte
(T-4)
B represents N or C-X3;
X1, X2, X3, X4 and X5 each independently represent hydrogen, halogen, C1 2 alkyl, Ci.n haloalkyl, nitro, Ci-12 alkoxy, CM2 haloalkoxy, cyano, Cu2 alkylsulfenyl, Cu2 alkylsulfinyl, Cu2 alkylsulfonyl, Cu2 haloalkylsulfenyl, C1.12 haloalkylsulfinyl, C1 2 haloalkylsulfonyl, hydroxy, mercapto, amino, C1.12 acylamino, C1 2 alkoxy-carbonylamino, C1.12 haloalkoxy-carbonylamino, C1 2 alkoxy-imino, C1.12 haloalkoxy- imino, C1 2 alkylsulfonylamino or sulfur pentafluoride;
Y1, Y2, Y3, Y4 and Y5 each independently represent hydrogen, halogen, C1 2 alkyl, Ci.n haloalkyl, nitro, C3.8 cycloalkyl, C3.8 cyclohaloalkyl, C1 2 alkoxy, C1 2 haloalkoxy, cyano, C1 2 alkylsulfenyl, C1.12 alkylsulfinyl, C1 2 alkylsulfonyl, C1.12 haloalkylsulfenyl, C1 2 haloalkylsulfinyl, C1 2 haloalkylsulfonyl, Ci-12 alkylsulfonyloxy, C1 2 alkylaminosulfonyl, C1 2 haloalkylaminosulfonyl, di(Ci_i2 alkyl)aminosulfonyl, di(Ci_i2 haloalkyl)aminosulfonyl, hydroxy, mercapto, amino, C1 2 alkylamino, di(Ci_i2 alkyl)amino, C1 2 acylamino, C1 2 alkoxy-carbonylamino, C1 2 haloalkoxy-carbonylamino, C1 2 alkylsulfonylamino, C1 2 haloalkylsulfonylamino, tri(Ci_i2 alkyl)silyl, C1 2 alkoxy-imino, C1 2 haloalkoxy-imino, C1.12 alkoxy-imino-Ci.12 alkyl, C1 2 haloalkoxy-imino-Ci.12 alkyl, C1.12 alkylsulfinylimino, C1.12 alkylsulfinylimino-Ci.12 alkyl, C1 2 alkylsulfinylimino-Ci.12 alkyl-carbonyl, C1 2 alkylsulfoximino, C1 2 alkylsulfoximino-Ci.12 alkyl, C1 2 alkoxy-carbonyl, C1 2 alkyl-carbonyl, aminocarbonyl, C1 2 alkyl-aminocarbonyl, amino-thiocarbonyl, C1.12 alkylamino-thiocarbonyl, di(Ci_i2 alkyl)amino-carbonyl, di(Ci_i2 alkyl)amino-thiocarbonyl or hydroxycarbonyl;
G represents any one of the following formulae Gl to G9:
Figure imgf000004_0001
Figure imgf000004_0002
G5 G6 G7
G8 G9
Z represents hydrogen, C1 2 haloalkyl, nitro, C1.12 alkoxy, cyano, C1 2 haloalkoxy, C1.12 alkylsulfenyl, Ci-12 alkylsulfinyl, C1.12 alkylsulfonyl, C1 2 haloalkylsulfenyl, C1.12 haloalkylsulfinyl, C1.12 haloalkylsulfonyl, hydroxy or thiol; k represents 0, 1, 2, 3 or 4;
R represents C1.12 alkyl or C1 2 haloalkyl;
R1 and R2 are absent, or each independently represent hydrogen, halogen, cyano, amino, azido, hydroxy, mercapto, hydroxy-carbonyl, C1.12 alkylamino-carbonyl, C1 2 alkoxy-carbonyl, C1 2 alkoxy, C1 2 alkyl, C2-12 alkenyl, C2-12 alkynyl, C1 2 alkylthio, C1 2 alkylsulfinyl or C1 2 alkylsulfonyl, provided that R1 and R2 are not simultaneously absent, and provided that R1 and R2 are not simultaneously hydrogen;
R3 represents hydrogen, amino, hydroxy, cyano, R8-CH2-, R8-CO-, R8-CS-, C1 2 alkyl, C1 2 haloalkyl, Ci-12 alkoxy, C1 2 haloalkoxy, C2-12 alkenyl, C2-12 alkynyl, C1.12 alkyl-carbonyl or C1.12 alkyl-carbonylamino, R4 represents hydrogen, cyano, carbonyl, thiocarbonyl, R8-CO-, R8-CS-, C1 2 alkyl-carbonyl, C1 2 alkyl-thiocarbonyl, C1 2 haloalkyl-carbonyl, C1 2 haloalkyl-thiocarbonyl, C1 2 alkylamino-carbonyl, Ci-12 alkylamino-thiocarbonyl, di(Ci_i2 alkyl)amino-carbonyl, di(Ci_i2 alkyl)amino-thiocarbonyl, C1.12 alkoxyamino-carbonyl, C1 2 alkoxyamino-thiocarbonyl, C1 2 alkoxy-carbonyl, C1 2 alkoxy-thiocarbonyl, Ci_i2thioalkoxy-carbonyl,
Figure imgf000004_0003
thioalkoxy-thiocarbonyl, C1 2 alkylsulfonyl, C1 2 haloalkylsulfonyl, C3.8 cycloalkyl-carbonyl, C2-12 alkenyl-carbonyl, C2-12 alkynyl-carbonyl, C3.8 cycloalkyl-Ci.12 alkyl-carbonyl, Ci-12 alkylsulfenyl-Ci.12 alkyl-carbonyl, C1.12 alkylsulfinyl-Ci.12 alkyl-carbonyl, C1 2 alkylsulfonyl-Ci.12 alkyl-carbonyl, C1 2 alkyl-carbonyl-Ci.12 alkyl-carbonyl, C3.8 cycloalkylamino-carbonyl, C2-12 alkenylamino-carbonyl or C2-12 alkynylamino-carbonyl, or
R3 and R4 may form a 3-, 4-, 5- or 6-membered, saturated or unsaturated heterocyclic ring together with the nitrogen atom to which they are bound, wherein the heterocyclic ring may be substituted with oxo, thioxo or nitro;
R5 represents hydrogen, cyano, C1.12 alkyl or C1 2 haloalkyl; R6 represents hydrogen, Cu2 alkyl,
Figure imgf000005_0001
alkylcarbonyl or Ci.n alkoxycarbonyl; R7 represents hydrogen or Cu2 alkyl;
R8 represents phenyl or a 3-, 4-, 5- or 6-membered, saturated or unsaturated heterocyclic ring;
Z1, Z2 and Z3 each independently represent -C(R9)(R10)-, -C(=0)-, -C(=N-ORu)-, -N(RU)-, -S-, -S(=0)-, -S(=0)2- or -S(0)(=N-Ru)-;
R9 and R10 each independently represent hydrogen, halogen, Cu2 alkyl or C1.12 haloalkyl;
R11 represents hydrogen, cyano, nitro, C1.12 alkyl, C1 2 haloalkyl, C3.8 cycloalkyl-Ci.12 alkyl, C1.12 alkyl-carbonyl, C1 2 haloalkyl-carbonyl, C1 2 alkoxy-carbonyl, C1.12 haloalkoxy-carbonyl, C1 2 alkylsulfonyl, haloalkylsulfonyl, aryl-Ci.12 alkyl, the aryl moiety of which may be substituted with 1, 2 or 3 times the group R12, or heterocyclic ring-Ci.12 alkyl, the heterocyclic ring moiety of which may be substituted with 1 , 2 or 3 times the group R12;
R12 represents hydrogen, halogen, cyano, nitro, C1 2 alkyl, C1 2 haloalkyl, Ci.n alkoxy, Ci.n haloalkoxy or Ci-12 alkoxy-carbonyl; m represents 1 or 2; whereas the groups defined above may be further substituted with at least one substituent selected from halogen, C1.12 alkyl, C1 2 haloalkyl, nitro,
Figure imgf000005_0002
alkoxy, cyano, Ci.n haloalkoxy, C1 2 alkylsulfenyl, C1.12 alkylsulfinyl, C1 2 alkylsulfonyl, C1.12 haloalkylsulfenyl, C1 2 haloalkylsulfinyl, C1 2 haloalkylsulfonyl, hydroxy and mercapto.
Preferred are compounds of Formula (I) wherein T represents
Figure imgf000005_0003
(T-1 ) (T-2) (T-3)
Figure imgf000006_0001
(T-4) (Τ-5) .
Β represents Ν or C-X3;
X1, X2, X3, X4 and X5 each independently represent hydrogen, halogen, Ci_6 alkyl,
Figure imgf000006_0002
nitro, Ci_6 alkoxy, Ci_6 haloalkoxy, cyano, Ci_6 alkylsulfenyl, Ci_6 alkylsulfinyl, Ci_6 alkylsulfonyl, Ci_6 haloalkylsulfenyl, Ci_6 haloalkylsulfinyl, Ci_6 haloalkylsulfonyl, hydroxy, mercapto, amino, Ci_6 acylamino, Ci_6 alkoxy-carbonylamino, Ci_6 haloalkoxy-carbonylamino, Ci_6 alkoxy- imino, Ci_6 haloalkoxy- imino, alkylsulfonylamino or sulfur pentafluoride;
Y1, Y2, Y3, Y4 and Y5 each independently represent hydrogen, halogen, Ci_6 alkyl,
Figure imgf000006_0004
nitro, C3.7 cycloalkyl, C3.7 cyclohaloalkyl, Ci_6 alkoxy, Ci_6 haloalkoxy, cyano, Ci_6 alkylsulfenyl, Ci_6 alkylsulfinyl, Ci_6 alkylsulfonyl, Ci_6 haloalkylsulfenyl, Ci_6 haloalkylsulfinyl, Ci_6 haloalkylsulfonyl, Ci_6 alkylsulfonyloxy, Ci_6 alkylaminosulfonyl, Ci_6 haloalkylaminosulfonyl, di(Ci_6 alkyl)aminosulfonyl, di(Ci_6 haloalkyl)aminosulfonyl, hydroxy, mercapto, amino, Ci_6 alkylamino, di(Ci_6 alkyl)amino, Ci_6 acylamino, Ci_6 alkoxy-carbonylamino, Ci_6 haloalkoxy-carbonylamino, Ci_6 alkylsulfonylamino, Ci_6 haloalkylsulfonylamino, tri(Ci_6 alkyl)silyl, Ci_6 alkoxy- imino, Ci_6 haloalkoxy- imino, Ci_6 alkoxy- imino-Ci_6 alkyl, Ci_6 haloalkoxy- imino-Ci.6 alkyl, Ci_6 alkylsulfinylimino, Ci_6 alkylsulfinylimino-Ci.6 alkyl, Ci_6 alkylsulfinylimino-Ci_6 alkyl-carbonyl, Ci_6 alkylsulfoximino, Ci_6 alkylsulfoximino-Ci.6 alkyl, Ci_6 alkoxy-carbonyl, Ci_6 alkyl-carbonyl, aminocarbonyl, Ci_6 alkyl-aminocarbonyl, amino-thiocarbonyl, Ci_6 alkylamino-thiocarbonyl, di(Ci_6 alkyl)amino-carbonyl, di(Ci_6 alkyl)amino-thiocarbonyl or hydroxycarbonyl; G represe
Figure imgf000006_0005
G5 G6 G7 G8 G9
Z represents hydrogen,
Figure imgf000006_0006
haloalkyl, nitro, Ci_6 alkoxy, cyano, Ci_6 haloalkoxy, Ci_6 alkylsulfenyl, Ci_6 alkylsulfinyl, Ci_6 alkylsulfonyl, Ci_6 haloalkylsulfenyl, Ci_6 haloalkylsulfinyl, Ci_6 haloalkylsulfonyl, hydroxy or thiol; k represents 0, 1, 2, 3 or 4; R represents Ci_6 alkyl or
Figure imgf000007_0001
R1 and R2 are absent, or each independently represent hydrogen, halogen, cyano, amino, azido, hydroxy, mercapto, hydroxy-carbonyl, Ci_6 alkylamino-carbonyl, lkoxy-carbonyl, alkoxy, Ci_6 alkyl, C2-6 alkenyl, C2_6 alkynyl,
Figure imgf000007_0002
alkylthio, alkylsulfinyl or alkylsulfonyl, provided that R1 and R2 are not simultaneously absent, and provided that R1 and R2 are not simultaneously hydrogen;
R3 represents hydrogen, amino, hydroxy, cyano, R8-CH2-, R8-CO-, R8-CS-, Ci_6 alkyl, Ci_6 haloalkyl, Ci_6 alkoxy,
Figure imgf000007_0003
C2-6 alkenyl, C2_6 alkynyl, Ci_6 alkyl-carbonyl or alkyl-carbonylamino, R4 represents hydrogen, cyano, carbonyl, thiocarbonyl, R8-CO-, R8-CS-, Ci_6 alkyl-carbonyl, Ci_6 alkyl-thiocarbonyl, Ci_6 haloalkyl-carbonyl, Ci_6 haloalkyl-thiocarbonyl, Ci_6 alkylamino-carbonyl, Ci_6 alkylamino-thiocarbonyl, di(Ci_6 alkyl)amino-carbonyl, di(Ci_6 alkyl)amino-thiocarbonyl, Ci_6 alkoxyamino-carbonyl, Ci_6 alkoxyamino-thiocarbonyl, Ci_6 alkoxy-carbonyl, Ci_6 alkoxy-thiocarbonyl, Ci_6 thioalkoxy-carbonyl, Ci_6 thioalkoxy-thiocarbonyl, Ci_6 alkylsulfonyl, Ci_6 haloalkylsulfonyl, C3.7 cycloalkyl-carbonyl, C2-6 alkenyl-carbonyl, C2-6 alkynyl-carbonyl, C3.7 cycloalkyl-Ci_6 alkyl-carbonyl, Ci-6 alkylsulfenyl-Ci.6 alkyl-carbonyl, Ci_6 alkylsulfinyl-Ci.6 alkyl-carbonyl, Ci_6 alkylsulfonyl-Ci.6 alkyl-carbonyl, Ci_6 alkyl-carbonyl-Ci_6 alkyl-carbonyl, C3.7 cycloalkylamino-carbonyl, C2-6 alkenylamino-carbonyl or C2-6 alkynylamino-carbonyl, or
R3 and R4 may form a 3-, 4-, 5- or 6-membered, saturated or unsaturated heterocyclic ring together with the nitrogen atom to which they are bonded, wherein the heterocyclic ring may be substituted with oxo, thioxo or nitro;
R5 represents hydrogen, cyano,
Figure imgf000007_0004
R6 represents hydrogen,
Figure imgf000007_0005
alkylcarbonyl or alkoxycarbonyl;
R7 represents hydrogen or Ci_6 alkyl; R8 represents phenyl or a 3-, 4-, 5- or 6-membered, saturated or unsaturated heterocyclic ring;
Z1, Z2 and Z3 each independently represent -C(R9)(R10)-, -C(=0)-, -C(=N-ORu)-, -N(RU)-, -S-, -S(=0)-, -S(=0)2- or -S(0)(=N-Ru)-;
R9 and R10 each independently represent hydrogen, halogen, Ci_6 alkyl or
Figure imgf000007_0006
R11 represents hydrogen, cyano, nitro, Ci_6 alkyl, Ci_6 haloalkyl, C3.7 cycloalkyl-Ci.6 alkyl, Ci_6 alkyl-carb onyl, C e haloalkyl-carbonyl, C e alkoxy-carbonyl, C e haloalkoxy-carbonyl, C e alkylsulfonyl,
Figure imgf000008_0001
aryl-Ci_6 alkyl, the aryl moiety of which may be substituted with 1 , 2 or 3 times the group R12, or heterocyclic ring-Ci.6 alkyl, the heterocyclic ring moiety of which may be substituted with 1 , 2 or 3 times the group R12; R12 represents hydrogen, halogen, cyano, nitro, Ci_6 alkyl,
Figure imgf000008_0002
or Ci-6 alkoxy-carbonyl; m represents 1 or 2; and the groups defined above may be further substituted with at least one substituent selected from halogen, Ci_6 alkyl,
Figure imgf000008_0003
haloalkyl, nitro, alkoxy, cyano, haloalkoxy, Ci_6 alkylsulfenyl, alkylsulfinyl, Ci_6 alkylsulfonyl, Ci_6 haloalkylsulfenyl, Ci_6 haloalkylsulfinyl, Ci_6 haloalkylsulfonyl, hydroxy and mercapto.
The novel pyrroline derivatives are preferably those given in the following embodiments , and such embodiments should be understood in any case as subgroups of the compounds represented by Formula (I) described above. [Embodiment 1 ] : Compounds of Formula (Γ):
Figure imgf000008_0004
wherein X1, X2, X4, X5, R, B and T have the same definition as described above, respectively, and Hal represents fluorine, chlorine, bromine or iodine.
[Embodiment 2] : Compounds of Formu -Ia):
Figure imgf000008_0005
wherein X1, X2, X4, X5, R, B and T have the same definition as described above, respectively and R represents hydrogen or Ci_6 alkyl.
[Embodiment 3] : Compounds of Formula (I-b):
Figure imgf000009_0001
wherein X1, X2, X4, X5, R, B and T have the same definition as described above, respectively and R represents hydrogen or Ci_6 alkyl.
[Embodiment 4] Compounds of Formulae (I), (Γ), (I-Ia) or (I-b), wherein
T is a group Tl , wherein Y2 or Y3 is cyano and wherein G is G4, G5 or G6, and wherein all other substituents and groups are as defined before for Formula (I).
[Embodiment 5] Compounds of Formulae (I), (Γ), (I-Ia) or (I-b), wherein
T is a group T2, wherein Y2 or Y3 is cyano and wherein G is G4, G5 or G6, and wherein all other substituents and groups are as defined before for Formula (I). If not defined otherwise, the term "alkyl" in the present specification represents linear or branched Ci_i2 alkyl such as methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl, preferably Ci_6 alkyl, and more preferably CM alkyl. In addition, for each alkyl moiety included in each group that has the alkyl as a constituent, those which are the same as "alkyl" described above can be exemplified. If not defined otherwise, the term "haloalkyl" represents, for example, CH2F, CHF2, CF3, CF2C1, CFCI2, CF2Br, CF2CF3, CFHCF3, CH2CF3, CFC1CF3, CC12CF3, CF2CH3, CF2CH2F, CF2CHF2, CF2CF2C1, CF2CF2Br, CFHCH3, CFHCHF2, CFHCHF2, CHFCF3, CHFCF2C1, CHFCF2Br, CFC1CF3, CC12CF3, CF2CF2CF3, CH2CF2CF3, CF2CH2CF3, CF2CF2CH3, CHFCF2CF3, CF2CHFCF3, CF2CF2CHF2, CF2CF2CH2F, CF2CF2CF2C1, CF2CF2CF2Br, CH(CF3)CF3, CF(CF3)CF3, CF(CF3)CF2Br, CF2CF2CF2CF3, CH(CF3)CF2CF3 or CF(CF3)CF2CF3, and represents a carbon chain in which at least one hydrogen on linear or branched Ci_i2 alkyl, preferably Ci_6 alkyl, more preferably CM alkyl is replaced by halogen, and also includes perfluoroalkyl in which all of the replaceable hydrogens on the alkyl are replaced by fluorine. The haloalkyl may be further substituted with any substituent.
If not defined otherwise, the term "alkoxy" represents, for example, methoxy, ethoxy, n-propoxy, i-propoxy, n-, iso-, sec- or tert-butoxy, pentyloxy or hexyloxy, and represents linear or branched Ci_i2, preferably Ci_6, and more preferably CM alkoxy. The alkoxy may be further substituted with any substituent.
If not defined otherwise, the term "halogen" and each halogen moiety included in each halogen-substituted group represent fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.
If not defined otherwise, the term "cycloalkyl" represents C3.8 cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, and preferably represents C3.7 cycloalkyl, more preferably C3.6 cycloalkyl. In addition, for each cycloalkyl moiety included in each group that has the cycloalkyl as a constituent, those which are the same as "cycloalkyl" described above can be exemplified.
If not defined otherwise, the term "cyclohaloalkyl" represents, for example, fluorocyclopropyl, chlorocyclopropyl, difluorocyclopropyl, dichlorocyclopropyl or undecafluorocyclohexyl.
If not defined otherwise, the term "alkenyl" represents C2-12 alkenyl, preferably C2-6 alkenyl such as vinyl, allyl, 1-propenyl, 1- (or 2-, or 3-) butenyl and 1-pentenyl, more preferably C2-5 alkenyl, and further preferably C2-4 alkenyl.
If not defined otherwise, the term "alkynyl" represents C2-12 alkynyl, preferably C2-6 alkynyl such as ethynyl, propargyl, 1-propynyl, butan-3-ynyl and pentan-4-ynyl, more preferably C2-5 alkynyl, and further preferably C2-4 alkynyl. If not defined otherwise, the term "aryl" represents a C&n aromatic hydrocarbon group, for example, phenyl, naphthyl, biphenyl, preferably a Ce-io aromatic hydrocarbon group, more preferably a Ce aromatic hydrocarbon group, phenyl.
If not defined otherwise, the term "heterocyclic ring" may represent a 5-membered or 6-membered heterocyclic group containing at least one N, O or S as a heteroatom, or the ring may represent a fused heterocyclic group that may be benzo-fused, and further the carbon atom on the ring may be substituted with oxo or thioxo.
Specific examples of the heterocyclic ring include pyrrolidinyl, piperidinyl, morpholinyl and thiomorpholinyl (examples of those saturated), dihydropyrrolyl, dihydroisoxazolyl, dihydropyrazolyl, dihydroxazolyl and dihydrothiazolyl (examples of those partially saturated), furyl, thienyl, pyrrolyl, isoxazolyl, pyrazolyl, oxazolyl, isothiazolyl, thiazolyl, imidazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, benzoxazolyl, benzothiazolyl, quinolyl and the like, wherein the heterocyclic ring may be substituted with any substituent.
If not defined otherwise, the substituent in the expression of "may be substituted with any substituent" represents, for example, amino, hydroxy, oxo, thioxo, halogen, nitro, cyano, isocyano, mercapto, isothiocyanate, carboxy, carbamide, SF5, aminosulfonyl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, monoalkylamino, dialkylamino, N-alkylcarbonyl-amino, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, cycloalkenyloxy, alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, aryloxycarbonyl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, arylcarbonyl, alkylthio, cycloalkylthio, alkenylthio, cycloalkenylthio, alkynylthio, alkylsulfenyl, alkylsulfinyl, alkylsulfinyl including the isomers, alkylsulfonyl, monoalkylammosulfonyl, dialkylaminosulfonyl, alkylphosphinyl, alkylphosphonyl, alkylphosphinyl including the isomers, alkylphosphonyl including the isomers, N-alkyl-aminocarbonyl, Ν,Ν-dialkyl-aminocarbonyl, N-alkylcarbonyl-aminocarbonyl, N-alkyl- carbonyl-N-alkylaminocarbonyl, aryl, aryloxy, benzyl, benzyloxy, benzylthio, arylthio, arylamino, benzylamino, heterocyclic ring, trialkylsilyl, alkoxyalkyl, alkylthioalkyl, alkylthioalkoxy, alkoxyalkoxy, phenethyl, benzyloxy, haloalkyl, haloalkoxy, haloalkylthio, haloalkylcarbonyl, haloalkoxycarbonyl, haloalkoxyalkoxy, haloalkoxyalkylthio, haloalkoxyalkylcarbonyl or haloalkoxyalkyl, and preferably represents chloro, fluoro, bromo, iodo, amino, nitro, cyano, hydroxy, thio or carboxy.
If not expressly mentioned otherwise, the terms "combating", "controlling" or "expelling" are used synonymously refers to the biological capability of the active compound which results in the killing, in the inhibition of the growth, or in the inhibition of the proliferation of the targeted organism.
The compounds of Formulae (I), (Γ), (I-Ia) or (I-b) of the present invention can be obtained by, for example, the preparation methods (a), (b) or (c) described below.
Preparation method (a):
A method in which the comp
Figure imgf000011_0001
wherein X1, X2, X4, X5, R, B and T are defined herein, are reacted with a halogenating agent in the presence of a suitable diluent if necessary.
Preparation method (b) for the preparation of compounds of Formula (I), wherein R2 represents hydroxy-carbonyl or
Figure imgf000011_0002
alkoxy-carbonyl Step (b-1): A method in which the compounds represented by Formula (III):
Figure imgf000012_0001
wherein X1, X2, X4, X5, B, R and R20 are as defined herein, are reacted with the compounds represented by Formula (IV):
Figure imgf000012_0002
wherein T is as described above, in the presence of a suitable diluent and/or copper reagent if necessary, whereby obtaining the comp
Figure imgf000012_0003
wherein X1, X2, X4, X5, R, B, T and R20 are as defined herein, Step (b-2):
Subsequently shifting the position of the double bond on the pyrroline ring in the presence of a suitable diluent and/or base if necessary, whereby obtaining the compounds encompassed by Formula (I) of the present
Figure imgf000012_0004
wherein X1, X2, X4, X5, R, B, T and R20 are as defined herein.
Preparation method (c) for the preparation of compounds of Formula (I), wherein
R represents hydroxy-carbonyl or Ci_6 alkoxy-carbonyl and T represents T-l :
A method in which the compounds represented by Formulae (I-IIa) and (I-IIb)
Figure imgf000013_0001
wherein X1, X2, X4, X5, Y1, Y2, Y3, Y4, R, B and R20 are as defined herein or a mixture of compounds (I-IIa) and (I-IIb),
or are reacted with the compounds represented by the following formula:
H-G
wherein H represents hydrogen and G represents any one of Gl to G9 as described above, in the presence of a suitable diluent and/or suitable base if necessary.
The preparation method (a) may be conducted according to conventional organic synthesis.
The halogenating agent in the preparation method (a) includes, for example, chlorine, bromine, iodine, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, l,3-dichloro-5,5-hydantoin, l,3-dibromo-5,5-dimethylhydantoin, benzyltrimethylammonium tetrachloroiodinate, sodium hypochlorite and the like.
The reaction of the preparation method (a) may be performed in a suitable diluent and examples of the diluent used at this time include aliphatic hydrocarbons (hexane, cyclohexane, heptane, and the like), aliphatic halogenated hydrocarbons (dichloromethane, chloroform, carbon tetrachloride, dichloroethane, and the like), aromatic hydrocarbons (benzene, toluene, xylene, chlorobenzene, and the like), ethers (diethyl ether, dibutyl ether, dimethoxyethane (DME), tetrahydrofuran, dioxane, and the like), esters (ethyl acetate, ethyl propionate, and the like) , acid amides (dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, and the like), nitriles (acetonitrile, propionitrile, and the like), dimethylsulfoxide (DMSO), water, or a mixed solvent thereof and the like.
The preparation method (a) may be performed in a substantially wide temperature range. Generally, the preparation method (a) may be performed at about -78 °C to about 200 °C, preferably at about -10 °C to about 100 °C. In addition, the reaction is desirably conducted at normal pressures, but may be also handled under elevated or reduced pressure. The reaction time is 0.1 to 72 hours, preferably 1 to 24 hours.
In performing the preparation method (a), for example, 1 mole of the compound of Formula (II) is reacted with 1 mole to 2 moles of the halogenating agent in a diluent, for example, carbon tetrachloride, whereby obtaining the corresponding compound of Formula (I). Representative examples of known compounds of Formula (II), which are starting materials in the preparation method (a), are exemplified with the reference documents respectively below:
When (T) is (T-l) in the compounds of Formula (I), 5-[3-(3,5-dichlorophenyl)-3-(trifluoro- methyl)-3,4-dihydro-2H-pyrrol-5-yl]-2-(lH-l,2,4-triazol-l-yl)benzonitrile, 2-(lH-l,2,4-tri- azol-l-yl)-5-[3-(3,4,5 richlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]benzonitrile, 5 - { 3 - [3 , 5 -bis(trifluoromethyl)phenyl] -3
ol-l-yl)benzonitrile, 5- {3-[3,4-dichloro-5-(trifluoromethyl)phenyl]-3-(trifluoromethyl)-3,4-dihydro-2H- pyrrol-5-yl}-2-(lH-l,2,4-triazol-l-yl)benzonitrile, 5- {3-[3-fluoro-5-(trifluoromethyl)phenyl]-3-(tri- fluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl} -2-(lH-l,2,4-triazol-l -yl)benzonitrile, 5-[3-(2,6-dichloro- pyridin-4-yl)-3-(trifluoromethyl)-3,4-dihydro-2
5- {3-[2-chloro-6-(trifluoromethyl)pyridin-4-yl]-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl} -2-(lH- l,2,4-triazol-l-yl)benzonitrile, 5- {3-[2,6-bis(trifluoromethyl)pyridin-4-yl]-3-(trifluoromethyl)-3,4-di- hydro-2H-pyrrol-5-yl}-2-(lH-l,2,4-triazol-l-yl)benzonitrile and l-(4- {3-[2,6-bis(trifluoromethyl)pyri- din-4-yl]-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl}-2-cyanophenyl)-lH-pyrazol-4-carbonitrile (Reference Document: WO2009/097992).
W h e n ( T ) i s ( T-2) in the compounds of Formula (I), N- {2-chlo- ro-4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]benzyl}propanamide, N- {2-chloro-4-[3-(3,4,5 richlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]benzyl}propan amide, N- {2-bromo-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyr- rol-5-yl]benzyl} acetamide, N- {2-bromo-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-di- hydro-2H-pyrrol-5-yl]benzyl}propanamide, N- {2-bromo-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoro- methyl)-3,4-dihydro-2H-pyrrol-5-yl]benzyl}cyclopropanecarboxamide, N- {2-bromo-4-[3-(3,4,5-tri- chlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]benzyl}-2-(methylsulfanyl)acetamide, N- {2-bromo-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]benzyl} -2-(me thylsulfinyl)acetamide, N- {2-bromo-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-di- hydro-2H-pyrrol-5-yl]benzyl}-2-(methylsulfonyl)acetamide, N- {4-[3-(3,4,5-trichloro- phenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]-2-(trifluoromethyl)benzyl}propanamide, N- {2-methyl-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]benzyl}propa namide, N- {2-nitro-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]ben- zyljpropanamide, N- {2-cyano-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyr- rol-5-yl]benzyl}propanamide, N-(2-bromo-4- {3-[3,4-dichloro-5-(trifluoromethyl)phenyl]-3-(trifluoro- methyl)-3,4-dihydro-2H-pyrrol-5-yl}benzyl)propanamide, N-(2-bromo-4- {3-[3-fluoro-5-(trifluoro- methyl)phenyl]-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl}benzyl)propanamide,
N-(4- {3-[3,5-bis(trifluoromethyl)phenyl]-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl}-2-bromobenz yl)propanamide, N-(4- {3-[2,6-bis(trifluoromethyl)pyridin-4-yl]-3-(trifluoromethyl)-3,4-dihydro-2H-pyr- rol-5-yl} -2-bromobenzyl)propanamide, N-(l - {4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-di- hydro-2H-pyrrol-5-yl]phenyl} ethyl)propanamide, and N-[l-(4- {3-[3,5-bis(trifluoro- methyl)phenyl]-3-(trifluoromethyl)-3,4-dihydro-2H^
(Reference Document: WO2009/097992);
When (T) is (T-3) in the compounds of Fo r m u l a ( I ) , N- {5-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]-2,3-dihydro-lH-inde yljpropanamide, N- {5-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyr- rol-5-yl]-2,3-dihydro-lH-inden-l-yl}acetamide, N- {5-[3-(3,4,5-trichlorophenyl)-3-(trifluoro- methyl)-3,4-dihydro-2H-pyrrol-5-yl]-2,3-dihydro-lH-inden-l -yl}propanamide, N- {5-[3-(3,4,5-tri- chlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]-2,3-dihydro-lH-inden-l-yl}cyclopropan ecarboxamide, 3,3,3-trifluoro-N- {5-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyr- rol-5-yl]-2,3-dihydro-lH-inden-l-yl}propanamide, 2-(methylsulfanyl)-N- {5-[3-(3,4,5-trichloro- phenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]-2,3-dihydro-lH-inden-l-yl}acetamide, 2-(methylsulfinyl)-N- {5-[3-(3,4,5 richlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]-2,3- dihydro-lH-inden-l-yl}acetamide, 2-(methylsulfonyl)-N- {5-[3-(3,4,5-trichlorophenyl)-3-(trifluoro- methyl)-3,4-dihydro-2H-pyrrol-5-yl]-2,3-dihydro-lH-inden-l -yl}acetamide, N-(5- {3-[3,4-di- chloro-5-(trifluoromethyl)phenyl]-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl}-2,3-dihydro-lH-inde n-l-yl)propanamide, N-(5- {3-[3,5-bis(trifluoromethyl)phenyl]-3-(trifluoromethyl)-3,4-di- hydro-2H-pyrrol-5-yl}-2,3-dihydro-lH-inden-l -yl)propanamide, N-(5- {3-[2,6-bis(tri- fluoromethyl)pyridin-4-yl]-3-(trifluoromem^
propanamide, and N-(5- {3-[2,6-bis(trifluoromethyl)pyridin-4-yl]-3-(trifluoromethyl)-3,4-di- hydro-2H-pyrrol-5-yl}-2,3-dihydro-lH-inden-l -yl)-2-(methylsulfonyl)acetamide (Reference Document: WO2009/112275);
W h e n ( T ) i s ( T-4) in the compounds of Formula (I), 4-[3-(3,5-dichlorophen- yl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]-2-methyl-N-(thiethan-3-yl)benzamide, 2-meth- yl-N-(thiethan-3-yl)-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]benza mide, 2-methyl-N-(l-oxidethiethan-3-yl)-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-dihy- dro-2H-pyrrol-5-yl]benzamide, 2-methyl-N-(l,l-dioxidethiethan-3-yl)-4-[3-(3,4,5-trichloro- phenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]benzamide, 2-chloro-N-(thi- ethan-3-yl)-4-[3-(3,4,5 richlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]benzamide, 2-chloro-N-(l,l-dioxidethiethan-3-yl)-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)
pyrrol-5-yl]benzamide, 2-bromo-N-(l,l-dioxidethiethan-3-yl)-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoro- methyl)-3,4-dihydro-2H-pyrrol-5-yl]benzamide, N-(l,l-dioxidethiethan-3-yl)-4-[3-(3,4,5-trichlorophen- yl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]-2-(trifluoromethyl)benzamide, N-(l , 1 -dioxidethi- ethan-3-yl)-2-nitro-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]benz- amide, 4- {3-[3,4-dichloro-5-(trifluoromethyl)phenyl]-3-(trifluoromethyl)-3,4-dihydro-2H-pyr- rol-5-yl}-2-methyl-N-(thiethan-3-yl)benzamide, 4- {3-[3,5-bis(trifluoromethyl)phenyl]-3-(trifluoro- methyl)-3,4-dihydro-2H-pyrrol-5-yl} -2-methyl-N-(thiethan-3-yl)benzaniide, 4- {3-[3,5-bis(trifluoro- methyl)phenyl]-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl} -2-methyl-N-(l -oxide thi- ethan-3-yl)benzamide, 4- {3-[3,5-bis(trifluoromethyl)phenyl]-3-(trifluoromethyl)-3,4-dihydro-2H-pyr- rol-5-yl} -2-methyl-N-(l , 1 -dioxidethiethan-3-yl)benzamide, 4- {3-[2,6-bis(trifluoro)pyridin-4-yl]-3-(tri- fluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl} -2-methyl-N-(thiethan-3-yl)benzamide, 4- {3-[2,6-bis(tri- fluoro)pyridin-4-yl]-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl} -2-methyl-N-(l-oxidethiethan-3 benzamide, and 4- {3-[2,6-bis(trifluoro)pyridin-4-yl]-3-(trifluoromethyl)-3,4-dihydro-2H-pyr- rol-5-yl} -2-methyl-N-(l , 1 -dioxidethiethan-3 -yl)benzamide(Reference Document: WO2009/080250); and W h e n ( T ) i s ( T-5) in the compounds of Formula (I), 5-[3-(3,5-dichloro- phenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]-2-fluorobenzonitrile, 2-fluoro-5-[3-(3,4,5-tri- chlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]benzonitrile, 5-(3-bromo-4-fluoro- phenyl)-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrole, methyl 2-methyl-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]benzoate, 2-methyl-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-y l j b enz o ic ac i d, 2-bromo-4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]benzonitrile, 4-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]-2-(trifluoromethyl)benzoni trile, 5- {3-[3,5-bis(trifluoromethyl)phenyl]-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl}-2-fluoro- benzonitrile, 3-[3,5-bis(trifluoromethyl)phenyl]-5-(3-bromo-4-fluorophenyl)-3-(trifluoromethyl)-3,4-di- hydro-2H-pyrrole, m e t h y l 4- {3-[3,5-bis(trifluoromethyl)phenyl]-3-(trifluoromethyl)-3,4-di- hydro-2H-pyrrol-5-yl}-2-methylbenzoate, 4- {3-[3,5-bis(trifluoromethyl)phenyl]-3-(trifluoro- methyl)-3,4-dihydro-2H-pyrrol-5-yl} -2-m e t h y l b e n z o i c a c i d, 4- { 3 - [3 , 5 -bis(trifluor o)phenyl] -3 - (trifle
4- {3-[3,5-bis(trifluoro)phenyl]-3-(trifl^
4-[5-(3-bromo-4-fluorophenyl)-3-(trifluorometh^
pyridine, 5- {3-[2,6-bis(trifluoromethyl)pyridin-4-yl]-3-(trifluoromethyl)-3,4-dihydro-2H-pyr- rol-5-yl}-2-fluorob e n z o n i t r i l e , m e t h y l 4- {3-[2,6-bis(trifluoromethyl)pyridin-4-yl]-3-(trifluoro- methyl)-3,4-dihydro-2H-pyrrol-5-yl} -2-methylbenzoate, 4- {3-[2,6-bis(trifluoromethyl)pyri- din-4-yl]-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl} -2-methylbenzoic acid, 4- {3-[2,6-bis(tri- fluoromethyl)pyridin-4-yl]-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl}-2-bromobenzonitrile, and 4- {3-[2,6-bis(trifluoromethyl)pyridin-4-yl]-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl} -2-methyl- benzonitrile. (Reference Documents: Japanese Patent Application Laid-Open (JP-A) No. 2007-91708, JP-ANo. 2008-133273, WO2009/072621, WO2009/097992 and WO2009/112275)
The step (b-1) in the preparation method (b) may be conducted according to the methods described in, for example, EP1538138 (Al) or WO2009-097992 (Al). The reaction of the step (b-1) in the preparation method (b) may be performed in a suitable diluent, and examples of the diluent used at this time are the same as the examples of the diluent in the preparation method (a).
The suitable copper reagent in the step (b-1) in the preparation method (b) includes copper oxide (I), copper oxide (II), copper acetylacetonate (II), copper acetate (II), copper cyanide (I) and the like.
The step (b-1) in the preparation method (b) may be performed in a substantially wide temperature range. Generally, the step (b-1) may be performed at about 20 °C to about 200 °C, preferably at about 40 °C to about 150 °C. In addition, the reaction is desirably conducted at normal pressures, but may be also handled under elevated or reduced pressure. The reaction time is 0.1 to 72 hours, preferably 1 to 24 hours.
In performing the step (b-1) in the preparation method (b), for example, 1 mole of the compound of Formula (III) is reacted with 0.5 mole to 2 moles of the compound of Formula (IV) and 0.1 mole to 2 mole of a copper reagent, for example, copper oxide (I) in a diluent, for example, toluene, whereby obtaining the corresponding compound of Formula (V). The compounds of Formula (III), which are the starting materials in the step (b-1) in the preparation metho d (b ) , are novel, and representative examples there o f inc lude methyl 3-(3,5-dichlorophenyl)-4,4,4-trifluorobuten-2-enoate, methyl 4,4,4-trifluoro-3-(3,4,5-trichloro- phenyl)-buten-2-enoate, ethyl 4,4,4-trifluoro-3-(3,4,5-trichlorophenyl)-buten-2-enoate, isopropyl 4,4,4-trifluoro-3-(3,4,5-trichlorophenyl)-buten-2-enoate, tert-butyl 4,4,4-trifluoro-3-(3,4,5-trichloro- phenyl)-buten-2-enoate, benzyl 4,4,4-trifluoro-3-(3,4,5-trichlorophenyl)-buten-2-enoate, methyl [3,5-bis(trifluoromethyl)phenyl]-4,4,4-trifluorobuten-2-e n o a t e , e t h y l [ 3 , 5-bis(trifluoro- methyl)phenyl]-4,4,4-trifluorobuten-2-enoate, isopropyl [3,5-bis(trifluoromethyl)phenyl]-4,4,4-trifluoro- buten-2-enoate and methyl 3-[2,6-bis(trifluoromethyl)pyridin-4-yl]-4,4,4-trifluorobuten-2-enoate.
Examples of the compounds of Formula (IV), which are the starting materials in the step (b-1) in the preparation method (b), include those known, and representative examples thereof include 3-bromo-4-fluorobenzylisocyanide, 2-fluoro-5-(isocyanomethyl)benzonitrile and 5-(isocyano- methyl)-2-(lH-l,2,4-triazol-l-yl)benzonitrile. The compounds may be prepared by the methods described in the documents, e.g., Tetrahedron Letters 29(27) (1988) pp. 3343-3346; Heterocycles 31 (1990) pp. 1855-1860; Journal of Organic Chemistry 70 (2005) pp. 3542-3553; or Organic & Biomolecular Chemistry 1(9) (2003) pp. 1475-1479.
The step (b-2) in the preparation method (b) may be performed according to the methods described in JP-ANo. 2007-91708, or Chem. Lett. (1985) pp. 1601-1604. The reaction of the step (b-2) in the preparation method (b) may be performed in a suitable diluent, and examples of the diluent used at this time are the same as the examples of the diluent in the preparation method (a).
The suitable base of the step (b-2) in the preparation method (b) includes alkaline metal bases such as sodium carbonate, potassium carbonate, sodium hydrocarbonate, potassium hydrocarbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide and potassium-tert-butoxide, and organic bases such as triethylamine, diisopropylethylamine, tributylamine, N-methylmorpholine, N,N-dimethylaniline, Ν,Ν-diethylaniline, 4-tert-butyl-N,N-dimethylaniline, pyridine, picoline, lutidine, diazabicycloundecene, diazabicyclooctane and imidazole, and the like. The reaction of the step (b-2) in the preparation method (b) may be performed in a substantially wide temperature range. Generally, the reaction may be performed at about -78 °C to about 200 °C, preferably at about -10 °C to about 100 °C. In addition, the reaction is desirably conducted at normal pressures, but may be also handled under elevated or reduced pressure. The reaction time is 0.1 to 72 hours, preferably 1 to 24 hours. In performing the step (b-2) in the preparation method (b), for example, 1 mole of the compound of Formula (V) is reacted with 1 to 0.1 mole of a base such as diazabicycloundecene in a diluent, for example, pyridine, whereby obtaining the objective compound of Formulae (I-Ia) and/or (I-Ib), which is encompassed by Formula (I) of the present invention.
Representative examples of the compounds of Formula (V) in the step (b-2) in the preparation method ( b ) , w h i c h a r e t h e s t a r t i n g materials, include methyl 2-(3-bromo-4-fluoro- phenyl)-4-(3,5-dichlorophenyl)-4-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-3-c arb o x y l at e , m e thy l 2-(3-bromo-4-fluorophenyl)-4-(3,4,5-trichlorophenyl)-4-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-3-carb o x y l a t e , e t h y l 2-(3-bromo-4-fluorophenyl)-4-(3,4,5-trichlorophenyl)-4-(trifluoromethyl)-3,4-di- hydro-2H-pyrrol-3-carboxylate, isopropyl 2-(3-bromo-4-fluorophenyl)-4-(3,4,5-trichlorophenyl)-4-(tri- fluoromethyl)-3,4-dihydro-2H-pyrrol-3-carboxylate, tert-butyl 2-(3-bromo-4-fluorophenyl)-4-(3,4,5-tri- chlorophenyl)-4-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-3-carboxylate, benzyl 2-(3-bromo-4-fluoro- phenyl)-4-(3 ,4,5-trichlorophenyl)-4-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-3-c arb oxylate, methyl 2-(3-cyano-4-fluorophenyl)-4-(3,4,5-trichlorophenyl)-4-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-3-carb o x y l a t e , e t h y l 2-(3-cyano-4-fluorophenyl)-4-(3,4,5-trichlorophenyl)-4-(trifluoromethyl)-3,4-di- hydro-2H-pyrrol-3-carboxylate, isopropyl 2-(3-cyano-4-fluorophenyl)-4-(3,4,5-trichlorophenyl)-4-(tri- fluoromethyl)-3,4-dihydro-2H-pyrrol-3-c a r b o x y l a t e , m e t h y l 2-[3-cyano-4-(lH-l,2,4-tri- azol-l-yl)phenyl]-4-(3,4,5-trichlorophenyl)-4-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-3-carboxylate, methyl 4-[3,5-bis(trifluoromethyl)phenyl]-2-(3-bromo-4-fluorophenyl)-4-(trifluoromethyl)-3,4-di- hydro-2H-pyrrol-3-carboxylate, methyl 4-[3,5-bis(trifluoromethyl)phenyl]-2-(3-cyano-4-fluoro- phenyl)-4-(trifluorophenyl)-3,4-dihydro-2H-pyrrol-3-carboxylate, and methyl 4-[2,6-bis(tri- fluoromethyl)pyridin-4-yl]-2-(3-bromo-4-fluorophenyl)-4-(trifluoromethyl)-3,4-dihydro-2H-pyr- rol-3-carboxylate.
The preparation method (c) may be conducted according to the method described in WO2009-097992 (Al).
The reaction of the preparation method (c) may be performed in a suitable diluent, and examples of the diluent used at this time are the same as the examples of the diluent in the preparation method (a).
Representative examples of the compounds of Formula (I-IIa) or (I-IIb) in the preparation method (c) i n c l u d e m e t h y l 5-(3-bromo-4-fluorophenyl)-3-(3,5-dichlorophenyl)-3-(trifluoromethyl)-3,4-di- hydro-2H-pyrrol-4-carboxylate, methyl 5-(3-bromo-4-fluorophenyl)-3-(3,4,5-trichloro- phenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-4-c a rb o x y l at e , m e t h y l 5-(3-cyano-4-fluoro- phenyl)-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-4-c arb o x y l at e , e thy l 5-(3-cyano-4-fluorophenyl)-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyr- rol-4-carboxylate, isopropyl 5-(3-cyano-4-fluorophenyl)-3-(3,4,5-trichlorophenyl)-3-(trifluoro- methyl)-3,4-dihydro-2H-pyrrol-4-carboxylate, tert-butyl 5-(3-cyano-4-fluorophenyl)-3-(3,4,5-trichloro- phenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-4-c ar b o x y l a t e , b e n z y l 5-(3-cyano-4-fluoro- phenyl)-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-4-c arb o xy 1 at e , me thy 1
3- [3,5-bis(trifluoromethyl)phenyl]-5-(3-cyano-4-fluorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyr- rol-4-carboxylate, methyl 5-(3 -cyano-4-fluorophenyl)-3 - [4-fluoro-3 -(trifluoromethyl)phenyl] -3 -(tri- fluoromethyl)-3,4-dihydro-2H-pyrrol-4-carboxylate, and methyl 3-[2,6-bis(trifluoromethyl)pyri- din-4-yl]-5-(3-cyano-4-fluorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-4-carboxylate.
The reaction of the preparation method (c) may be performed using, as a base, an alkaline metal base such as lithium hydride, sodium hydride, potassium hydride, lithium amide, sodium amide, lithium diisopropylamide, butyl lithium, tert-butyl lithium, trimethylsilyl lithium, lithium hexamethyldisilazide, sodium carbonate, potassium carbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide and potassium-tert-butoxide, an organic base such as triethylamine, diisopropylethylamine, tri b uty l ami n e , N-methyl morpholine, Ν,Ν-dimethylaniline, N,N-diethylaniline,
4- tert-butyl-N,N-dimethylaniline, pyridine, picoline, lutidine, diazabicycloundecene, diazabicyclooctane and imidazole, and the like. The preparation method (c) may be performed in a substantially wide temperature range. Generally, the preparation method (c) may be performed at about -78 °C to about 200 °C, preferably at about -10 °C to about 200 °C. In addition, the reaction is desirably conducted at normal pressures, but may be also handled under elevated or reduced pressure. The reaction time is 0.1 to 72 hours, preferably 0.1 to 48 hours. In performing the preparation method (c), for example, 1 mole of the compound of Formulae (I-IIa) and/or (I-IIb) is reacted with 1 mole to 3 moles of H-G, for example, H-G6 in a diluent, for example, DMF in the presence of 1 mole to 3 moles of a base such as potassium carbonate, whereby obtaining the corresponding compound of Formula (I) of the present invention. The compounds of Formulae (I-IIa-Br) and/or (I-IIb-Br) and Formulae (I-IIa-CN) and/or (I-IIb-CN), which are encompassed by Formulae (I-IIa) and/or (I-IIb) that is a starting material in the preparation method (c), may be prepared by the method described in the scheme 1 :
Scheme 1 :
Figure imgf000020_0001
wherein in above formulae X1, X2, X4, X5, Y1, Y2, Y4, R, B and R20 are as defined herein, and Step c-1 and Step c-2 may be conducted according to the preparation method (b); in Step c-3, the compounds of Formula (I-IIa-Br) are reacted with a cyano reagent and/or a catalyst in the presence of a suitable diluent if necessary, whereby obtaining the compounds of Formula (I-IIa-CN); the reaction of Step c-3 may be performed in a suitable diluent, and examples of the diluent used at this time are the same as the examples of the diluent in the preparation method (a), desirably dimethylformamide (DMF); the reaction of Step c-3 may be performed in the presence of a suitable catalyst, and examples of the catalyst used at this time include a transitional metal such as Pd(PPh3)4, Pd2(dba)3, Pd2(dba)3CHCl3, (dba=dibenzylideneacetone), Pd(PPh3)2Cl2, Pd(OAc)2, Cul and CuCN; in addition, the reaction of Step c-3 may be performed, if necessary, using a phosphine-based ligand such as triphenylphosphine, l,2-bis(diphenylphosphino)ethane, l,3-bis(diphenylphosphino)propane, 1 ,4-bis(diphenylphos- phino)butane, l , l '-bis(diphenylphosphino)ferrocene, 2,2'-bis(diphenylphosphino)-l, -binaphthalene (ΒΓΝΑΡ), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos) and tributylphosphine; representative examples of the cyanating agent used in the reaction of Step c-3 include zinc cyanide, copper cyanide, sodium cyanide, potassium cyanide, silver cyanide (I), copper cyanide (I), trimethylsilyl cyanide and potassium hexacyanoferrate (II) trihydrate; and Step c-3 may be performed in a substantially wide temperature range. Generally, Step c-3 may be performed at about 0 °C to about 200 °C, preferably at about 30 °C to about 180 °C. In addition, the reaction is desirably conducted at normal pressures, but may be also handled under elevated or reduced pressure. The reaction time is 0.1 to 72 hours, preferably 0.1 to 24 hours; and in performing Step c-3, for example, 1 mole of the compound of Formula (I-IIa-Br) is reacted with 0.5 mole to 3 moles of the cyanating agent, for example, zinc cyanide in a diluent, for example, DMF, in the presence of catalytic amount of Pd(PPh3)4, whereby obtaining the compound of Formula (I-IIa-CN), which is encompassed by the compounds of Formula (I-IIa) of the present invention. As the compounds of Formula (H-G) which are the starting materials in the preparation method (c), there are many known compounds represented by H-G2, H-G3, H-G4, H-G5, H-G6, H-G8 or H-G9, and the specific examples thereof include
lH-imidazole, lH-pyrazole, 4-methyl-lH-pyrazole, 4-fluoro-lH-pyrazole, 4-chloro-lH-pyrazole,
4- bromo-lH-pyrazole, 4-iodo-lH-pyrazole, 4-nitro-lH-pyrazole, 3-trifluoromethyl-lH-pyrazole, 4-trifluoromethyl-lH-pyrazole, 4-cyano-lH-pyrazole, lH-l,2,3-triazole, lH-l,2,4-triazole, lH-tetrazole,
5- methyl-lH-tetrazole, and 5-(methylthio)-lH-tetrazole.
The compounds according to the invention may have one or more asymmetrical carbons, and accordingly, the compounds of the present invention encompass the optical isomers thereof.
The compounds according to the invention may be used in combination with suitable synergists or other active compounds, such as for example insecticides, acaricides, nematicides, fungicides, biological control agents, and bacterizides. Such combinations can also result in a synergistic effect, i.e. the biological activity of such a combination is synergistically increased. Such combinations may called mixtures.
Examples of such combination partners are the following insecticides, acaricides, nematicides: The active ingredients specified herein by their "common name" are known and described, for example, in the Pesticide Manual ("The Pesticide Manual", 14th Ed., British Crop Protection Council 2006) or can be searched in the internet (e.g. http://www.alanwood.net/pesticides).
(1 ) Acetylcholinesterase (AChE) inhibitors, for example carbamates, e.g. Alanycarb, Aldicarb, Bendiocarb, Benfuracarb, Butocarboxim, Butoxycarboxim, Carbaryl, Carbofuran, Carbosulfan, Ethiofencarb, Fenobucarb, Formetanate, Furathiocarb, Isoprocarb, Methiocarb, Methomyl, Metolcarb, Oxamyl, Pirimicarb, Propoxur, Thiodicarb, Thiofanox, Triazamate, Trimethacarb, XMC, and Xylylcarb; or organophosphates, e.g. Acephate, Azamethiphos, Azinphos-ethyl, Azinphos-methyl, Cadusafos, Chlorethoxyfos, Chlorfenvinphos, Chlormephos, Chlorpyrifos, Chlorpyrifos-methyl, Coumaphos, Cyanophos, Demeton-S -methyl, Diazinon, Dichlorvos/DDVP, Dicrotophos, Dimethoate, Dimethylvinphos, Disulfoton, EPN, Ethion, Ethoprophos, Famphur, Fenamiphos, Fenitrothion, Fenthion, Fosthiazate, Heptenophos, Imicyafos, Isofenphos, Isopropyl O-(methoxyaminothio-phosphoryl) salicylate, Isoxathion, Malathion, Mecarbam, Methamidophos, Methidathion, Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion, Parathion-methyl, Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimiphos-methyl, Profenofos, Propetamphos, Prothiofos, Pyraclofos, Pyridaphenthion, Quinalphos, Sulfotep, Tebupirimfos, Temephos, Terbufos, Tetrachlorvinphos, Thiometon, Triazophos, Triclorfon, and Vamidothion.
(2) GABA-gated chloride channel antagonists, for example cyclodiene organochlorines, e.g. Chlordane and Endosulfan; or phenylpyrazoles (fiproles), e.g. Ethiprole and Fipronil.
(3) Sodium channel modulators / voltage-dependent sodium channel blockers, for example pyrethroids, e.g. Acrinathrin, Allethrin, d-cis-trans Allethrin, d-trans Allethrin, Bifenthrin, Bioallethrin, Bioallethrin S-cyclopentenyl isomer, Bioresmethrin, Cycloprothrin, Cyfluthrin, beta-Cyfluthrin, Cyhalothrin, lambda-Cyhalothrin, gamma-Cyhalothrin, Cypermethrin, alpha-Cypermethrin, beta-Cypermethrin, theta-Cypermethrin, zeta-Cypermethrin, Cyphenothrin [(lR)-trans isomers], Deltamethrin, Empenthrin [(EZ)-(IR) isomers), Esfenvalerate, Etofenprox, Fenpropathrin, Fenvalerate, Flucythrinate, Flumethrin, tau-Fluvalinate, Halfenprox, Imiprothrin, Kadethrin, Permethrin, Phenothrin [(l R)-trans isomer), Prallethrin, Pyrethrine (pyrethrum), Resmethrin, Silafluofen, Tefluthrin, Tetramethrin, Tetramethrin [(1R) isomers)], Tralomethrin, and Transfluthrin; or DDT; or Methoxychlor. (4) Nicotinic acetylcholine receptor (nAChR) agonists, for example neonicotinoids, e.g. Acetamiprid, Clothianidin, Dinotefuran, Imidacloprid, Nitenpyram, Thiacloprid, and Thiamethoxam; or
Nicotine.
(5) Nicotinic acetylcholine receptor (nAChR) allosteric activators, for example spinosyns, e.g. Spinetoram and Spinosad. (6) Chloride channel activators, for example avermectins/milbemycins, e.g. Abamectin, Emamectin benzoate, Lepimectin, and Milbemectin.
(7) Juvenile hormone mimics, for example juvenile hormon analogues, e.g. Hydroprene, Kinoprene, and Methoprene; or Fenoxycarb; or Pyriproxyfen.
(8) Miscellaneous non-specific (multi-site) inhibitors, for example alkyl halides, e.g. Methyl bromide and other alkyl halides; or Chloropicrin; or Sulfuryl fluoride; or Borax; or Tartar emetic.
(9) Selective homopteran feeding blockers, e.g. Pymetrozine; or Flonicamid. (10) Mite growth inhibitors, e.g. Clofentezine, Hexythiazox, and Diflovidazin; or Etoxazole.
(11) Microbial disruptors of insect midgut membranes, e.g. Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis, and BT crop proteins: CrylAb, CrylAc, CrylFa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34/35Abl .
(12) Inhibitors of mitochondrial ATP synthase, for example Diafenthiuron; or organotin miticides, e.g. Azocyclotin, Cyhexatin, and Fenbutatin oxide; or Propargite; or Tetradifon.
(13) Uncouplers of oxidative phoshorylation via disruption of the proton gradient, for example Chlorfenapyr, DNOC, and Sulfluramid. (14) Nicotinic acetylcholine receptor (nAChR) channel blockers, for example Bensultap, Cartap hydrochloride, Thiocyclam, and Thiosultap-sodium.
(15) Inhibitors of chitin biosynthesis, type 0, for example Bistrifluron, Chlorfluazuron, Diflubenzuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Lufenuron, Novaluron, Noviflumuron, Teflubenzuron, and Triflumuron. (16) Inhibitors of chitin biosynthesis, type 1, for example Buprofezin.
(17) Moulting disruptors, for example Cyromazine.
(18) Ecdysone receptor agonists, for example Chromafenozide, Halofenozide, Methoxyfenozide, and Tebufenozide.
(19) Octopamine receptor agonists, for example Amitraz. (20) Mitochondrial complex III electron transport inhibitors, for example Hydramethylnon; or Acequinocyl; or Fluacrypyrim.
(21 ) Mitochondrial complex I electron transport inhibitors, for example METI acaricides, e.g. Fenazaquin, Fenpyroximate, Pyrimidifen, Pyridaben, Tebufenpyrad, and Tolfenpyrad; or
Rotenone (Derris). (22) Voltage-dependent sodium channel blockers, e.g. Indoxacarb; or Metaflumizone.
(23) Inhibitors of acetyl CoA carboxylase, for example tetronic and tetramic acid derivatives, e.g. Spirodiclofen, Spiromesifen, and Spirotetramat. (24) Mitochondrial complex IV electron transport inhibitors, for example phosphines, e.g. Aluminium phosphide, Calcium phosphide, Phosphine, and Zinc phosphide; or Cyanide.
(25) Mitochondrial complex II electron transport inhibitors, for example Cyenopyrafen.
(28) Ryanodine receptor modulators, for example diamides, e.g. Chlorantraniliprole and Flubendiamide. Further active ingredients with unknown or uncertain mode of action, for example Amidoflumet, Azadirachtin, Benclothiaz, Benzoximate, Bifenazate, Bromopropylate, Chinomethionat, Cryolite, Cyantraniliprole (Cyazypyr), Cyflumetofen, Dicofol, Diflovidazin, Fluensulfone, Flufenerim, Flufiprole, Fluopyram, Fufenozide, Imidaclothiz, Iprodione, Meperfluthrin, Pyridalyl, Pyrifluquinazon, Tetramethylfluthrin, and iodomethane; furthermore products based on Bacillus firmus (including but not limited to strain CNCM 1-1582, such as, for example,VOTiVO™, BioNem) or one of the following known active compounds:
3- bromo-N-{2-bromo-4-chloro-6-[(l-cyclopropylethyl)carbamoyl]phenyl}-l-(3-chloropyridin-2-yl)-lH- pyrazole-5-c a r b o x a m i d e ( k n o w n f r o m W O 2 0 0 5 / 077934),
4- {[(6-bromopyridin-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-o n e ( k n o w n f r o m WO2007/115644), 4- { [(6-fluoropyridin-3-yl)methyl] (2,2-difluoroethyl)amino} furan-2(5H)-one (known from WO2007/115644), 4-{[(2-chloro-l,3-thiazol-5-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-one (known from WO2007/115644), 4-{[(6-chlo^yridin-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-one (known from WO2007/115644), Flupyradifurone (known from WO2007/115644), 4-{[(6-chlor-5-fluoropyridin-3-yl)methyl](methyl)amino}furan-2(5H)-one (known from WO2007/115643), 4-{[(5,6-dichloropyridin-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-one (known f r o m W O 2 0 0 7 / 1 1 5 6 4 6 ) , 4-{[(6-chloro-5-fluoropyridin-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-o ne (known from WO2007/115643), 4-{[(6-chloropyridin-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-one (known from EP-A-0539588 ) , 4-{[(6-chlo^yridin-3-yl)methyl](methyl)amino}furan-2(5H)-one (known from EP-A-0539588), {[l-(6-chloropyridin-3-yl)ethyl](methyl)oxido-λ4-sulfanylidene}cyanamide (known f r o m W O 2 0 0 7 / 1 4 9 1 3 4 ) a n d i t s d i a s t e r e o m e r s {[(lR)-l-(6-chloropyridin-3-yl)ethyl](methyl)oxido-λ4-s u 1 f any 1 i d e n e } c y an am i d e (A) and {[(lS)-l-(6-chloropyridin-3-yl)ethyl](methyl)oxido-λ4-sulfanylidene}cyanamide (B) (also known from WO2007/149134) as well as Sulfoxaflor (also known from WO2007/149134) and its diastereomers [(R)-methyl(oxido){(lR)-l-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-λ4-sulfanylidene]cyanamide (Al) and [(S)-methyl(oxido) {(lS)-l- [6-(trifluoromethyl)pyridin-3 -yl] ethyl} ^4-sulfanylidene]cyanamide (A2), referred to as group of diastereomers A (known from WO2010/074747, WO2010/074751), [(R)-methyl(oxido){(lS)-l-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-λ4-sulfanylidene]cyanamide (Bl) and [(S)-methyl(oxido){(lR)-l-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-λ4-sulfanylidene]cyanamide (B2), referred to as group of diastereomers B (also known from WO2010/074747, WO2010/074751), and ll-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-l,4-dioxa-9-azadispiro[4.2.4.2]tetradec-ll-en-10-one ( k n o w n f r o m W O 2 0 0 6 / 0 8 9 6 3 3 ) ,
3- (4'-fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-l-azaspiro[4.5]dec-3-en-2-one (known from WO2008/067911),
1 - {2-fluoro-4-methyl-5- [(2,2,2-trifluorethyl)sulfinyl]phenyl} -3-(trifluoromethyl)- 1 H- 1 ,2,4-triazol-5-ami n e ( k n ow n f r o m W O 2 0 0 6 / 0 4 3 6 3 5 ) ,
[(3S,4aR,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-6,12-dihydroxy-4,12b-dimethyl-ll-oxo-9-(pyri din-3-yl)- 1 ,3,4,4a,5,6,6a, 12,12a, 12b-decahydro-2H, 11 H-benzo[f]pyrano[4,3-b]chromen-4-yl]methyl cyclopropanecarboxylate (known from WO2008/066153), 2-cyano-3-(difluoromethoxy)-N,N-dimethylbenzenesulfonamide (known from WO2006/056433), 2-cyano-3-(difluoromethoxy)-N-methylbenzenesulfonamide (known from WO2006/100288),
2- cyano-3-(difluoromethoxy)-N-ethylbenzenesulfonamide (known from WO2005/035486),
4- (difluoromethoxy)-N-ethyl-N-methyl-l,2-benzothiazol-3-amine 1,1-dioxide (known from WO2007/057407),
N-[l-(2,3-dimethylphenyl)-2-(3,5-dimethylphenyl)ethyl]-4,5-dihydro-l,3-thiazol-2-amine (known from WO2008/104503),
{l'-[(2E)-3-(4-chlorophenyl)prop-2-en-l-yl]-5-fluorospiro[indole-3,4'-piperidin]-l(2H)-yl}(2-chlorop din-4-y l ) m e t h a n o n e ( k n o w n f r o m W O 2 0 0 3 / 1 0 6 4 5 7 ) ,
3- (2,5-dimethylphenyl)-4-hydroxy-8-methoxy-l,8-diazaspiro[4.5]dec-3-en-2-o ne (known from WO2009/049851), 3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-l,8-diazaspiro[4.5]dec-3-en-4-yl ethyl c a r b o n a t e ( k n o w n f r o m W O 2 0 0 9 / 0 4 9 8 5 1 ) ,
4- (but-2-yn-l-yloxy)-6-(3,5-dimethylpiperidin-l-yl)-5-fluoropyrimidine (known from WO2004/099160), (2,2,3, 3,4,4,5, 5-octafluoropentyl)(3,3,3-trifluoropropyl)malononitrile (known from WO2005/063094), (2,2,3, 3,4,4,5, 5-octafluoropentyl)(3,3,4,4,4-p entaf lu or obutyl)malononitrile (known from WO2005/063094),
8- [2-(cyclopropylmethoxy)-4-(trifluoromethyl)phenoxy] -3 - [6-(trifluoromethyl)pyridazin-3 -yl] -3 -azabic y c l o [ 3 . 2 . 1 ] o c t a n e ( k n o w n from W O 2007/040280 ) , 2-ethyl-7-methoxy-3 -methyl-6- [(2,2,3 ,3 -tetrafluoro
m e t h y l c a r b o n a t e ( k n o w n f r o m J P 2 0 0 8 / 1 1 0 9 5 3 ) , 2-ethyl-7-methoxy-3-methyl-6-[(2,2,3,3-tetrafluoro-2,3-dihydro-l,4-benzodioxin-6-yl)oxy]quinolin-4-yl acetate (known from JP2008/110953), PF1364 (CAS-Reg.No.1204776-60-2) (known from JP2010/018586),
5- [5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro-l,2-oxazol-3-yl]-2-(lH-l,2,4-triazol-l-yl)ben z o n i t r i l e ( k n o w n f r o m W O 2 0 0 7 / 0 7 5 4 5 9 ) , 5-[5-(2-chloropyridin-4-yl)-5-(trifluoromethyl)-4,5-dihydro-l,2-oxazol-3-yl]-2-(lH-l,2,4-triazol-l-yl)be n z o n i t r i l e ( k n o w n f r o m W O 2 0 0 7 / 0 7 5 4 5 9 ) , 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro-l,2-oxazol-3-yl]-2-methyl-N-{2-oxo-2-[(2,2, 2-trifluoroethyl) amino]ethyl}benzamide (known from WO2005/085216), 4-{[(6-chloropyridin-3-yl)methyl](cyclopropyl)amino}-l,3-oxazol-2(5H)-one,
4-{[(6-chloropyridin-3-yl)methyl](2,2-difluoroethyl)amino}-l,3-oxazol-2(5H)-one,
4-{[(6-chloropyridin-3-yl)methyl](ethyl)amino}-l,3-oxazol-2(5H)-one,
4-{[(6-chloropyridin-3-yl)methyl](methyl)amino}-l,3-oxazol-2(5H)-o n e (all known from WO 2010/005692), NNI-071 1 ( kn o wn fr o m W O 2002 / 096882 ) , 1 -acetyl-N-[4-(l , 1 , 1 ,3,3,3-hexafluoro-2-methoxypropan-2-yl)-3-isobutylphenyl]-N-isobutyryl-3,5-dimet hyl-lH-pyrazole-4-c arboxamide (known from WO2002/096882), methyl 2-[2-({[3-bromo-l-(3-chloropyridin-2-yl)-lH-pyrazol-5-yl]carbonyl}amino)-5-chloro-3-methylbenzoyl] -2-m e thy 1 hy dr az i n e c ar b o x y 1 at e (known from WO2005/085216), methyl 2-[2-({[3-bromo-l-(3-chloropyridin-2-yl)-lH-pyrazol-5-yl]carbonyl}amino)-5-cyano-3-methylbenzoyl]- 2-e t h y 1 h y dr a z i n e c ar b o x y 1 a t e (known from WO2005/085216), methyl 2-[2-({[3-bromo-l-(3-chloropyridin-2-yl)-lH-pyrazol-5-yl]carbonyl}amino)-5-cyano-3-methylbenzoyl]- 2-methylhydrazinecarboxy late (known from WO2005/085216) , methyl 2-[3,5-dibromo-2-( { [3-bromo- 1 -(3-chloropyridin-2-yl)- 1 H-pyrazol-5-yl]carbonyl} amino)benzoyl] - 1 ,2-d i e t h y 1 h y d r a z i n e c a r b o x y 1 a t e (known from W O 2005 / 085216 ) , methyl 2-[3,5-dibromo-2-({[3-bromo-l-(3-chloropyridin-2-yl)-lH-pyrazol-5-yl]carbonyl}amino)benzoyl]-2-eth y lhydrazine c arb o xy l at e (kno wn from W O 2005 / 08521 6 ) , (5RS,7RS;5RS,7SR)-l-(6-chloro-3-pyridylmethyl)-l,2,3,5,6,7-hexahydro-7-methyl-8-nitro-5-propoxyi midazo[l,2-a ] p y r i d i n e ( k n o w n f r o m W O 2 0 0 7 / 1 0 1 3 6 9 ) , 2-{6-[2-(5-fluoropyridin-3-yl)-l,3-thiazol-5-yl]pyridin-2-yl}pyrimidine (known from WO2010/006713), 2-{6-[2-(pyridin-3-yl)-l,3-thiazol-5-yl]pyridin-2-yl}pyrimidine (known from WO2010/006713), 1 -(3 -chloropyridin-2-yl)-N- [4-cyano-2-methyl-6-(methylcarbamoyl)phenyl] -3 - { [5-(trifluoromethyl)- 1 H- tetrazol-l-yl]methyl}-lH-pyrazole-5-c ar b o x am i d e (known from W O 2010 / 069502 ) , l-(3-chloropyridin-2-yl)-N-[4-cyano-2-methyl-6-(methylcarbamoyl)phenyl]-3-{[5-(trifluoromethyl)-2H- tetrazol-2-yl]methyl}-lH-pyrazole-5-c arboxamide (known from W 02010/069502), N-[2-(tert-butylcarbamoyl)-4-cyano-6-methylphenyl]-l-(3-chloropyridin-2-yl)-3-{[5-(trifluoromethyl)-l H-tetrazol-l-yl]methyl}-lH-pyrazole-5-c arb o x ami de (known from W O 2010 /069502 ) , N-[2-(tert-butylcarbamoyl)-4-cyano-6-methylphenyl]-l-(3-chloropyridin-2-yl)-3-{[5-(trifluoromethyl)-2 H-tetrazol-2-yl]methyl}-lH-pyrazole-5-c arb o x ami de (known from W O 2010 /069502 ) , ( 1 E)-N- [(6-chloropyridin-3 -yl)methyl] -N'-cyano-N-(2,2-difluoroethyl)ethanimidamide (known from WO2008/009360),
N-[2-(5-amino-l,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-l-(3-chloropyridin-2-yl)-lH-p yrazole-5-c arboxamide (known from CN 102057925), and methyl 2-[3,5-dibromo-2-({[3-bromo-l-(3-chloropyridin-2-yl)-lH-pyrazol-5-yl]carbonyl}amino)benzoyl]-2-eth yl-l-methylhydrazinecarboxylate (known from WO2011/049233). Further examples of such combination partners are the following fungicides:
( 1 ) Inhibitors of the ergosterol biosynthesis, for example aldimorph, azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, diniconazole-M, dodemorph, dodemorph acetate, epoxiconazole, etaconazole, fenarimol, fenbuconazole, fenhexamid, fenpropidin, fenpropimorph, fluquinconazole, flurprimidol, flusilazole, flutriafol, furconazole, furconazole-cis, hexaconazole, imazalil, imazalil sulfate, imibenconazole, ipconazole, metconazole, myclobutanil, naftifme, nuarimol, oxpoconazole, paclobutrazol, pefurazoate, penconazole, piperalin, prochloraz, propiconazole, prothioconazole, pyributicarb, pyrifenox, quinconazole, simeconazole, spiroxamine, tebuconazole, terbinafme, tetraconazole, triadimefon, triadimenol, tridemorph, triflumizole, tri forine , tritic onazo le , unic onazo le , unic onazo l e-p , vinic onazo l e , v oric onazo l e , l-(4-chlorophenyl)-2-(lH-l,2,4-triazol-l-yl)cyclohe p t a n o l , m e t h y l 1 -(2,2-dimethyl-2,3-dihydro- 1 H-inden- 1 -yl)- 1 H-imidazole-5-carboxylate,
N'- {5-(difluoromethyl)-2-methyl-4-[3-(trimethylsilyl)propoxy]phenyl}-N-ethyl-N-methylimidoformami de,
N-ethyl-N-methyl-N'- {2-methyl-5-(trifluoromethyl)-4-[3-(trimethylsilyl)propoxy]phenyl}imidoformami de and 0-[l-(4-methoxyphenoxy)-3,3-dimethylbutan-2-yl] lH-imidazole-l-carbothioate.
(2) inhibitors of the respiratory chain at complex I or II, for example bixafen, boscalid, carboxin, diflumetorim, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, furmecyclox, isopyrazam (mixture of syn-epimeric racemate 1RS,4SR,9RS and anti-epimeric racemate I RS, 4SR,9SR), isopyrazam (anti-epimeric racemate 1RS,4SR,9SR), isopyrazam (anti-epimeric enantiomer 1R,4S,9S), isopyrazam (anti-epimeric enantiomer 1 S,4R,9R), isopyrazam (syn epimeric racemate 1RS,4SR,9RS), isopyrazam (syn-epimeric enantiomer 1R,4S,9R), isopyrazam (syn-epimeric enantiomer 1 S,4R,9S), mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, thifluzamide,
1 -methyl-N- [2-( 1 , 1 ,2,2-tetrafluoroethoxy)phenyl] -3 -(trifluoromethyl)- 1 H-pyrazole-4-carboxamide, 3 -(difluoromethyl)- 1 -methyl-N- [2-( 1 , 1 ,2,2-tetrafluoroethoxy)phenyl] - 1 H-pyrazole-4-carboxamide,
3 -(difluoromethyl)-N- [4-fluoro-2-( 1 , 1 ,2,3 ,3 ,3 -hexafluoropropoxy)phenyl] - 1 -methyl- 1 H-pyrazole-4-carb oxamide,
N-[l-(2,4-dichlorophenyl)-l-methoxypropan-2-yl]-3-(difluoromethyl)-l-methyl-lH-pyrazole-4-carboxa mide,
5,8-difluoro-N-[2-(2-fluoro-4- {[4-(trifluoromethyl)pyridin-2-yl]oxy}phenyl)ethyl]quinazolin-4-amine, N- [9-(dichloromethylene)- 1 ,2,3 ,4-tetrahydro- 1 ,4-methanonaphthalen-5-yl] -3 -(difluoromethyl)- 1 -methyl - 1 H-pyrazole-4-carboxamide,
N-[(l S,4R)-9-(dichloromethylene)-l,2,3,4-tetrahydro-l ,4-methanonaphthalen-5-yl]-3-(difluoromethyl)- 1 -methyl- lH-pyrazole-4-c a r b o x a m i d e a n d N-[(lR,4S)-9-(dichloromethylene)-l,2,3,4-tetrahydro-l ,4-methanonaphthalen-5-yl]-3-(difluoromethyl)- 1 -methyl- 1 H-pyrazole-4-carboxamide. (3) inhibitors of the respiratory chain at complex III, for example ametoctradin, amisulbrom, azoxystrobin, cyazofamid, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, famoxadone, fenamidone, fenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, triclopyricarb, trifloxystrobin, (2E)-2-(2- {[6-(3-chloro-2-methylphenoxy)-5-fluoropyrimidin-4-yl]oxy}phenyl)-2-(methoxyimino)-N-m ethylethanamide,
(2E)-2-(methoxyimino)-N-methyl-2-(2- {[( {(lE)-l-[3-(trifluoromethyl)phenyl]ethylidene}amino)oxy]m ethyl} phenyl)ethanamide,
(2E)-2-(methoxyimino)-N-methyl-2- {2- [(E)-( { 1 - [3 -(trifluoromethyl)phenyl] ethoxy } imino)methyl]phen yljethanamide,
(2E)-2- {2-[( {[(1E)-1 -(3- {[(E)-l-fluoro-2-phenylethenyl]oxy}phenyl)ethylidene]amino} oxy)methyl]phe nyl}-2-(methoxyimino)-N-methylethanamide,
(2E)-2- {2-[( {[(2E,3E)-4-(2,6-dichlorophenyl)but-3-en-2-ylidene]amino}oxy)methyl]phenyl}-2-(methox yimino)-N-methylethanamide,
2-chloro-N-(l ,l,3-trimethyl-2,3-dihydro-lH-inden-4-yl)pyridine-3-carboxamide,
5-methoxy-2-methyl-4-(2- {[( {(lE)-l-[3-(trifluoromethyl)phenyl]ethylidene}amino)oxy]methyl}phenyl) -2,4-dihydro-3H-l,2,4-triazol-3-o n e , m e t h y l (2E)-2- {2-[( {cyclopropyl[(4-methoxyphenyl)imino]methyl} sulfanyl)methyl] phenyl} -3-methoxyprop-2- e n o a t e , N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-(formylamino)-2-hydroxybenzamide,
2- {2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-m e t h y l a c e t a m i d e a n d (2R)-2- {2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide.
(4) Inhibitors of the mitosis and cell division, for example benomyl, carbendazim, chlorfenazole, diethofencarb, ethaboxam, fluopicolide, fuberidazole, pencycuron, thiabendazole, thiophanate-methyl,t h i o p h a n a t e , z o x a m i d e ,
5-chloro-7-(4-methylpiperidin-l -yl)-6-(2,4,6-trifluorophenyl)[l ,2,4]triazolo[l ,5-a J p yr i m i d i n e an d
3- chloro-5-(6-chloropyridin-3-yl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine.
(5) Compounds capable to have a multisite action, for example bordeaux mixture, captafol, captan, chlorothalonil, copper hydroxide, copper naphthenate, copper oxide, copper oxychloride, copper(2+) sulfate, dichlofluanid, dithianon, dodine, dodine free base, ferbam, fluorofolpet, folpet, guazatine, guazatine acetate, iminoctadine, iminoctadine albesilate, iminoctadine triacetate, mancopper, mancozeb, maneb, metiram, metiram zinc, oxine-copper, propamidine, propineb, sulphur and sulphur preparations including calcium polysulphide, thiram, tolylfluanid, zineb and ziram.
(6) Compounds capable to induce a host defence, for example acibenzolar-S-methyl, isotianil, probenazole and tiadinil. (7) Inhibitors of the amino acid and/or protein biosynthesis, for example andoprim, blasticidin-S, cyprodinil, kasugamycin, kasugamycin hydrochloride hydrate, mepanipyrim, pyrimethanil and 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-l-yl)quinoline.
(8) Inhibitors of the ATP production, for example fentin acetate, fentin chloride, fentin hydroxide and silthiofam.
(9) Inhibitors of the cell wall synthesis, for example benthiavalicarb, dimethomorph, flumorph, iprovalicarb, mandipropamid, polyoxins, polyoxorim, validamycin A and valifenalate.
(10) Inhibitors of the lipid and membrane synthesis, for example biphenyl, chloroneb, dicloran, edifenphos, etridiazole, iodocarb, iprobenfos, isoprothiolane, propamocarb, propamocarb hydrochloride, prothiocarb, pyrazophos, quintozene, tecnazene and tolclofos-methyl.
(11) Inhibitors of the melanine biosynthesis, for example carpropamid, diclocymet, fenoxanil, phthalide, p y r o q u i l o n , t r i c y c l a z o l e a n d 2 , 2 , 2-trifluoroethyl {3-methyl-l-[(4-methylbenzoyl)amino]butan-2-yl}carbamate.
(12) Inhibitors of the nucleic acid synthesis, for example benalaxyl, benalaxyl-M (kiralaxyl), bupirimate, clozylacon, dimethirimol, ethirimol, furalaxyl, hymexazol, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl and oxolinic acid.
(13) Inhibitors of the signal transduction, for example chlozolinate, fenpiclonil, fludioxonil, iprodione, procymidone, quinoxyfen and vinclozolin.
(14) Compounds capable to act as an uncoupler, for example binapacryl, dinocap, ferimzone, fluazinam and meptyldinocap.
(15) Further compounds, for example benthiazole, bethoxazin, capsimycin, carvone, chinomethionat, pyriofenone (chlazafenone), cufraneb, cyflufenamid, cymoxanil, cyprosulfamide, dazomet, debacarb, dichlorophen, diclomezine, difenzoquat, difenzoquat methylsulphate, diphenylamine, ecomate, fenpyrazamine, flumetover, fluoroimide, flusulfamide, flutianil, fosetyl-aluminium, fosetyl-calcium, fosetyl-sodium, hexachlorobenzene, irumamycin, methasulfocarb, methyl isothiocyanate, metrafenone, mildiomycin, natamycin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, octhilinone, oxamocarb, oxyfenthiin, pentachlorophenol and salts, phenothrin, phosphorous acid and its salts, propamocarb-f osetylate, propanosine-s odium, proquinazid, pyrimorph, (2E)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-l-(morpholin-4-yl)prop-2-en-l-one,
(2Z)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-l-(morpholin-4-yl)prop-2-en-l-one, pyrrolnitrine, tebufloquin, tecloftalam, tolnifanide, triazoxide, trichlamide, zarilamid, (3S,6S,7R,8R)-8-benzyl-3-[({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)amino]-6-m ethyl-4,9-dioxo- 1 ,5-dioxonan-7-yl 2-methylpropanoate, l-(4- {4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro-l,2-oxazol-3-yl]-l,3-thiazol-2-yl}piperidin-l-yl)-2-[5- methyl-3 -(trifluoromethyl)- 1 H-pyrazol- 1 -yl] ethanone,
l-(4- {4-[(5S)-5-(2,6-difluorophenyl)-4,5-dihydro-l,2-oxazol-3-yl]-l,3-thiazol-2-yl}piperidin-l-yl)-2-[5- methyl-3 -(trifluoromethyl)- 1 H-pyrazol- 1 -yl] ethanone,
1- (4- {4-[5-(2,6-difluorophenyl)-4,5-dihydro-l,2-oxazol-3-yl]-l,3-thiazol-2-yl}piperidin-l-yl)-2-[5-meth yl-3 -(trifluoromethyl)- 1 H-pyrazol- 1-y 1 ] e t h a n o n e , l-(4-methoxyphenoxy)-3,3-dimethylbutan-2-yl lH-imidazole-l-carboxylate, 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, 2,3-dibutyl-6-chlorothieno[2,3-d]pyrimidin-4(3H)-one,
2,6-dimethyl-lH,5H-[l,4]dithiino[2,3-c:5,6-c']dipyrrole-l,3,5,7(2H,6H)-tetrone,
2- [5-methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]-l -(4- {4-[(5R)-5-phenyl-4,5-dihydro-l,2-oxazol-3-yl]- l,3-thiazol-2-yl}piperidin-l-yl)ethanone,
2-[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]-l -(4- {4-[(5S)-5-phenyl-4,5-dihydro-l,2-oxazol-3-yl]- l,3-thiazol-2-yl}piperidin-l-yl)ethanone,
2-[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]-l - {4-[4-(5-phenyl-4,5-dihydro-l,2-oxazol-3-yl)-l,3-th iazol-2-yl]piperidin-l-y 1 } e t h a n o n e , 2-butoxy-6-iodo-3-propyl-4H-chromen-4-one, 2-chloro-5-[2-chloro-l -(2,6-difluoro-4-methoxyphenyl)-4-methyl-lH-imidazol-5-yl]pyridine,
2- phenylphenol and salts, 3-(4,4,5-nifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-l-yl)quinoline, 3,4,5-trichloropyridine-2,6-dicarbonitrile,
3-[5-(4-chlorophenyl)-2,3-dimethyl-l,2-oxazolidin-3-yl]pyridine,
3- chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine,
4- (4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine, 5-amino-l,3,4-thiadiazole-2-thiol,
5- chloro-N'-phenyl-N'-(prop-2-yn-l -yl)thiophene-2-sulfonohydrazide,
5-fluoro-2-[(4-fluorobenzyl)oxy]pyrimidin-4-amine,
5-fluoro-2-[(4-methylbenzyl)oxy]pyrimidin-4-amine,
5-methyl-6-octyl[l,2,4]triazolo[l,5-a]pyrimidin-7-a m i n e , e t h y l (2Z)-3-amino-2-cyano-3-phenylprop-2-enoate,
N'-(4- {[3-(4-chlorobenzyl)-l,2,4-thiadiazol-5-yl]oxy} -2,5-dimethylphenyl)-N-ethyl-N-methylimidoform a m i d e , N-(4-chlorobenzyl)-3-[3-methoxy-4-(prop-2-yn-l-yloxy)phenyl]propanamide, N- [(4-chlorophenyl)(cyano)methyl] -3 - [3 -methoxy-4-(prop-2-yn- 1 -yloxy)phenyl]propanamide,
N-[(5-bromo-3-chloropyridin-2-yl)methyl]-2,4-dichloropyridine-3-carboxamide,
N-[l-(5-bromo-3-chloropyridin-2-yl)ethyl]-2,4-dichloropyridine-3-carboxamide,
N-[l-(5-bromo-3-chloropyridin-2-yl)ethyl]-2-fluoro-4-iodopyridine-3-carboxamide,
N- {(E)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2-phenylacetam ide,
N- {(Z)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2-phenylacetam ide, N'- {4-[(3-tert-butyl-4-cyano-l,2-thiazol-5-yl)oxy]-2-chloro-5-methylphenyl} -N-ethyl-N-methylimidofo mamide,
N-methyl-2-(l- {[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4-yl)-N-(l, 2,3,4-tetrah ydronaphthalen- 1 -yl)- 1 ,3-thiazole-4-carboxamide,
N-methyl-2-( 1 - { [5-methyl-3 -(trifluoromethyl)- 1 H-pyrazol- 1 -yl] acetyl} piperidin-4-yl)-N- [( 1 R)- 1 ,2,3 ,4-t etrahydronaphthalen- 1 -yl] - 1 ,3 -thiazole-4-carboxamide,
N-methyl-2-(l- {[5-methyl-3-(trifluoromethy^
etrahydronaphthalen-l-yl]-l,3-thiazole-4-c a r b o x a m i d e , p e n t y l {6-[({[(l-methyl-lH-tetrazol-5-yl)(phenyl)methylidene]amino}oxy)methyl]pyridin-2-yl}carbamate, phenazine-l-carboxylic acid, quinolin-8-ol, quinolin-8-ol sulfate (2:1) and tert-butyl {6-[({[(l-methyl-lH-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate.
(1 6 ) F u r t h e r c o m p o u n d s , f o r e x a m p l e 1 -methyl-3 -(trifluoromethyl)-N- [2'-(trifluoromethyl)biphenyl-2-yl] - 1 H-pyrazole-4-carboxamide, N-(4'-chlorobiphenyl-2-yl)-3-(difluoromethyl)-l-methyl-lH-pyrazole-4-carboxamide,
N-(2',4'-dichlorobiphenyl-2-yl)-3 -(difluoromethyl)- 1 -methyl- 1 H-pyrazole-4-carboxamide,
3 -(difluoromethyl)- 1 -methyl-N- [4'-(trifluoromethyl)biphenyl-2-yl] - 1 H-pyrazole-4-carboxamide, N-(2',5'-difluorobiphenyl-2-yl)-l-methyl-3-(trifluoromethyl)-lH-pyrazole-4-carboxamide,
3 -(difluoromethyl)- 1 -methyl-N- [4'-(prop-l-yn-l -yl)biphenyl-2-yl]-lH-pyrazole-4-carboxamide, 5-fluoro- 1 ,3 -dimethyl-N- [4'-(prop- 1 -yn- 1 -yl)biphenyl-2-yl] - 1 H-pyrazole-4-carboxamide,
2-chloro-N-[4'-(prop-l-yn-l -yl)biphenyl-2-yl]pyridine-3-carboxamide,
3 -(difluoromethyl)-N- [4'-(3 ,3 -dimethylbut- 1 -yn- 1 -yl)biphenyl-2-yl] - 1 -methyl- 1 H-pyrazole-4-carboxami de, N-[4'-(3,3-dimethylbut-l-yn-l-yl)biphenyl-2-yl]-5-fluoro-l,3-dimethyl-lH-pyrazole-4-carboxamide,
3- (difluoromethyl)-N-(4'-ethynylbiphenyl-2-yl)-l -methyl-lH-pyrazole-4-carboxamide,
N-(4'-ethynylbiphenyl-2-yl)-5-fluoro-l,3-dimethyl-lH-pyrazole-4-carboxamide,
2-chloro-N-(4'-ethynylbiphenyl-2-yl)pyridine-3-carboxamide,
2-chloro-N- [4'-(3 ,3 -dimethylbut- 1 -yn- 1 -yl)biphenyl-2-yl]pyridine-3 -carboxamide,
4- (difluoromethyl)-2-methyl-N-[4'-(trifluoromethyl)biphenyl-2-yl]-l,3-thiazole-5-carboxamide,
5- fluoro-N-[4'-(3-hydroxy-3-methylbut-l-yn-l -yl)biphenyl-2-yl]-l,3-dimethyl-lH-pyrazole-4-carboxam i d e , 2-chloro-N-[4'-(3-hydroxy-3-methylbut-l-yn-l-yl)biphenyl-2-yl]pyridine-3-carboxamide, 3 -(difluoromethyl)-N- [4'-(3 -methoxy-3 -methylbut- 1 -yn- 1 -yl)biphenyl-2-yl] - 1 -methyl- 1 H-pyrazole-4-car boxamide,
5-fluoro-N- [4'-(3 -methoxy-3 -methylbut- 1 -yn- 1 -yl)biphenyl-2-yl] - 1 ,3 -dimethyl- 1 H-pyrazole-4-carboxa m i d e , 2-chloro-N-[4'-(3-methoxy-3-methylbut-l-yn-l-yl)biphenyl-2-yl]pyridine-3-carboxamide, (5-bromo-2-methoxy-4-methylpyridin-3-yl)(2,3,4-trimethoxy-6-methylphenyl)methanone,
N- [2-(4- { [3 -(4-chlorophenyl)prop-2-yn- 1 -yl] oxy} -3 -methoxyphenyl) ethyl] -N2-(methylsulfonyl)valinam i d e , 4-0X0-4- [(2 -phenylethyl)amino]butanoic acid and but-3-yn-l -yl {6-[({[(Z)-(l-methyl-lH etrazol-5-yl)(phenyl)methylene]amino} oxy)methyl]pyridin-2-yl}carbamate.
All named fungicide mixing partners of the classes (1) to (16) can, if their functional groups enable this, optionally form salts with suitable bases or acids.
Further examples of such combination partners are moreover the following herbicides: Herbicidal compounds which can be used in combination with the active compounds according to the invention in mixed formulations or in tank mix are, for example, known active compounds as they are described in, for example, Weed Research 26, 441-445 (1986), or "The Pesticide Manual", 15th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 2006, and the literature cited therein, and which for example act as inhibitor of acetolactate synthase, acetyl-CoA-carboxylase, cellulose-s ynth a s e , e n o lp yruvy l s hikimat-3-phosphat-synthase, glutamin-synthetase, p-hydroxyphenylpyruvat-dioxygenase, phytoendesaturase, photosystem I, photosystem II and/or protoporphyrinogen-oxidase.
Examples of active compounds which may be mentioned as herbicides or plant growth regulators which are known from the literature and which can be combined with the compounds according to the invention are the following (compounds are either described by "common name" in accordance with the International Organization for Standardization (ISO) or by chemical name or by a customary code number), and always comprise all applicable forms such as acids, salts, ester, or modifications such as isomers, like stereoisomers and optical isomers. As an example at least one applicable from and/or modifications can be mentioned.: acetochlor, acibenzolar, acibenzolar-S-methyl, acifluorfen, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim-sodium, ametryn, amicarbazone, amidochlor, amidosulfuron, aminocyclopyrachlor, aminocyclopyrachlor-methyl, aminocyclopyrachlor-potassium, aminopyralid, amitrole, ammoniumsulfamat, ancymidol, anilofos, asulam, atrazine, azafenidin, azimsulfuron, aziprotryn, beflubutamid, benazolin, benazolin-ethyl, bencarbazone, benfluralin, benfuresate, bensulide, bensulfuron, bensulfuron-methyl, bentazone, benzfendizone, benzobicyclon, benzofenap, benzofluor, benzoylprop, bicyclopyrone, bifenox, bilanafos, bilanafos-sodium, bispyribac, bispyribac-sodium, bromacil, bromobutide, bromofenoxim, bromoxynil, bromuron, buminafos, busoxinone, butachlor, butafenacil, butamifos, butenachlor, butralin, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone, carfentrazone-ethyl, chlomethoxyfen, chloramben, chlorazifop, chlorazifop-butyl, chlorbromuron, chlorbufam, chlorfenac, chlorfenac-sodium, chlorfenprop, chlorflurenol, chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron- ethyl, chlormequat-chlorid, chlornitrofen, chlorophthalim, chlorthal- dimethyl, chlorotoluron, chlorsulfuron, cinidon, cinidon- ethyl, cinmethylin, cinosulfuron, clethodim, clodinafop, clodinafop-propargyl, clofencet, clomazone, clomeprop, cloprop, clopyralid, cloransulam, cloransulam-methyl, cumyluron, cyanamide, cyanazine, cyclanilide, cycloate, cyclosulfamuron, cycloxydim, cycluron, cyhalofop, cyhalofop-butyl, cyperquat, cyprazine, cyprazole,
2.4- D, 2,4-DB, daimuron/dymron, dalapon, daminozide, dazomet, n-decanol, desmedipham, desmetryn, detosyl-pyrazolate (DTP), diallate, dicamba, dichlobenil, dichlorprop, dichlorprop-P, diclofop, diclofop-methyl, diclofop-P-methyl, diclosulam, diethatyl, diethatyl-ethyl, difenoxuron, difenzoquat, diflufenican, diflufenzopyr, diflufenzopyr-sodium, dikegulac-s odium, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimethipin, dimetrasulfuron, dinitramine, dinoseb, dinoterb, diphenamid, dipropetryn, diquat, diquat-dibromide, dithiopyr, diuron, DNOC, eglinazine- ethyl, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron, ethametsulfuron-methyl, ethephon, ethidimuron, ethiozin, ethofumesate, ethoxyfen, ethoxyfen- ethyl, ethoxysulfuron, etobenzanid, F-5 3 3 1 i . e .
N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-lH-tetrazol-l-yl]-phenyl]-ethansulfonam i d e , F-7 9 6 7 i . e .
3- [7-chloro-5-fluoro-2-(trifluoromethyl)-lH-benzimidazol-4-yl]-l-methyl-6-(trifluoromethyl)pyrimidin- 2,4(lH,3H)-dione, fenoprop, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, fentrazamide, fenuron, flamprop, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazifop-butyl, fluazifop-P-butyl, fluazolate, flucarbazone, flucarbazone-sodium, flucetosulfuron, fluchloralin, flufenacet (thiafluamide), flufenpyr, flufenpyr- ethyl, flumetralin, flumetsulam, flumiclorac, flumiclorac-pentyl, flumioxazin, flumipropyn, fluometuron, fluorodifen, fluoroglycofen, fluoroglycofen-ethyl, flupoxam, flupropacil, flupropanate, flupyrsulfuron, flupyrsulfuron-methyl-s odium, flurenol, flurenol-butyl, fluridone, flurochloridone, fluroxypyr, fluroxypyr-meptyl, flurprimidol, flurtamone, fluthiacet, fluthiacet-methyl, fluthiamide, fomesafen, foramsulfuron, forchlorfenuron, fosamine, furyloxyfen, gibberellinic acid, glufosinate, glufosinate-ammonium, glufosinate-P, glufosinate-P-ammonium, glufosinate-P-sodium, glyphosate, glyphosate-i s o p r o p y l a m m o n i u m , H-9 2 0 1 , i . e . 0-(2,4-dimethyl-6-nitrophenyl)-0-ethyl-isopropylphosphoramidothioate, halosafen, halosulfuron, halosulfuron-methyl, haloxyfop, haloxyfop-P, haloxyfop-ethoxyethyl, haloxyfop-P-ethoxyethyl, haloxyfop-m ethyl, haloxyfo p-P-methyl, hexazinone, HW-0 2 , i . e .
1 -(dimethoxyphosphoryl)-ethyl-(2,4-d ichlorophenoxy)acetate, imazamethabenz, imazamethabenz-methyl, imazamox, imazamox-ammonium, imazapic, imazapyr, imazapyr- isopropylammonium, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosulfuron, inabenfide, indanofan, indaziflam, indol-3-ylacetic acid (IAA),
4- indol-3-ylbutyric acid (IBA), i o d o s ulfuron, iodosulfuron-methyl-s odium, iofensulfuron, iofensulfuron-sodium, ioxynil, ipfencarbazone, isocarbamid, isopropalin, isoproturon, isouron, isoxaben, isoxachlortole, isoxaflutole, isoxapyrifop, KUH-0 4 3 , i . e . 3-({[5-(difluoromethyl)-l-methyl-3-(trifluoromethyl)-lH-pyrazol-4-yl]methyl}sulphonyl)-5,5-dimethyl-
4.5- dihydro-l,2-oxazole, karbutilate, ketospiradox, lactofen, lenacil, linuron, maleic hydrazide, MCPA, MCPB, MCPB-methyl, -ethyl, and -sodium, mecoprop, mecoprop-sodium, mecoprop-butotyl, mecoprop-P-butotyl, mecoprop-P-dimethylammonium, mecoprop-P-2-ethylhexyl, mecoprop-P-potassium, mefenacet, mefluidide, mepiquat-chlorid, mesosuliuron, mesosulfuron-methyl, mesotrione, methabenzthiazuron, metam, metamifop, metamitron, metazachlor, metazasulfuron, methazole, methiopyrsulfuron, methiozolin, methoxyphenone, methyldymron, 1 -methylcyclopropen, methylisothiocyanat, metobenzuron, metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron, metribuzin, metsulfuron, metsulfuron-methyl, molinate, monalide, monocarbamide, monocarbamide-dihydrogensulphate, monolinuron, monosulfuron, monosulfuron ester, monuron, MT-128, i.e. 6-chloro-N-[(2E)-3-chloroprop-2-en-l-yl]-5-methyl-N-phenylpyridazin-3-amine, MT-5950, i.e. N-[3-chloro-4-(l -methylethyl)-phenyl]-2-methylpentanamide, NGGC-01 1 , naproanilide, napropamide, naptalam, NC-310, i.e. 4-(2,4-dichlorobenzoyl)-l-methyl-5-benzyloxypyrazole, neburon, nicosulfuron, nipyraclofen, nitralin, nitrofen, nitrophenolat-sodium (mixture of isomers), nitrofluorfen, nonanoic acid, norflurazon, orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paclobutrazol, paraquat, paraquat-dichloride, pelargonic acid (nonanoic acid), pendimethalin, pendralin, penoxsulam, pentanochlor, pentoxazone, perfluidone, pethoxamid, phenisopham, phenmedipham, phenmedipham-ethyl, picloram, picolinafen, pinoxaden, piperophos, pirifenop, pirifenop-butyl, pretilachlor, primisulfuron, primisulfuron-methyl, probenazole, profluazol, procyazine, prodiamine, prifluraline, profoxydim, prohexadione, prohexadione-calcium, prohydrojasmone, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propoxycarbazone-sodium, propyrisulfuron, propyzamide, prosulfalin, prosulfocarb, prosulfuron, prynachlor, pyraclonil, pyraflufen, pyraflufen-ethyl, pyrasulfotole, pyrazolynate (pyrazolate), pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen, pyribambenz, pyribambenz-isopropyl, pyribambenz-propyl, pyribenzoxim, pyributicarb, pyridafol, pyridate, pyriftalid, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quizalofop, quizalofop-ethyl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron, saflufenacil, secbumeton, sethoxydim, siduron, s i m a z i n e , s i m e t r y n , S N-l 0 6 2 7 9 , i . e . methyl-(2R)-2-({7-[2-chloro-4-(trifluoromethyl)phenoxy]-2-naphthyl} oxy)propanoate, sulcotrione, sulfallate (CDEC), sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosate (glyphosate-trimesium), sulfosulfuron, SW-065, SYN-523, SYP-2 4 9 , i . e . 1 -ethoxy-3 -methyl- 1 -oxobut-3 -en-2-yl-5 - [2-chloro-4-(trifluoromethyl)phenoxy] -2-nitrobenzoate,
SYP-300, i.e. l-[7-fluoro-3-oxo-4-(prop-2-yn-l-yl)-3,4-dihydro-2H-l ,4-benzoxazin-6-yl]-3-propyl-2-thioxoimidazolid in-4,5-dione, tebutam, tebuthiuron, tecnazene, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbuchlor, terbumeton, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazafluron, thiazopyr, thidiazimin, thidiazuron, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, tiocarbazil, topramezone, tralkoxydim, triafamone, triallate, triasulfuron, triaziflam, triazofenamide, tribenuron, tribenuron-methyl, trichloroacetic acid (TCA), triclopyr, tridiphane, trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifluralin, triflusulfuron, triflusulfuron-methyl, trimeturon, trinexapac, trinexapac-ethyl, tritosulfuron, tsitodef, uniconazole, uniconazole-P, vernolate, ZJ-0 8 6 2 , i . e .
3,4-dichloro-N- {2-[(4,6-dimethoxypyrimidin-2-yl)oxy]benzyl} aniline, as well as the following compounds:
Figure imgf000035_0001
Figure imgf000035_0002
The compounds and mixtures according to the invention show strong pesticidal actions, and accordingly, can be used as pesticides. Furthermore, the compounds or the mixtures according to the invention do not have harmful drug-adverse action on cultivated plants, and show strong expelling effects against harmful insects. Accordingly, the compounds or mixtures according to the invention can be used to combat harmful insects which occure in the agriculture, in particular on plants, such as harmful sucking plant insects, chewing plant insects and other plant-parasitic pests, stored-product insects, sanitarily harmful organisms and the like, and can be applied for the purpose of suh combatting. The harmful / organisms insects are for example:
Coleoptera, for example, Callosobruchus chinensis, Sitophilus zeamais, Tribolium castaneum, Epilachna vigintioctomaculata, Agriotes fuscicollis, Anomala rufocuprea, Leptinotarsa decemlineata, Diabrotica spp., Monochamus alternatus, Lissorhoptrus oryzophilus, Lyctus bruneus and Aulacophora femoralis; Lepidoptera, for example, Lymantria dispar, Malacosoma neustria, Pieris rapae, Spodoptera litura, Mamestra brassicae, Chilo suppressalis, Pyrausta nubilalis, Ephestia cautella, Adoxophyes orana, Carpocapsa pomonella, Agrotisfucosa, Galleria mellonella, Plutella maculipennis, Heliothis virescens and Phyllocnistis citrella; Hemiptera, for example, Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki, Unapsis yanonensis, Myzus persicas, Aphis pomi, Aphis gossypii, Rhopalosiphum pseudobrassicas, Stephanitis nashi, Nezara spp., Trialeurodes vaporariorm and Psylla spp.; Thysanoptera, for example, Thrips palmi and Franklinella occidental; Orthoptera, for example, Blatella germanica, Periplaneta americana, Gryllotalpa Africana and Locusta migratoria migratoriodes; Isoptera, for example, Reticulitermes speratus and Coptotermes formosanus; and Diptera, for example, Musca domestica, Aedes aegypti, Hylemia platura, Culex pipiens, Anopheles sinensis, Culex tritaeniorhynchus and Liriomyza torifolii.
Acari such as Tetranychus cinnabarinus, Tetranychus urticae, Panonychus cirri, Aculops pelekassi and Tarsonemus spp.
Nematoda such as Meloidogyne incognita, Bursaphelenchus lignicolus Mamiya et Kiyohara, Aphelenchoides besseyi, Heterodera glycines and Pratylenchus spp. Furthermore, the compounds of the present invention show excellent plant tolerability and a desirable toxicity profile for warm-blooded animals, and are well tolerable by the environment, and accordingly, suitable in protecting plants and parts of plants.
The application of the compounds of the present invention can lead to the increase of the harvested amount, and the improvement of the quality of harvested materials. Furthermore, the above-described compounds are suitable in protecting preserved products and materials, in the sanitary field, in the agriculture, gardening or veterinary field, and in expelling harmful pests, particularly insects, acari, helminthes, nematoda and mollusks encountered in the forest, garden or recreational facilities. The compounds of the present invention can be used preferably as plant-protecting agents. The compounds of the present invention have activity to normally sensitive and resistant species in all or some of the growth steps thereof. Especially, the above-described harmful insects include those described below:
As for Anoplura (Phthiraptera), for example, there are Damalinia spp., Haematopinus, Linognathus spp., Pediculus spp. and Trichodectes spp.
As for Arachnida, for example, there are Acarus siro, Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Chorioptes spp., Dermanyssus gallinae, Eotetranychus spp., Epitrimerus pyri, Eutetranyctus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans, Metatetranychus spp., Oligonychus spp., Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Stenotarsonemus spp., Tarsonemus spp., Tetranychus spp. and Vasates lycopersici.
As for Bivalvia, for example, there is Dreissena spp.
As for Chilopoda, for example, there are Geophilus spp. and Scutigera spp.
As for Coleoptera, for example, there are Acanthoscelides obtectus, Adoretus spp., Agelastica alni, Agriotes spp., Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp., Anthrenus spp., Apogonia spp., Atomaria spp., Attagenus spp., Bruchidius obtectus, Bruchus spp., Ceuthorhynchus spp., Cleonus mendicus, Conoderus spp., Cosmopolites spp., Costelytra zeal andica, Curculio spp., Cryptorhynchus lapathi, Dermestes spp., Diabrotica spp., Epilachna spp., Faustinus cubae, Gibbium psylloides, Heteronychus arator, Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypothenemus spp., Lachnosterna consanguinea, Leptinotarsa decemlineata, Lissorhoptrus oryzophilus, Lixus spp., Lyctus spp., Meligethes aeneus, Melolontha melolontha, Migdolus spp., Monochamus spp., Naupactus xanthographus, Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Otiorrhynchus sulcatus, Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga spp., Popillia japonica, Premnotrypes spp., Psylliodes chrysocephala, Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus spp., Sphenophorus spp., Sternechus spp., Symphyletes spp., Tenebrio molitor, Tribolium spp., Trogoderma spp., Tychius spp., Xylotrechus spp. and Zabrus spp.
As for Collembola, for example, there is Onychiurus armatus.
As for Dermaptera, for example, there is Forficula auricularia.
As for Diplopoda, for example, there is Blaniulus guttulatus. As for Diptera, for example, there are Aedes spp., Anopheles spp., Bibio hortulanus, Calliphora erythrocephala, Ceratitis capitata, Chrysomyia spp., Cochliomyia spp., Cordylobia anthropophaga, Culex spp., Cuterebra spp., Dacus oleae, Dermatobia hominis, Drosophila spp., Fannia spp., Gastrophilus spp., Hylemyia spp., Hyppobosca spp., Hypoderma spp., Liriomyza spp., Lucilia spp., Musca spp., Nezara spp., Oestrus spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Stomoxys spp., Tabanus spp., Tannia spp., Tipula paludosa and Wohlfahrtia spp.
As for Gastropoda, for example, there are Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp. and Succinea spp.
As for Helminths, for example, there are Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp., Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medeinensis, Echinococcus granulosus, Echinococcus multiocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp., Strongyloides fuelleborni, Strongyloides stercoralis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria and Wuchereria bancrofti.
Furthermore, Protozoa such as Eimeria can be expelled by the compounds of the present invention.
As for Heteroptera, for example, there are Anasa tristis, Antestiopsis spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus,spp., Euschistus spp., Eurygaster spp., Heliopeltis spp., Horchias nobiellus, Leptocorisa spp., Leptoglossus phyllopus, Lygus spp., Macropes excavatus, Miridae, Nezara spp., Oebalus spp., Pentomidae, Piesma quadrata, Piezodorus spp., Psallus seriatus, Pseudacysta persea, Rhodonius spp., Sahlbergella singularis, Scotinophora spp., Stephanitis nashi, Tibraca spp. and Triatoma spp. As for Homoptera, for example, there are Acyrthosipon spp., Aeneolamia spp., Agonoscena spp., Aleurodes spp., Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anuraphis cardui, Aonidiella spp., Aphanostigma piri, Aphis spp., Arboridia apicalis, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp., Brachycaudus helichrysii, Brachycolus spp., Brevicoryne brassicae, Calligypona marginata, Carneocephala fulgida, Ceratovacuna lanigera, Cercopidae, Ceroplastes spp., Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus spp., Chryptomyzus ribis, Dalbulus spp., Dialeurodes spp., Diaphorina spp., Diaspis spp., Doralis spp., Drosicha spp., Dysaphis spp., Dysmicoccus spp., Empoasca spp., Eriosoma spp., Erythroneura spp., Euscelis bilobatus, Geococcus coffeae, Homalodisca coagulata, Hyalopterus arundinis, Icerya spp., Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi, Macrosiphum spp., Mahanarva fimbriolata, Melanaphis sacchari, Metcalfiella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp., Nasonovia ribisnigri, Nephotettix spp., Nilaparvata lugens, Oncometopia spp., Orthezia praelonga, Parabemisia myricae, Paratorioza spp., Parlatoria spp., Pemphigus spp., Peregrinus maidis, Phenacoccus spp., Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp., Pinnaspis aspidistrae, Planococcus spp., Protopulvinaria pyriformis, Pseudaulacaspis pentagona, Pseudococcus spp., Psylla spp., Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesda gigas, Rastrococcus spp., Rhopalosiphum spp., Saissetia spp., Scaphoides titanus, Schizaphis graminum, Selenaspidus articulatus, Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina, Tenalaphara malayensis, Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., Trialeurodes vaporariorum, Trioza spp., Typhlocyba spp., Unaspis spp. and Viteus vitifolii. As for Hymenoptera, for example, there are Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.
As for Isopoda, for example, there are Armadillidium vulgare, Oniscus asellus and Porcellio scaber.
As for Isoptera, for example, there are Reticulitermes spp. and Odontotermes spp. As for Lepidoptera, for example, there are Acronicta major, Aedia leucomelas, Agrotis spp., Alabama argillacea, Anticarsia spp., Barathra brassicae, Bucculatrix thurberiella, Bupalus piniarius, Cacoecia podana, Capua reticulana, Carpocapsa pomonella, Cheimatobia brumata, Chilo spp., Choristoneura fumiferana, Clysia ambiguella, Cnaphalocerus spp., Earias insulana, Ephestia kuehniella, Euproctis chrysorrhoea, Euxoa spp., Feltia spp., Galleria mellonella, Helicoverpa spp., Heliothis spp., Hofmannophila pseudospretella, Homona magnanima, Hyponomeuta padella, Laphygma spp., Lithocolletis blancardella, Lithophane antennata, Loxagrotis albicosta, Lymantria spp., Malacosoma neustria, Mamestra brassicae, Mocis repanda, Mythimna separata, Oria spp., Oulema oryzae, Panolis flammea, Pectinophora gossypiella, Phyllocnistis citrella, Pieris spp., Plutella xylostella, Prodenia spp., Pseudaletia spp., Pseudoplusia includens, Pyrausta nubilalis, Spodoptera spp., Thermesia gemmatalis, Tinea pellionella, Tineola bisselliella, Tortrix viridana and Trichoplusia spp.
As for Orthoptera, for example, there are Acheta domesticus, Blatta orientalis, Blattella germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta Americana and Schistocerca gregaria.
As for Siphonaptera, for example, there are Ceratophyllus spp. and Xenopsylla cheopis. As for Symphyla, for example, there is Scutigerella immaculata.
As for Thynsanoptera, for example, there are Baliothrips biformis, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni and Thrips spp.
As for Thysanura, for example, there is Lepisma saccharina. Examples of the plant-parasitic Nematoda include Anguina spp., Aphelenchoides spp., Belonoaimus spp., Bursaphelenchus spp., Ditylenchus dipsaci, Globodera spp., Heliocotylenchus spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus similis, Rotylenchus spp., Trichodorus spp., Tylenchorhynchus spp., Tylenchulus spp., Thlenchulus semipenetrans and Xiphinema spp. According to the present invention, all plants and parts of plants can be treated. In the present invention, it should be understood that the plant refer to all plants and plant populations including desirable and undesirable wild plants or genetically modified plants (including naturally occurring genetically modified plants). The genetically modified plants may be plants that can be obtained by conventional improvement of plant variety and optimization or biotechnology and genetic engineering, or a combination method thereof. Transgenic plants, and plant varieties that can be protected or non-protected by the plant breeders, are included in the term "genetically modified plant" or "genetically modified plants". The parts of plants should be understood to refer to all the parts or organs of plants existing above and under the ground such as a bud, leaf, flower and root and the like. The examples include a leaf, needle-like leaf (needle), stalk, stem, flower, fruiting body, fruit, seed, root, tuber and stalk under the ground. The parts of plants also include harvested materials, and materials propagating sexually or asexually, for example, a cuttage, tuber, stalk under the ground, lateral branch and seed.
The treatment of plants or parts of plants with the active compounds or mixtures according to the present invention is performed directly, or by conventional treatments, for example, immersion, spray, evaporation, atomization, scattering, coating or injection. Particularly when the plant or part of the plant is a propagating material, particularly a seed, the treatment is performed by coating it with one or more compounds so that the compounds are applied to the surroundings, the inhabitant environment or preservation place.
The compounds of the present invention have a systemic activity, which means that the compounds can permeate into a plant and move from the underground part to the above-ground part of the plant.
As described above, all of plants and parts of plants can be treated according to the present invention. In a desirable embodiment, wild plant species and plant variants, or those obtained by traditional plant breeding methods such as crossbreeding or protoplast fusion and the like, and parts thereof are treated. In a further desirable embodiment, transgenic plants and plant varieties (genetically modified organisms), which are obtained by combination of genetic engineering and suitable conventional methods, and parts thereof are treated. The terms "parts," "parts of plants," and "plant parts" are as explained above. Particularly preferably, in each case, plants of plant varieties commercially available or used are treated according to the present invention. The plant varieties are understood to refer to plants that have new characteristic ("trail") obtained by conventional breed improvement, mutation introduction or recombination DNA technology. They may be plant varieties, biotypes or genotypes.
The treatment according to the present invention may have ultra-additive ("synergic") effects depending on plant species or plant varieties, their habitat and proliferation conditions (soil, weather, growth period, nutrition). Accordingly, beyond the effects practically expected, it is possible to obtain, for example, reduction of application rate and/or expansion of activity spectrum and/or increase of the activity of the substances and the compositions that can be used according to the present invention, improvement of plant growth, increase of tolerability for high or low temperature, increase of tolerability for drought or moisture or salts contained in the soil, improvement of flowering ability, simplification of harvest, acceleration of maturation, increase of harvest yield, improvement of quality of harvest products and/or increase of the nutrition value and improvement of preservation stability and/or processability of harvested products. The desirable transgenic plants or plant varieties (obtained by genetic engineering) treated according to the present invention include all plants having genetic substances that can provide the plants with very advantageous and useful traits based on genetic modification. Examples of such traits include improvement of plant growth, increase of tolerability for high or low temperature, increase of tolerability for drought or moisture or salts contained in the soil, improvement of flowering ability, simplification of harvest, acceleration of maturation, increase of harvest yield, improvement of quality of harvested products and/or increase of the nutrition value and improvement of preservation stability and/or prosessability of harvested products. Examples where such traits are particularly emphasized include improvement of the protection of plants against harmful pests and harmful microorganisms such as insect, tick, plant pathogenic fungus, bacteria and/or virus, and increase of tolerability of plants against compounds having certain type of herbicidal activities. Examples of the transgenic plant include important cereal plants such as cereals (barley, rice), corn, soybean, potato, sugar beet, tomato, bean and other plant variants, important cereal plants such as cotton, tobacco or rape and fruit plants (fruits like an apple, a pear or a citrus fruits and fruit-bearing plants like a grape), particularly importantly, corn, soybean, potato, cotton, tobacco and rape. The trait considered to be important is the increase of protection of plants against insects, acari, nematodes, slugs and snails by a toxin formed in the plant, particularly by a toxin formed in the plant particularly by genetic substances derived from Bacillus thuringiensis (for example, genes CrylA(a), CrylA(b), CrylA(c), CryllA, CrylllA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CrylF and combinations thereof). Such a plant is hereinafter called as "Bt plant." Likewise, other trait considered to be important is the increase of protection of plants against fungus, bacteria and virus by systemic acquired resistance (SAR), systemine, phytoalexin, elicitor and resistant gene, and corresponding expressed proteins and toxins. Further particularly stressed trait is the increase of tolerability of plants against a certain kind of an active compound having a herbicidal activity, for example, imidazolinone, sulfonyl urea, glyphosate or phosphinotricine (for example, "PTA" gene). Genes giving desired trait can be present in combination each other in a transgenic plant. Examples of the "Bt plant" include corn variants, cotton variants, soybean variants and potato variants marketed under the trade name of YIELD GARD(R) (for example, corn, cotton, soybean), KnockOut(R) (for example, corn), StarLink(R) (for example, corn), Bollgard(R) (cotton), Nucotn(R) (cotton) and NewLeaf^ (potato). Examples of the herbicide-resistant plants include corn variants, cotton variants and soybean variants marketed under the trade name of Roundup Ready(R) (resistant for glyphosate, for example, corn, cotton, soybean), Lib ertyLink(R) (resistant for phosphinotricine, for example, rape), IMI(R) (resistant for imidazolinones) and STS(R) (resistant for sulfonyl urea, for example, corn). The herbicide-resistant plants (i.e., the plant obtained by conventional breeding methods to have resistance to herbicides) also include variants marketed under the trade name of Clearfield(R) (for example, corn). Of course, such descriptions are also applied to plant varieties which have already had the genetic traits or will have genetic traits to be developed in future, and such plant varieties will be developed and/or marketed in future. The listed plants may be particularly advantageously treated with the compounds of the present invention at appropriate concentration.
Furthermore, in the veterinary field, the novel compounds of the present invention can be effectively used for various harmful parasitic pests (endo- and ecto-parasitic pests), for example, insects and helminthes. Examples of such harmful parasitic pests include harmful organisms described below. Examples of insects include Gasterophilus spp., Stomoxys spp., Trichodectes spp., Rhodonius spp., Ctenocephalides canis, Cimx lecturius, Ctenocephalides felis, Lucilia cuprina and the like. Examples of Acari include Ornithodoros spp., Ixodes spp., Boophilus spp. and the like.
In the veterinary field, i.e. in a veterinary medicine, the active compounds of the present invention are active against parasitic pests, in particularly, endo-parasitic pests or ecto-parasitic pests. The term of the endo-parasitic pests includes particularly helminthes such as cestode, Nematoda or fluke, Protozoa such as coccidia and the like. The ecto-parasitic pests include typically and preferably arthropod pests, particularly, insects such as fly (bite fly and licking fly), larvae of parasitic fly, louse, public lice, bird louse and flea, or acari such as mites, e.g., hard tick or soft tick, or itch mite, trombiculid mite and Ornithonyssus sylviarum (bird mite). Additionally, the parasitic pests which can be expelled by the active compound according to the invention are the following:
From Anoplurida, for example, there are Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp. Specific examples thereof include Linognathus setosus, Linognathus vituli, Linognathus ovillus, Linognathus oviformis, Linognathus pedalis, Linognathus stenopsis, Haematopinus asini macrocephalus, Haematopinus eurysternus, Haematopinus suis, Pediculus humanus capitis, Pediculus humanus corporis, Phylloera vastatrix, Phthirus pubis and Solenopotes capillatus.
From Mallophagida and Amblycerina and Ischnocerina, for example, there are Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp. and Felicola spp. Specific examples thereof include Bovicola bovis, Bovicola ovis, Bovicola limbata, Damalina bovis, Trichodectes canis, Felicola subrostratus, Bovicola caprae, Lepikentron ovis and Werneckiella equi.
From Diptera, Nematocerina and Brachycerina, for example, there are Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Odagmia spp., Wilhelmia spp., Hybomitora spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp., Rhinoestrus spp. and Tipula spp. Specific examples thereof include Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles gambiae, Anopheles maculipennis, Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Fannia canicularis, Sarcophaga carnaria, Stomoxys calcitrans, Tipula paludos, Lucilia cuprina, Lucilia sericata, Simulium reptans, Phlebotomus papatasi, Phlebotomus longipalpis, Odagmia ornata, Wilhelmia equina, Boophthora erythrocephala, Tabanus bromius, Tabanus spodopterus, Tabanus atratus, Tabanus sudeticus, Hybomitra ciurea, Chrysops caecutiens, Chrysops relictus, Haematopota pluvialis, Haematopota italica, Musca autumnalis, Musca domestica, Haematobia irritans irritans, Haematobia irritans exigua, Haematobia stimulans, Hydrotaea irritans, Hydrotaea albipuncta, Chrysomya chloropyga, Chrysomya bezziana, Oestrus ovis, Hypoderma bovis, Hypoderma lineatum, Przhevalskiana silenus, Dermatobia hominis, Melphagus ovinus, Lipoptena capreoli, Lipoptena cervi, Hippobosca variegata, Hippobosca equina, Gasterophilus intestinalis, Gasterophilus haemorroidalis, Gasterophilus inermis, Gasterophilus nasalis, Gasterophilus nigricornis, Gasterophilus pecorum and Braulra coeca. From Siphonapterida, for example, there are Pulex spp., Ctenocephalides spp., Tunga spp., Xenopsylla spp. and Ceratophyllus spp. Specific examples thereof include Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans and Xenopsylla cheopsis.
From Heteropterida, for example, there are Cimex spp., Triatoma spp., Rhodnius spp. and Panstrongylus spp. From Blattarida, for example, there are Blatta orientalis, Periplaneta americana, Blattela germanica and Supella spp. (for example, Supella longipalpa).
From Acari (Acarina) and Metastigmata and Mesostigmata, for example, there are Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Rhipicephalus (Boophilus) spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Dermanyssus spp., Rhipicephalus spp. (original genus of multi-host Acari), Ornithonyssus spp., Pneumonyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa spp. and Acarapis spp. Specific examples thereof include Argas persicus, Argas reflexus, Ornithodorus moubata, Otobius megnini, Rhipicephalus (Boophilus) microplus, Rhipicephalus (Boophilus) decoloratus, Rhipicephalus (Boophilus) annulatus, Rhipicephalus (Boophilus) calceratus, Hyalomma annatolicum, Hyalomma aegypticum, Hyalomma marginatum, Hyalomma transiens, Rhipicephalus evertsi, Ixodes ricinus, Ixodes hexagonus, Ixodes canisuga, Ixodes pilosus, Ixodes rubicundus, Ixodes scapularis, Ixodes holocyclus, Haemaphysalis concinna, Haemaphysalis punctata, Haemaphysalis cinnabarina, Haemaphysalis otophila, Haemaphysalis leachi, Haemaphysalis longicorni, Dermacentor marginatus, Dermacentor reticulatus, Dermacentor pictus, Dermacentor albipictus, Dermacentor andersoni, Dermacentor variabilis, Hyalomma mauritanicum, Rhipicephalus sanguineus, Rhipicephalus bursa, Rhipicephalus appendiculatus, Rhipicephalus capensis, Rhipicephalus turanicus, Rhipicephalus zambeziensis, Amblyomma americanum, Amblyomma variegatum, Amblyomma maculatum, Amblyomma hebraeum, Amblyomma cajennense, Dermanyssus gallinae, Ornithonyssus bursa, Ornithonyssus sylviarum and Varroa jacobsoni; From Actinedida (Prostigmata) and Acaridida (Astigmata), for example, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp. Specific examples thereof include Cheyletiella yasguri, Cheyletiella blakei, Demodex canis, Demodex bovis, Demodex ovis, Demodex caprae, Demodex equi, Demodex caballi, Demodex suis, Neotrombicula autumnalis, Neotrombicula desaleri, Neoschongastia xerothermobia, Trombicula akamushi, Otodectes cynotis, Notoedres cati, Sarcoptis canis, Sarcoptes bovis, Sarcoptes ovis, Sarcoptes rapicaprae (S. caprae), Sarcoptes equi, Sarcoptes suis, Psoroptes ovis, Psoroptes cuniculi, Psoroptes equi, Chorioptes bovis, Psoergates ovis, Pneumonyssoidic mange, Pneumonyssoides caninum and Acarapis woodi.
The active compounds of the present invention are also suitable in expelling arthropodal pests, helminthes and protozoa attacking animals (in particular vertebrates). The animals include agricultural domestic animals such as a cow, a sheep, a goat, a horse, a pig, a donkey, a camel, a buffalo, a rabbit, a chicken, a turkey, a duck, a goose, a nursery fish and a honeybee. Furthermore, the term "animals" in this context also include companion animals such as a dog, a cat, a caged bird, an aquarium fish and the like, and animals known as experimental animals such as a hamster, a guinea pig, a rat and a mouse.
With expelling these arthropods, helminths and/or protozoas by using the active compounds of the present invention, death ratio of the host animal is reduced, productivity (for obtaining meat, milk, wool, leather, eggs and honey, etc.) and health of the host animal are expected to be improved, and also economically more favorable and convenient breeding of the animal can be achieved.
For example, (if applicable) it is desirable to inhibit or interrupt parasitic organisms from uptaking the blood from a host. In addition, expelling of the parasitic organisms may help to inhibit the transfer of infectious factors.
The term "expelling" used in the present specification with respect to the veterinary field means that the active compounds are effective in reducing occurrence of parasitic organisms in each animal infected by such parasitic organisms to harmless level. More specifically, the term "expelling" used in the present specification means that the active compounds are effective in killing each parasitic pest, inhibiting the growth thereof, or inhibiting the proliferation thereof. Generally, the compounds of the present invention can be directly applied in the treatment of animals. Preferably, the compounds of the present invention are applied as pharmaceutical compositions that may include pharmaceutically acceptable excipients and/or adjuvants known in this field.
In a veterinary medicine field and livestock farming, the active compounds are applied (= administered) in various known ways such as enteral administration, e.g., a tablet, a capsule, a beverage, a liquid medicine, granules, a paste, a bolus or a feed staff, or suppository; or parenteral administration, e.g., injection (intramuscular, subcutaneous, intravenous, interperitoneal and the like), implant or nasal administration; by administration on skin, e.g., immersion or liquid immersion, spray, pouring on and spotting on, washing and powder spray; or with aid of shaped products containing the active compounds such as a head ring, an ear tag, a tail tag, a leg ring, a halter, a marking tool and the like. The active compounds may be prepared as shampoo, an appropriate formulation usable in aerosol, or as an no-pressure spray, for example, a pump spray and aerosol spray.
When used for domestic animals, poultry, pet and the like, the active compounds of the present invention can be applied directly or after dilution (for example, 100 to 10,000 fold dilution) as a formulation containing 1 % to 80 % by weight amount of the active compounds (for example, powders, wettable powders ("WP"), emulsion, emulsifiable concentrate ("EC"), flowable formulation (flowable), uniform solution and suspendable concentrate ("SC"), or can be used as a chemical bath.
When used in the veterinary field, the active compounds of the present invention may be used in combination with appropriate synergic agents such as acaricides, pesticides, helminthicides or protozoacides, etc., or with other active compounds. In the present invention, substances that have a pesticidal activity for harmful organisms encompassing all of the above are called pesticides.
When the active compounds of the present invention are used as pesticides, they can be prepared in conventional formulation forms. Examples of the formulation form include solution, emulsion, wettable powders, water-dispersible granules, suspension, powders, foam, paste, tablet, granules, aerosol, and natural and synthetic substances to which the active compounds are impregnated, microcapsule, seed coating agents, formulation used with a combustion device (for example, a fumatory and fuming cartridge, can, coil and the like as a combustion device) or ULV (cold mist, warm mist) and the like. These formulations can be prepared by methods known per se. For example, the formulations can be prepared by mixing the active compounds with a spreading agent, i.e., liquid diluent or carrier, liquefied gas diluent or carrier, or solid diluent or carrier, and optionally with a surfactant, i.e., emulsifier and/or dispersant and/or foaming agent. When water is used as the spreading agent, for example, organic solvents can be also used as auxiliary solvents.
Examples of the liquid diluent or carrier include aromatic hydrocarbons (for example, xylene, toluene, alkyl naphthalene), chlorinated aromatic, or chlorinated aliphatic hydrocarbons (for example, chlorobenzene, ethylene chloride or methylene chloride), aliphatic hydrocarbons (for example, cyclohexane), paraffins (for example, mineral oil fraction), alcohols (for example, butanol or glycol, and ethers or esters thereof and the like), ketones (for example, acetone, methylethyl ketone, methylisobutyl ketone, cyclohexanone and the like), strong polar solvents (for example, dimethylformamide, dimethylsulfoxide and the like), water and the like.
The liquefied gas diluent or carrier may be gas at normal temperature and pressure such as butane, propane, nitrogen gas, carbon dioxide and aerosol propellents such as halogenated hydrocarbon.
Examples of the solid diluent include pulverized natural minerals (kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatom earth and the like), pulverized synthetic minerals (for example, highly dispersed silicic acid, alumina, silicate and the like) and the like.
Examples of the solid carrier for granules include pulverized and sieved rocks (for example, calcite, marble, pumice, meerschaum, dolomite and the like), synthetic granules of inorganic and organic powders, particulates of an organic material (for example, sawdust, coconut shells, corn cob and tobacco stalk and the like) and the like.
Examples of the emulsifier and/or the foaming agent include non-ionic and anionic emulsifiers (for example, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid alcohol ether (for example, alkylarylpolyglycol ether), alkylsulfonate, alkylsulfate, arylsulfonate and the like), albumin hydrolysate and the like.
Examples of the dispersant include lignin-sulfite waste liquor and methyl cellulose.
Anchoring agents can be also used in the formulation (powders, granules or emulsion), and examples of the anchoring agents include carboxymethylcellulose, natural and synthetic polymers (for example, gum arabic, polyvinyl alcohol, polyvinyl acetate and the like) and the like.
Colorants can be also used, and examples of the colorants include inorganic pigments (for example, iron oxide, titanium oxide, Prussian blue and the like), organic dyes (alizarin dye, azoic dye or metal phthalocyanine dye and the like), and further trace elements such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The above-described formulations may contain the active ingredients in an amount range of generally 0.1 % to 95 % by weight, preferably 0.5 % to 90 % by weight.
As aleady mentioned, the compounds of the present invention may also exist as a mixture with other active compounds, for example, pesticides, poison baits, bactericides, acaricides, nematodacides, fungicides, growth control substances, herbicides and the like in a form of commercially useful formulation and an application form adjusted from the formulation thereof. The content of the compounds of the present invention in the commercially useful applicatiion form may vary in a broad range.
The concentration of the active compounds of the present invention in a practical use may be in a range of, for example, 0.0000001 % to 100 % by weight, preferably 0.00001 % to 1 % by weight.
The compounds of the present invention can be used according to any conventional methods suitable for each application form.
The compounds of the present invention have stability that is effective for alkaline substances present on lime materials when the compounds are used against hygienic pests and other stored product pests. In addition, they exhibit excellent residual effectiveness in woods and soils.
In addition, the active compounds of the present invention have low toxicity for warm-blooded animals, and thus can be used safely.
Examples
Hereinafter, the present invention will be further specifically explained by the Examples, but the present invention should not be limited thereto. Synthesis Example 1
S y n t h e s i s o f 5-[4-chloro-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyr- rol-5-yl] -2-fluorobenzonitrile
Figure imgf000048_0001
2-Fluoro-5-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]benzon (0.3 g) was dissolved in carbon tetrachloride (10 mL), then N-chlorosuccinimide (0.3 g) was added thereto, and the reaction mixture solution was stirred for 3 hours at 40 °C. The reaction mixture solution was filtered, and the filtrate was diluted with methylene chloride (20 mL). The diluted filtrate was washed with water, brine and then dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled under reduced pressure, and the residue was purified with silica-gel column chromatography to obtain 5-[4-chloro-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]-2-fluoro- benzonitrile (0.26 g) in 80 % yield. 1H-NMR(CDCl3)8: 4.58(1H, d), 4.90(1H, d), 5.51(1H, s), 7.33-7.38(3H, m), 8.20-8.35(2H, m).
Synthesis Example 2
Synthesis of 5-[4-chloro-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro- rol-5-yl]-2-(l -l,2,4-triazol-l -yl)benzonitrile (Compound No. 5-2)
Figure imgf000048_0002
2-(l H- 1 ,2,4-triazol- 1 -yl)-5- [3-(3 ,4,5-trichlorophenyl)-3 -(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]be nzonitrile (0.25 g) was dissolved in carbon tetrachloride (10 mL), and N-chlorosuccinimide (0.3 g) was added thereto, and the reaction mixture solution was stirred for 3 hours at 40°C. The reaction mixture solution was filtered, and the filtrate was diluted with methylene chloride (20 mL). The diluted filtrate was washed with water, brine and then dried with anhydrous magnesium sulfate. After filtration, the solvent was distilled under reduced pressure, and the residue was purified with silica-gel column chromatography to obtain 5-[4-chloro-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-di- hydro-2H-pyrrol-5-yl]-2-(lH-l,2,4-triazol-l-yl)benzonitrile (0.25 g) in 86 % yield.
Ti-NMR CDCL.) δ: 4.63(1 H, d), 4.96(1 H, d), 5.59(1 H, s), 7.41 (2H, s), 7.98(1 H, d), 8.23(1H, s), 8.35(1H, d), 8.45(1H, s), 8.92(1H, s). Synthesis Example 3
Synthesis of N-(4- {3-[3,5-bis(trifluoromethyl)phenyl]-4-chloro-3-(trifluoromethyl)-3,4-dihydro rol-5-yl}-2-bromobenzyl)cycl )
Figure imgf000049_0001
S t e p 3-1 : Synthesis of tert-butyl(4- {3-[3,5-bis(trifluoromethyl)phenyl]-4-chloro-3-(trifluoro-
Figure imgf000049_0002
Tert-butyl(4- {3-[3,5-bis(trifluoromethyl)phenyl]-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl^ mobenzyl)carbamate (470 mg, 0.74 mmol) was dissolved in carbon tetrachloride (100 mL). N-chlorosuccinimide (99.1 mg, 0.74 mmol) was added thereto, and the reaction mixture was stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure and the residue was dissolved in tert-butylmethyl ether and washed with water and brine. The organic layer was dried over anhydrous magnesium sulfate, filtered and then concentrated under reduced pressure, and purified with silica-gel column chromatography to obtain the desired product (360 mg).
'H-NMR CDCls) δ: 1.46(9H, s), 4.44(2H, d), 4.64(1H, d), 5.09-4.98(2H, m), 5.64(1H, s), 7.51(1H, d), 7.81(2H, s), 7.88(1H, dd), 7.96(1H, s), 8.19(1H, d).
Step 3-2: Synthesis of l-(4- {3-[3,5-bis(trifluoromethyl)phenyl]-4-chloro-3-(trifluoromethyl)-3,4-di- hydro-2H-pyrrol-5-yl}-2-bromophenyl)methaneamine
Figure imgf000049_0003
Tert-butyl(4- {3 - [3 ,5-bis(trifluoromethyl)phenyl] -4-chloro-3 -(trifluoromethyl)-3 ,4-dihydro-2H-pyrrol-5- yl}-2-bromobenzyl)carbamate (300 mg, 0.44 mmol) was dissolved in 1 ,2-dichloromethane (30 mL). Trifluoroacetic acid (256 mg, 22.4 mmol) was added thereto, and the reaction mixture was stirred for 1 hour at room temperature. The reaction mixture was concentrated under reduced pressure, the residue was dissolved in tert-butylmethyl ether, and washed with an aqueous solution of saturated sodium hydrogen carbonate and brine. The organic layer was dried over anhydrous magnesium sulfate, filtered and then concentrated under reduced pressure (212 mg). The desired product was used in the next step without further purification.
S t e p 3-3: Synthesis of N-(4- {3-[3,5-bis(trifluoromethyl)phenyl]-4-chloro-3-(trifluoro- methyl)- -dihydro-2H-pyrrol-5-yl} -2-bromobenzyl)cyclopropanecarboxamide
Figure imgf000050_0001
l-(4- {3-[3,5-bis(trifluoromethyl)phenyl]-4-chloro-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5 -yl} -2-bromophenyl)methaneamine (100 mg, 0.17 mmol) was dissolved in tetrahydrofuran (5 mL), pyridine (139 mg, 1.76 mmol) and cyclopropane carbonyl chloride (22 mg, 0.21 mmol) were added thereto, and the reaction mixture was stirred overnight. The reaction mixture was diluted with tert-butylmethyl ether, and then washed with 2N hydrochloric acid, water and brine. The organic layer was dried over anhydrous magnesium sulfate, filtered, and then concentrated under reduced pressure. The obtained residue was purified with silica-gel column chromatography to obtain the desired product (100 mg). Ti-NMR CDCls) δ: 0.75-0.81(2H, m), 0.98-1.04(2H, m), 1.37-1.43(1H, m), 4.57-4.67(3H, m), 5.01(1H, d), 5.64(1H, s), 6.21(1H, br s), 7.53(1H, d), 7.81(2H, s), 7.86(1H, dd), 7.96(1H, s), 8.20(1H, d).
Synthesis Example 4
Synthesis of 4- {3-[3,5-bis(trifluoromethyl)phenyl]-4-bromo-3-(trifluoromethyl)-3,4-dihydro-2H-pyr- rol-5-yl}-2-bromo-N-(thiethan-3-yl)benzeneamide (Compound No. 7-7)
Figure imgf000051_0001
Step 4-1 : Synthesis of 4- {3-[3,5-bis(trifluoromethyl)phenyl]-4-bromo-3-(trifluoromethyl)-3,4-di- hydro-2H-p
Figure imgf000051_0002
4- {3-[3,5-bis(trifluoromethyl)phenyl]-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl}-2-bromoben^ acid (100 mg, 0.18 mmol) was dissolved in carbon tetrachloride (5 mL), N-bromosuccinimide (32.5 mg, 0.18 mmol) was added thereto and the reaction mixture was stirred overnight. The reaction mixture was concentrated under reduced pressure, and the residue was dissolved in tert-butylmethyl ether, and washed with water and brine. The organic layer was dried over anhydrous magnesium sulfate, and filtered to obtain the targeted product (110 mg). It was used in the next step without further purification.
'H-NMRCCDCls) δ: 4.62(1H, d), 5.05(1H, d), 5.69(1H, s), 7.81(2H, s), 8.00-7.97(2H, m), 8.08(1H, d), 8.33(1H, d).
Step 4-2: Synthesis of 4- {3-[3,5-bis(trifluoromethyl)phenyl]-4-bromo-3-(trifluoromethyl)-3,4-di- hydro-2H-p
Figure imgf000051_0003
Thiethan-3 -amine bromide (34 mg, 0.19 mmol) was dissolved in N,N-dimethylformamide (5 mL), triethylamine (50 mg, 0.49 mmol) was added thereto at 0 °C, and the reaction mixture was stirred for 30 minutes at ro om temp erature . To this solution was added l-(3-dimethylamino- propyl)-3-ethylcarbodiimide hydrochloride (45 mg, 0.19 mmol), 1-hydroxybenzotriazole (27 mg, 0.19 mmol) and 4- {3-[3,5-bis(trifluoromethyl)phenyl]-4-bromo-3-(trifluoromethyl)-3,4-dihydro-2H-pyr- rol-5-yl} -2-bromobenzoic acid (1 10 mg, 0.19 mmol) at 0 °C, and the reaction mixture was stirred overnight at room temperature. The reaction mixture was diluted with tert-butylmethyl ether, and then washed with 2N hydrochloric acid, water and brine. The organic layer was dried over anhydrous magnesium sulfate, filtered, and then concentrated under reduced pressure. The obtained residue was purified with silica-gel column chromatography to obtain the desired product (30 mg).
¾-NMR(CDCl3) δ: 3.52-3.41(4H, m), 4.59(1H, d), 5.01(1H, d), 5.35-5.51(lH, m), 5.68(1H, s), 6.64(1H, d), 7.63(1H, d), 7. 80(2H, s), 7.92-7.97(2H, m), 8.23(1H, d).
Synthesis Example 5
Synthesis of methyl 5-(3-cyano-4-fluorophenyl)-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-di- hydro-2H-pyrrol-4-carboxylate
Figure imgf000052_0001
A mixture of 2,2,2-trifluoro-l-(3,4,5-trichlorophenyl)ethanone (20 g, 72 mmol), anhydrous acetic acid (100 ml) and sodium acetate (11.8 g, 144 mmol) was stirred for 5 hours at 100 °C. The reaction mixture was cooled and then stirred in an ice water bath. Water (200 ml) was added over about 30 minutes and then stirred for 2 hours at room temperature. The product was extracted with tert-butylmethyl ether, The organic layer was washed with water and dried over anhydrous magnesium sulfate. The solvent was distilled under reduced pressure, and the remaining acetic acid was removed by distillation in presence of toluene to obtain 30 g of a crude product. The crude product was recrystallized from hexane to obtain the titled compound in 17.9 g and 85.5 % yield. The mother liquor was distilled under reduced pressure and treated in the same manner to obtain 2.6 g of the titled compound as a second crystal.
1H-NMR(CDCl3+DMSO-d6) δ: 6.67(1H, s), 7.35(2H, s)
Step 5-2: Synthesis of methyl (2E)-4,4,4-trifluoro-3-(3,4,5-trichlorophenyl)buta-2-enoate
Figure imgf000053_0001
(2E)-4,4,4-trifluoro-3-(3,4,5-trichlorophenyl)buta-2-enoic acid (5.0 g, 15.6 mmol) and 4-toluenesulfonic acid monohydrate (0.3 g, 1.56 mmol) were refluxed in 100 ml of methyl alcohol for 12 hours. After the completion of the reaction, the solvent was distilled under reduced pressure, and the residue was dissolved in ethyl acetate, washed with an aqueous solution of saturated sodium hydrogen carbonate and, brine, and then dried over anhydrous magnesium sulfate. The solvent was distilled under reduced pressure, and the residue was purified with silica-gel column chromatography (solvent: hexane/ethyl acetate = 95/5) to obtain 3.8 g of the titled compound. 73 % yield.
'H-NMRCCDCls) δ: 3.69(3H, s), 6.66(1H, s), 7.31(2H, s) Step 5-3: Synthesis of methyl 2-(3-bromo-4-fluorophenyl)-4-(3,4,5-trichlorophenyl)-4-(trifluoro-
Figure imgf000053_0002
(2E)-4,4,4-trifluoro-3-(3,4,5-trichlorophenyl)-buta-2-e n o n e ( 5 0 0 m g , 1 . 5 0 m m o l ) , 2-bromo-l-fluoro-4-(isocyanomethyl)benzene (331 mg, 1.50 mmol), and copper(I) oxide (21 mg, 0.15 mmol) were refluxed in toluene (5 ml) for 10 hours. After the completion of the reaction, the reaction mixture was poured into 50 ml of water, and extracted with ethyl acetate (30 ml three times). The organic layer was washed with brine, and then dried over anhydrous magnesium sulfate. Then, the solvent was distilled under reduced pressure, and the residue was purified with silica gel column chromatography to obtain the desired compound (Solvent: hexane:ethyl acetate = 98:2 and then 95:5) in 500 mg and 61 % yield.
'H-NMRCCDCls) δ: 3.21 (d)&3.41(d)(lH), 3.54(s)&3.88(s)(3H), 4.08-4.16(m, 1H), 5.67-5.71 (m, 1H), 7.05-7.87(m, 6H)
Step 5-4: Synthesis of methyl 5-(3-bromo-4-fluorophenyl)-3-(3,4,5-trichlorophenyl)-3-(trifluoro- methyl)-3,4-dihydro-2H-pyrrol-4-carboxylate
Figure imgf000054_0001
Methyl 2-(3-bromo-4-fluorophenyl)-4-(3,4,5-trichlorophenyl)-4-(trifluoromethyl)-3,4-dihydro-2H-pyr- rol-3-carboxylate (450 mg, 0.82 mmol) and l,8-diazabicyclo(5,4,0)undec-7-ene (25 mg, 0.16 mmol) were refluxed with pyridine (10 ml) for 2 hours. The solvent was distilled under reduced pressure, and then the residue was dissolved in ethyl acetate, and washed with water, and then brine. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. Then, the residue was purified with silica gel column chromatography to obtain the desired compound (Solvent: hexane:ethyl acetate = 98:2 and then 95:5) in 310 mg and 69 % yield.
'H-NMRCCDCls) δ: 3.50(3H, s), 4.66-4.91(3H, m), 7.17-8.22(5H, m) Step 5-5: Synthesis of methyl 5-(3-cyano-4-fluorophenyl)-3-(3,4,5-trichlorophenyl)-3-(trifluoro- methyl)- -dihydro-2H-pyrrol-4-carboxylate
Figure imgf000054_0002
Methyl 5-(3-bromo-4-fluorophenyl)-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyr- rol-4-carboxylate (250 mg, 0.475 mmol), zinc cyanide (112 mg, 0.95 mmol) and tetrakis(triphenylphosphine)palladium (110 mg, 0.095 mmol) were mixed in N,N-dimethylformamide (15 ml) under Argon at 100 °C for 2 hours. After the completion of the reaction, the reaction mixture was poured into water, and extracted with ethyl acetate. The organic layer was washed with water, brine and dried over anhydrous magnesium sulfate. The solvent was distilled under reduced pressure, and the residue was purified with silica gel column chromatography to obtain the desired compound (Solvent: hexane:ethyl acetate = 90:10) in 85 mg and 36 % yield.
'H-NMRCCDCls) δ: 3.51(3H, s), 4.67-4.93(3H, m), 7.29-8.23(5H, m)
Synthesis Example 6 Synthesis of methyl 5-(3-cyano-4-fluorophenyl)-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-di- hydro-2H-pyrrol-4-carboxylate
Figure imgf000055_0001
Step 6-1 : Synthesis of methyl 2-(3-cyano-4-fluorophenyl)-4-(3,4,5-trichlorophenyl)-4-(trifluoro-
Figure imgf000055_0002
(2E)-4,4,4-trifluoro-3-(3,4,5-trichlorophenyl)-buta-2-e n o n e ( 7 0 0 m g , 2 . 1 0 m m o l ) , 2-fluoro-5-isocyanomethyl-benzonitrile (336 mg, 2.10 mmol) and copper(I) oxide (21 mg, 0.15 mmol) were refluxed in toluene (10 ml) for 8 hours. After the completion of the reaction, the reaction mixture was poured into 50 ml of water, and extracted with ethyl acetate (30 ml three times). The organic layer was washed with brine, and then dried over anhydrous magnesium sulfate. The solvent was distilled under reduced pressure, and the residue was purified with silica gel column chromatography to obtain the desired compound (Solvent: hexane:ethyl acetate = 90:10) in 410 mg and 40 % yield.
¾-NMR(CDCl3) δ: 3.37(1H, d), 3.61(3H, s), 4.11-4.18(1H, m), 5.73-5.78(lH, m), 7.07-7.72(6H, m) Step 6-2: Synthesis of methyl 5-(3-cyano-4-fluorophenyl)-3-(3,4,5-trichlorophenyl)-3-(trifluoro- methyl)-3 -dihydro-2H-pyrrol-4-carboxylate
Figure imgf000055_0003
Methyl 2-(3-cyano-4-fluorophenyl)-4-(3,4,5-trichlorophenyl)-4-(trifluoromethyl)-3,4-dihydro-2H-pyr- rol-3-carboxylate (100 mg, 0.20 mmol) and l,8-diazabicyclo(5,4,0)undec-7-ene (6 mg, 0.04 mmol) were refluxed in pyridine (4 ml) for 1 hour. The solvent was distilled under reduced pressure, and the residue was dissolved in ethyl acetate, and washed with water and brine. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The residue was purified with silica gel column chromatography to obtain the desired compound (Solvent: hexane:ethyl acetate = 85/15) in 40 mg and 40 % yield.
'H-NMRCCDCls) δ: 3.51(3H, s), 4.67-4.93(3H, m), 7.29-8.23(5H, m)
Synthesis Example 7
Synthesis of methyl 5-[3-cyano-4-(lH-l,2,4-triazolo-l -yl)phenyl]-3-(3,4,5-trichlorophenyl)-3-(trifluoro- methyl)-3,4-dihydro-2H-pyrrol-4-carboxylate, and methyl 2-[3-cyano-4-(lH-l,2,4-triazolo-l -yl)phe- nyl]-4-(3,4,5-trichlorophenyl)-4-(trifluoromethyl)-4,5-dihydro-lH-pyrrol-3-carboxylate (Compound No. -6)
Figure imgf000056_0001
Methyl 2-(3-cyano-4-fluorophenyl)-4-(3,4,5-trichlorophenyl)-4-(trifluoromethyl)-3,4-dihydro-2H-pyr- rol-3-carboxylate (180 mg, 0.37 mmol), lH-l,2,4-triazole (33 mg, 0.47 mmol) and potassium carbonate (76 mg, 0.55 mmol) were stirred in N,N-dimethylformamide (10 ml) at 100 °C for 2 hours. The reaction mixture was poured into water, and extracted with ethyl acetate. The organic layer was washed with brine, and then dried over anhydrous magnesium sulfate. Then, the solvent was distilled under reduced pressure, and the residue was purified with silica gel column chromatography (Solvent: the ratio of ethyl acetate increased from hexane/ethyl acetate 60/40 to 0/100) to obtain 1 10 mg mixture of methyl 5-[3-cyano-4-(lH-l,2,4-triazolo-l-yl)phenyl]-3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-3,4-di- hydro-2H-pyrrol-4-carboxylate ('H-NMRCCDCls) δ: 3.52(3H, s), 4.72-4.99(3H, m), 7.41-8.93(7H, m)) a n d m e t h y l 2-[3-cyano-4-(lH-l,2,4-triazolo-l -yl)phenyl]-4-(3,4,5-trichlorophenyl)-4-(trifluoro- methyl)-4,5-dihydro-lH-pyrrol-3-carboxylate ('H-NMRCCDCls) δ: 3.46(3H, s), 3.80(1H, dd), 4.34(1H, dd), 4.48(1H, s), 7.25-8.89(8H, m)) in 55 % yield. Synthesis Example of benzonitrile intermediate
Synthesis of 2-fluoro-5-(isocyanomethyl)benzonitrile
Figure imgf000057_0001
N-(3-cyano-4-fluorobenzyl)formamide (550 mg, 3.09 mmol) and N,N-diisopropylethylamine (1.80 g, 13.9 mmol) were stirred with dichloromethane (20 ml) in ice-cold water bath, and the solution of phosphorus oxychloride (710 mg, 4.63 mmol) in dichloromethane (10 ml) was added dropwise thereto. After the complete addition, the reaction mixture was stirred for 0.5 hour, and further stirred for 2 hours at room temperature. The reaction mixture was poured into dichloromethane, and then washed with water, an aqueous solution of sodium hydrogen carbonate and brine. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The residue was purified with silica gel column chromatography to obtain the desired compound (Solvent: hexane/ethyl acetate 80/20) in 330 mg and 67 % yield.
'H-NMRCCDCls) δ: 4.67(2H, s), 7.25-7.65(3H, m)
Synthesis of 2-
Figure imgf000057_0002
N-(3-bromo-4-fluorobenzyl)formamide (280 mg, 1.21 mmol), and N,N-diisopropylethylamine (702 mg, 5.43 mmol) were stirred in dichloromethane (10 ml) under ice-cooling. A solution of phosphorus oxychloride (278 mg, 1.81 mmol) in dichloromethane (5 ml) was added dropwise thereto. After the complete addition, the reaction mixture was stirred for 0.5 hour, and further stirred for 2 hours at room temperature. The reaction mixture was poured into dichloromethane, and then washed with water, an aqueous solution of sodium hydrogen carbonate and brine. The organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The residue was purified with silica gel column chromatography to obtain the desired compound (Solvent: hexane/ethyl acetate 95/5 and subsequently 90/10) in 150 mg and 58 % yield.
'H-NMRCCDCls) δ: 4.61(2H, s), 7.13-7.58(3H, m)
The compounds of Formula (I) of the present invention and intermediates thereof, which are obtained in similar manners to the above-described Synthesis Examples, and in accordance with the methods specifically explained above, are shown in the combination of Table a and Tables 1 to 4. In addition, each compound that was obtained in the above-described Synthesis Examples, and the materials property values thereof are shown in Tables 5 to 7 and NMR Table, respectively.
The abbreviations in the Tables are as below:
Figure imgf000058_0001
Figure imgf000058_0002
wherein the moiety represented by the following formula:
Figure imgf000059_0001
represents any one of Al to Al 0 or Al ' to Al 0' in Table
X1 B X2 R A1 A2 A4 G (Z)k
1-1 CI C-H CI CF3 C-H C-H C-H F -
1-2 CI C-H CI CF3 C-H C-H C-H Gl H
1-3 CI C-H CI CF3 C-H C-H C-H G2 H
1-4 CI C-H CI CF3 C-H C-H C-H G2 4-F
1-5 CI C-H CI CF3 C-H C-H C-H G2 4-Cl
1-6 CI C-H CI CF3 C-H C-H C-H G2 4-Br
1-7 CI C-H CI CF3 C-H C-H C-H G2 4-CN
1-8 CI C-H CI CF3 C-H C-H C-H G2 4-NC-2
1-9 CI C-H CI CF3 C-H C-H C-H G3 H
1-10 CI C-H CI CF3 C-H C-H C-H G4 H
1-11 CI C-H CI CF3 C-H C-H C-H G5 H
1-12 CI C-H CI CF3 C-H C-H C-H G6 H
1-13 CI C-H CI CF3 C-H C-H C-H G7 H
1-14 CI C-H CI CF3 C-H C-H C-H G8 H
1-15 CI C-H CI CF3 C-H C-H C-H G9 H
1-16 CI C-H CI CF3 C-H C-H C-H F -
1-17 CI C-H CI CF3 C-H C-H C-Cl Gl H
1-18 CI C-H CI CF3 C-H C-H C-Cl G2 H
1-19 CI C-H CI CF3 C-H C-H C-Cl G2 4-F
1-20 CI C-H CI CF3 C-H C-H C-Cl G2 4-Cl
1-21 CI C-H CI CF3 C-H C-H C-Cl G2 4-Br
1-22 CI C-H CI CF3 C-H C-H C-Cl G2 4-CN
1-23 CI C-H CI CF3 C-H C-H C-Cl G2 4-NC-2
1-24 CI C-H CI CF3 C-H C-H C-Cl G3 H
1-25 CI C-H CI CF3 C-H C-H C-Cl G4 H
1-26 CI C-H CI CF3 C-H C-H C-Cl G5 H
1-27 CI C-H CI CF3 C-H C-H C-Cl G6 H
1-28 CI C-H CI CF3 C-H C-H C-Cl G7 H
1-29 CI C-H CI CF3 C-H C-H C-Cl G8 H
1-30 CI C-H CI CF3 C-H C-H C-Cl G9 H X1 B X2 R A1 A2 A4 G (Z)k-31 CI C-H CI CF3 C-H C-H C-Br F --32 CI C-H CI CF3 C-H C-H C-Br Gl H-33 CI C-H CI CF3 C-H C-H C-Br G2 H-34 CI C-H CI CF3 C-H C-H C-Br G2 4-F-35 CI C-H CI CF3 C-H C-H C-Br G2 4-Cl-36 CI C-H CI CF3 C-H C-H C-Br G2 4-Br-37 CI C-H CI CF3 C-H C-H C-Br G2 4-CN-38 CI C-H CI CF3 C-H C-H C-Br G2 4-NO2-39 CI C-H CI CF3 C-H C-H C-Br G3 H-40 CI C-H CI CF3 C-H C-H C-Br G4 H-41 CI C-H CI CF3 C-H C-H C-Br G5 H-42 CI C-H CI CF3 C-H C-H C-Br G6 H-43 CI C-H CI CF3 C-H C-H C-Br G7 H-44 CI C-H CI CF3 C-H C-H C-Br G8 H-45 CI C-H CI CF3 C-H C-H C-Br G9 H-46 CI C-H CI CF3 C-H C-H C-N02 F --47 CI C-H CI CF3 C-H C-H C-NO2 Gl H-48 CI C-H CI CF3 C-H C-H C-NO2 G2 H-49 CI C-H CI CF3 C-H C-H C-NO2 G2 4-F-50 CI C-H CI CF3 C-H C-H C-NO2 G2 4-Cl-51 CI C-H CI CF3 C-H C-H C-NO2 G2 4-Br-52 CI C-H CI CF3 C-H C-H C-NO2 G2 4-CN-53 CI C-H CI CF3 C-H C-H C-NO2 G2 4-NO2-54 CI C-H CI CF3 C-H C-H C-NO2 G3 H-55 CI C-H CI CF3 C-H C-H C-NO2 G4 H-56 CI C-H CI CF3 C-H C-H C-NO2 G5 H-57 CI C-H CI CF3 C-H C-H C-NO2 G6 H-58 CI C-H CI CF3 C-H C-H C-NO2 G7 H-59 CI C-H CI CF3 C-H C-H C-NO2 G8 H-60 CI C-H CI CF3 C-H C-H C-NO2 G9 H-61 CI C-H CI CF3 C-H C-H C-CN F --62 CI C-H CI CF3 C-H C-H C-CN Gl H-63 CI C-H CI CF3 C-H C-H C-CN G2 H-64 CI C-H CI CF3 C-H C-H C-CN G2 4-F X1 B X2 R A1 A2 A4 G (Z)k-65 CI C-H CI CF3 C-H C-H C-CN G2 4-Cl-66 CI C-H CI CF3 C-H C-H C-CN G2 4-Br-67 CI C-H CI CF3 C-H C-H C-CN G2 4-CN-68 CI C-H CI CF3 C-H C-H C-CN G2 4-NC-2-69 CI C-H CI CF3 C-H C-H C-CN G3 H-70 CI C-H CI CF3 C-H C-H C-CN G4 H-71 CI C-H CI CF3 C-H C-H C-CN G5 H-72 CI C-H CI CF3 C-H C-H C-CN G6 H-73 CI C-H CI CF3 C-H C-H C-CN G7 H-74 CI C-H CI CF3 C-H C-H C-CN G8 H-75 CI C-H CI CF3 C-H C-H C-CN G9 H-76 CF3 C-H H CF3 C-H C-H C-H F --77 CF3 C-H H CF3 C-H C-H C-H Gl H-78 CF3 C-H H CF3 C-H C-H C-H G2 H-79 CF3 C-H H CF3 C-H C-H C-H G2 4-F-80 CF3 C-H H CF3 C-H C-H C-H G2 4-Cl-81 CF3 C-H H CF3 C-H C-H C-H G2 4-Br-82 CF3 C-H H CF3 C-H C-H C-H G2 4-CN-83 CF3 C-H H CF3 C-H C-H C-H G2 4-NC-2-84 CF3 C-H H CF3 C-H C-H C-H G3 H-85 CF3 C-H H CF3 C-H C-H C-H G4 H-86 CF3 C-H H CF3 C-H C-H C-H G5 H-87 CF3 C-H H CF3 C-H C-H C-H G6 H-88 CF3 C-H H CF3 C-H C-H C-H G7 H-89 CF3 C-H H CF3 C-H C-H C-H G8 H-90 CF3 C-H H CF3 C-H C-H C-H G9 H-91 CF3 C-H H CF3 C-H C-H C-H F --92 CF3 C-H H CF3 C-H C-H C-Cl Gl H-93 CF3 C-H H CF3 C-H C-H C-Cl G2 H-94 CF3 C-H H CF3 C-H C-H C-Cl G2 4-F-95 CF3 C-H H CF3 C-H C-H C-Cl G2 4-Cl-96 CF3 C-H H CF3 C-H C-H C-Cl G2 4-Br-97 CF3 C-H H CF3 C-H C-H C-Cl G2 4-CN-98 CF3 C-H H CF3 C-H C-H C-Cl G2 4-NC-2 X1 B X2 R A1 A2 A4 G (Z)k-99 CF3 C-H H CF3 C-H C-H C-Cl G3 H-100 CF3 C-H H CF3 C-H C-H C-Cl G4 H-101 CF3 C-H H CF3 C-H C-H C-Cl G5 H-102 CF3 C-H H CF3 C-H C-H C-Cl G6 H-103 CF3 C-H H CF3 C-H C-H C-Cl G7 H-104 CF3 C-H H CF3 C-H C-H C-Cl G8 H-105 CF3 C-H H CF3 C-H C-H C-Cl G9 H-106 CF3 C-H H CF3 C-H C-H C-Br F --107 CF3 C-H H CF3 C-H C-H C-Br Gl H-108 CF3 C-H H CF3 C-H C-H C-Br G2 H-109 CF3 C-H H CF3 C-H C-H C-Br G2 4-F-110 CF3 C-H H CF3 C-H C-H C-Br G2 4-Cl-111 CF3 C-H H CF3 C-H C-H C-Br G2 4-Br-112 CF3 C-H H CF3 C-H C-H C-Br G2 4-CN-113 CF3 C-H H CF3 C-H C-H C-Br G2 4-NO2-114 CF3 C-H H CF3 C-H C-H C-Br G3 H-115 CF3 C-H H CF3 C-H C-H C-Br G4 H-116 CF3 C-H H CF3 C-H C-H C-Br G5 H-117 CF3 C-H H CF3 C-H C-H C-Br G6 H-118 CF3 C-H H CF3 C-H C-H C-Br G7 H-119 CF3 C-H H CF3 C-H C-H C-Br G8 H-120 CF3 C-H H CF3 C-H C-H C-Br G9 H-121 CF3 C-H H CF3 C-H C-H C-N02 F --122 CF3 C-H H CF3 C-H C-H C-NO2 Gl H-123 CF3 C-H H CF3 C-H C-H C-NO2 G2 H-124 CF3 C-H H CF3 C-H C-H C-NO2 G2 4-F-125 CF3 C-H H CF3 C-H C-H C-NO2 G2 4-Cl-126 CF3 C-H H CF3 C-H C-H C-NO2 G2 4-Br-127 CF3 C-H H CF3 C-H C-H C-NO2 G2 4-CN-128 CF3 C-H H CF3 C-H C-H C-NO2 G2 4-NO2-129 CF3 C-H H CF3 C-H C-H C-NO2 G3 H-130 CF3 C-H H CF3 C-H C-H C-NO2 G4 H-131 CF3 C-H H CF3 C-H C-H C-NO2 G5 H-132 CF3 C-H H CF3 C-H C-H C-NO2 G6 H X1 B X2 R A1 A2 A4 G (Z)k-133 CF3 C-H H CF3 C-H C-H C-N02 G7 H-134 CF3 C-H H CF3 C-H C-H C-NO2 G8 H-135 CF3 C-H H CF3 C-H C-H C-NO2 G9 H-136 CF3 C-H H CF3 C-H C-H C-CN F --137 CF3 C-H H CF3 C-H C-H C-CN Gl H-138 CF3 C-H H CF3 C-H C-H C-CN G2 H-139 CF3 C-H H CF3 C-H C-H C-CN G2 4-F-140 CF3 C-H H CF3 C-H C-H C-CN G2 4-Cl-141 CF3 C-H H CF3 C-H C-H C-CN G2 4-Br-142 CF3 C-H H CF3 C-H C-H C-CN G2 4-CN-143 CF3 C-H H CF3 C-H C-H C-CN G2 4-NO2-144 CF3 C-H H CF3 C-H C-H C-CN G3 H-145 CF3 C-H H CF3 C-H C-H C-CN G4 H-146 CF3 C-H H CF3 C-H C-H C-CN G5 H-147 CF3 C-H H CF3 C-H C-H C-CN G6 H-148 CF3 C-H H CF3 C-H C-H C-CN G7 H-149 CF3 C-H H CF3 C-H C-H C-CN G8 H-150 CF3 C-H H CF3 C-H C-H C-CN G9 H-151 CF3 C-H CF3 CF3 C-H C-H C-H F --152 CF3 C-H CF3 CF3 C-H C-H C-H Gl H-153 CF3 C-H CF3 CF3 C-H C-H C-H G2 H-154 CF3 C-H CF3 CF3 C-H C-H C-H G2 4-F-155 CF3 C-H CF3 CF3 C-H C-H C-H G2 4-Cl-156 CF3 C-H CF3 CF3 C-H C-H C-H G2 4-Br-157 CF3 C-H CF3 CF3 C-H C-H C-H G2 4-CN-158 CF3 C-H CF3 CF3 C-H C-H C-H G2 4-NO2-159 CF3 C-H CF3 CF3 C-H C-H C-H G3 H-160 CF3 C-H CF3 CF3 C-H C-H C-H G4 H-161 CF3 C-H CF3 CF3 C-H C-H C-H G5 H-162 CF3 C-H CF3 CF3 C-H C-H C-H G6 H-163 CF3 C-H CF3 CF3 C-H C-H C-H G7 H-164 CF3 C-H CF3 CF3 C-H C-H C-H G8 H-165 CF3 C-H CF3 CF3 C-H C-H C-H G9 H-166 CF3 C-H CF3 CF3 C-H C-H C-H F - X1 B X2 R A1 A2 A4 G (Z)k-167 CF3 C-H CF3 CF3 C-H C-H C-Cl Gl H-168 CF3 C-H CF3 CF3 C-H C-H C-Cl G2 H-169 CF3 C-H CF3 CF3 C-H C-H C-Cl G2 4-F-170 CF3 C-H CF3 CF3 C-H C-H C-Cl G2 4-Cl-171 CF3 C-H CF3 CF3 C-H C-H C-Cl G2 4-Br-172 CF3 C-H CF3 CF3 C-H C-H C-Cl G2 4-CN-173 CF3 C-H CF3 CF3 C-H C-H C-Cl G2 4-NO2-174 CF3 C-H CF3 CF3 C-H C-H C-Cl G3 H-175 CF3 C-H CF3 CF3 C-H C-H C-Cl G4 H-176 CF3 C-H CF3 CF3 C-H C-H C-Cl G5 H-177 CF3 C-H CF3 CF3 C-H C-H C-Cl G6 H-178 CF3 C-H CF3 CF3 C-H C-H C-Cl G7 H-179 CF3 C-H CF3 CF3 C-H C-H C-Cl G8 H-180 CF3 C-H CF3 CF3 C-H C-H C-Cl G9 H-181 CF3 C-H CF3 CF3 C-H C-H C-Br F --182 CF3 C-H CF3 CF3 C-H C-H C-Br Gl H-183 CF3 C-H CF3 CF3 C-H C-H C-Br G2 H-184 CF3 C-H CF3 CF3 C-H C-H C-Br G2 4-F-185 CF3 C-H CF3 CF3 C-H C-H C-Br G2 4-Cl-186 CF3 C-H CF3 CF3 C-H C-H C-Br G2 4-Br-187 CF3 C-H CF3 CF3 C-H C-H C-Br G2 4-CN-188 CF3 C-H CF3 CF3 C-H C-H C-Br G2 4-NO2-189 CF3 C-H CF3 CF3 C-H C-H C-Br G3 H-190 CF3 C-H CF3 CF3 C-H C-H C-Br G4 H-191 CF3 C-H CF3 CF3 C-H C-H C-Br G5 H-192 CF3 C-H CF3 CF3 C-H C-H C-Br G6 H-193 CF3 C-H CF3 CF3 C-H C-H C-Br G7 H-194 CF3 C-H CF3 CF3 C-H C-H C-Br G8 H-195 CF3 C-H CF3 CF3 C-H C-H C-Br G9 H-196 CF3 C-H CF3 CF3 C-H C-H C-N02 F --197 CF3 C-H CF3 CF3 C-H C-H C-NO2 Gl H-198 CF3 C-H CF3 CF3 C-H C-H C-NO2 G2 H-199 CF3 C-H CF3 CF3 C-H C-H C-NO2 G2 4-F-200 CF3 C-H CF3 CF3 C-H C-H C-NO2 G2 4-Cl X1 B X2 R A1 A2 A4 G (Z)k-201 CF3 C-H CF3 CF3 C-H C-H C-N02 G2 4-Br-202 CF3 C-H CF3 CF3 C-H C-H C-NO2 G2 4-CN-203 CF3 C-H CF3 CF3 C-H C-H C-NO2 G2 4-NO2-204 CF3 C-H CF3 CF3 C-H C-H C-NO2 G3 H-205 CF3 C-H CF3 CF3 C-H C-H C-NO2 G4 H-206 CF3 C-H CF3 CF3 C-H C-H C-NO2 G5 H-207 CF3 C-H CF3 CF3 C-H C-H C-NO2 G6 H-208 CF3 C-H CF3 CF3 C-H C-H C-NO2 G7 H-209 CF3 C-H CF3 CF3 C-H C-H C-NO2 G8 H-210 CF3 C-H CF3 CF3 C-H C-H C-NO2 G9 H-211 CF3 C-H CF3 CF3 C-H C-H C-CN F --212 CF3 C-H CF3 CF3 C-H C-H C-CN Gl H-213 CF3 C-H CF3 CF3 C-H C-H C-CN G2 H-214 CF3 C-H CF3 CF3 C-H C-H C-CN G2 4-F-215 CF3 C-H CF3 CF3 C-H C-H C-CN G2 4-Cl-216 CF3 C-H CF3 CF3 C-H C-H C-CN G2 4-Br-217 CF3 C-H CF3 CF3 C-H C-H C-CN G2 4-CN-218 CF3 C-H CF3 CF3 C-H C-H C-CN G2 4-NO2-219 CF3 C-H CF3 CF3 C-H C-H C-CN G3 H-220 CF3 C-H CF3 CF3 C-H C-H C-CN G4 H-221 CF3 C-H CF3 CF3 C-H C-H C-CN G5 H-222 CF3 C-H CF3 CF3 C-H C-H C-CN G6 H-223 CF3 C-H CF3 CF3 C-H C-H C-CN G7 H-224 CF3 C-H CF3 CF3 C-H C-H C-CN G8 H-225 CF3 C-H CF3 CF3 C-H C-H C-CN G9 H-226 Br C-H Br CF3 C-H C-H C-H F --227 Br C-H Br CF3 C-H C-H C-H Gl H-228 Br C-H Br CF3 C-H C-H C-H G2 H-229 Br C-H Br CF3 C-H C-H C-H G2 4-F-230 Br C-H Br CF3 C-H C-H C-H G2 4-Cl-231 Br C-H Br CF3 C-H C-H C-H G2 4-Br-232 Br C-H Br CF3 C-H C-H C-H G2 4-CN-233 Br C-H Br CF3 C-H C-H C-H G2 4-NO2-234 Br C-H Br CF3 C-H C-H C-H G3 H X1 B X2 R A1 A2 A4 G (Z)k-235 Br C-H Br CF3 C-H C-H C-H G4 H-236 Br C-H Br CF3 C-H C-H C-H G5 H-237 Br C-H Br CF3 C-H C-H C-H G6 H-238 Br C-H Br CF3 C-H C-H C-H G7 H-239 Br C-H Br CF3 C-H C-H C-H G8 H-240 Br C-H Br CF3 C-H C-H C-H G9 H-241 Br C-H Br CF3 C-H C-H C-H F --242 Br C-H Br CF3 C-H C-H C-Cl Gl H-243 Br C-H Br CF3 C-H C-H C-Cl G2 H-244 Br C-H Br CF3 C-H C-H C-Cl G2 4-F-245 Br C-H Br CF3 C-H C-H C-Cl G2 4-Cl-246 Br C-H Br CF3 C-H C-H C-Cl G2 4-Br-247 Br C-H Br CF3 C-H C-H C-Cl G2 4-CN-248 Br C-H Br CF3 C-H C-H C-Cl G2 4-NC-2-249 Br C-H Br CF3 C-H C-H C-Cl G3 H-250 Br C-H Br CF3 C-H C-H C-Cl G4 H-251 Br C-H Br CF3 C-H C-H C-Cl G5 H-252 Br C-H Br CF3 C-H C-H C-Cl G6 H-253 Br C-H Br CF3 C-H C-H C-Cl G7 H-254 Br C-H Br CF3 C-H C-H C-Cl G8 H-255 Br C-H Br CF3 C-H C-H C-Cl G9 H-256 Br C-H Br CF3 C-H C-H C-Br F --257 Br C-H Br CF3 C-H C-H C-Br Gl H-258 Br C-H Br CF3 C-H C-H C-Br G2 H-259 Br C-H Br CF3 C-H C-H C-Br G2 4-F-260 Br C-H Br CF3 C-H C-H C-Br G2 4-Cl-261 Br C-H Br CF3 C-H C-H C-Br G2 4-Br-262 Br C-H Br CF3 C-H C-H C-Br G2 4-CN-263 Br C-H Br CF3 C-H C-H C-Br G2 4-NC-2-264 Br C-H Br CF3 C-H C-H C-Br G3 H-265 Br C-H Br CF3 C-H C-H C-Br G4 H-266 Br C-H Br CF3 C-H C-H C-Br G5 H-267 Br C-H Br CF3 C-H C-H C-Br G6 H-268 Br C-H Br CF3 C-H C-H C-Br G7 H X1 B X2 R A1 A2 A4 G (Z)k-269 Br C-H Br CF3 C-H C-H C-Br G8 H-270 Br C-H Br CF3 C-H C-H C-Br G9 H-271 Br C-H Br CF3 C-H C-H C-N02 F --272 Br C-H Br CF3 C-H C-H C-NO2 Gl H-273 Br C-H Br CF3 C-H C-H C-NO2 G2 H-274 Br C-H Br CF3 C-H C-H C-NO2 G2 4-F-275 Br C-H Br CF3 C-H C-H C-NO2 G2 4-Cl-276 Br C-H Br CF3 C-H C-H C-NO2 G2 4-Br-277 Br C-H Br CF3 C-H C-H C-NO2 G2 4-CN-278 Br C-H Br CF3 C-H C-H C-NO2 G2 4-NO2-279 Br C-H Br CF3 C-H C-H C-NO2 G3 H-280 Br C-H Br CF3 C-H C-H C-NO2 G4 H-281 Br C-H Br CF3 C-H C-H C-NO2 G5 H-282 Br C-H Br CF3 C-H C-H C-NO2 G6 H-283 Br C-H Br CF3 C-H C-H C-NO2 G7 H-284 Br C-H Br CF3 C-H C-H C-NO2 G8 H-285 Br C-H Br CF3 C-H C-H C-NO2 G9 H-286 Br C-H Br CF3 C-H C-H C-CN F --287 Br C-H Br CF3 C-H C-H C-CN Gl H-288 Br C-H Br CF3 C-H C-H C-CN G2 H-289 Br C-H Br CF3 C-H C-H C-CN G2 4-F-290 Br C-H Br CF3 C-H C-H C-CN G2 4-Cl-291 Br C-H Br CF3 C-H C-H C-CN G2 4-Br-292 Br C-H Br CF3 C-H C-H C-CN G2 4-CN-293 Br C-H Br CF3 C-H C-H C-CN G2 4-NO2-294 Br C-H Br CF3 C-H C-H C-CN G3 H-295 Br C-H Br CF3 C-H C-H C-CN G4 H-296 Br C-H Br CF3 C-H C-H C-CN G5 H-297 Br C-H Br CF3 C-H C-H C-CN G6 H-298 Br C-H Br CF3 C-H C-H C-CN G7 H-299 Br C-H Br CF3 C-H C-H C-CN G8 H-300 Br C-H Br CF3 C-H C-H C-CN G9 H-301 CI C-Cl CI CF3 C-H C-H C-H F --302 CI C-Cl CI CF3 C-H C-H C-H Gl H X1 B X2 R A1 A2 A4 G (Z)k-303 CI C-Cl CI CF3 C-H C-H C-H G2 H-304 CI C-Cl CI CF3 C-H C-H C-H G2 4-F-305 CI C-Cl CI CF3 C-H C-H C-H G2 4-Cl-306 CI C-Cl CI CF3 C-H C-H C-H G2 4-Br-307 CI C-Cl CI CF3 C-H C-H C-H G2 4-CN-308 CI C-Cl CI CF3 C-H C-H C-H G2 4-NC-2-309 CI C-Cl CI CF3 C-H C-H C-H G3 H-310 CI C-Cl CI CF3 C-H C-H C-H G4 H-311 CI C-Cl CI CF3 C-H C-H C-H G5 H-312 CI C-Cl CI CF3 C-H C-H C-H G6 H-313 CI C-Cl CI CF3 C-H C-H C-H G7 H-314 CI C-Cl CI CF3 C-H C-H C-H G8 H-315 CI C-Cl CI CF3 C-H C-H C-H G9 H-316 CI C-Cl CI CF3 C-H C-H C-H F --317 CI C-Cl CI CF3 C-H C-H C-Cl Gl H-318 CI C-Cl CI CF3 C-H C-H C-Cl G2 H-319 CI C-Cl CI CF3 C-H C-H C-Cl G2 4-F-320 CI C-Cl CI CF3 C-H C-H C-Cl G2 4-Cl-321 CI C-Cl CI CF3 C-H C-H C-Cl G2 4-Br-322 CI C-Cl CI CF3 C-H C-H C-Cl G2 4-CN-323 CI C-Cl CI CF3 C-H C-H C-Cl G2 4-NC-2-324 CI C-Cl CI CF3 C-H C-H C-Cl G3 H-325 CI C-Cl CI CF3 C-H C-H C-Cl G4 H-326 CI C-Cl CI CF3 C-H C-H C-Cl G5 H-327 CI C-Cl CI CF3 C-H C-H C-Cl G6 H-328 CI C-Cl CI CF3 C-H C-H C-Cl G7 H-329 CI C-Cl CI CF3 C-H C-H C-Cl G8 H-330 CI C-Cl CI CF3 C-H C-H C-Cl G9 H-331 CI C-Cl CI CF3 C-H C-H C-Br F --332 CI C-Cl CI CF3 C-H C-H C-Br Gl H-333 CI C-Cl CI CF3 C-H C-H C-Br G2 H-334 CI C-Cl CI CF3 C-H C-H C-Br G2 4-F-335 CI C-Cl CI CF3 C-H C-H C-Br G2 4-Cl-336 CI C-Cl CI CF3 C-H C-H C-Br G2 4-Br X1 B X2 R A1 A2 A4 G (Z)k-337 CI C-Cl CI CF3 C-H C-H C-Br G2 4-CN-338 CI C-Cl CI CF3 C-H C-H C-Br G2 4-NO2-339 CI C-Cl CI CF3 C-H C-H C-Br G3 H-340 CI C-Cl CI CF3 C-H C-H C-Br G4 H-341 CI C-Cl CI CF3 C-H C-H C-Br G5 H-342 CI C-Cl CI CF3 C-H C-H C-Br G6 H-343 CI C-Cl CI CF3 C-H C-H C-Br G7 H-344 CI C-Cl CI CF3 C-H C-H C-Br G8 H-345 CI C-Cl CI CF3 C-H C-H C-Br G9 H-346 CI C-Cl CI CF3 C-H C-H C-N02 F --347 CI C-Cl CI CF3 C-H C-H C-NO2 Gl H-348 CI C-Cl CI CF3 C-H C-H C-NO2 G2 H-349 CI C-Cl CI CF3 C-H C-H C-NO2 G2 4-F-350 CI C-Cl CI CF3 C-H C-H C-NO2 G2 4-Cl-351 CI C-Cl CI CF3 C-H C-H C-NO2 G2 4-Br-352 CI C-Cl CI CF3 C-H C-H C-NO2 G2 4-CN-353 CI C-Cl CI CF3 C-H C-H C-NO2 G2 4-NO2-354 CI C-Cl CI CF3 C-H C-H C-NO2 G3 H-355 CI C-Cl CI CF3 C-H C-H C-NO2 G4 H-356 CI C-Cl CI CF3 C-H C-H C-NO2 G5 H-357 CI C-Cl CI CF3 C-H C-H C-NO2 G6 H-358 CI C-Cl CI CF3 C-H C-H C-NO2 G7 H-359 CI C-Cl CI CF3 C-H C-H C-NO2 G8 H-360 CI C-Cl CI CF3 C-H C-H C-NO2 G9 H-361 CI C-Cl CI CF3 C-H C-H C-CN F --362 CI C-Cl CI CF3 C-H C-H C-CN Gl H-363 CI C-Cl CI CF3 C-H C-H C-CN G2 H-364 CI C-Cl CI CF3 C-H C-H C-CN G2 4-F-365 CI C-Cl CI CF3 C-H C-H C-CN G2 4-Cl-366 CI C-Cl CI CF3 C-H C-H C-CN G2 4-Br-367 CI C-Cl CI CF3 C-H C-H C-CN G2 4-CN-368 CI C-Cl CI CF3 C-H C-H C-CN G2 4-NO2-369 CI C-Cl CI CF3 C-H C-H C-CN G3 H-370 CI C-Cl CI CF3 C-H C-H C-CN G4 H X1 B X2 R A1 A2 A4 G (Z)k-371 CI C-Cl CI CF3 C-H C-H C-CN G5 H-372 CI C-Cl CI CF3 C-H C-H C-CN G6 H-373 CI C-Cl CI CF3 C-H C-H C-CN G7 H-374 CI C-Cl CI CF3 C-H C-H C-CN G8 H-375 CI C-Cl CI CF3 C-H C-H C-CN G9 H-376 CI N CI CF3 C-H C-H C-H F --377 CI N CI CF3 C-H C-H C-H Gl H-378 CI N CI CF3 C-H C-H C-H G2 H-379 CI N CI CF3 C-H C-H C-H G2 4-F-380 CI N CI CF3 C-H C-H C-H G2 4-Cl-381 CI N CI CF3 C-H C-H C-H G2 4-Br-382 CI N CI CF3 C-H C-H C-H G2 4-CN-383 CI N CI CF3 C-H C-H C-H G2 4-NC-2-384 CI N CI CF3 C-H C-H C-H G3 H-385 CI N CI CF3 C-H C-H C-H G4 H-386 CI N CI CF3 C-H C-H C-H G5 H-387 CI N CI CF3 C-H C-H C-H G6 H-388 CI N CI CF3 C-H C-H C-H G7 H-389 CI N CI CF3 C-H C-H C-H G8 H-390 CI N CI CF3 C-H C-H C-H G9 H-391 CI N CI CF3 C-H C-H C-H F --392 CI N CI CF3 C-H C-H C-Cl Gl H-393 CI N CI CF3 C-H C-H C-Cl G2 H-394 CI N CI CF3 C-H C-H C-Cl G2 4-F-395 CI N CI CF3 C-H C-H C-Cl G2 4-Cl-396 CI N CI CF3 C-H C-H C-Cl G2 4-Br-397 CI N CI CF3 C-H C-H C-Cl G2 4-CN-398 CI N CI CF3 C-H C-H C-Cl G2 4-NC-2-399 CI N CI CF3 C-H C-H C-Cl G3 H-400 CI N CI CF3 C-H C-H C-Cl G4 H-401 CI N CI CF3 C-H C-H C-Cl G5 H-402 CI N CI CF3 C-H C-H C-Cl G6 H-403 CI N CI CF3 C-H C-H C-Cl G7 H-404 CI N CI CF3 C-H C-H C-Cl G8 H X1 B X2 R A1 A2 A4 G (Z)k-405 CI N CI CF3 C-H C-H C-Cl G9 H-406 CI N CI CF3 C-H C-H C-Br F --407 CI N CI CF3 C-H C-H C-Br Gl H-408 CI N CI CF3 C-H C-H C-Br G2 H-409 CI N CI CF3 C-H C-H C-Br G2 4-F-410 CI N CI CF3 C-H C-H C-Br G2 4-Cl-411 CI N CI CF3 C-H C-H C-Br G2 4-Br-412 CI N CI CF3 C-H C-H C-Br G2 4-CN-413 CI N CI CF3 C-H C-H C-Br G2 4-NO2-414 CI N CI CF3 C-H C-H C-Br G3 H-415 CI N CI CF3 C-H C-H C-Br G4 H-416 CI N CI CF3 C-H C-H C-Br G5 H-417 CI N CI CF3 C-H C-H C-Br G6 H-418 CI N CI CF3 C-H C-H C-Br G7 H-419 CI N CI CF3 C-H C-H C-Br G8 H-420 CI N CI CF3 C-H C-H C-Br G9 H-421 CI N CI CF3 C-H C-H C-N02 F --422 CI N CI CF3 C-H C-H C-NO2 Gl H-423 CI N CI CF3 C-H C-H C-NO2 G2 H-424 CI N CI CF3 C-H C-H C-NO2 G2 4-F-425 CI N CI CF3 C-H C-H C-NO2 G2 4-Cl-426 CI N CI CF3 C-H C-H C-NO2 G2 4-Br-427 CI N CI CF3 C-H C-H C-NO2 G2 4-CN-428 CI N CI CF3 C-H C-H C-NO2 G2 4-NO2-429 CI N CI CF3 C-H C-H C-NO2 G3 H-430 CI N CI CF3 C-H C-H C-NO2 G4 H-431 CI N CI CF3 C-H C-H C-NO2 G5 H-432 CI N CI CF3 C-H C-H C-NO2 G6 H-433 CI N CI CF3 C-H C-H C-NO2 G7 H-434 CI N CI CF3 C-H C-H C-NO2 G8 H-435 CI N CI CF3 C-H C-H C-NO2 G9 H-436 CI N CI CF3 C-H C-H C-CN F --437 CI N CI CF3 C-H C-H C-CN Gl H-438 CI N CI CF3 C-H C-H C-CN G2 H X1 B X2 R A1 A2 A4 G (Z)k-439 CI N CI CF3 C-H C-H C-CN G2 4-F-440 CI N CI CF3 C-H C-H C-CN G2 4-Cl-441 CI N CI CF3 C-H C-H C-CN G2 4-Br-442 CI N CI CF3 C-H C-H C-CN G2 4-CN-443 CI N CI CF3 C-H C-H C-CN G2 4-NC-2-444 CI N CI CF3 C-H C-H C-CN G3 H-445 CI N CI CF3 C-H C-H C-CN G4 H-446 CI N CI CF3 C-H C-H C-CN G5 H-447 CI N CI CF3 C-H C-H C-CN G6 H-448 CI N CI CF3 C-H C-H C-CN G7 H-449 CI N CI CF3 C-H C-H C-CN G8 H-450 CI N CI CF3 C-H C-H C-CN G9 H-451 CF3 N CF3 CF3 C-H C-H C-H F --452 CF3 N CF3 CF3 C-H C-H C-H Gl H-453 CF3 N CF3 CF3 C-H C-H C-H G2 H-454 CF3 N CF3 CF3 C-H C-H C-H G2 4-F-455 CF3 N CF3 CF3 C-H C-H C-H G2 4-Cl-456 CF3 N CF3 CF3 C-H C-H C-H G2 4-Br-457 CF3 N CF3 CF3 C-H C-H C-H G2 4-CN-458 CF3 N CF3 CF3 C-H C-H C-H G2 4-NC-2-459 CF3 N CF3 CF3 C-H C-H C-H G3 H-460 CF3 N CF3 CF3 C-H C-H C-H G4 H-461 CF3 N CF3 CF3 C-H C-H C-H G5 H-462 CF3 N CF3 CF3 C-H C-H C-H G6 H-463 CF3 N CF3 CF3 C-H C-H C-H G7 H-464 CF3 N CF3 CF3 C-H C-H C-H G8 H-465 CF3 N CF3 CF3 C-H C-H C-H G9 H-466 CF3 N CF3 CF3 C-H C-H C-H F --467 CF3 N CF3 CF3 C-H C-H C-Cl Gl H-468 CF3 N CF3 CF3 C-H C-H C-Cl G2 H-469 CF3 N CF3 CF3 C-H C-H C-Cl G2 4-F-470 CF3 N CF3 CF3 C-H C-H C-Cl G2 4-Cl-471 CF3 N CF3 CF3 C-H C-H C-Cl G2 4-Br-472 CF3 N CF3 CF3 C-H C-H C-Cl G2 4-CN X1 B X2 R A1 A2 A4 G (Z)k-473 CF3 N CF3 CF3 C-H C-H C-Cl G2 4-NO2-474 CF3 N CF3 CF3 C-H C-H C-Cl G3 H-475 CF3 N CF3 CF3 C-H C-H C-Cl G4 H-476 CF3 N CF3 CF3 C-H C-H C-Cl G5 H-477 CF3 N CF3 CF3 C-H C-H C-Cl G6 H-478 CF3 N CF3 CF3 C-H C-H C-Cl G7 H-479 CF3 N CF3 CF3 C-H C-H C-Cl G8 H-480 CF3 N CF3 CF3 C-H C-H C-Cl G9 H-481 CF3 N CF3 CF3 C-H C-H C-Br F --482 CF3 N CF3 CF3 C-H C-H C-Br Gl H-483 CF3 N CF3 CF3 C-H C-H C-Br G2 H-484 CF3 N CF3 CF3 C-H C-H C-Br G2 4-F-485 CF3 N CF3 CF3 C-H C-H C-Br G2 4-Cl-486 CF3 N CF3 CF3 C-H C-H C-Br G2 4-Br-487 CF3 N CF3 CF3 C-H C-H C-Br G2 4-CN-488 CF3 N CF3 CF3 C-H C-H C-Br G2 4-NO2-489 CF3 N CF3 CF3 C-H C-H C-Br G3 H-490 CF3 N CF3 CF3 C-H C-H C-Br G4 H-491 CF3 N CF3 CF3 C-H C-H C-Br G5 H-492 CF3 N CF3 CF3 C-H C-H C-Br G6 H-493 CF3 N CF3 CF3 C-H C-H C-Br G7 H-494 CF3 N CF3 CF3 C-H C-H C-Br G8 H-495 CF3 N CF3 CF3 C-H C-H C-Br G9 H-496 CF3 N CF3 CF3 C-H C-H C-N02 F --497 CF3 N CF3 CF3 C-H C-H C-NO2 Gl H-498 CF3 N CF3 CF3 C-H C-H C-NO2 G2 H-499 CF3 N CF3 CF3 C-H C-H C-NO2 G2 4-F-500 CF3 N CF3 CF3 C-H C-H C-NO2 G2 4-Cl-501 CF3 N CF3 CF3 C-H C-H C-NO2 G2 4-Br-502 CF3 N CF3 CF3 C-H C-H C-NO2 G2 4-CN-503 CF3 N CF3 CF3 C-H C-H C-NO2 G2 4-NO2-504 CF3 N CF3 CF3 C-H C-H C-NO2 G3 H-505 CF3 N CF3 CF3 C-H C-H C-NO2 G4 H-506 CF3 N CF3 CF3 C-H C-H C-NO2 G5 H X1 B X2 R A1 A2 A4 G (Z)k-507 CF3 N CF3 CF3 C-H C-H C-N02 G6 H-508 CF3 N CF3 CF3 C-H C-H C-NO2 G7 H-509 CF3 N CF3 CF3 C-H C-H C-NO2 G8 H-510 CF3 N CF3 CF3 C-H C-H C-NO2 G9 H-511 CF3 N CF3 CF3 C-H C-H C-CN F --512 CF3 N CF3 CF3 C-H C-H C-CN Gl H-513 CF3 N CF3 CF3 C-H C-H C-CN G2 H-514 CF3 N CF3 CF3 C-H C-H C-CN G2 4-F-515 CF3 N CF3 CF3 C-H C-H C-CN G2 4-Cl-516 CF3 N CF3 CF3 C-H C-H C-CN G2 4-Br-517 CF3 N CF3 CF3 C-H C-H C-CN G2 4-CN-518 CF3 N CF3 CF3 C-H C-H C-CN G2 4-NO2-519 CF3 N CF3 CF3 C-H C-H C-CN G3 H-520 CF3 N CF3 CF3 C-H C-H C-CN G4 H-521 CF3 N CF3 CF3 C-H C-H C-CN G5 H-522 CF3 N CF3 CF3 C-H C-H C-CN G6 H-523 CF3 N CF3 CF3 C-H C-H C-CN G7 H-524 CF3 N CF3 CF3 C-H C-H C-CN G8 H-525 CF3 N CF3 CF3 C-H C-H C-CN G9 H-526 CI C-Cl CF3 CF3 C-H C-H C-Br F --527 CI C-Cl CF3 CF3 C-H C-H C-Br G6 H-528 CF3 C-F H CF3 C-H C-H C-Br F --529 CF3 C-F H CF3 C-H C-H C-Br G6 H-530 CF3 C-H F CF3 C-H C-H C-Br F --531 CF3 C-H F CF3 C-H C-H C-Br G6 H-532 CF3 N H CF3 C-H C-H C-Br F --533 CF3 N H CF3 C-H C-H C-Br G6 H-534 CF3 N F CF3 C-H C-H C-Br F --535 CF3 N F CF3 C-H C-H C-Br G6 H-536 CI C-Cl CF3 CF3 C-H C-H C-CN F --537 CI C-Cl CF3 CF3 C-H C-H C-CN G6 H-538 CF3 C-F H CF3 C-H C-H C-CN F --539 CF3 C-F H CF3 C-H C-H C-CN G6 H-540 CF3 C-H F CF3 C-H C-H C-CN F - X1 B X2 R A1 A2 A4 G (Z)k-541 CF3 C-H F CF3 C-H C-H C-CN G6 H-542 CF3 N H CF3 C-H C-H C-CN F --543 CF3 N H CF3 C-H C-H C-CN G6 H-544 CF3 N F CF3 C-H C-H C-CN F --545 CF3 N F CF3 C-H C-H C-CN G6 H
Table 2
Figure imgf000076_0001
wherein the moiety represented by the following formula:
Figure imgf000076_0002
represents any one of Al to Al 0 or of Al ' to Al 0' as defined in Table a.
X1 B X2 R Y R3 R4 R5
2-1 CI C-H CI CF3 CI H H H
2-2 CI C-H CI CF3 CI H CH3CO H
2-3 CI C-H CI CF3 CI H CH3CH2CO H
2-4 CI C-H CI CF3 CI H n-CH3CH2CH2CO H
2-5 CI C-H CI CF3 CI H cyclo-PrCO H
2-6 CI C-H CI CF3 CI H cyclo-PrCH2CO H
2-7 CI C-H CI CF3 CI H CF3CH2CO H
2-8 CI C-H CI CF3 CI H CH3SCH2CO H
2-9 CI C-H CI CF3 CI H CH3SOCH2CO H
2-10 CI C-H CI CF3 CI H CH3S02CH2CO H
2-11 CI C-H CI CF3 CI H CH3CH2NHCO H
2-12 CI C-H CI CF3 CI H CH3CH2OC(=0) H
2-13 CI C-H CI CF3 CI H CH3OCH2CH2CO H
2-14 CI C-H CI CF3 CI H CH3OCH(CH3)CH2CO H
2-15 CI C-H CI CF3 CI H tert-BuOC(=0) H
2-16 CI C-H CI CF3 CI H CH3S02 H
2-17 CF3 C-H H CF3 CI H H H
2-18 CF3 C-H H CF3 CI H CH3CH2CO H
2-19 CF3 C-H H CF3 CI H n-CH3CH2CH2CO H
2-20 CF3 C-H H CF3 CI H cyclo-PrCO H
2-21 CF3 C-H H CF3 CI H CF3CH2CO H
2-22 CF3 C-H H CF3 CI H CH3S02CH2CO H
2-23 CF3 C-H H CF3 CI H tert-BuOC(=0) H X1 B X2 R Y R3 R4 R5-24 CF3 C-H CF3 CF3 CI H H H-25 CF3 C-H CF3 CF3 CI H CH3CO H-26 CF3 C-H CF3 CF3 CI H CH3CH2CO H-27 CF3 C-H CF3 CF3 CI H n-CH3CH2CH2CO H-28 CF3 C-H CF3 CF3 CI H cyclo-PrCO H-29 CF3 C-H CF3 CF3 CI H cyclo-PrCH2CO H-30 CF3 C-H CF3 CF3 CI H CF3CH2CO H-31 CF3 C-H CF3 CF3 CI H CH3SCH2CO H-32 CF3 C-H CF3 CF3 CI H CH3SOCH2CO H-33 CF3 C-H CF3 CF3 CI H CH3S02CH2CO H-34 CF3 C-H CF3 CF3 CI H CH3CH2NHCO H-35 CF3 C-H CF3 CF3 CI H CH3CH2OC(=0) H-36 CF3 C-H CF3 CF3 CI H CH3OCH2CH2CO H-37 CF3 C-H CF3 CF3 CI H CH3OCH(CH3)CH2CO H-38 CF3 C-H CF3 CF3 CI H tert-BuOC(=0) H-39 CF3 C-H CF3 CF3 CI H CH3S02 H-40 Br C-H Br CF3 CI H CH3CH2CO H-41 Br C-H Br CF3 CI H cyclo-PrCO H-42 Br C-H Br CF3 CI H CH3S02CH2CO H-43 CI C-Cl CI CF3 CI H H H-44 CI C-Cl CI CF3 CI H HCO H-45 CI C-Cl CI CF3 CI H CH3CO H-46 CI C-Cl CI CF3 CI H CH3CH2CO H-47 CI C-Cl CI CF3 CI H n-CH3CH2CH2CO H-48 CI C-Cl CI CF3 CI H cyclo-PrCO H-49 CI C-Cl CI CF3 CI H cyclo-PrCH2CO H-50 CI C-Cl CI CF3 CI H CF3CH2CO H-51 CI C-Cl CI CF3 CI H CH3OCH(CH3)CH2CO H-52 CI C-Cl CI CF3 CI H CH3OCH(CH3)CH2CO H-53 CI C-Cl CI CF3 CI H CH3S02CH2CO H-54 CI C-Cl CI CF3 CI H CH3CH2NHCO H-55 CI C-Cl CI CF3 CI H CH3CH2OC(=0) H-56 CI C-Cl CI CF3 CI H CH3OCH2CH2CO H-57 CI C-Cl CI CF3 CI H CH3OCH(CH3)CH2CO H X1 B X2 R Y R3 R4 R5-58 CI C-Cl CI CF3 CI H tert-BuOC(=0) H-59 CI C-Cl CI CF3 CI H CH3S02 H-60 CI N CI CF3 CI H CH3CH2CO H-61 CI N CI CF3 CI H cyclo-PrCO H-62 CF3 N CF3 CF3 CI H H H-63 CF3 N CF3 CF3 CI H CH3CH2CO H-64 CF3 N CF3 CF3 CI H n-CH3CH2CH2CO H-65 CF3 N CF3 CF3 CI H cyclo-PrCO H-66 CF3 N CF3 CF3 CI H cyclo-PrCH2CO H-67 CF3 N CF3 CF3 CI H CF3CH2CO H-68 CF3 N CF3 CF3 CI H CH3SCH2CO H-69 CF3 N CF3 CF3 CI H CH3SOCH2CO H-70 CF3 N CF3 CF3 CI H CH3S02CH2CO H-71 CF3 N CF3 CF3 CI H CH3CH2NHCO H-72 CF3 N CF3 CF3 CI H CH3CH2OC(=0) H-73 CF3 N CF3 CF3 CI H CH3OCH2CH2CO H-74 CF3 N CF3 CF3 CI H CH3OCH(CH3)CH2CO H-75 CF3 N CF3 CF3 CI H tert-BuOC(=0) H-76 CF3 N CF3 CF3 CI H CH3S02 H-77 CI C-Cl CF3 CF3 CI H CH3CH2CO H-78 CF3 C-F H CF3 CI H CH3CH2CO H-79 CF3 C-H F CF3 CI H CH3CH2CO H-80 CF3 N H CF3 CI H CH3CH2CO H-81 CF3 N F CF3 CI H CH3CH2CO H-82 CI C-H CI CF3 Br H H H-83 CI C-H CI CF3 Br H CH3CO H-84 CI C-H CI CF3 Br H CH3CH2CO H-85 CI C-H CI CF3 Br H n-CH3CH2CH2CO H-86 CI C-H CI CF3 Br H cyclo-PrCO H-87 CI C-H CI CF3 Br H cyclo-PrCH2CO H-88 CI C-H CI CF3 Br H CF3CH2CO H-89 CI C-H CI CF3 Br H CH3SCH2CO H-90 CI C-H CI CF3 Br H CH3SOCH2CO H-91 CI C-H CI CF3 Br H CH3S02CH2CO H X1 B X2 R Y R3 R4 R5-92 CI C-H CI CF3 Br H CH3CH2NHCO H-93 CI C-H CI CF3 Br H CH3CH2OC(=0) H-94 CI C-H CI CF3 Br H CH3OCH2CH2CO H-95 CI C-H CI CF3 Br H CH3OCH(CH3)CH2CO H-96 CI C-H CI CF3 Br H tert-BuOC(=0) H-97 CI C-H CI CF3 Br H CH3S02 H-98 CF3 C-H H CF3 Br H H H-99 CF3 C-H H CF3 Br H CH3CH2CO H-100 CF3 C-H H CF3 Br H n-CH3CH2CH2CO H-101 CF3 C-H H CF3 Br H cyclo-PrCO H-102 CF3 C-H H CF3 Br H CF3CH2CO H-103 CF3 C-H H CF3 Br H CH3S02CH2CO H-104 CF3 C-H H CF3 Br H tert-BuOC(=0) H-105 CF3 C-H CF3 CF3 Br H H H-106 CF3 C-H CF3 CF3 Br H CH3CO H-107 CF3 C-H CF3 CF3 Br H CH3CH2CO H-108 CF3 C-H CF3 CF3 Br H n-CH3CH2CH2CO H-109 CF3 C-H CF3 CF3 Br H cyclo-PrCO H-110 CF3 C-H CF3 CF3 Br H cyclo-PrCH2CO H-111 CF3 C-H CF3 CF3 Br H CF3CH2CO H-112 CF3 C-H CF3 CF3 Br H CH3SCH2CO H-113 CF3 C-H CF3 CF3 Br H CH3SOCH2CO H-114 CF3 C-H CF3 CF3 Br H CH3S02CH2CO H-115 CF3 C-H CF3 CF3 Br H CH3CH2NHCO H-116 CF3 C-H CF3 CF3 Br H CH3CH2OC(=0) H-117 CF3 C-H CF3 CF3 Br H CH3OCH2CH2CO H-118 CF3 C-H CF3 CF3 Br H CH3OCH(CH3)CH2CO H-119 CF3 C-H CF3 CF3 Br H tert-BuOC(=0) H-120 CF3 C-H CF3 CF3 Br H CH3S02 H-121 Br C-H Br CF3 Br H CH3CH2CO H-122 Br C-H Br CF3 Br H cyclo-PrCO H-123 Br C-H Br CF3 Br H CH3S02CH2CO H-124 CI C-Cl CI CF3 Br H H H-125 CI C-Cl CI CF3 Br H HCO H X1 B X2 R Y R3 R4 R5-126 CI C-Cl CI CF3 Br H CH3CO H-127 CI C-Cl CI CF3 Br H CH3CH2CO H-128 CI C-Cl CI CF3 Br H n-CH3CH2CH2CO H-129 CI C-Cl CI CF3 Br H cyclo-PrCO H-130 CI C-Cl CI CF3 Br H cyclo-PrCH2CO H-131 CI C-Cl CI CF3 Br H CF3CH2CO H-132 CI C-Cl CI CF3 Br H CH3SCH2CO H-133 CI C-Cl CI CF3 Br H CH3SOCH2CO H-134 CI C-Cl CI CF3 Br H CH3S02CH2CO H-135 CI C-Cl CI CF3 Br H CH3CH2NHCO H-136 CI C-Cl CI CF3 Br H CH3CH2OC(=0) H-137 CI C-Cl CI CF3 Br H CH3OCH2CH2CO H-138 CI C-Cl CI CF3 Br H CH3OCH(CH3)CH2CO H-139 CI C-Cl CI CF3 Br H tert-BuOC(=0) H-140 CI C-Cl CI CF3 Br H CH3S02 H-141 CI N CI CF3 Br H CH3CH2CO H-142 CI N CI CF3 Br H cyclo-PrCO H-143 CF3 N CF3 CF3 Br H H H-144 CF3 N CF3 CF3 Br H CH3CH2CO H-145 CF3 N CF3 CF3 Br H n-CH3CH2CH2CO H-146 CF3 N CF3 CF3 Br H cyclo-PrCO H-147 CF3 N CF3 CF3 Br H cyclo-PrCH2CO H-148 CF3 N CF3 CF3 Br H CF3CH2CO H-149 CF3 N CF3 CF3 Br H CH3SCH2CO H-150 CF3 N CF3 CF3 Br H CH3SOCH2CO H-151 CF3 N CF3 CF3 Br H CH3S02CH2CO H-152 CF3 N CF3 CF3 Br H CH3CH2NHCO H-153 CF3 N CF3 CF3 Br H CH3CH2OC(=0) H-154 CF3 N CF3 CF3 Br H CH3OCH2CH2CO H-155 CF3 N CF3 CF3 Br H CH3OCH(CH3)CH2CO H-156 CF3 N CF3 CF3 Br H tert-BuOC(=0) H-157 CF3 N CF3 CF3 Br H CH3S02 H-158 CI C-Cl CF3 CF3 Br H CH3CH2CO H-159 CF3 C-F H CF3 Br H CH3CH2CO H X1 B X2 R Y R3 R4 R5-160 CF3 C-H F CF3 Br H CH3CH2CO H-161 CF3 N H CF3 Br H CH3CH2CO H-162 CF3 N F CF3 Br H CH3CH2CO H-163 CI C-Cl CI CF3 Br H CH3OCH2CH2CO H-164 CI C-Cl CI CF3 Br H CH3OCH(CH3)CH2CO H-165 CI C-Cl CI CF3 Br H tert-BuOC(=0) H-166 CI C-Cl CI CF3 Br H CH3S02 H-167 CI N CI CF3 Br H H H-168 CI N CI CF3 Br H HCO H-169 CI N CI CF3 Br H CH3CO H-170 CI N CI CF3 Br H CH3CH2CO H-171 CI N CI CF3 Br H n-CH3CH2CH2CO H-172 CI N CI CF3 Br H cyclo-PrCO H-173 CI N CI CF3 Br H cyclo-PrCH2CO H-174 CI N CI CF3 Br H CF3CH2CO H-175 CI N CI CF3 Br H CH3SCH2CO H-176 CI N CI CF3 Br H CH3SOCH2CO H-177 CI N CI CF3 Br H CH3S02CH2CO H-178 CI N CI CF3 Br H CH3CH2NHCO H-179 CI N CI CF3 Br H CH3CH2OC(=0) H-180 CI N CI CF3 Br H CH3OCH2CH2CO H-181 CI N CI CF3 Br H CH3OCH(CH3)CH2CO H-182 CI N CI CF3 Br H tert-BuOC(=0) H-183 CI N CI CF3 Br H CH3S02 H-184 CF3 N CF3 CF3 Br H H H-185 CF3 N CF3 CF3 Br H HCO H-186 CF3 N CF3 CF3 Br H CH3CO H-187 CF3 N CF3 CF3 Br H CH3CH2CO H-188 CF3 N CF3 CF3 Br H n-CH3CH2CH2CO H-189 CF3 N CF3 CF3 Br H cyclo-PrCO H-190 CF3 N CF3 CF3 Br H cyclo-PrCH2CO H-191 CF3 N CF3 CF3 Br H CF3CH2CO H-192 CF3 N CF3 CF3 Br H CH3SCH2CO H-193 CF3 N CF3 CF3 Br H CH3SOCH2CO H X1 B X2 R Y R3 R4 R5-194 CF3 N CF3 CF3 Br H CH3S02CH2CO H-195 CF3 N CF3 CF3 Br H CH3CH2NHCO H-196 CF3 N CF3 CF3 Br H CH3CH2OC(=0) H-197 CF3 N CF3 CF3 Br H CH3OCH2CH2CO H-198 CF3 N CF3 CF3 Br H CH3OCH(CH3)CH2CO H-199 CF3 N CF3 CF3 Br H tert-BuOC(=0) H-200 CF3 N CF3 CF3 Br H CH3S02 H-201 CI C-Cl CF3 CF3 Br H CH3CH2CO H-202 CI C-Cl CF3 CF3 Br H CH3CH2CO H-203 CF3 C-F H CF3 Br H CH3CH2CO H-204 CF3 C-F H CF3 Br H CH3CH2CO H-205 CF3 C-H F CF3 Br H CH3CH2CO H-206 CF3 C-H F CF3 Br H CH3CH2CO H-207 CF3 N H CF3 Br H CH3CH2CO H-208 CF3 N H CF3 Br H CH3CH2CO H-209 CF3 N F CF3 Br H CH3CH2CO H-210 CF3 N F CF3 Br H CH3CH2CO H-211 CI C-H CI CF3 CF3 H H H-212 CI C-H CI CF3 CF3 H CH3CO H-213 CI C-H CI CF3 CF3 H CH3CH2CO H-214 CI C-H CI CF3 CF3 H n-CH3CH2CH2CO H-215 CI C-H CI CF3 CF3 H cyclo-PrCO H-216 CI C-H CI CF3 CF3 H cyclo-PrCH2CO H-217 CI C-H CI CF3 CF3 H CF3CH2CO H-218 CI C-H CI CF3 CF3 H CH3SCH2CO H-219 CI C-H CI CF3 CF3 H CH3SOCH2CO H-220 CI C-H CI CF3 CF3 H CH3S02CH2CO H-221 CI C-H CI CF3 CF3 H CH3CH2NHCO H-222 CI C-H CI CF3 CF3 H CH3CH2OC(=0) H-223 CI C-H CI CF3 CF3 H CH3OCH2CH2CO H-224 CI C-H CI CF3 CF3 H CH3OCH(CH3)CH2CO H-225 CI C-H CI CF3 CF3 H tert-BuOC(=0) H-226 CI C-H CI CF3 CF3 H CH3S02 H-227 CF3 C-H H CF3 CF3 H H H X1 B X2 R Y R3 R4 R5-228 CF3 C-H H CF3 CF3 H CH3CH2CO H-229 CF3 C-H H CF3 CF3 H n-CH3CH2CH2CO H-230 CF3 C-H H CF3 CF3 H cyclo-PrCO H-231 CF3 C-H H CF3 CF3 H CF3CH2CO H-232 CF3 C-H H CF3 CF3 H CH3S02CH2CO H-233 CF3 C-H H CF3 CF3 H tert-BuOC(=0) H-234 CF3 C-H CF3 CF3 CF3 H H H-235 CF3 C-H CF3 CF3 CF3 H CH3CO H-236 CF3 C-H CF3 CF3 CF3 H CH3CH2CO H-237 CF3 C-H CF3 CF3 CF3 H n-CH3CH2CH2CO H-238 CF3 C-H CF3 CF3 CF3 H cyclo-PrCO H-239 CF3 C-H CF3 CF3 CF3 H cyclo-PrCH2CO H-240 CF3 C-H CF3 CF3 CF3 H CF3CH2CO H-241 CF3 C-H CF3 CF3 CF3 H CH3SCH2CO H-242 CF3 C-H CF3 CF3 CF3 H CH3SOCH2CO H-243 CF3 C-H CF3 CF3 CF3 H CH3S02CH2CO H-244 CF3 C-H CF3 CF3 CF3 H CH3CH2NHCO H-245 CF3 C-H CF3 CF3 CF3 H CH3CH2OC(=0) H-246 CF3 C-H CF3 CF3 CF3 H CH3OCH2CH2CO H-247 CF3 C-H CF3 CF3 CF3 H CH3OCH(CH3)CH2CO H-248 CF3 C-H CF3 CF3 CF3 H tert-BuOC(=0) H-249 CF3 C-H CF3 CF3 CF3 H CH3S02 H-250 Br C-H Br CF3 CF3 H CH3CH2CO H-251 Br C-H Br CF3 CF3 H cyclo-PrCO H-252 Br C-H Br CF3 CF3 H CH3S02CH2CO H-253 CI C-Cl CI CF3 CF3 H H H-254 CI C-Cl CI CF3 CF3 H HCO H-255 CI C-Cl CI CF3 CF3 H CH3CO H-256 CI C-Cl CI CF3 CF3 H CH3CH2CO H-257 CI C-Cl CI CF3 CF3 H n-CH3CH2CH2CO H-258 CI C-Cl CI CF3 CF3 H cyclo-PrCO H-259 CI C-Cl CI CF3 CF3 H cyclo-PrCH2CO H-260 CI C-Cl CI CF3 CF3 H CF3CH2CO H-261 CI C-Cl CI CF3 CF3 H CH3SCH2CO H X1 B X2 R Y R3 R4 R5-262 CI C-Cl CI CF3 CF3 H CH3SOCH2CO H-263 CI C-Cl CI CF3 CF3 H CH3S02CH2CO H-264 CI C-Cl CI CF3 CF3 H CH3CH2NHCO H-265 CI C-Cl CI CF3 CF3 H CH3CH2OC(=0) H-266 CI C-Cl CI CF3 CF3 H CH3OCH2CH2CO H-267 CI C-Cl CI CF3 CF3 H CH3OCH(CH3)CH2CO H-268 CI C-Cl CI CF3 CF3 H tert-BuOC(=0) H-269 CI C-Cl CI CF3 CF3 H CH3S02 H-270 CI N CI CF3 CF3 H CH3CH2CO H-271 CI N CI CF3 CF3 H cyclo-PrCO H-272 CF3 N CF3 CF3 CF3 H H H-273 CF3 N CF3 CF3 CF3 H CH3CH2CO H-274 CF3 N CF3 CF3 CF3 H n-CH3CH2CH2CO H-275 CF3 N CF3 CF3 CF3 H cyclo-PrCO H-276 CF3 N CF3 CF3 CF3 H cyclo-PrCH2CO H-277 CF3 N CF3 CF3 CF3 H CF3CH2CO H-278 CF3 N CF3 CF3 CF3 H CH3SCH2CO H-279 CF3 N CF3 CF3 CF3 H CH3SOCH2CO H-280 CF3 N CF3 CF3 CF3 H CH3S02CH2CO H-281 CF3 N CF3 CF3 CF3 H CH3CH2NHCO H-282 CF3 N CF3 CF3 CF3 H CH3CH2OC(=0) H-283 CF3 N CF3 CF3 CF3 H CH3OCH2CH2CO H-284 CF3 N CF3 CF3 CF3 H CH3OCH(CH3)CH2CO H-285 CF3 N CF3 CF3 CF3 H tert-BuOC(=0) H-286 CF3 N CF3 CF3 CF3 H CH3S02 H-287 CI C-Cl CF3 CF3 CF3 H CH3CH2CO H-288 CF3 C-F H CF3 CF3 H CH3CH2CO H-289 CF3 C-H F CF3 CF3 H CH3CH2CO H-290 CF3 N H CF3 CF3 H CH3CH2CO H-291 CF3 N F CF3 CF3 H CH3CH2CO H-292 CI C-H CI CF3 H H H CH3-293 CI C-H CI CF3 H H CH3CO CH3-294 CI C-H CI CF3 H H CH3CH2CO CH3-295 CI C-H CI CF3 H H n-CH3CH2CH2CO CH3 X1 B X2 R Y R3 R4 R5-296 CI C-H CI CF3 H H cyclo-PrCO CH3-297 CI C-H CI CF3 H H cyclo-PrCH2CO CH3-298 CI C-H CI CF3 H H CF3CH2CO CH3-299 CI C-H CI CF3 H H CH3SCH2CO CH3-300 CI C-H CI CF3 H H CH3SOCH2CO CH3-301 CI C-H CI CF3 H H CH3S02CH2CO CH3-302 CI C-H CI CF3 H H CH3CH2NHCO CH3-303 CI C-H CI CF3 H H CH3CH2OC(=0) CH3-304 CI C-H CI CF3 H H CH3OCH2CH2CO CH3-305 CI C-H CI CF3 H H CH3OCH(CH3)CH2CO CH3-306 CI C-H CI CF3 H H tert-BuOC(=0) CH3-307 CI C-H CI CF3 H H CH3S02 CH3-308 CF3 C-H H CF3 H H H CH3-309 CF3 C-H H CF3 H H CH3CH2CO CH3-310 CF3 C-H H CF3 H H n-CH3CH2CH2CO CH3-311 CF3 C-H H CF3 H H cyclo-PrCO CH3-312 CF3 C-H H CF3 H H CF3CH2CO CH3-313 CF3 C-H H CF3 H H CH3S02CH2CO CH3-314 CF3 C-H H CF3 H H tert-BuOC(=0) CH3-315 CF3 C-H CF3 CF3 H H H CH3-316 CF3 C-H CF3 CF3 H H CH3CO CH3-317 CF3 C-H CF3 CF3 H H CH3CH2CO CH3-318 CF3 C-H CF3 CF3 H H n-CH3CH2CH2CO CH3-319 CF3 C-H CF3 CF3 H H cyclo-PrCO CH3-320 CF3 C-H CF3 CF3 H H cyclo-PrCH2CO CH3-321 CF3 C-H CF3 CF3 H H CF3CH2CO CH3-322 CF3 C-H CF3 CF3 H H CH3SCH2CO CH3-323 CF3 C-H CF3 CF3 H H CH3SOCH2CO CH3-324 CF3 C-H CF3 CF3 H H CH3S02CH2CO CH3-325 CF3 C-H CF3 CF3 H H CH3CH2NHCO CH3-326 CF3 C-H CF3 CF3 H H CH3CH2OC(=0) CH3-327 CF3 C-H CF3 CF3 H H CH3OCH2CH2CO CH3-328 CF3 C-H CF3 CF3 H H CH3OCH(CH3)CH2CO CH3-329 CF3 C-H CF3 CF3 H H tert-BuOC(=0) CH3 X1 B X2 R Y R3 R4 R5-330 CF3 C-H CF3 CF3 H H CH3S02 CH3-331 Br C-H Br CF3 H H CH3CH2CO CH3-332 Br C-H Br CF3 H H cyclo-PrCO CH3-333 Br C-H Br CF3 H H CH3S02CH2CO CH3-334 CI C-Cl CI CF3 H H H CH3-335 CI C-Cl CI CF3 H H HCO CH3-336 CI C-Cl CI CF3 H H CH3CO CH3-337 CI C-Cl CI CF3 H H CH3CH2CO CH3-338 CI C-Cl CI CF3 H H n-CH3CH2CH2CO CH3-339 CI C-Cl CI CF3 H H cyclo-PrCO CH3-340 CI C-Cl CI CF3 H H cyclo-PrCH2CO CH3-341 CI C-Cl CI CF3 H H CF3CH2CO CH3-342 CI C-Cl CI CF3 H H CH3SCH2CO CH3-343 CI C-Cl CI CF3 H H CH3SOCH2CO CH3-344 CI C-Cl CI CF3 H H CH3S02CH2CO CH3-345 CI C-Cl CI CF3 H H CH3CH2NHCO CH3-346 CI C-Cl CI CF3 H H CH3CH2OC(=0) CH3-347 CI C-Cl CI CF3 H H CH3OCH2CH2CO CH3-348 CI C-Cl CI CF3 H H CH3OCH(CH3)CH2CO CH3-349 CI C-Cl CI CF3 H H tert-BuOC(=0) CH3-350 CI C-Cl CI CF3 H H CH3S02 CH3-351 CI N CI CF3 H H CH3CH2CO CH3-352 CI N CI CF3 H H cyclo-PrCO CH3-353 CF3 N CF3 CF3 H H H CH3-354 CF3 N CF3 CF3 H H CH3CH2CO CH3-355 CF3 N CF3 CF3 H H n-CH3CH2CH2CO CH3-356 CF3 N CF3 CF3 H H cyclo-PrCO CH3-357 CF3 N CF3 CF3 H H cyclo-PrCH2CO CH3-358 CF3 N CF3 CF3 H H CF3CH2CO CH3-359 CF3 N CF3 CF3 H H CH3SCH2CO CH3-360 CF3 N CF3 CF3 H H CH3SOCH2CO CH3-361 CF3 N CF3 CF3 H H CH3S02CH2CO CH3-362 CF3 N CF3 CF3 H H CH3CH2NHCO CH3-363 CF3 N CF3 CF3 H H CH3CH2OC(=0) CH3 X1 B X2 R Y R3 R4 R5
2-364 CF3 N CF3 CF3 H H CH3OCH2CH2CO CH3
2-365 CF3 N CF3 CF3 H H CH3OCH(CH3)CH2CO CH3
2-366 CF3 N CF3 CF3 H H tert-BuOC(=0) CH3
2-367 CF3 N CF3 CF3 H H CH3S02 CH3
2-368 CI C-Cl CF3 CF3 H H CH3CH2CO CH3
2-369 CF3 C-F H CF3 H H CH3CH2CO CH3
2-370 CF3 C-H F CF3 H H CH3CH2CO CH3
2-371 CF3 N H CF3 H H CH3CH2CO CH3
2-372 CF3 N F CF3 H H CH3CH2CO CH3
2-373 CF3 C-H CF3 CF3 H CH3 CH3CH2CO H
2-374 CI C-Cl CI CF3 H CH3 CH3CH2CO H
2-375 CF3 C-H CF3 CF3 H N02 CH3CH2CO H
2-376 CI C-Cl CI CF3 H N02 CH3CH2CO H
2-377 CF3 C-H CF3 CF3 H CN CH3CH2CO H
2-378 CI C-Cl CI CF3 H CN CH3CH2CO H
2-379 CF3 C-H CF3 CF3 H SCH3 CH3CH2CO H
2-380 CI C-Cl CI CF3 H SCH3 CH3CH2CO H
Table 3
Figure imgf000087_0001
wherein the moiety represented by the following formula:
Figure imgf000087_0002
represents any one of Al to Al 0 or of Al ' to Al 0' as defined in Table a.
X1 B X2 R R3 R4 m
3-1 CI C-H CI CF3 H H 1
3-2 CI C-H CI CF3 H HCO 1
3-3 CI C-H CI CF3 H CH3CO 1 X1 B X2 R R3 R4 m-4 CI C-H CI CF3 H CH3CH2CO 1-5 CI C-H CI CF3 H CH3CH2CH2CO 1-6 CI C-H CI CF3 H cyclo-PrCO 1-7 CI C-H CI CF3 H cyclo-PrCH2CO 1-8 CI C-H CI CF3 H CF3CH2CO 1-9 CI C-H CI CF3 H CH3SCH2CO 1-10 CI C-H CI CF3 H CH3SOCH2CO 1-11 CI C-H CI CF3 H CH3S02CH2CO 1-12 CI C-H CI CF3 H CH3CH2NHCO 1-13 CI C-H CI CF3 H CH3CH2OC(=0) 1-14 CI C-H CI CF3 H CH3OCH2CH2CO 1-15 CI C-H CI CF3 H CH3OCH(CH3)CH2CO 1-16 CI C-H CI CF3 H tert-BuOC(=0) 1-17 CI C-H CI CF3 H CH3S02 1-18 CF3 C-H H CF3 H H 1-19 CF3 C-H H CF3 H HCO 1-20 CF3 C-H H CF3 H CH3CO 1-21 CF3 C-H H CF3 H CH3CH2CO 1-22 CF3 C-H H CF3 H CH3CH2CH2CO 1-23 CF3 C-H H CF3 H cyclo-PrCO 1-24 CF3 C-H H CF3 H cyclo-PrCH2CO 1-25 CF3 C-H H CF3 H CF3CH2CO 1-26 CF3 C-H H CF3 H CH3SCH2CO 1-27 CF3 C-H H CF3 H CH3SOCH2CO 1-28 CF3 C-H H CF3 H CH3S02CH2CO 1-29 CF3 C-H H CF3 H CH3CH2NHCO 1-30 CF3 C-H H CF3 H CH3CH2OC(=0) 1-31 CF3 C-H H CF3 H CH3OCH2CH2CO 1-32 CF3 C-H H CF3 H CH3OCH(CH3)CH2CO 1-33 CF3 C-H H CF3 H tert-BuOC(=0) 1-34 CF3 C-H H CF3 H CH3S02 1-35 CF3 C-H CF3 CF3 H H 1-36 CF3 C-H CF3 CF3 H HCO 1-37 CF3 C-H CF3 CF3 H CH3CO 1 X1 B X2 R R3 R4 m-38 CF3 C-H CF3 CF3 H CH3CH2CO 1-39 CF3 C-H CF3 CF3 H CH3CH2CH2CO 1-40 CF3 C-H CF3 CF3 H cyclo-PrCO 1-41 CF3 C-H CF3 CF3 H cyclo-PrCH2CO 1-42 CF3 C-H CF3 CF3 H CF3CH2CO 1-43 CF3 C-H CF3 CF3 H CH3SCH2CO 1-44 CF3 C-H CF3 CF3 H CH3SOCH2CO 1-45 CF3 C-H CF3 CF3 H CH3S02CH2CO 1-46 CF3 C-H CF3 CF3 H CH3CH2NHCO 1-47 CF3 C-H CF3 CF3 H CH3CH2OC(=0) 1-48 CF3 C-H CF3 CF3 H CH3OCH2CH2CO 1-49 CF3 C-H CF3 CF3 H CH3OCH(CH3)CH2CO 1-50 CF3 C-H CF3 CF3 H tert-BuOC(=0) 1-51 CF3 C-H CF3 CF3 H CH3S02 1-52 Br C-H Br CF3 H H 1-53 Br C-H Br CF3 H HCO 1-54 Br C-H Br CF3 H CH3CO 1-55 Br C-H Br CF3 H CH3CH2CO 1-56 Br C-H Br CF3 H CH3CH2CH2CO 1-57 Br C-H Br CF3 H cyclo-PrCO 1-58 Br C-H Br CF3 H cyclo-PrCH2CO 1-59 Br C-H Br CF3 H CF3CH2CO 1-60 Br C-H Br CF3 H CH3SCH2CO 1-61 Br C-H Br CF3 H CH3SOCH2CO 1-62 Br C-H Br CF3 H CH3S02CH2CO 1-63 Br C-H Br CF3 H CH3CH2NHCO 1-64 Br C-H Br CF3 H CH3CH2OC(=0) 1-65 Br C-H Br CF3 H CH3OCH2CH2CO 1-66 Br C-H Br CF3 H CH3OCH(CH3)CH2CO 1-67 Br C-H Br CF3 H tert-BuOC(=0) 1-68 Br C-H Br CF3 H CH3S02 1-69 CI C-Cl CI CF3 H H 1-70 CI C-Cl CI CF3 H HCO 1-71 CI C-Cl CI CF3 H CH3CO 1 X1 B X2 R R3 R4 m-72 CI C-Cl CI CF3 H CH3CH2CO 1-73 CI C-Cl CI CF3 H CH3CH2CH2CO 1-74 CI C-Cl CI CF3 H cyclo-PrCO 1-75 CI C-Cl CI CF3 H cyclo-PrCH2CO 1-76 CI C-Cl CI CF3 H CF3CH2CO 1-77 CI C-Cl CI CF3 H CH3SCH2CO 1-78 CI C-Cl CI CF3 H CH3SOCH2CO 1-79 CI C-Cl CI CF3 H CH3S02CH2CO 1-80 CI C-Cl CI CF3 H CH3CH2NHCO 1-81 CI C-Cl CI CF3 H CH3CH2OC(=0) 1-82 CI C-Cl CI CF3 H CH3OCH2CH2CO 1-83 CI C-Cl CI CF3 H CH3OCH(CH3)CH2CO 1-84 CI C-Cl CI CF3 H tert-BuOC(=0) 1-85 CI C-Cl CI CF3 H CH3S02 1-86 CI N CI CF3 H H 1-87 CI N CI CF3 H HCO 1-88 CI N CI CF3 H CH3CO 1-89 CI N CI CF3 H CH3CH2CO 1-90 CI N CI CF3 H CH3CH2CH2CO 1-91 CI N CI CF3 H cyclo-PrCO 1-92 CI N CI CF3 H cyclo-PrCH2CO 1-93 CI N CI CF3 H CF3CH2CO 1-94 CI N CI CF3 H CH3SCH2CO 1-95 CI N CI CF3 H CH3SOCH2CO 1-96 CI N CI CF3 H CH3S02CH2CO 1-97 CI N CI CF3 H CH3CH2NHCO 1-98 CI N CI CF3 H CH3CH2OC(=0) 1-99 CI N CI CF3 H CH3OCH2CH2CO 1-100 CI N CI CF3 H CH3OCH(CH3)CH2CO 1-101 CI N CI CF3 H tert-BuOC(=0) 1-102 CI N CI CF3 H CH3S02 1-103 CF3 N CF3 CF3 H H 1-104 CF3 N CF3 CF3 H HCO 1-105 CF3 N CF3 CF3 H CH3CO 1 X1 B X2 R R3 R4 m-106 CF3 N CF3 CF3 H CH3CH2CO 1-107 CF3 N CF3 CF3 H CH3CH2CH2CO 1-108 CF3 N CF3 CF3 H cyclo-PrCO 1-109 CF3 N CF3 CF3 H cyclo-PrCH2CO 1-110 CF3 N CF3 CF3 H CF3CH2CO 1-111 CF3 N CF3 CF3 H CH3SCH2CO 1-112 CF3 N CF3 CF3 H CH3SOCH2CO 1-113 CF3 N CF3 CF3 H CH3S02CH2CO 1-114 CF3 N CF3 CF3 H CH3CH2NHCO 1-115 CF3 N CF3 CF3 H CH3CH2OC(=0) 1-116 CF3 N CF3 CF3 H CH3OCH2CH2CO 1-117 CF3 N CF3 CF3 H CH3OCH(CH3)CH2CO 1-118 CF3 N CF3 CF3 H tert-BuOC(=0) 1-119 CF3 N CF3 CF3 H CH3S02 1-120 CI C-Cl CF3 CF3 H CH3CH2CO 1-121 CI C-Cl CF3 CF3 H CH3CH2CO 1-122 CF3 C-F H CF3 H CH3CH2CO 1-123 CF3 C-F H CF3 H CH3CH2CO 1-124 CF3 C-H F CF3 H CH3CH2CO 1-125 CF3 C-H F CF3 H CH3CH2CO 1-126 CF3 N H CF3 H CH3CH2CO 1-127 CF3 N H CF3 H CH3CH2CO 1-128 CF3 N F CF3 H CH3CH2CO 1-129 CF3 N F CF3 H CH3CH2CO 1-130 CI C-H CI CF3 H H 2-131 CI C-H CI CF3 H HCO 2-132 CI C-H CI CF3 H CH3CO 2-133 CI C-H CI CF3 H CH3CH2CO 2-134 CI C-H CI CF3 H CH3CH2CH2CO 2-135 CI C-H CI CF3 H cyclo-PrCO 2-136 CI C-H CI CF3 H cyclo-PrCH2CO 2-137 CI C-H CI CF3 H CF3CH2CO 2-138 CI C-H CI CF3 H CH3SCH2CO 2-139 CI C-H CI CF3 H CH3SOCH2CO 2 X1 B X2 R R3 R4 m-140 CI C-H CI CF3 H CH3S02CH2CO 2-141 CI C-H CI CF3 H CH3CH2NHCO 2-142 CI C-H CI CF3 H CH3CH2OC(=0) 2-143 CI C-H CI CF3 H CH3OCH2CH2CO 2-144 CI C-H CI CF3 H CH3OCH(CH3)CH2CO 2-145 CI C-H CI CF3 H tert-BuOC(=0) 2-146 CI C-H CI CF3 H CH3S02 2-147 CF3 C-H H CF3 H H 2-148 CF3 C-H H CF3 H HCO 2-149 CF3 C-H H CF3 H CH3CO 2-150 CF3 C-H H CF3 H CH3CH2CO 2-151 CF3 C-H H CF3 H CH3CH2CH2CO 2-152 CF3 C-H H CF3 H cyclo-PrCO 2-153 CF3 C-H H CF3 H cyclo-PrCH2CO 2-154 CF3 C-H H CF3 H CF3CH2CO 2-155 CF3 C-H H CF3 H CH3SCH2CO 2-156 CF3 C-H H CF3 H CH3SOCH2CO 2-157 CF3 C-H H CF3 H CH3S02CH2CO 2-158 CF3 C-H H CF3 H CH3CH2NHCO 2-159 CF3 C-H H CF3 H CH3CH2OC(=0) 2-160 CF3 C-H H CF3 H CH3OCH2CH2CO 2-161 CF3 C-H H CF3 H CH3OCH(CH3)CH2CO 2-162 CF3 C-H H CF3 H tert-BuOC(=0) 2-163 CF3 C-H H CF3 H CH3S02 2-164 CF3 C-H CF3 CF3 H H 2-165 CF3 C-H CF3 CF3 H HCO 2-166 CF3 C-H CF3 CF3 H CH3CO 2-167 CF3 C-H CF3 CF3 H CH3CH2CO 2-168 CF3 C-H CF3 CF3 H CH3CH2CH2CO 2-169 CF3 C-H CF3 CF3 H cyclo-PrCO 2-170 CF3 C-H CF3 CF3 H cyclo-PrCH2CO 2-171 CF3 C-H CF3 CF3 H CF3CH2CO 2-172 CF3 C-H CF3 CF3 H CH3SCH2CO 2-173 CF3 C-H CF3 CF3 H CH3SOCH2CO 2 X1 B X2 R R3 R4 m-174 CF3 C-H CF3 CF3 H CH3S02CH2CO 2-175 CF3 C-H CF3 CF3 H CH3CH2NHCO 2-176 CF3 C-H CF3 CF3 H CH3CH2OC(=0) 2-177 CF3 C-H CF3 CF3 H CH3OCH2CH2CO 2-178 CF3 C-H CF3 CF3 H CH3OCH(CH3)CH2CO 2-179 CF3 C-H CF3 CF3 H tert-BuOC(=0) 2-180 CF3 C-H CF3 CF3 H CH3S02 2-181 Br C-H Br CF3 H H 2-182 Br C-H Br CF3 H HCO 2-183 Br C-H Br CF3 H CH3CO 2-184 Br C-H Br CF3 H CH3CH2CO 2-185 Br C-H Br CF3 H CH3CH2CH2CO 2-186 Br C-H Br CF3 H cyclo-PrCO 2-187 Br C-H Br CF3 H cyclo-PrCH2CO 2-188 Br C-H Br CF3 H CF3CH2CO 2-189 Br C-H Br CF3 H CH3SCH2CO 2-190 Br C-H Br CF3 H CH3SOCH2CO 2-191 Br C-H Br CF3 H CH3S02CH2CO 2-192 Br C-H Br CF3 H CH3CH2NHCO 2-193 Br C-H Br CF3 H CH3CH2OC(=0) 2-194 Br C-H Br CF3 H CH3OCH2CH2CO 2-195 Br C-H Br CF3 H CH3OCH(CH3)CH2CO 2-196 Br C-H Br CF3 H tert-BuOC(=0) 2-197 Br C-H Br CF3 H CH3S02 2-198 CI C-Cl CI CF3 H H 2-199 CI C-Cl CI CF3 H HCO 2-200 CI C-Cl CI CF3 H CH3CO 2-201 CI C-Cl CI CF3 H CH3CH2CO 2-202 CI C-Cl CI CF3 H CH3CH2CH2CO 2-203 CI C-Cl CI CF3 H cyclo-PrCO 2-204 CI C-Cl CI CF3 H cyclo-PrCH2CO 2-205 CI C-Cl CI CF3 H CF3CH2CO 2-206 CI C-Cl CI CF3 H CH3SCH2CO 2-207 CI C-Cl CI CF3 H CH3SOCH2CO 2 X1 B X2 R R3 R4 m-208 CI C-Cl CI CF3 H CH3S02CH2CO 2-209 CI C-Cl CI CF3 H CH3CH2NHCO 2-210 CI C-Cl CI CF3 H CH3CH2OC(=0) 2-211 CI C-Cl CI CF3 H CH3OCH2CH2CO 2-212 CI C-Cl CI CF3 H CH3OCH(CH3)CH2CO 2-213 CI C-Cl CI CF3 H tert-BuOC(=0) 2-214 CI C-Cl CI CF3 H CH3S02 2-215 CI N CI CF3 H H 2-216 CI N CI CF3 H HCO 2-217 CI N CI CF3 H CH3CO 2-218 CI N CI CF3 H CH3CH2CO 2-219 CI N CI CF3 H CH3CH2CH2CO 2-220 CI N CI CF3 H cyclo-PrCO 2-221 CI N CI CF3 H cyclo-PrCH2CO 2-222 CI N CI CF3 H CF3CH2CO 2-223 CI N CI CF3 H CH3SCH2CO 2-224 CI N CI CF3 H CH3SOCH2CO 2-225 CI N CI CF3 H CH3S02CH2CO 2-226 CI N CI CF3 H CH3CH2NHCO 2-227 CI N CI CF3 H CH3CH2OC(=0) 2-228 CI N CI CF3 H CH3OCH2CH2CO 2-229 CI N CI CF3 H CH3OCH(CH3)CH2CO 2-230 CI N CI CF3 H tert-BuOC(=0) 2-231 CI N CI CF3 H CH3S02 2-232 CF3 N CF3 CF3 H H 2-233 CF3 N CF3 CF3 H HCO 2-234 CF3 N CF3 CF3 H CH3CO 2-235 CF3 N CF3 CF3 H CH3CH2CO 2-236 CF3 N CF3 CF3 H CH3CH2CH2CO 2-237 CF3 N CF3 CF3 H cyclo-PrCO 2-238 CF3 N CF3 CF3 H cyclo-PrCH2CO 2-239 CF3 N CF3 CF3 H CF3CH2CO 2-240 CF3 N CF3 CF3 H CH3SCH2CO 2-241 CF3 N CF3 CF3 H CH3SOCH2CO 2 X1 B X2 R R3 R4 m
3-242 CF3 N CF3 CF3 H CH3S02CH2CO 2
3-243 CF3 N CF3 CF3 H CH3CH2NHCO 2
3-244 CF3 N CF3 CF3 H CH3CH2OC(=0) 2
3-245 CF3 N CF3 CF3 H CH3OCH2CH2CO 2
3-246 CF3 N CF3 CF3 H CH3OCH(CH3)CH2CO 2
3-247 CF3 N CF3 CF3 H tert-BuOC(=0) 2
3-248 CF3 N CF3 CF3 H CH3S02 2
3-249 CI C-Cl CF3 CF3 H CH3CH2CO 2
3-250 CI C-Cl CF3 CF3 H CH3CH2CO 2
3-251 CF3 C-F H CF3 H CH3CH2CO 2
3-252 CF3 C-F H CF3 H CH3CH2CO 2
3-253 CF3 C-H F CF3 H CH3CH2CO 2
3-254 CF3 C-H F CF3 H CH3CH2CO 2
3-255 CF3 N H CF3 H CH3CH2CO 2
3-256 CF3 N H CF3 H CH3CH2CO 2
3-257 CF3 N F CF3 H CH3CH2CO 2
3-258 CF3 N F CF3 H CH3CH2CO 2
Table 4
Figure imgf000095_0001
wherein the moiety represented by the following formula:
Figure imgf000095_0002
represents any one of Al to Al 0 or of Al ' to Al 0' as defined in Table a.
X1 B X2 R Y R7 n
4-1 CI C-H CI CF3 H H 0
4-2 CI C-H CI CF3 H H 1
4-3 CI C-H CI CF3 H H 2 X1 B X2 R Y R7 n-4 CI C-H CI CF3 CH3 H 0-5 CI C-H CI CF3 CH3 H 1-6 CI C-H CI CF3 CH3 H 2-7 CI C-H CI CF3 CI H 0-8 CI C-H CI CF3 CI H 1-9 CI C-H CI CF3 CI H 2-10 CI C-H CI CF3 Br H 0-11 CI C-H CI CF3 Br H 1-12 CI C-H CI CF3 Br H 2-13 CI C-H CI CF3 CF3 H 0-14 CI C-H CI CF3 CF3 H 1-15 CI C-H CI CF3 CF3 H 2-16 CI C-H CI CF3 CF3 H 0-17 CI C-H CI CF3 CF3 H 1-18 CI C-H CI CF3 CF3 H 2-19 CF3 C-H H CF3 CF3 H 0-20 CF3 C-H H CF3 CF3 H 1-21 CF3 C-H H CF3 CF3 H 2-22 CF3 C-H H CF3 CF3 H 0-23 CF3 C-H H CF3 CF3 H 1-24 CF3 C-H H CF3 CF3 H 2-25 CF3 C-H H CF3 CF3 H 0-26 CF3 C-H H CF3 CF3 H 1-27 CF3 C-H H CF3 CF3 H 2-28 CF3 C-H H CF3 CF3 H 0-29 CF3 C-H H CF3 CF3 H 1-30 CF3 C-H H CF3 CF3 H 2-31 CF3 C-H H CF3 CF3 H 0-32 CF3 C-H H CF3 CF3 H 1-33 CF3 C-H H CF3 CF3 H 2-34 CF3 C-H H CF3 N02 H 0-35 CF3 C-H H CF3 N02 H 1-36 CF3 C-H H CF3 N02 H 2-37 CF3 C-H CF3 CF3 H H 0 X1 B X2 R Y R7 n-38 CF3 C-H CF3 CF3 H H 1-39 CF3 C-H CF3 CF3 H H 2-40 CF3 C-H CF3 CF3 CH3 H 0-41 CF3 C-H CF3 CF3 CH3 H 1-42 CF3 C-H CF3 CF3 CH3 H 2-43 CF3 C-H CF3 CF3 CI H 0-44 CF3 C-H CF3 CF3 CI H 1-45 CF3 C-H CF3 CF3 CI H 2-46 CF3 C-H CF3 CF3 Br H 0-47 CF3 C-H CF3 CF3 Br H 1-48 CF3 C-H CF3 CF3 Br H 2-49 CF3 C-H CF3 CF3 CF3 H 0-50 CF3 C-H CF3 CF3 CF3 H 1-51 CF3 C-H CF3 CF3 CF3 H 2-52 CF3 C-H CF3 CF3 N02 H 0-53 CF3 C-H CF3 CF3 N02 H 1-54 CF3 C-H CF3 CF3 N02 H 2-55 Br C-H Br CF3 H H 0-56 Br C-H Br CF3 H H 1-57 Br C-H Br CF3 H H 2-58 Br C-H Br CF3 CH3 H 0-59 Br C-H Br CF3 CH3 H 1-60 Br C-H Br CF3 CH3 H 2-61 Br C-H Br CF3 CI H 0-62 Br C-H Br CF3 CI H 1-63 Br C-H Br CF3 CI H 2-64 Br C-H Br CF3 Br H 0-65 Br C-H Br CF3 Br H 1-66 Br C-H Br CF3 Br H 2-67 Br C-H Br CF3 CF3 H 0-68 Br C-H Br CF3 CF3 H 1-69 Br C-H Br CF3 CF3 H 2-70 Br C-H Br CF3 N02 H 0-71 Br C-H Br CF3 N02 H 1 X1 B X2 R Y R7 n-72 Br C-H Br CF3 N02 H 2-73 CI C-Cl CI CF3 H H 0-74 CI C-Cl CI CF3 H H 1-75 CI C-Cl CI CF3 H H 2-76 CI C-Cl CI CF3 CH3 H 0-77 CI C-Cl CI CF3 CH3 H 1-78 CI C-Cl CI CF3 CH3 H 2-79 CI C-Cl CI CF3 CI H 0-80 CI C-Cl CI CF3 CI H 1-81 CI C-Cl CI CF3 CI H 2-82 CI C-Cl CI CF3 Br H 0-83 CI C-Cl CI CF3 Br H 1-84 CI C-Cl CI CF3 Br H 2-85 CI C-Cl CI CF3 CF3 H 0-86 CI C-Cl CI CF3 CF3 H 1-87 CI C-Cl CI CF3 CF3 H 2-88 CI C-Cl CI CF3 N02 H 0-89 CI C-Cl CI CF3 N02 H 1-90 CI C-Cl CI CF3 N02 H 2-91 CI N CI CF3 H H 0-92 CI N CI CF3 H H 1-93 CI N CI CF3 H H 2-94 CI N CI CF3 CH3 H 0-95 CI N CI CF3 CH3 H 1-96 CI N CI CF3 CH3 H 2-97 CI N CI CF3 CI H 0-98 CI N CI CF3 CI H 1-99 CI N CI CF3 CI H 2-100 CI N CI CF3 Br H 0-101 CI N CI CF3 Br H 1-102 CI N CI CF3 Br H 2-103 CI N CI CF3 CF3 H 0-104 CI N CI CF3 CF3 H 1-105 CI N CI CF3 CF3 H 2 X1 B X2 R Y R7 n-106 CI N CI CF3 N02 H 0-107 CI N CI CF3 N02 H 1-108 CI N CI CF3 N02 H 2-109 CF3 N CF3 CF3 H H 0-110 CF3 N CF3 CF3 H H 1-111 CF3 N CF3 CF3 H H 2-112 CF3 N CF3 CF3 CH3 H 0-113 CF3 N CF3 CF3 CH3 H 1-114 CF3 N CF3 CF3 CH3 H 2-115 CF3 N CF3 CF3 CI H 0-116 CF3 N CF3 CF3 CI H 1-117 CF3 N CF3 CF3 CI H 2-118 CF3 N CF3 CF3 Br H 0-119 CF3 N CF3 CF3 Br H 1-120 CF3 N CF3 CF3 Br H 2-121 CF3 N CF3 CF3 CF3 H 0-122 CF3 N CF3 CF3 CF3 H 1-123 CF3 N CF3 CF3 CF3 H 2-124 CF3 N CF3 CF3 N02 H 0-125 CF3 N CF3 CF3 N02 H 1-126 CF3 N CF3 CF3 N02 H 2-127 CI C-Cl CF3 CF3 CH3 H 1-128 CI C-Cl CF3 CF3 CH3 H 2-129 CF3 C-F H CF3 CH3 H 0-130 CF3 C-F H CF3 CH3 H 1-131 CF3 C-H F CF3 CH3 H 1-132 CF3 C-H F CF3 CH3 H 2-133 CF3 N H CF3 CH3 H 0-134 CF3 N H CF3 CH3 H 1-135 CF3 N F CF3 CH3 H 1-136 CF3 N F CF3 CH3 H 2-137 CI CI CI CF3 CH3 CH3 0-138 CI CI CI CF3 CH3 CH3 1-139 CI CI CI CF3 CH3 CH3 2 X1 B X2 R Y R7 n
4-140 CF3 C-H CF3 CF3 CH3 CH3 0
4-141 CF3 C-H CF3 CF3 CH3 CH3 1
4-142 CF3 C-H CF3 CF3 CH3 CH3 2
Table 5
Figure imgf000100_0001
G5 G6 G7 G8 G9 wherein the moiety represented by the following formula:
Figure imgf000100_0002
represents any one of Al to Al 0 or of Al ' to Al 0' as defined in Table a.
X1 B X2 R R1 R2 A1 A2 A4 G (Z)k
5-1 CI C-Cl CI CF3 H CI C-H C-H C-CN F -
5-2 CI C-Cl CI CF3 H CI C-H C-H C-CN G6 H
5-3 CI C-Cl CI CF3 H Br C-H C-H C-CN G6 H
5-4 CI C-Cl CI CF3 H C02CH3 C-H C-H C-Br F -
5-5 CI C-Cl CI CF3 H C02CH3 C-H C-H C-CN F -
5-6 CI C-Cl CI CF3 H C02CH3 C-H C-H C-CN G6 H
5-7 CF3 C-H CF3 CF3 H C02CH3 C-H C-H C-CN F H
5-8 CF3 C-H CF3 CF3 H C02CH3 C-H C-H C-CN G6 H
5-9 CI N CI CF3 H CI C-H C-H C-CN G6 H able 6
Figure imgf000101_0001
wherein the moiety represented by the following formula:
Figure imgf000101_0002
represents any one of Al to Al 0 or of Al ' to Al 0' as defined in Table a.
Figure imgf000101_0005
Table 7
Figure imgf000101_0003
wherein the moiety represented by the following formula:
Figure imgf000101_0004
represents any one of Al to Al 0 or of Al ' to Al 0' as defined in Table a.
X1 B X2 R R1 R2 Y R7 n
7-1 CI C-Cl CI CF3 H CI Br H 0
7-2 CI C-H CI CF3 H CI Br H 2
7-3 CF3 C-H CF3 CF3 H CI Br H 0
7-4 CF3 C-H CF3 CF3 H CI Br H 1
7-5 CF3 C-H CF3 CF3 H CI Br H 1 X1 B X2 R R1 R2 Y R7 n
7-6 CF3 C-H CF3 CF3 H CI Br H 2
7-7 CF3 C-H CF3 CF3 H Br Br H 0
NMR Table
Figure imgf000102_0001
Figure imgf000103_0001
The test solutions were prepared as described below unless otherwise mentioned.
Solvent: 3 parts by weight of Dimethylformamide
Emulsifier: 1 part by weight of Polyoxyethylene alkylphenyl ether To prepare a suitable concoction of the active compound, 1 part by weight of the active compound was mixed with the above amount of the solvent containing the above amount of the emulsifier, and the resulting mixture was diluted with water to a predetermined concentration.
Biological test example 1 : Test on Spodoptera litura larvae Leaves of sweet potato were immersed in the test solution at the appropriate concentration, and the leaves were dried in air. The leaves were then placed in a petri dish having a diameter of 9 cm, and ten Spodoptera litura at third instar larvae were released therein. The petri dishes were placed in a temperature-controlled chamber at 25 °C. After 2 days and 4 days more sweet potato leaves were added. After 7 days, the number of dead larvae was counted to calculate the insecticidal activity. An insecticidal activity of 100 % means that all larvae were killed, whereas an insecticidal activity of 0 % means that no larva was killed. In the current test, the results of two petri dishes for each treatment were averaged.
In the biological test example 1, the compound Nos. 5-2, 5-3, 5-4, 5-6, 6-2, 6-3, 6-4, 7-1 , 7-2, 7-3, 7-4, 7-5, 7-6 and 7-7 showed an insecticidal activity of 100 % at an active compound concentration of 100 ppm.
Biological test example 2: Test on Tetranychus urticae 50 to 100 adult mites of Tetranychus urticae were inoculated to leaves of kidney bean at two-leaf stage planted in a pot of 6 cm in diameter. After one day, test solution at the appropriate concentration was sprayed thereon in a sufficient amount using a spray gun. After the spraying, the plant pot was placed inside a greenhouse, and after 7 days, the acaricidal activity was calculated. An acaricidal activity of 100 % means that all mites were killed, whereas an acaricidal activity of 0 % means that no mite was killed.
In the biological test example 2, the compound Nos. 5-2, 5-3, 5-6, 6-4, 7-1 , 7-2, 7-3, 7-4, 7-5, 7-6 and 7-7 showed an acaricidal activity of 100 % at an active compound concentration of 100 ppm.
Biological test example 3: Test on Aulacophora femoralis
Leaves of cucumber were immersed in the test solution at the appropriate concentration, and the leaves were dried in air. The leaves were then put in a plastic cup containing sterilized black soil and five Aulacophora femoralis at second instar larvae were released in the cup. The cups were placed in a temperature-controlled chamber at 25 °C. After 7 days, the number of dead larvae was counted, and thus the insecticidal activity was calculated. An insecticidal activity of 100 % means that all larvae were killed, whereas an insecticidal activity of 0 % means that no larva was killed.
In the biological test example 3, the compound Nos. 5-2, 5-3, 5-6, 6-4, 7-1 , 7-2, 7-3, 7-4, 7-5, 7-6 and 7-7 showed an insecticidal activity of 100 % at an active compound concentration of 100 ppm.
Biological test example 4: Test on Ctenocephalides felis (CTECFE) Solvent: Dimethyl sulfoxide
To produce a suitable preparation of active compound, 10 mg of active compound are dissolved in 0.5 ml solvent, and the concentrate is diluted with cattle blood to the desired concentration. Approximately 20 adult unfed (Ctenocepahlides felis) are placed in flea chambers. The blood chamber, sealed with parafilm on the bottom, are filled with cattle blood supplied with compound solution and placed on top of the flea chamber, so that the fleas are able to suck the blood. The blood chamber is heated to 37 °C whereas the flea chamber is kept at room temperature. After 2 days mortality in % is determined. 100 % means that all the fleas have been killed; 0 % means that none of the fleas have been killed.
In this test for example, the following compounds from the preparation examples showed good activity of 100 % at an application rate of 100 ppm: 5-2, 6-3, 6-4, 7-1, 7-2, 7-3, 7-4, 7-5, 7-6 Biological test example 5: Test on Lucillia cuprina
Species: Lucilia cuprina 1st instar larvae (age 24 hrs)
Solvent: Dimethyl sulfoxide 10 mg active compound are dissolve in 0,5 ml Dimethylsulfoxid. Serial dilutions are made to obtain the desired rates. Approximately 20 Lucilia cuprina 1 st instar larvae are transferred into a test tube containing 1 cm3 of minced horse meat and 0.5 ml aqueous dilution of test compound. After 48 hrs percentage of larval mortality are recorded. 100 % efficacy = all larvae are killed, 0 % efficacy = normally developed larvae after 48 hrs. In this test for example, the following compounds from the preparation examples showed good activity of 100 % at an application rate of 100 ppm: 5-2, 6-2, 6-3, 6-4, 7-1, 7-2, 7-3, 7-4, 7-5, 7-6
Biological test example 6: Test on Musca domestica Solvent: Dimethyl sulfoxide To produce a suitable preparation of active compound, 10 mg of active compound are dissolved in 0.5 ml solvent, and the concentrate is diluted with water to the desired concentration. Prior to the assay, a piece of kitchen sponge is soaked with a mixture of sugar and compound solution and placed into a container. 10 adults (Musca domestica) are placed into the container and closed with a perforated lid. After 2 days mortality in % is determined. 100 % means that all the flies have been killed; 0 % means that none of the flies have been killed.
In this test for example, the following compound from the preparation examples showed good activity of 90 % at an application rate of 100 ppm: 6-3
In this test for example, the following compounds from the preparation examples showed good activity of 100 % at an application rate of 100 ppm: 5-2, 6-4, 7-1, 7-2, 7-3, 7-4, 7-5, 7-6
Biological test example 7: Immersion test on Boophilus microplus Solvent: Dimethyl sulfoxide
To produce a suitable preparation of active compound, 10 mg of active compound are dissolved in 0.5 ml solvent, and the concentrate is diluted with water to the desired concentration. Eight to ten adult engorged female Boophilus microplus ticks are placed in perforated plastic beakers and immersed in aqueous compound solution for one minute. Ticks are transferred to a filter paper in a plastic tray. Egg deposition of fertile eggs is monitored after. After 7 days mortality in % is determined. 100 % means that all the ticks have been killed; 0 % means that none of the ticks have been killed.
In this test for example, the following compounds from the preparation examples showed good activity of 100 % at an application rate of 100 ppm: 5-2, 6-4, 7-1, 7-2, 7-3, 7-4, 7-5, 7-6
Biological test example 8: Injection test on Boophilus microplus Solvent: Dimethyl sulfoxide
To produce a suitable preparation of active compound, 10 mg of active compound are dissolved in 0.5 ml solvent, and the concentrate is diluted with solvent to the desired concentration. Five adult engorged female ticks (Boophilus microplus) are injected with 1 μΐ compound solution into the abdomen. Ticks are transferred into replica plates and incubated in a climate chamber for a period of time. Egg deposition of fertile eggs is monitored. After 7 days, mortality in % is determined. 100 % means that all eggs are infertile; 0 % means that all eggs are fertile.
In this test for example, the following compounds from the preparation examples showed good activity of 100 % at an application rate of 20 μg/animal: 5-1, 5-2, 5-3, 5-4, 5-5, 5-6, 6-2, 6-3, 6-4, 7-1, 7-2, 7-3, 7-4, 7-5, 7-6
Biological test example 9: Test on Ambly omnia hebraeum (AMBYHE) Solvent: Dimethyl sulfoxide
To produce a suitable preparation of active compound, 10 mg of active compound are dissolved in 0.5 ml solvent, and the concentrate is diluted with water to the desired concentration. Nymphs of the tick Amblyomma hebraeum are placed in perforated plastic beakers and immersed in aqueous compound solution for one minute. Ticks are transferred to a filter paper in a petridish and incubated in a climate chamber for 42 days. After 42 days, mortality in % is determined. 100 % means that all the ticks have been killed; 0 % means that none of the ticks have been killed.
In this test for example, the following compounds from the preparation examples showed good activity of 100 % at an application rate of 100 ppm: 7-4, 7-5 Formulation Example 1 (Granular formulation)
To a mixture of 10 parts of the compound of the present invention (No. 5-2), 30 parts of bentonite (montmorillonite), 58 parts of talc and 2 parts of lignin sulfonate, 25 parts of water are added. The mixture is well kneaded, and made to 10 to 40 meshes of granules by an extrusion granulating machine, and dried at 40 to 50 °C to obtain a granular formulation.
Formulation Example 2 (Granular formulation)
95 parts of clay mineral particles having particle size distribution in the range of 0.2 to 2 mm are added to a rotation mixer. By spraying 5 parts of the compound of the present invention (No. 5-2) together with a liquid diluent under rotation, the clay mineral particles are uniformly moistened followed by drying at 40 to 50 °C to obtain a granular formulation.
Formulation Example 3 (Emulsifiable concentrate)
30 parts of the compound of the present invention (No. 5-2), 55 parts of xylene, 8 parts of polyoxyethylene alkylphenyl ether and 7 parts of calcium alkylbenzenesulfonate are mixed and stirred to obtain an emulsifiable concentrate.
Formulation Example 4 (Wettable powders)
15 parts of the compound of the present invention (No. 5-2), 80 parts of a mixture of white carbon (micropowders of hydrous amorphous silicon oxide) and powder clay ( 1 :5), 2 parts of sodium alkylbenzene sulfonate and 3 parts of sodium alkymaphthalene sulfonate formalin condensate are pulverized and mixed to obtain wettable powders.
Formulation Example 5 (Wettable granules)
20 parts of the compound of the present invention (No. 5-2), 30 parts of sodium lignin sulfonate, 15 parts of bentonite and 35 parts of calcined diatomite powders are sufficiently mixed. After adding water thereto, the mixture is extruded with 0.3 mm screen and dried to obtain wettable granules.

Claims

Claims
1. Compounds of Formula (I)
Figure imgf000108_0001
wherein, the chemical moiety represented by the following formula:
Figure imgf000108_0002
stands for the following chemical moiety (a):
Figure imgf000108_0003
or stands for one of the following chemical moieties (β) or (γ), which are positional isomers:
Figure imgf000108_0004
T is selected among the following chemical groupings (T-1), (T-2), (T-3), (T-4) and (T-5):
Figure imgf000108_0005
Figure imgf000109_0001
(T- ) (Τ-5)
Β represents Ν or C-X3;
Χ', X2, X3, X4 and X5 each independently represent hydrogen, halogen, Ct-i2 alkyl, Ci.12 haloalkyl, nitro, Ci.|2 alkoxy, C,.|2 haloalkoxy, cyano, CM2 alkylsulfenyl, Ci.|2 alkylsulfinyl, C|.n alkylsulfonyl, CM2 haloalkylsulfenyl, C,.|2 haloalkylsulfinyl, Ci.i2 haloalkylsulfonyl, hydroxy, mercapto, amino, Ct. acylamino, Ci.i2 alkoxy-carbonylamino, Ci.i2 haloalkoxy-carbonylamino, C| .|2 alkoxy-imino, Cj.n haloalkoxy-imino, Ci.|2 alkylsulfonylamino or sulfur pentafluoride;
Y1, Y2, Y3, Y4 and Ys each independently represent hydrogen, halogen, Ci.12 alkyl, CM2 haloalkyl, nitro, C3.8 cycloalkyl, C3.g cycloha]oalkyl, C 2 alkoxy, C|.12 haloalkoxy, cyano, C|.|2 alkylsulfenyl, C,.i2 alkylsulfinyl, Ct.|2 alkylsulfonyl, C,.i2 haloalkylsulfenyl, CM2 haloalkylsulfinyl, Ci.n haloalkylsulfonyl, 0.)2 alkylsulfonyloxy, Ci.]2 alkylaminosulfonyl, CM2 haloalkylaminosulfonyl, di(CM2 alkyl)aminosulfonyl, di(C,.12 haloalkyl)aminosulfonyl, hydroxy, mercapto, amino, Ci.n alkyla nino, di(Ci.i2 alkyl)amino, C^.n acylamino, CM2 alkoxy-carbonylamino, C|.)2 haloalkoxy-carbonylamino, Ci.!2 alkylsulfonylamino, Ci.)2 haloalkylsulfonylamino, tri(C|,|2 alkyl)silyl, CM 2 alkoxy-imino, CM 2 haloalkoxy-imino, CM2 alkoxy-imino-Ci.!2 alkyl, C).n haloalkoxy-imino-C|.i2 alkyl, CM2 alkylsulfmylimino, Ci.i2 alkylsulfinylimino-CM2 alkyl, C|.!2 alkylsulfinylimino-Ci- alkyl-carbonyl, C].|2 alkylsulfoximino, C).|2 alkylsulfoximino-Ci.n alkyl, C|.|2 alkoxy-carbonyl, C|.|2 alkyl-carbonyl, aminocarbonyl, CM2 alkyl-aminocarbonyl, amino-thiocarbonyl, C|.)2 alkylamino-thiocarbonyl, di(C|-)2 alkyl)amino-carbonyl, di(C|.]2 alkyl)amino-thiocarbonyl or hydroxycarbonyl;
G rep
Figure imgf000109_0002
G5 G6 G7 G8 G9 Z represents hydrogen, CM2 haloalkyl, nitro, Cj.n alkoxy, cyano, CM2 haloalkoxy, C|.i2 alkylsulfenyl, Q. alkylsulfinyl, CM2 alkylsulfonyl, Ci.i2 haloalkylsulfenyl, Ci.|2 haloalkylsulfmyl, C|.|2 haloalkylsulfonyl, hydroxy or thiol; k represents 0, 1 ,
2,
3 or 4; R represents CM2 alky I or C].|2 haloalkyl;
R1 and R2 are absent, or each independently represent hydrogen, halogen, cyano, amino, azido, hydroxy, mercapto, hydroxy-carbonyl, C\.n alkylamino-carbonyl, C|.n alkoxy-carbonyl, Q.n alkoxy, Ci.u alkyl, C2.|2 alkenyl, C2-i2 alkynyl, C\.\2 alkylthio, C|.)2 alkylsulfinyl or C).12 alkylsulfonyl, provided that R1 and R2 are not simultaneously absent, and provided that R1 and RJ are not simultaneously hydrogen;
R3 represents hydrogen, amino, hydroxy, cyano, RS-CH2-, R8-CO, R8-CS-, C1.12 alkyl, C\.n haloalkyl, CM2 alkoxy, C|.|2 haloalkoxy, C2.|2 alkenyl, C2.t2 alkynyl, Ci. . alkyl-carbonyl or Ci.t2 alkyl-carbonylam ino,
R* represents hydrogen, cyano, carbonyl, thiocarbonyl, R8-CO-, R8-CS-, C].\2 alkyl-carbonyl, Ci_|2 alkyl-thiocarbonyl, C].|2 haloalkyl-carbonyl, Ci.]2 haloalkyl-thiocarbonyl, CM2 alkylamino-carbonyl, C).i2 alkylamino-thiocarbonyl, di(Ci.,2 alkyl)amino-carbonyl, di(Ci.n alkyl)amino-thiocarbonyl, C|.i2 alkoxyamino-carbonyl, Cj.a alkoxyamino-thiocarbonyl, C|.) 2 alkoxy-carbonyl, Ci_|2 alkoxy-thiocarbonyl, C|.n thioalkoxy-carbonyl, C|.i2 thioalkoxy-thiocarbonyl, C i2 alkylsulfonyl, C|.]2 haloalkylsulfonyl, C3-8 cycloalkyl-carbonyl, C2.)2 alkenyl-carbonyl, C alkynyl-carbonyl, C3 cycloalkyl-C|.]2 alkyl-carbonyl, C1.12 alkylsulfenyl-CM2 alkyl-carbonyl, C|.i2 alky 1 su If my 1-Ci .12 alkyl-carbonyl, C,.|2 aIkylsulfonyl-Ci.|2 alkyl-carbonyl, C|.) 2 alkyl-carbonyl-CM2 alkyl-carbonyl, C3 cycloalkylamino-carbonyl, C2-i2 alkenylamino-carbonyl or C2.|2 alkynylamino-carbonyl, or
RJ and R" may form a 3-, 4-, 5- or 6-membered, saturated or unsaturated heterocyclic ring together with the nitrogen atom to which they are bound, wherein the heterocyclic ring may be substituted with oxo, thioxo or nitro;
Rs represents hydrogen, cyano, C|.)2 alkyl or CM2 haloalkyl;
R6 represents hydrogen, C].^ alkyl, Ci.]2 alkylcarbonyl or CM2 alkoxycarbonyl;
R7 represents hydrogen or CH2 alkyl; R8 represents phenyl or a 3-,
4-, 5- or 6-membered, saturated or unsaturated heterocyclic ring; - no ¬
Z1, Z2 and Z3 each independently represent -C(R9)(R10)-, -C(=0)-, -C(=N-OR")-. -N(R )-, -S-, -S(=0)-, -S(=0) or -S(0)(=N-R")-;
R9 and R10 each independently represent hydrogen, halogen, CM2 alkyl or CM2 haloalkyl;
R11 represents hydrogen, cyano, nitro, CM. alkyl, C|.]2 haloalkyl, C3.8 cycloalkyl-C|.i2 alkyl, C1.12 alkyl-carbonyl, CM2 haloalkyl-carbonyl, C1.12 alkoxy-carbonyl, Cj. haloalkoxy-carbonyl, CM2 alkylsulfonyl, C .\2 haloalkylsulfonyl, aryl-Ci.I2 alkyl, the aryl moiety of which may be substituted with 1 , 2 or 3 times the group R,Z, or heterocyclic ring-C].i2 alkyl, the heterocyclic ring moiety of which may be substituted with 1, 2 or 3 times the group R12;
R12 represents hydrogen, halogen, cyano, nitro, Ci.|2 alkyl, Ci.)2 haloalkyl, Ci.|2 alkoxy, C|.)2 l o haloalkoxy or Ci.|2 alkoxy-carbonyl; and m represents 1 or 2; whereas the groups defined above may be further substituted with at least one substituent selected from halogen, Q.u alkyl, CMJ haloalkyl, nitro, C 2 alkoxy, cyano, C|.|2 haloalkoxy, Q.12 alkylsulfenyl, CM. alkylsulfinyl, C|.]2 alkylsulfonyl, C 2 haloalkylsulfenyl, Ci.I2 haloalkylsulfinyl, Ci.|2 haloalkylsulfonyl, hydroxy and mercapto.
Figure imgf000111_0001
Compounds according to claim 1 having the following Formula (]')
Figure imgf000111_0002
wherein X1, X2, X4, X5, R, B and T are as defined in claim 1 , and wherein Hal represents fluorine, chlorine, bromine or iodine. 0 Compounds according to claim 1 having the following Formula (I-Ia)
Figure imgf000111_0003
wherein X', X3, X4, X5, R, B and T are as defined in claim 1, and wherein R20 represents hydrogen or C1-5 alkyl. J/. Compounds according to claim I having the following Formula (I-Ib)
Figure imgf000112_0001
wherein X1, X2, X4, X3, R, B and T are as defined in claims 1, and wherein R20 represents hydrogen or C^ alkyl.
5.
Compounds according to any of claims 1 to , wherein
T is a group Tl, with Y2 or Y3 being cyano and wherein G is selected from the groups G4, GS or G6.
7 Compounds according to any of claims 1 to β, wherein T is a group T2, with Y or Y being cyano and wherein G is selected from the groups G4, G5 or G6. positition containg as an effective ingredient, a compound as defined in any of
Figure imgf000112_0002
The pesticidal composition according to claim ? for expelling parasitic arthropods.
I he pesticidal composition according to claim Jf for expelling pests which occure in the agriculture.
AO- X. Method for the manufacturing of compounds of Formulae (I-Ia) or (I-Ib):
Figure imgf000112_0003
( wherein X1, X2, X4, X5, R, B, T and R20 are as defined herein, as defined in claim /or
comprising the following steps (b- 1) and (b-2):
Step (b-1 ): Reacting compounds of Formula (ΠΙ):
Figure imgf000113_0001
wherein X1, X2, X4, X3, B, R and R20 are as defined in
Figure imgf000113_0002
with compounds of Formula (IV):
Figure imgf000113_0003
wherein T is defined in
Figure imgf000113_0004
in the presence of a suitable diluent and/or if necessary a copper reagent selected from copper oxide (1), copper oxide (II), copper acetylacetonate (II), copper acetate (II), copper cyanide (I) whereby obtaining compounds represented by Formula (V):
Figure imgf000113_0005
0 are as defined in claim 3 *t
wherein X1, X2, X4, X5, R, B, T and R2 / or ; and
Step (b-2): Subsequently shifting the position of the double bond on the pyrroline ring in compound of Formula (V) in the presence of a suitable diluent and/or base if necessary, so to obtaing the compound of Formula (I-Ia) or (I-Ib).
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