WO2009112275A1 - Pesticidal condensed - ring aryl compounds - Google Patents

Pesticidal condensed - ring aryl compounds Download PDF

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Publication number
WO2009112275A1
WO2009112275A1 PCT/EP2009/001841 EP2009001841W WO2009112275A1 WO 2009112275 A1 WO2009112275 A1 WO 2009112275A1 EP 2009001841 W EP2009001841 W EP 2009001841W WO 2009112275 A1 WO2009112275 A1 WO 2009112275A1
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Prior art keywords
carbonyl
alkyl
carbonylamino
spp
thiocarbonyl
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PCT/EP2009/001841
Other languages
French (fr)
Inventor
Tetsuya Murata
Yasushi Yoneta
Jun Mihara
Kei Domon
Mamoru Hatazawa
Koichi Araki
Eiichi Shimojo
Katsuhiko Shibuya
Teruyuki Ichihara
Ulrich Görgens
Arnd Voerste
Angela Becker
Eva-Maria Franken
Klaus-Helmut Müller
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Bayer Cropscience Ag
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Publication date
Priority to JP2010550093A priority Critical patent/JP2011517663A/en
Application filed by Bayer Cropscience Ag filed Critical Bayer Cropscience Ag
Priority to BRPI0909504-7A priority patent/BRPI0909504A2/en
Priority to KR1020137022697A priority patent/KR20130100387A/en
Priority to CN2009801090426A priority patent/CN101970403A/en
Priority to AU2009224896A priority patent/AU2009224896A1/en
Priority to CA2718199A priority patent/CA2718199A1/en
Priority to KR1020107021871A priority patent/KR101349629B1/en
Priority to US12/922,501 priority patent/US20110071141A1/en
Priority to MX2010009904A priority patent/MX2010009904A/en
Priority to EP09719152A priority patent/EP2254863A1/en
Publication of WO2009112275A1 publication Critical patent/WO2009112275A1/en
Priority to IL207426A priority patent/IL207426A0/en
Priority to ZA2010/06502A priority patent/ZA201006502B/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • A01N43/42—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 condensed with carbocyclic 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
    • 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
    • A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • A61P33/10—Anthelmintics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • A61P33/14—Ectoparasiticides, e.g. scabicides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/04—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • the present invention relates to novel condensed-ring aryl compounds and use of the same as a agrochemical for controlling noxious organisms.
  • isoxazoline derivatives can be used as noxious organisms control agent (e.g. WO2005/085216, WO2007/026965, WO2007/074789, WO2007/070606, WO2007/075459, WO2007/079162, WO2007/105814, WO2007/12 5984, Japanese Patent Application Laid-open No. 2007-16017, Japanese Patent Application Laid-open No. 2007-106756, and Japanese Patent Application Laid-open No. 2007-308471, WO2007/026965, and WO2007/105814).
  • WO2005/085216 WO2007/026965
  • WO2007/074789 WO2007/070606
  • WO2007/075459 WO2007/079162
  • WO2007/105814 WO2007/12 5984
  • Japanese Patent Application Laid-open No. 2007-16017 Japanese Patent Application Laid-open No. 2007-106756
  • EP-A-I 731 512 discloses certain arylisoxazoline compounds having condensed rings and which are supposed to exhibit insecticidal action.
  • X represents halogen; nitro; cyano; hydroxy; thiol; amino; Ci.i 2 alkyl, Ci.i 2 haloalkyl, Ci.i 2 alkoxy, C 1-12 haloalkoxy, C M2 alkylsulfenyl, C M2 alkylsulfinyl, Ci -I2 alkyl- sulfonyl, Ci_i 2 haloalkylsulfenyl, C] -I2 haloalkylsulfinyl, Ci_i 2 haloalkylsulfonyl, Cj -J2 alkylamino,
  • Cj -J2 alkylsulfonylamino, or Cj -J2 haloalkylsulfonylamino preferably chloro, bromo, iodo, fluoro; nitro; cyano; hydroxy; thiol; amino; Ci -6 alkyl, Cj. 6 haloalkyl, Cj -6 alkoxy, Cj -6 haloalkoxy, Cj -6 alkylsulfenyl, Cj -6 alkylsulfinyl, Ci -6 alkylsulfonyl, C t . 6 haloalkylsulfenyl, C] -6 haloalkylsulfinyl,
  • Ci -6 haloalkylsulfonyl Ci -6 alkylamino, C 2-J2 (total carbon number) dialkylamino, Cj -6 acylamino,
  • Ci -6 alkoxy-carbonylamino Ci -6 haloalkoxy-carbonylamino, Ci -6 alkylsulfonylamino, or
  • Q represents substitutable phenyl, substitutable naphtyl or a substitutable 5- or 6- membered heterocyclic group; preferably represents a optionally substituted group selected among Q-I to Q-54
  • Y represents halogen; nitro; cyano; hydroxy; thiol; amino; C 1-12 alkyl,
  • R 1 represents cyano; C 1 . 12 alkyl, C 3 . 8 cycloalkyl, C 4-2 o (total carbon number) alkyl- cycloalkyl, C 4 . 2 o (total carbon number) cycloalkylalkyl, C 2 - 12 alkenyl, C 2 - 12 alkynyl, Ci.i 2 haloalkyl, or C 3-8 halocycloalkyl; preferably cyano; Ci -6 alkyl, C 3-6 cycloalkyl, C 4-I2 (total carbon number) alkylcycloalkyl, C 4-12 (total carbon number) cycloalkylalkyl, C 2-6 alkenyl, C 2 - 6 alkynyl,
  • n 0, 1, 2, 3, 4 or 5;
  • n 0, 1, 2 or 3;
  • A represents O, S, CH 2 or N-R 2 ; preferably O;
  • R 2 represents hydrogen; cyano; formyl; Q -I2 alkyl, C 2-I2 alkenyl, C 2-I2 alkynyl, C 3-8 cycloalkyl, C 4-20 (total carbon number) alkylcycloalkyl, C 4-20 (total carbon number) cycloalkylalkyl, C M2 haloalkyl, Ci -I2 alkylsulfonyl, Ci.i 2 haloalkylsulfonyl, phenyl, C 1-I2 alkyl-carbonyl, Ci -I2 alkoxy-carbonyl, C M2 alkylamino-carbonyl, or C 2-24 dialkylamino-carbonyl; preferably represents hydrogen; cyano; formyl; Ci -6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-6 CyClOaIlCyI, C 4-I2 (total carbon number) alkylcycloal
  • W 1 , W 2 , W 3 and W 4 each independently may be omitted to yield a 4- or 5-membered ring, and/or each independently represents a single bond, CH 2 , CH, N, -N + (O " )-, -S(O)-, -S(O) 2 -, -O-S(O)-, O, S, C(R 3 )-R 3 , C-R 3 , C-R 4 , C(R 3 )-R 4 , C(R 3 )-R 4 , C(R 4 )-R 4 , C-N(R 3 )-R 3 , C(R 3 )-N(R 3 )-N(R 3 )-R 3 , C-N(R 3 )-N(R 3 )-R 3 , C(R 3 )-N(R 4 )-N(R 3 )-R 3 , C-N(R 4 )-N(R 3 )-R 3 ,
  • U represents CH 2 , O, S, or N-R 3 or N-R 4 ;
  • R 3 each independently represents hydrogen; hydroxy; thiol; amino; cyano; formyl; halogen; nitro; Ci -6 alkyl, C 2-I2 (total carbon number) alkoxyalkyl, C 2 . ]2 (total carbon number) haloalkoxyalkyl, C 2-6 alkenyl, C 2 - I2 alkynyl, C 3-8 cycloalkyl, C 4-12 (total carbon number) alkylcyclo- alkyl, C 4-I2 (total carbon number) cycloalkylalkyl, Cj ⁇ haloalkyl, C ⁇ alkylcarbonyl, C 1-6 alkyl- carbonyl-Ci.
  • R 4 represents phenyl or 5- or 6-membered saturated or unsaturated heterocyclic ring, preferably is selected among the groups R 4 -l to R 4 -83
  • G represents O, S or N, and wherein each group R 4 -l to R 4 -83 may be substituted with at least one group selected among hydrogen; halogen; cyano, nitro; Ci -6 alkyl, Ci. 6 haloalkyl, C 3-6 cycloalkyl, C 3-6 halocycloalkyl, Ci -6 alkoxy, Ci. 6 haloalkoxy, Ci -6 alkylsulfenyl, Ci -6 haloalkyl- sulfenyl, Ci -6 alkylsulfinyl, Ci -6 haloalkylsulfmyl, Ci -6 alkylsulfonyl, Ci -6 haloalkylsulfonyl,
  • the group -W 1 -W 2 -W 3 -W 4 - is selected among the 4- 5- or 6-membered groups W-I to W-580
  • U represents CH 2 , O, S, N-R 3 or N-R 4 , preferably represents CH 2 , O, S, N-R 3 ,
  • R 3 and R 4 are selected among hydroxy, Ci -6 alkoxy, Ci -6 haloalkoxy, Ci. 6 haloalkyl, alkyl Q -6 alkyl, Ci -6 alkylamino, C 2-I2 dialkylamino, pyridin-2-yl-Ci -6 alkyl, pyridin-2-yl-Ci -6 alkoxy, C 1-6 alkylcarbonyl, Ci -6 alkyl-carbonylamino and Ci -6 haloalkylamino.
  • k 0, 1 or 2
  • W represents O " , R 3 , OR 3 , SR 3 , NHR 3 , N(R 3 ) 2 , N(R 3 )N(R 3 )R 3 , N(R 4 )N(R 3 )R 3 ,
  • W preferably represents CT R 3 , OR 3 , SR 3 , NHR 3 , N(R 3 ) 2 , N(R 3 )N(R 3 )R 3 , N(R 4 )N(R 3 )R 3 , N(R 3 )OR 3 , R 4 , NR 4 , or N 3 wherein R 3 and R 4 are selected among hydrogen, formyl, Ci -6 alkyl, C 2-I2 alkoxyalkyl, C 2-12 haloalkoxyalkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-8 cycloalkyl, C 4-I2 alkylcycloalkyl, C 4-I2 cycloalkylalkyl, Q ⁇ haloalkyl, Ci -6 alkylimino, Ci -6 haloalkylimino, Ci ⁇ alkenyl-carbonyl, Ci -6 alkynyl-carbonyl, Ci -6 haloalkyl-carbonyl,
  • R 3 and R 4 are selected among hydrogen, formyl, Ci.ghydroxyalkyl-carbonyl, Ci -6 alkoxy-carbonyl, Ci -6 alkylamino-
  • Ci ⁇ haloalkylamino-carbonyl Ci ⁇ haloalkylamino-carbonyl, C 2 - 12 dialkylamino-carbonyl, Ci -6 alkylcarbonyl, Ci-ehaloalkylcarbonyl, Ci ⁇ alkyl-thiocarbonyl, Ci -6 alkylamino-thiocarbonyl, Ci -6 alkylsulfonyl, pyrimidinyl, and pyridyl.
  • the present invention does not include the following compounds, which are known from WO 2005/085216, namely
  • X represents halogen, Ci_i 2 alkyl, Ci -J2 haloalkyl, nitro, cyano, Ci -J2 alkoxy, Cj. 12 haloalkoxy, C M2 alkylthio, C M2 alkylsulfinyl, Cj. ⁇ alkylsulfonyl, Ci.] 2 haloalkylthio, Ci -I2 haloalkylsulfmyl, C].i 2 haloalkylsulfonyl, hydroxy, mercapto, amino, C M2 alkylamino, C 2-24 (total carbon number) dialkylamino, C M2 (total carbon number) acylamino, C M2 alkoxy-carbonyl- amino, Ci -I2 haloalkoxy-carbonylamino, Ci. ⁇ alkyl-sulfonylamino group, or Cj.nhaloalkyl- -sulfonylamin
  • Y represents halogen, Q -12 alkyl, C 1-I2 haloalkyl, C 3 . 12 cycloalkyl, C 3-12 cyclo- haloalkyl, nitro, cyano, C 2-I2 alkenyl, C 2-I2 haloalkenyl, C ⁇ 2 alkoxy, C M2 haloalkoxy, Ci -]2 alkylthio, Ci -I2 alkylsulfinyl, Q- 12 alkylsulfonyl, Ci -I2 haloalkylthio, Ci -I2 haloalkylsulfinyl, C M2 haloalkyl- sulfonyl, hydroxy, mercapto, amino, Ci -I2 alkylamino, C 2-24 (total carbon number) dialkylamino, aminocarbonyl, Ci -I2 alkylaminocarbonyl, C 2-24 (total carbon number) dialkylamino
  • R 1 represents C ⁇ 2 alkyl, C 3-J2 (total carbon number) cycloalkyl, C 4-I2 (total carbon number) alkylcycloalkyl, C 4-I2 (total carbon number) cycloalkylalkyl, C 2-I2 alkenyl, C 2-I2 alkynyl, Ci -I2 haloalkyl, C 3-I2 (total carbon number) halocycloalkyl, or cyano;
  • n 0, 1, 2, 3, 4 or 5;
  • n 0, 1, 2 or 3;
  • A represents O, CH 2 or N-R x ,
  • R x independently represents hydrogen, cyano, formyl, Cj -I2 alkyl, C 2 . ]2 alkenyl,
  • Ci -I2 alkoxy-carbonyl Ci -I2 alkyl-aminocarbonyl, C 2-24 (total carbon number) dialkyl-amino- carbonyl;
  • U represents CH 2 , O, S, N-R y or N-R z ;
  • R y independently represents hydrogen, hydroxy, amino, Ci.i 2 alkyl, C 2 - I2 alkenyl, C 2-J2 alkenyloxy, C 2-J2 alkynyl, C 2-]2 alkynyloxy, C 3-I2 cycloalkyl, C 4-I2 (total carbon number) alkyl- cycloalkyl, C 4-I2 (total carbon number) cycloalkylalkyl, Ci -I2 haloalkyl, C M2 alkylamino, C 2-24 (total carbon number) dialkyl-amino, Cj -I2 alkoxy, Ci -J2 haloalkoxy, formyl, Cj -J2 alkyl-carbonyl, Ci -J2 haloalkyl-carbonyl, Cj -J2 alkyl-carbonylamino, C M2 haloalkyl-carbonylamino, Ci.i 2 alkyl- sulfony
  • R z is selected among the groups R 4 -l to R 4 -83 wherein G represents O, S or N, and which may be substituted with at least one group selected among hydrogen, halogen, Cj -J2 alkyl Ci -I2 haloalkyl, C 3 _i 2 cycloalkyl, C 3 _i 2 halocycloalkyl, C J .
  • the invention is also directed to compounds of formula (I) wherein
  • X independently represents halogen, C M2 alkyl, C M2 haloalkyl, nitro, cyano,
  • Q is selected among Q-I to Q-54;
  • Y independently represents halogen, Ci -12 alkyl, Ci -I2 haloalkyl, C 3 _i 2 cycloalkyl, C 3 _ J2 cyclohaloalkyl, nitro, cyano, C 2-I2 alkenyl, C 2-I2 haloalkenyl, Ci.i 2 alkoxy, C M2 haloalkoxy,
  • Ci -I2 alkylthio C M2 alkylsulfinyl, C M2 alkylsulfonyl, Ci -I2 haloalkylthio, C 1-I2 haloalkylsulf ⁇ nyl,
  • Ci -I2 haloalkylsulfonyl hydroxy, mercapto, amino, C M2 alkylamino, C 2-24 (total carbon number) dialkylamino, aminocarbonyl, C 2-13 (total carbon number) alkylaminocarbonyl, C 3-2S (total carbon number) dialkylaminocarbonyl, C M2 (total carbon number) acylamino, C 2-13 (total carbon number) alkoxy-carbonylamino, benzyloxy-carbonylamino, C 2-I3 haloalkoxy-carbonylamino, Ci -12 alkyl- sulfonylamino, C M2 haloalkylsulfonylamino, a C 3-2 ⁇ (total carbon number) trialkylsilyl;
  • R 1 represents C ]-12 alkyl , C 3 _ 12 (total carbon number) cycloalkyl, C 4-24 (total carbon number) alkylcycloalkyl, C 4-24 (total carbon number) cycloalkylalkyl, C 2 . 12 alkenyl, C 2-I2 alkynyl, Ci -12 haloalkyl, C 3-12 (total carbon number) halocycloalkyl, cyano;
  • n 0, 1, 2, 3, 4 or 5
  • n 0, 1, 2 or 3
  • A represents O, CH 2 or N— R x ;
  • R x independently represents hydrogen, cyano, formyl, C M2 alkyl, C 2-I2 alkenyl,
  • C 2-I2 alkynyl C 3-12 (total carbon number) cycloalkyl, C 4-12 (total carbon number) alkylcycloalkyl, C 4-24 (total carbon number) cycloalkylalkyl, C 1-12 haloalkyl, phenyl, C 2-I3 (total carbon number) alkylcarbonyl, C 2-13 (total carbon number) alkoxycarbonyl, C 2-13 (total carbon number) alkylaminocarbonyl or C 3-25 (total carbon number) dialkylaminocarbonyl,
  • R y independently represents hydroxy, amino, cyano, formyl, halogen, nitro
  • U represents CH 2 , O, S, N-R z or N-R ** ;
  • R z represents hydrogen, hydroxy, amino, Ci -I2 alkyl, Ci -I2 haloalkyl, C 2-I2 alkenyl,
  • R * " is selected among the groups R 4 -l to R 4 -83 wherein G represents O, S or N, and which may be substituted with at least one group selected among hydrogen, halogen, Ci -)2 alkyl, Ci -J2 haloalkyl, C 3-I2 cycloalkyl, C 3-I2 halocycloalkyl, Ci_i 2 alkoxy, C M2 haloalkoxy, C M2 alkylthio, C M2 haloalkylthio, Q -I2 alkylsulfinyl, C M2 haloalkylsulfinyl, C M2 alkylsulfonyl, Ci -]2 haloalkylsulfonyl, C M2 alkylamino, C M2 haloalkylamino, cyano, nitro, aminocarbonyl, alkyl-amino- carbonyl, C 2-24 (total carbon number) dialkyl-amin
  • Embodiment A Compounds having the structure (I-a-1) or (I-a-2), wherein the chemical groups A, R 1 , W 1 , W 2 , W 3 and W 4 are as defined herein, and wherein each X 1 , X 2 and X 3 are as defined herein for X, and wherein each Yi, Y 2 and Y 3 are as defined herein for Y.
  • Embodiment B Compounds as defined in embodiment A, wherein the group -W'-W ⁇ W ⁇ W 4 - is selected among W-5, W-8, W-12 , W-16, W-17, W-18, W-20, W-22, W-23, W-24, W-30, W-31,
  • W-315, W-337, W-339, W-344, W-345, W-348, W-351 and W-357 preferably W-5, W-7, W-Il,
  • Embodiment C Compounds as defined in embodiment A or B, wherein A represents oxygen or CH 2 , R 1 represents CF 3 , and/or X 1 , X 2 , X 3 are independently selected among hydrogen, halogen, amino, Ci_ 6 alkylamino, C 2-12 dialkylamino, nitro, Q. 6 alkoxy, and Q. 6 haloalkyl and Y 1 , Y 2 , Y 3 is H.
  • Embodiment D Compounds having the structure (I-d-1), wherein the chemical groups A, R 1 , Q, X, Y, m, n and W are as defined herein and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, C ⁇ alkyl, Ci -6 haloalkyl, Ci. 6 alkoxy, Ci -6 alkylsulfenyl, Ci -6 alkylsulfinyl,
  • Embodiment Dl Compounds as defined in embodiment D, wherein the group Q is selected among Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Ci ⁇ alkylamino, C 2 - 12 dialkylamino, nitro, C ]-6 alkoxy, and Ci -6 haloalkyl.
  • Embodiment D2 Compounds as defined in embodiment D or Dl, wherein A represents oxygen or CH 2 , R 1 represents CF 3 , and Y is H.
  • W preferably represents amino, hydroxy, carbonylamino Ci -6 alkyl-carbonylamino, C ]-6 alkylcarbonyl-Ci_ 6 alkyl-carbonylamino, Q -6 alkylsulfenyl-Ci -6 alkyl- -carbonylamino, Ci -6 alkylsulfenyl-Ci -6 alkyl-carbonylamino, Ci -6 alkylsulfinyl-Ci -6 alkyl-carbonylamino, C 1-6 alkylsulfonyl-Ci -6 alkyl-carbonylamino, Ci ⁇ haloalkyl-carbonylamino, cyano-Ci -6 alkyl- -carbonylamino C 1 -6 alkenyl-carbonylamino, C 1 -6 haloalkenyl-carbonylamino, C 1 -6 alkynyl- -carbonylamino, Ci -6
  • Ci -6 alkylcarbonyloxy more preferably represents amino, hydroxy, carbonylamino, Ci ⁇ alkyl- sulfonylamino, Ci. 6 alkylamino-carbonylamino, Ci -6 alkylthiocarbonylamino, Ci.
  • Embodiment E Compounds having the structure (I-e-1), wherein the chemical groups A, R 1 , Q, X, Y, m, n, and W are as defined herein and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, Ci -6 alkyl, Ci- ⁇ haloalkyl, Ci. 6 alkoxy, Ci -6 alkylsulfenyl, Ci -6 alkylsulfinyl,
  • Embodiment El Compounds as defined in embodiment E, wherein the group Q is selected among Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, C ⁇ alkylamino, C 2 - 12 dialkylamino, nitro, Cj ⁇ alkoxy, and Ci_ 6 haloalkyl.
  • Embodiment E2 Compounds as defined in embodiment E or El, wherein A represents oxygen or CH 2 , R 1 represents CF 3 , and Y is H.
  • W preferably represents hydrogen, Ci -6 alky, C ⁇ haloalky, Ci -6 alkyl- carbonyl, Ci -6 haloalkylcarbonyl, Ci ⁇ alkenylcarbonyl, Ci -6 haloalkenylcarbonyl, Ci- ⁇ alkynyl- carbonyl, Ci ⁇ haloalkynylcarbonyl, Ci ⁇ alkoxycarbonyl, aminocarbonyl, Ci_ 6 alkylaminocarbonyl,
  • Ci ⁇ haloalkylaminocarbonyl Ci. ⁇ hydroxyalkylaminocarbonyl, C 2 - 12 dialkylamino-carbonyl,
  • C 2 - 6 di(haloalkyl)aminocarbonyl C 2 - 6 alkenylaminocarbonyl, C 2 - 6 alkynylaminocarbonyl, phenyaminocarbonyl, halophenylaminocarbonyl, Ci -6 alkyl-thiocarbonyl, C 3-6 cycloalkylcarbonyl, C 4 . 12 cycloalkylalkyl-carbonyl, C 3-6 cycloalkyl-thiocarbonyl, C ⁇ cycloalkylalkyl-thiocarbonyl,
  • Ci_ 6 haloalkyl-thiocarbonyl, Q -6 alkylamino-thiocarbonyl, C 3-6 cycloalkylamino-carbonyl,
  • -thiocarbonyl phenyl-Ci -6 alkylcarbonyl, 2-pyridyl-Ci. 6 alkylcarbonyl, 3-pyridyl-Ci. 6 alkylcarbonyl, 4-pyridyl-Ci. 6 alkylcarbonyl, phenyl-CV ⁇ alkyl-thiocarbonyl, 2-pyridyl-Ci -6 alkyl-thiocarbonyl, 3-pyridyl-Ci -6 alkyl-thiocarbonyl, 4-pyridyl-Ci.
  • dialkylaminocarbonyl C 2-6 alkenylaminocarbonyl, C 2-6 alkynyl- aminocarbonyl, phenylaminocarbonyl, halophenylaminocarbonyl, Ci -6 alkylamino-thiocarbonyl, C 3-6 cycloalkylamino-carbonyl, C 4 . 12 cycloalkylalkylamino-carbonyl, phenyl-Ci -6 alkyl, pyridin-2-yl-Ci -6 alkyl, phenyl-Ci. 6 alkylamino-carbonyl, halophenyl-C]. 6 alkylamino-carbonyl, pyridin-2-yl-Ci -6 alkylamino-carbonyl.
  • Embodiment F Compounds having the structure (I-f-1), wherein the chemical groups A, R 1 , Q, X, Y, m, n, and W are as defined herein and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, Ci -6 alkyl, Ci -6 haloalkyl, Cj. 6 alkoxy, Ci -6 alkylsulfenyl, C]. 6 alkylsulfinyl, C 1 . 6 alkylsulfonyl.
  • Embodiment Fl Compounds as defined in embodiment F, wherein the group Q is selected among Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Ci -6 alkylamino, C 2-J2 dialkylamino, nitro, Ci -6 alkoxy, and Ci -6 haloalkyl.
  • Embodiment F2 Compounds as defined in embodiment F or Fl, wherein A represents oxygen or CH 2 , R 1 represents CF 3 , and/or Y is H.
  • W preferably represents amino, hydroxy, carbonylamino, C )-6 alkyl- -carbonylamino, Ci -6 alkylcarbonyl-Ci -6 alkyl-carbonylamino, Q -6 alkylsulfenyl-C 1-6 alkyl-carbonyl- amino, Ci -6 alkylsulfenyl-Ci -6 alkyl-carbonylamino, Ci -6 alkylsulf ⁇ nyl-Ci -6 alkyl-carbonylamino, Ci -6 alkylsulfonyl-Ci -6 alkyl-carbonylamino, Ci -6 haloalkyl-carbonylamino, cyano-Ci -6 alkyl- -carbonylamino Ci -6 alkenyl-carbonylamino, Ci -6 haloalkenyl-carbonylamino, Ci -6 alkynyl- -carbonylamino, Ci -6 -6 alkyn
  • Embodiment G Compounds having the structure (I-g-1) or (I-g-2), wherein the chemical groups A, R 1 , Q, X, Y, m, n, and W are as defined herein and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, Ci -6 alkyl, Ci -6 haloalkyl, C 1-6 alkoxy, Ci -6 alkylsulfenyl, Ci -6 alkyl- sulfinyl, Ci -6 alkylsulfonyl.
  • Embodiment Gl Compounds as defined in embodiment G, wherein the group Q is selected among Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Ci -6 alkylamino, C 2-H dialkylamino, nitro, Ci. 6 alkoxy, and Ci -6 haloalkyl.
  • Embodiment G2 Compounds as defined in embodiment G or Gl, wherein A represents oxygen or CH 2 , R 1 represents CF 3 , and Y is H.
  • W preferably represents hydrogen, Ci ⁇ alkyl, Ci -6 alkylcarbonyl, Ci- ⁇ haloalkylcarbonyl, Ci -6 alkenylcarbonyl, Ci ⁇ haloalkenylcarbonyl, Ci -6 alkynylcarbonyl, Ci -6 haloalkynylcarbonyl, C].
  • 6 alkylamino- -thiocarbonyl more preferably represents hydrogen, Ci. 6 alkyl, Ci -6 alkylcarbonyl, Ci -6 alkylamino- carbonyl, Ci -6 haloalkylaminocarbonyl, C 2-6 alkenylaminocarbonyl, C 2-6 alkynylaminocarbonyl, C 3-6 cycloalkylamino-carbonyl, C 4-I2 cycloalkylalkylamino-carbonyl.
  • Embodiment H Compounds having the following structure (I-h-1) or (I-h-2), wherein the chemical groups A, R 1 , Q, X, Y, m, n, W and U are as defined herein, and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, Ci -6 alkyl, Ci. 6 haloalkyl, Ci -6 alkoxy, Ci -6 alkyl- sulfenyl, Ci -6 alkylsulfinyl, Ci -6 alkylsulfonyl.
  • Embodiment Hl Compounds as defined in embodiment H, wherein the group Q is selected among Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Ci -6 alkylamino, C 2-I2 dialkylamino, nitro, C ]-6 alkoxy, and Ci -6 haloalkyl.
  • Embodiment H2 Compounds as defined in embodiment H or Hl, wherein A represents oxygen or CH 2 , R 1 represents CF 3 , and Y is H and/or U stands for O, Ci- ⁇ alkyl-N, pyridin-2-yl-Ci. 6 alkyl-N or H-N.
  • Embodiment I Compounds having the structure (I-i-1) or (I-i-2) wherein the chemical groups A, R 1 , Q, X, Y, m, n, W and U are as defined herein, and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, Ci -6 alkyl, Ci -6 haloalkyl, Ci -6 alkoxy, Ci -6 alkylsulfenyl, C )-6 alkyl- sulf ⁇ nyl, Ci_ 6 alkylsulfonyl.
  • Embodiment II Compounds as defined in embodiment I, wherein the group Q is selected among Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Ci -6 alkylamino, C 2- i 2 dialkylamino, nitro, Ci -6 alkoxy, and Ci -6 haloalkyl.
  • Embodiment 12 Compounds as defined in embodiment I or II, wherein A represents oxygen or CH 2 , R 1 represents CF 3 , and Y is H and/or U stands for O or Ci -6 alkyl-carbonyl-N.
  • W preferably represents hydrogen; formyl; Ci -6 alkyl, C 2-I2 (total carbon number) alkoxyalkyl, C 2-I2 (total carbon number) haloalkoxyalkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-8 cycloalkyl, C 4-I2 (total carbon number) alkylcycloalkyl, C 4-J2 (total carbon number) cycloalkylalkyl, phenyl, halophenyl, pyrimidin-2-yl, C 1-6 haloalkyl, C 1-6 alkylimino, Ci -6 haloalkylimino, Ci -6 alkyl- -carbonyl, Ci -6 alkenyl-carbonyl, Ci -6 alkynyl-carbonyl, Ci -6 haloalkyl-carbonyl,
  • Embodiment J Compounds having the structure (I-j-1), wherein the chemical groups A, R 1 , Q, X, Y, m, n, W and U are as defined herein, and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, C 1-6 alkyl, Ci -6 haloalkyl, Ci -6 alkoxy, Ci -6 alkylsulfenyl, Ci -6 alkylsulf ⁇ nyl, Ci. 6 alkylsulfonyl.
  • Embodiment Jl Compounds as defined in embodiment J, wherein the group Q is selected among
  • Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Ci -6 alkylamino, C 2-I2 dialkylamino, nitro, Ci. 6 alkoxy, and Ci ⁇ haloalkyl.
  • Embodiment J2 Compounds as defined in embodiment J or Jl, wherein A represents oxygen or CH 2 , R 1 represents CF 3 , and Y is H.
  • W preferably represents hydrogen; formyl; C ]-6 alkyl, C 2 .i 2 (total carbon number) alkoxyalkyl, C 2 . 12 (total carbon number) haloalkoxyalkyl, C 2 . 6 alkenyl, C 2-6 alkynyl, C 3-S cycloalkyl, C 4- ⁇ (total carbon number) alkylcycloalkyl, C 4- i 2 (total carbon number) cycloalkylalkyl, Ci -6 haloalkyl, Ci -6 alkylimino, Ci. 6 haloalkylimino, Ci.
  • Embodiment K Compounds having the structure (I-k-1), wherein the chemical groups A, R 1 , Q, X,
  • Y, m, n, W and U are as defined herein, and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, Ci. 6 alkyl, Ci -6 haloalkyl, C ⁇ alkoxy, Ci. 6 alkylsulfenyl, C] -6 alkylsulfinyl, C i . 6 alky 1 sulfonyl .
  • Embodiment Kl Compounds as defined in embodiment K, wherein the group Q is selected among Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Cj.6 alkylamino, C 2 - 12 dialkylamino, nitro, Q -6 alkoxy, and Ci -6 haloalkyl.
  • Embodiment K2 Compounds as defined in embodiment K or Kl, wherein A represents oxygen or CH 2 , R 1 represents CF 3 , and Y is H and/or U stands for O, hydroxy-N, Ci -6 alkoxy-N, C ⁇ haloalkoxy-N, Ci -6 alkylamino-N, C 2- i 2 di(alkyl)amino-N, 2-pyridyl-Ci_ 6 alkoxy-N, Ci -6 alkyl- -carbonylamino-N, or Ci. 6 haloalkylamino-N.
  • Embodiment L Compounds having the structure (1-1-1), wherein the chemical groups A, R 1 , Q, X, Y, m, n, W and U are as defined herein, and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, Ci -6 alkyl, C 1-6 haloalkyl, Ci_ 6 alkoxy, Ci_ 6 alkylsulfenyl, Ci -6 alkylsulf ⁇ nyl, Ci_ 6 alkylsulfonyl.
  • Embodiment Ll Compounds as defined in embodiment L, wherein the group Q is selected among
  • Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Q -6 alkylamino, C 2 . ]2 dialkylamino, nitro, C )-6 alkoxy, and C 1-6 haloalkyl.
  • Embodiment L2 Compounds as defined in embodiment L or Ll, wherein A represents oxygen or CH 2 , R 1 represents CF 3 , Y is H and/or U stands for O.
  • W preferably represents hydrogen; formyl; Q -6 alkyl, C 2 - 12 (total carbon number) alkoxyalkyl, C 2-I2 (total carbon number) haloalkoxyalkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-8 cycloalkyl, C 4-12 (total carbon number) alkylcycloalkyl, C 4-12 (total carbon number) cycloalkylalkyl, Q. 6 haloalkyl, Q. 6 alkylimino, Q -6 haloalkylimino, Q -6 alkenyl-carbonyl, Q.
  • alkyloxy-carbonyl 4-pyridyl-Ci -6 alkyloxy-carbonyl, phenyl-amino- carbonyl, 2-pyridyl-aminocarbonyl, 3-pyridyl-aminocarbonyl, 4-pyridyl-aminocarbonyl, phenyl- -Ci -6 alkylamino-carbonyl, 2-pyridyl-Ci -6 alkylamino-carbonyl, 3-pyridyl-Ci. 6 alkylamino-carbonyl or 4-pyridyl-Ci -6 alkylamino-carbonyl, more preferably represents hydrogen or Ci -6 alkyl
  • Embodiment M Compounds having the following structure (I-m-1), wherein the chemical groups A, R 1 , Q, X, Y, m, n, W and U are as defined herein, and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, Cj- ⁇ alkyl, Ci -6 haloalkyl, Ci. 6 alkoxy, Ci -6 alkylsulfenyl, Ci -6 alkyl- sulfinyl, Ci -6 alkylsulfonyl.
  • Embodiment Ml Compounds as defined in embodiment M, wherein the group Q is selected among Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Ci. 6 alkylamino, C 2- i 2 dialkylamino, nitro, Ci_ 6 alkoxy, and Ci. 6 haloalkyl.
  • Embodiment M2 Compounds as defined in embodiment M or Ml, wherein A represents oxygen or CH 2 , R 1 represents CF 3 , Y is H and/or U stands for O.
  • W preferably represents hydrogen; formyl; C ⁇ alkyl, C 2-I2 (total carbon number) alkoxyalkyl, C 2-I2 (total carbon number) haloalkoxyalkyl, C 2 _ 6 alkenyl, C 2 _ 6 alkynyl, C 3 . 8 cycloalkyl, C 4-I2 (total carbon number) alkylcycloalkyl, C 4 . 12 (total carbon number) cycloalkylalkyl, Ci ⁇ haloalkyl, Cj. 6 alkylimino, Q -6 haloalkylimino, Q -6 alkenyl-carbonyl, Ci.
  • Embodiment N Compounds having the structure (I-n-1), wherein the chemical groups A, R 1 , Q, X, Y, m, n and W are as defined herein.
  • Embodiment Nl Compounds as defined in embodiment N, wherein the group Q is selected among Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Ci ⁇ alkylamino, C 2-I2 dialkylamino, nitro, C ⁇ alkoxy, and C 1-6 haloalkyl.
  • Embodiment N2 Compounds as defined in embodiment N or Nl, wherein A represents oxygen or CH 2 , R 1 represents CF 3 , and Y is H.
  • W preferably represents amino, hydroxy, Ci- ⁇ alkyl-carbonylamino, Ci. 6 haloalkyl-carbonylamino, C]. 6 alkenyl-carbonylamino, Ci -6 haloalkenyl-carbonylamino, Ci_ 6 alkynyl-carbonylamino, Ci-ghaloalkynyl-carbonylamino, Q -6 alkoxy-carbonylamino, amino- -carbonylamino, Ci -6 alkylamino-carbonylamino, Ci_ 6 haloalkylamino-carbonylamino, Ci.ehydroxyalkylamino-carbonylamino, C 2 -i 2 dialkylamino-carbonylamino, C 2 - 6 di(haloalkyl)- amino-carbonylamino, C 2 .
  • alkyloxy-carbonylamino 4-pyridyl- -Ci -6 alkyloxy-carbonylamino, phenyl-amino-carbonylamino, 2-pyridyl-amino-carbonylamino, 3-pyridyl-amino-carbonylamino, 4-pyridyl-amino-carbonylamino, phenyl-amino-thiocarbonyl- amino, 2-pyridylamino-thiocarbonylamino, 3-pyridylamino-thiocarbonylamino, 4-pyridylamino- -thiocarbonylamino, phenyl-Ci.e alkylamino-carbonylamino, 2-pyridyl-Ci -6 alkylamino-carbonyl- amino, 3-pyridyl-Ci -6 alkylamino-carbonylamino, 4-pyridyl-C]. 6 alkylamino, 2-
  • Embodiment O Compounds having the structure (I-o-l), wherein the chemical groups A, R 1 , Q, X, Y, m, W and n are as defined herein, and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, Ci -6 alkyl, Ci -6 haloalkyl, Ci -6 alkoxy, C 1-6 alkylsulfenyl, Ci. 6 alkylsulfmyl, Ci ⁇ alkylsulfonyl.
  • Embodiment Ol Compounds as defined in embodiment O, wherein the group Q is selected among Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Ci_ 6 alkylamino, C 2 - 12 dialkylamino, nitro, Ci_ 6 alkoxy, and Ci_ 6 haloalkyl.
  • Embodiment O2 Compounds as defined in embodiment O or Ol , wherein A represents oxygen or CH 2 , R 1 represents CF 3 , and Y is H.
  • W preferably represents hydrogen; cyano, halogen, formyl; Ci_ 6 alkyl, C 2 - 12 (total carbon number) alkoxyalkyl, C 2 . 12 (total carbon number) haloalkoxyalkyl, C 2 _ 6 alkenyl, C 2 - 6 alkynyl, C 3-8 cycloalkyl, C 4 . 12 (total carbon number) alkylcycloalkyl, C 4 . 12 (total carbon number) cycloalkylalkyl, C]. 6 haloalkyl, Ci.
  • Ci -6 haloalkylimino Ci ⁇ alkenyl-carbonyl, Ci_ 6 alkynyl-carbonyl, Cj ⁇ haloalkyl-carbonyl, Ci -6 alkoxy-carbonyl, Ci -6 haloalkoxy-carbonyl, aminocarbonyl, Q -6 alkylamino-carbonyl, Ci ⁇ haloalkylamino-carbonyl, Ci. 6 hydroxyalkylamino- -carbonyl, C 2 - 12 (total carbon number)dialkylamino-carbonyl, C 2-6 (total carbon number) di(haloalkyl)aminocarbonyl, C 2 .
  • Embodiment V Compounds having the structure (I-v-1), wherein the chemical groups A, R 1 , Q, X, Y, m, n, W, and U are as defined herein, and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, Ci_ 6 alkyl, Ci -6 haloalkyl, Ci_ 6 alkoxy, Ci -6 alkylsulfenyl, Ci -6 alkylsulfmyl, Ci. 6 alkylsulfonyl.
  • Embodiment Vl Compounds as defined in embodiment V, wherein the group Q is selected among Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Ci -6 alkylamino, C 2 -n dialkylamino, nitro, Ci -6 alkoxy, and Ci -6 haloalkyl.
  • Embodiment V2 Compounds as defined in embodiment V or Vl, wherein A represents oxygen or CH 2 , R 1 represents CF 3 , and Y is H.
  • W preferably represents hydrogen.
  • Embodiment Z Compounds having the structure (I-z-1), wherein the chemical groups A, R 1 , Q, X, Y, m, n, W, and U are as defined herein, and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, Ci -6 alkyl, Ci -6 haloalkyl, Ci -6 alkoxy, Ci. 6 alkylsulfenyl, Ci. 6 alkylsulfinyl,
  • Embodiment Zl Compounds as defined in embodiment Z, wherein the group Q is selected among Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Ci. 6 alkylamino, C 2-I2 dialkylamino, nitro, Ci -6 alkoxy, and Ci. 6 haloalkyl.
  • Embodiment Z2 Compounds as defined in embodiment Z or Zl, wherein A represents oxygen or CH 2 , R 1 represents CF 3 , and Y is H and/or U stands for O, hydroxy-N, Ci -6 alkoxy-N, Ci -6 haloalkoxy-N.
  • alkyl refers to linear or branched C M2 alkyl including, for example, ethyl, methyl, 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, and preferably refers to Ci -6 alkyl.
  • the alkyl moiety in a group having alkyl as a part of its formula may have the same meaning as described for the aforementioned "alkyl".
  • the alkyl group can be unsubstituted or substituted with at least one suitable substituent.
  • halogen and a halogen moiety in a group substituted with halogen represents fluorine, chlorine, bromine and iodine. Preferred halogens are fluorine, chlorine and bromine.
  • haloalkyl used alone or combined with other terms refers to alkyl groups which are partially or fully substituted with halogen atoms which may be the same or different.
  • haloalkyl includes for example CF 3 , CH 2 F, CHF 2 , CCl 3, CH 2 Cl, CHCl 2 , CF 2 CF 3 , CHFCF 3,
  • the haloalkyl group can additionally be unsubstituted or substituted with at least one suitable substituent.
  • cycloalkyl refers to C 3 .s cycloalkyl including, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, and preferably refers to C 3-7 cycloalkyl.
  • the cycloalkyl group can be unsubstituted or substituted with with at least one suitable substituent.
  • alkenyl refers to C 2 - 5 alkenyl including, for example, vinyl, allyl, 1-propenyl, l-(or 2- or 3-) butenyl and 1-pentenyl, and preferably refers to C 2-4 alkenyl.
  • the alkenyl group can be unsubstituted or substituted with at least one suitable substituent.
  • alkynyl used either alone or combined with other terms preferably stands for alkynyl having 2 to 6 or 2 to 5 carbon atoms. Examples include ethynyl, propargyl, 1-propynyl, but-3-ynyl or pent-4-ynyl. More preferred it stands for alkynyl having 2 to 4 carbon atoms.
  • the alkinyl group can be unsubstituted or substituted with at least one suitable substituent.
  • heterocyclic group preferably refers to a 5- or 6-membered heterocyclic group containing at least one of hetero atoms selected from N, O or S, and said heterocyclic group also refers to a condensed heterocyclic group which may be benzo-condensed.
  • a heterocyclic group contains no more than 4 nitrogens, 2 oxygens and 2 sulfur atoms.
  • the cyclic group can be saturated, unsaturated or partially saturated. If not mentioned otherwise, then a heterocyclic group can be can be attached through any available carbon or heteroatom.
  • Heterocyclic group include for example furyl, thienyl, pyrrolyl, isoxazolyl, pyrazolyl, oxazolyl, oxathiazolyl, imidazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, benzoxazolyl or quinolyl.
  • the heterocyclic group can be unsubstituted or substituted with with at least one suitable substituent.
  • acylamino refers to, for example, alkyl-carbonylamino, cycloalkyl-carbonylamino and benzoylamino, wherein the alkyl moiety may the same meaning as described for the aforementioned "alkyl", and cycloalkyl moiety may have the same meaning as described below.
  • the acylamino group can be unsubstituted or substituted with with at least one suitable substituent.
  • Suitable substituents include for example the following chemical groups, namely amino, hydroxy, halogen, nitro, cyano, isocyano, mercapto, isothiocyanato, carboxy, carbonamide, SF5, amino- sulfonyl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkinyl, monoalkyl-amino, dialkyl-amino, N-alkanoyl-amino, alkoxy, alkenyloxy, alkinyloxy, cycloalkoxy, cycloalkenyloxy, alkoxy-carbonyl, alkenyloxy-carbonyl, alkinyloxy-carbonyl, aryloxycarbonyl, alkanoyl, alkenyl-carbonyl, alkinyl-carbonyl, aryl-carbonyl, alkylthio, cycloalkylthio, alkenylthio, cycloalkeny
  • Substituents which are further substituted like for example alkoxyalkyl, alkylthioalkyl, alkylthioalkoxy, alkoxyalkoxy, phenethyl, benzyloxy, haloalkyl, haloalkoxy, haloalkylthio, haloalkanoyl, haloalkylcarbonyl, haloalkoxycarbonyl, haloalkoxyalkoxy, haloalkoxyalkylthio, haloalkoxyalkanoyl, haloalkoxyalkyl are also included.
  • Preferred substituents are chloro, fluoro, bromo, iodo, NH 2 , NO 2 , CN, OH, SH and COOH.
  • Compounds according to the invention may be prepared by using generally known methods or by combining known methods with the preparation methods described herein.
  • preparation method (a-1) and (a-2) can be carried out according to the method described in WO2007/021308.
  • Preparation method Ca-I " is
  • L 1 stands for halogen, alkylsulfonyloxy (e.g. methanesulfonyloxy), or arylsulfonyloxy (e.g. para-toluenesulfonyloxy), and L 2 stands for alkoxy (e.g. methoxy) or aryloxy (e.g. phenoxy), and wherein (X) m , (Y) n , A, R 1 and Q have the same meaning as described herein, particulary as described for embodiment I, Il or 12, with a compound of the formula (III):
  • L 3 stands for hydroxy, thiol or amino
  • T 1 stands for either R 3 or R 4 ,
  • 1 mole of a compound of formula (II-a) can be reacted with 1 to 2 moles of a compound of formula (ITT) in a diluent, such as toluene, and in the presence of a base, such as potassium carbonate, to obtain the desired compound.
  • a diluent such as toluene
  • a base such as potassium carbonate
  • Known compounds of formula (III) include for example water, hydrogen sulfide, ammonia, methylamine, ethylamine, benzylamine, 2-pyridinomethylamine, acetamide.
  • Compounds of formula (I-i-2) as defined in embodiment I, wherein U represents oxygen and W stands for a group T 1 can also be prepared by preparation method (a-1), namely by
  • L 1 stands for halogen, alkylsulfonyloxy or arylsulfonyloxy
  • L 2 stands for alkoxy (e.g. methoxy) or aryloxy (e.g. phenoxy)
  • (X) m , (Y) n , A, R 1 and Q have the same meaning as described herein, particulary as described for embodiment I, Il or 12, with a compound of formula (III).
  • T 1 stand for either R 3 or R 4 , and include, among other, methylhydrazine or ethylhydrazine,
  • a compound of formula (II-a) in carrying out Preparation method (a-2), 1 mole of a compound of formula (II-a) can be reacted with 1 to 2 moles of a compound of formula (IV) in a diluent, such as toluene, and in the presence of a base, such as potassium carbonate to obtain the desired compound.
  • a diluent such as toluene
  • a base such as potassium carbonate
  • L 4 stands for halogen, alkylsulfonyloxy, arylsulfonyloxy or alkylcarbonyloxy, and T 1 stand for either R 3 or R 4 ; or with
  • T 1 stands for R 3 or R 4 ; in case T 1 stands for a carbonyl-containing moiety, formula (VI-b) is an acid anhydride;
  • compounds of formula (I-i-2) can be prepared by reacting a compound of formula (V-b):
  • 1 mole of a compound of formula (V-a) or (V-b) can be reacted with 1 to 10 moles of a compound of formula (VI-a) or (VI-b) in a diluent, for example toluene, in the presence of base to obtain the desired compound.
  • a diluent for example toluene
  • Compounds of formula (VI-a) and (VI-b) include, for example, acetic acid anhydride, acetyl chloride, methyl iodide, and benzyl bromide.
  • Preparation method (c) can be carried out according to the method described in Synlett (2006), 801-803 which is hereby incorporated by reference.
  • a compound of formula (VII-a) can be reacted with 1 to 2 moles of methane sulfonyl chloride in a diluent, for example tetrahydrofuran, in the presence of a base to obtain the desired compound.
  • a diluent for example tetrahydrofuran
  • T 1 stands for either R 3 or R 4 , if appropriate, in the presence of a base, and/or in the presence of a diluent.
  • Preparation method (d) can be carried out according to the methods described in US 6,376,530, and which preparation methods are hereby incorporated by reference.
  • Compounds of formula (VI-a) or (VI-b) include for example acetic acid anhydride, acetyl chloride, methyl iodide, and benzyl bromide.
  • Preparation method (e) is a known organic synthetic reaction. In the presence of an appropriate base a substitution reaction can occur.
  • a compound of formula (X) in carrying out preparation method (e), 1 mole of a compound of formula (X) can be reacted with 1 to 1.5 moles of a compound of formula (VI) in a diluent, for example tetrahydrofuran, in the presence of pyridine to obtain a desired compound.
  • a diluent for example tetrahydrofuran
  • Compounds aof formula (Iu) are for example methylamine, ethylamine, benzylamine, 2-pyridinomethylamine or acetamide.
  • Preparation method (f) can be carried out according to the methods disclosed in Tetrahedron Lett., 2005, 5927-5930 which are hereby incorporated by reference.
  • 1 mole of a compound of formula (XI) can be reacted with 1 to 2 moles of a compound of formula (HI) in a diluent, for example tetrahydrofuran, in the presence of 1 to 2 moles of sodium hydride as the base, to obtain the desired product.
  • a diluent for example tetrahydrofuran
  • Preparation method (g) can be carried out according to the methods disclosed in WO2004/018410, WO2005/085216, Tetrahedron, 2000, VoI 56, 1057-1064.
  • compositions according to the invention wherein A is nitrogen or oxygen can be prepared according to preparation method (h), namely by
  • Examples of the compound of formula (XV) include hydrazine, methylhydrazine and ethylhydrazine.
  • Compounds according to the invention wherein A is CH 2 can be prepared according to preparation methods (i) and (j).
  • Preparation method (i) can be carried out according to the methods disclosed in Japanese Patent Application Laid-Open 2007-91708 and Chem. Lett., 1985, 1601-1604 which are hereby incorporated by reference.
  • Ri', R 2 ' and R 3 ' each independently represent Q. ⁇ alkyl, or phenyl;
  • R 4 ' represents hydrogen; or is selected among Ci -I2 alkyl, C M2 alkenyl, Cj -I2 alkynyl and benzyl;
  • W 1 to W 4 and (Y) n have the same meaning as described herein, if appropriate, in the presence of a fluoride reagent, such as potassium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, or tetrabutylammonium fluoride.
  • a fluoride reagent such as potassium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, or tetrabutylammonium fluoride.
  • Preparation method (j) can be carried out according to the methods described in J. Org. Chem., Vol. 52, 1027-1035, 1987 which is hereby incorporated by reference.
  • l,3-dichloro-5-(3,3,3-trifluoroprop-l-en-2-yl)benzene and methyl l-[(tert-butoxycarbonyl- )amino]-N-[(trimethylsilyl)methyl]-2,3-dihydro-lH-inden-5-carboimide thioate are used as starting material.
  • Compounds of formula (V-a) or (V-b) can be obtained through preparation method (a-1) and include 5-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]-2,3-
  • Compounds of formula (VII-a) or (VII-b) include for example 4-[5-(3,5-dichlorophenyl) ⁇ 5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]-2-(hydroxymethyl)-N-methylbenzamide,
  • Compounds of formula (XIX-a) or (XDC-b) include for example 5-[5-(3,5-dichlorophenyl) ⁇ 5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]-2-benzofuran-l(3H)-one,
  • Compounds of formula (XX-a) and (XX-b) include for example Methyl 2-[(acetyloxy)methyl]-4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro- isoxazol-3-yl]benzoate, Methyl 2-[(acetyloxy)methyl]-5-[5-(3,5-dichlorophenyl) ⁇
  • Compounds of formula (V ⁇ i-a) or (VIII-b) include for example 2-(bromomethyl) ⁇ 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]benzonitrile, 2-(bromomethyl)-5-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro- soxazol-3-yl]benzonitrile, 2-(bromomethyl)-4-[5-(3,5-dichlorophenyl)- 1 -methyl-
  • Compounds of formula (DC) include for example methylamine, ethylamine, benzylamine, 2-pyridinomethylamine, and acetamide.
  • Compounds of formula (X-a) or (X-b) include for example 5-[5-(3,5-dichlorophenyl) ⁇
  • Compounds of formula (XVII-a) or (XVII-b) are for example methyl 2-methyl-4-[5-(3,5-dichloro- phenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]benzoate, methyl 2-methyl-
  • Compounds of formula (XI) include for example 3-[3,4-bis(bromomethyl)phenyl]- -5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazole, and
  • Compounds of formula (XXI) include for example 5-(3,5-dichlorophenyl)-3-(3,4-dimethylphenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazole, 5-(3,5-dichlorophenyl)-3-(3,4-dimethylphenyl)-l-methyl-5-(trifluoromethyl)— 4,5-dihydro-lH-pyrazole.
  • Compounds of formula (XII) include for example [l-(trifluoromethyl)vinyl]benzene, 1,3-difluoro- -5-[l-(trifluoromethyl)vinyl]benzene, l-chloro-3-[l-(trifluoromethyl)vinyl]benzene, 1,3-dichloro- -5-[ 1 -(trifluoromethyl)vinyl]benzene, 1 -trifluoromethyl-3 -[ 1 -(trifluoromethyl)vinyl]benzene,
  • W 1 to W 4 and (Y) n have the same meaning as described herein, with hydroxyamine or a salt thereof.
  • Compounds of formula (XXI ⁇ ) include for example lH-indol-5-carbaldehyde,
  • Boc represents a t-butoxycarbonyl group
  • MeCN represents acetonitrile
  • cat.DMAP represents a catalytic amount of 4-dimethylaminopyridine
  • Pd-C represents palladium charcoal
  • ETOH represents ethanol
  • Halogenating agents which are suitable for the preparation of compounds of the formula (XIII) include chlorine, bromine, iodine, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, l,3-dichloro-5,5-hydantoin, l,3-dibromo-5,5-dimethylhydantoin, benzyl trimethyl ammonium tetrachloroiodate, and sodium hypochlorite.
  • Compounds of formula (XXIH) include for example N-hydroxy-lH-indol-5-carboxyimidoyl chloride, t-butyl 5-[chloro(hydroxyimino)methyl]-lH-indol-l-carboxyate, t-butyl-5-[chloro- (hydroxyimino)methyl]-2,3-dihydro-lH-indol-l-carboxyate, N-hydroxy-lH-indol-6-carboxy- imidoyl chloride, N-hydroxy-2,3-dihydro-l-benzofuran-5-carboxyimidoyl chloride, N-hydroxy-l,3-benzodioxol-5-carboxyimidoyl chloride, N-hydroxy-2,3-dihydro-l,4-benzo- dioxin-6-carboxyimidoyl chloride, N-hydroxy-l-oxo-l,3-di
  • Me represents a methyl group
  • DEAD represents diethyl azodicarboxyate
  • Ph represents a phenyl group
  • Et represents an ethyl group
  • THF represents tetrahydrofuran
  • Preparation method (g) can be applied to the synthetic method comprising reacting the compounds of formula (XXXI) which fall under the general formula (XXXI-a):
  • T 2 stands for O, N-OH and N-NH-R 2
  • W 1 to W 4 and (Y) n have the same meaning as defined herein.
  • Compounds of formula (XXIV) are for example 3-(3,5-dichlorophenyl) ⁇ 4,4,4-trifiuoro-3-hydroxy-l -(lH-indol-5-yl)butan-l -one, 5-[3-(3,5-dichlorophenyl)-4,4,4-trifluoro- -3-hydroxybutanoyl]-2-benzofuran-l(3H)-one, 5-[3-(3,5-dichlorophenyl)-4,4,4-trifluoro-
  • Compounds of formula (XXV) include for example trifluoroacetophenone, 3',5'-dichloro-2,2,2-trifluoroacetophenone, 3',4'-dichloro-2,2,2-trifluoroacetophenone, 3',4',5'- -trichloro-2,2,2-trifluoroacetophenone, 3 '-fluoro-2,2,2-trifiuoroacetophenone, 3 '-chloro— 2,2,2-trifiuoroacetophenone, 3 '-bromo-2,2,2-trifluoroacetophenone, 3 '-iodo-2,2,2-trifluoroaceto- phenone, 3'-nitro-2,2,2-trifluoroacetophenone, 3'-cyano-2,2,2-trifluoroacetophenone, 3'-(trifluoro- methyl)-2,2,2-trifluoroacetophenone, and 3 ',5 '-bis(
  • Compounds of formula (XXVI) include for example 5-acetylindane, 6-acetyltetraline, 3',4'-(methylenedioxy)acetophenone, 1, 4-benzodioxane-6-yl methyl ketone, 5-acetyl-2,3-dihydro- -1-benzofuran, 5-acetyl-lH-indole, 5-acetyl-2-benzofuran-l(3H)-one, and 5-acetyl-2-(pyridin-2-yl- methyl)-2,3-dihydro- 1 H-isoindol- 1 -one.
  • Compounds of formula (XlV) include for example 3-(3,5-dichlorophenyl)-4,4,4- -trifluoro-l-(lH-indol-5-yl)but-2-ene-l-one, 5-[3-(3,5-dichlorophenyl)-4,4,4-trifluoro-2-enoyl]-2-
  • Preparation method (h) can also be used to prepare compounds of formula (XVII-a) and (XVII-b) from the compounds of formula (XVIU-a) and (XVIII-b).
  • Representative examples of the compound of formula (XVI) include 5-[4-(3,5-dichlorophenyl) ⁇ 4-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-2-yl]-2-(pyridin-2-ylmethyl) ⁇
  • the compound of formula (XXVII) can be synthesized according to the method disclosed in Chem. Lett., 1977, 697-698, or by reacting compounds of the formula (XXVIII)
  • Compounds of formula (XXVI) include for example 5-(isocyanomethyl)-2-(pyridin-2-ylmethyl) ⁇ 2,3-dihydro-lH-isoindol-l-one, N-[5-(isocyanomethyl)-2-(pyridin-2-ylmethyl)--
  • Compounds of formula (XXIX) include for example N- ⁇ [l-oxo-2-(pyridin-2-ylmethyl)- 2,3-dihydro-lH-isoindol-5-yl]methyl ⁇ formamide, N-[5-[(formylamino)methyl]-2-(pyridin-2-ylmethyl)-2,3-dihydro-lH-isoindol-l-yliden]acetamide.
  • Methyl 5-[(t-butoxycarbonyl)amino]-N-[(trimethylsilyl)methyl]-5,6,7,8-tetrahydronaphthalen-2 ⁇ carboimide thioate can be synthesized according to the method shown in reaction scheme 16, by using 6-bromo-3,4-dihydronaphthalen-l(2H)-one as a starting material.
  • the compounds of formula (XXX) are intermediates for the preparation of compounds according to the invention. Namely, as compounds according to the invention can be prepared by reacting a compound of formula (XII) with compounds of formula (XXX) in the presence of a fluorine reagent if R 4 ' does not stands for H. In case that R 4 ' stands for H, the reaction can be carried out in a one pot reaction by firstly adding an alkylating reagent, such as methyl iodide and then adding an appropriate fluorine reagent.
  • an alkylating reagent such as methyl iodide
  • Reaction scheme 17 shows a synthetic method example for introducing various substituents on condensed-ring moiety. Reaction scheme 17
  • Bu-t represents a t-butyl group
  • Et represents an ethyl group
  • THF represents tetrahydrofuran
  • Appropriate diluents for the preparation methods disclosed herein, particularly for preparation methods (a-1), (a-2), (b), (c), (d), (e), (f), (g), (i) include aliphatic, alicyclic, and aromatic hydrocarbons (which may be chlorinated in some cases), for example, pentane, hexane, cyclo- hexane, petroleum ether, ligroin, benzene, toluene, xylene, chlorobenzene, dichlorobenzene and the like; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM) and the like; ketones, for example, acetone, methyl ethyl ketone (MEK), methyl
  • Appropriate diluents for the preparation method (j) include for example aliphatic, alicyclic, and aromatic hydrocarbons (which may be chlorinated in some cases), for example, pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1 ,2-dichloroethane, chlorobenzene, dichlorobenzene and the like; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM) and the like; ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isoprop
  • Appropriate bases for the preparation methods disclosed herein, particularly for preparation methods (a-1), (a-2), (b), (c), (d), (e), (f), (g) include inorganic bases such as hydrides, hydroxides, carbonates and bicarbonates of alkaline metals and alkaline earth metals, for example, sodium hydride, lithium hydride, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and the like; and organic bases such as alcoholate, tertiary amines, dialkyl- aminoanilines and pyridines, for example, triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP), l,4-diazabicyclo[2,2,2]octane (DABCO),
  • alkaline metal bases such as for example, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, potassium-tert-butoxide and the like; and an organic base such as triethylamine, diisopropylethylamine, tributylamine, N-methylmorpholine, N,N-dimethylaniline, N,N-diethylaniline, 4-tert-butyl-N,N-dimethylaniline, pyridine, picoline, lutidine, diazabicyclo- undecene, diazabicyclooctane, imidazole and the like.
  • alkaline metal bases such as for example, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, potassium-tert-butoxide and the like
  • organic base such as tri
  • the preparation methods disclosed herein can be carried out within a substantially broad range of temperatures, i.e. in range of -78 0 C to about 200 0 C. Generally, it can be carried out at a temperature in the range of about 10 to about 150 0 C, preferably in the range of about 30 to about 12 0 0 C. They can be carried out at any pressure, i.e. at a pressure of about 1013 mbar, at a pressure lower than 1013 mbar and a pressure higher than 1013 mbar. Reaction time may vary from about 0.1 hours to about 72 hours, preferably from 1 to 24 hours.
  • Preparation method (j) can be carried out within a substantially broad range of temperatures, generally, it can be carried out at a temperature in a range of about -78 and about 100 0 C, preferably in a range of about -10 and about 50 0 C.
  • reaction time is from 0.1 to 10 hours, and preferably from 1 to 5 hours.
  • the compounds according to the present invention show a potent insecticidal action and can therefore be used as an insecticide. Furthermore, the compounds according to the present invention exhibit a strong control effect against harmful insects, without imposing any harmful side effects of drug to cultivated plants.
  • the compounds of the present invention can thus be used for the control of a wide range of pest species, for example, harmful sucking insects, chewing insects, as well as other plant parasitic pests, storage insects, hygiene pests and the like, and can be applied for the purpose of disinfestations and extermination thereof.
  • Harmful animal pest are for example:
  • coleopterans for example, Callosobruchus cninensis, Sitophilus zeamais, Tribolium castaneum, Epilachna vigintioctomaculata, Agriotes fuscicollis, Anomala rufocuprea, Leptinotarsa decemlineata, Diabrotica spp., Monochamus alternatus, Lissorhoptrus oryzophilus, Lyctus bruneus,
  • Aulacophora femoralis lepidopterans, 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, Phyllocnistis citrella; hemipterans, for example, Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki, Unaspis yanonensis, Myzus persicas, Aphis pomi, Aphis gossypii, Rhopalosiphum pseudobrassicas, Stephanitis nashi, Nezara spp.,
  • acari for example, Tetranychus cinnabarinus, Tetranychus urticae, Panonychus citri, Aculops pelekassi, Tarsonemus spp.
  • nematodes for example, Meloidogyne incognita, Bursaphelenchus lignicolus Mamiya et Kiyohara, Aphelenchoides besseyi, Heterodera glycines, Pratylenchus spp..
  • the compounds according to the present invention show a good plant tolerance and favourable toxicity to warm-blooded animals and being tolerated well by the environment, and thus are suitable for protecting plants and plant parts.
  • the compounds of the invention may result in increasing the harvest yields, improving the quality of the harvested material.
  • the compounds can be used for controlling animal pests, in particular insects, arachnids, helminths, nematodes and molluscs, which are encountered in agriculture, in horticulture, the field of veterinary medicine, in forests, in gardens and leisure facilities, in the protection of stored products and of materials, and in the hygiene sector. They may be preferably employed as plant protection agents. They are active against normally sensitive and resistant species and against all or some stages of development. These pests include inter alia:
  • Anoplura for example, Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectes spp.
  • 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, Eutetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans, Metatetranychus spp., Oligonychus spp., Ornithodoros spp., Panonychus spp., Phyllocoptmta oleivora, Polyphagotarsonemus la
  • 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., Trogo- derma spp., Tychius spp., Xylotrechus spp., Zabrus spp.
  • gastropoda From the class of the gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.
  • helminths from the class of the helminths, for example, 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 medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Lo
  • Heliopeltis spp. Horcias nobilellus, Leptocorisa spp., Leptoglossus phyllopus, Lygus spp.,
  • Hymenoptera From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
  • Isopoda for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber.
  • Siphonaptera for example, Ceratophyllus spp., Xenopsylla cheopis.
  • Symphyla for example, Scutigerella immaculata.
  • Thysanoptera From the order of the Thysanoptera, for example, Basothrips biformis, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentarus, Scirtothrips spp., Taeniothrips cardamoni, Thrips spp.
  • Thysanura for example, Lepisma saccharina.
  • the phytoparasitic nematodes include, for example, 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., Tylenchulus semipenetrans, Xiphinema spp.
  • Plants are to be understood as meaning in the present context all plants and plant populations such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
  • Crop plants can be plants which can be obtained by conventional plant breeding and optimization methods or by biotechnological and genetic engineering methods or by combinations of these methods, including the transgenic plants and including the plant cultivars protectable or not protectable by plant breeders' rights.
  • Plant parts are to be understood as meaning all parts and organs of plants above and below the ground, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes.
  • the plant parts also include harvested material, and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.
  • Treatment according to the invention of the plants and plant parts with the active compounds is carried out directly or by allowing the compounds to act on their surroundings, habitat or storage space by the customary treatment methods, for example by immersion, spraying, evaporation, fogging, scattering, painting on, injecting and, in the case of propagation material, in particular in the case of seed, also by applying one or more coats.
  • wild plant species and plant cultivars or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and parts thereof, are treated.
  • transgenic plants and plant cultivars obtained by genetic engineering methods if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof, are treated.
  • the terms "parts”, “parts of plants” and “plant parts” have been explained above.
  • plants of the plant cultivars which are in each case commercially available or in use are treated according to the invention.
  • Plant cultivars are understood as meaning plants having novel properties ("traits") which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be cultivars, bio- or genotypes.
  • the treatment according to the invention may also result in superadditive "synergistic" effects.
  • reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the substances and compositions which can be used according to the invention better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, higher quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products are possible, which exceed the effects which were actually to be expected.
  • the preferred transgenic plants or plant cultivars which are to be treated according to the invention include all plants which, by virtue of the genetic modification, received genetic material which imparts particularly advantageous, useful traits to these plants. Examples of such traits are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, higher quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products.
  • transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice), maize, soya beans, potatoes, sugar beet, tomatoes, peas and other vegetable varieties, cotton, tobacco, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes), and particular emphasis is given to maize, soya beans, potatoes, cotton, tobacco and oilseed rape.
  • Traits that are emphasized in particular are the increased defence of the plants against insects, arachnids, nematodes and slugs and snails by virtue of toxins formed in the plants, in particular those formed in the plants by the genetic material from Bacillus thuringiensis (for example by the genes Cry ⁇ A(a), Cry ⁇ A(b), Cry ⁇ A(c), CryllA, CrylllA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF and also combinations thereof) (referred to hereinbelow as "Bt plants").
  • Traits that are also particularly emphasized are the increased defence of the plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. Traits that are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulphonylureas, glyphosate or phosphinotricin (for example the "PAT" gene).
  • the genes which impart the desired traits in question can also be present in combination with one another in the transgenic plants.
  • Bt plants are maize varieties, cotton varieties, soya bean varieties and potato varieties which are sold under the trade names YIELD gARD® (for example maize, cotton, soya beans), KnockOut® (for example maize), StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato).
  • YIELD gARD® for example maize, cotton, soya beans
  • KnockOut® for example maize
  • StarLink® for example maize
  • Bollgard® cotton
  • Nucotn® cotton
  • NewLeaf® potato
  • herbicide-tolerant plants examples include maize varieties, cotton varieties and soya bean varieties which are sold under the trade names Roundup Ready® (tolerance to glyphosate, for example maize, cotton, soya beans), Liberty Link® (tolerance to phosphinotricin, for example oilseed rape), IMI® (tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, for example maize).
  • Herbicide-resistant plants plants bred in a conventional manner for herbicide tolerance
  • Clearf ⁇ eld® for example maize.
  • the plants listed can be treated according to the invention in a particularly advantageous manner with the compounds according to the invention at a suitable concentration.
  • the novel compounds of the present invention can be effectively used against various harmful animal parasitic pests (endoparasites and ectoparasites), for example, insects and helminthes.
  • animal parasitic pests include the pests as described below.
  • the insects include gasterophilus spp., Stomoxys spp., Trichodectes spp., Rhodnius 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 according to the present invention are active against animal parasites, in particular ectoparasites or endoparasites.
  • animal parasites in particular ectoparasites or endoparasites.
  • endoparasites includes in particular helminths, such as cestodes, nematodes or trematodes, and protozoae, such as coccidia.
  • Ectoparasites are typically and preferably arthropods, in particular insects such as flies (stinging and licking), parasitic fly larvae, lice, hair lice, bird lice, fleas and the like; or acarids, such as ticks, for examples hard ticks or soft ticks, or mites, such as scab mites, harvest mites, bird mites and the like.
  • insects such as flies (stinging and licking), parasitic fly larvae, lice, hair lice, bird lice, fleas and the like
  • acarids such as ticks, for examples hard ticks or soft ticks, or mites, such as scab mites, harvest mites, bird mites and the like.
  • These parasites include:
  • Haematopinus spp. for example Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.; particular examples are: 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, Solenopotes capillatus;
  • Nematocerina and Brachycerina for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Odagmia spp., Wilhelmia spp., Hybomitra 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.,
  • Pulex spp. Ctenocephalides spp., Tunga spp., Xenopsylla spp., Ceratophyllus spp.
  • particular examples are: Ctenocephalides cards, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis;
  • Ornithonyssus spp. Pneumonyssus spp., Raillietia spp., Pneumonyssus spp., Stemostoma spp., Varroa spp., Acarapis spp.; particular examples are: Argas persicus, Argas reflexus, Ornithodorus moubata, Otobius megnini, Rhipicephalus (Boophilus) microplus, Rhipicephalus (Boophilus) decoloratus, Rhipicephalus (Boophilus) annulatus, Rhipicephalus (Boophilus) calceratus, Hyalomma anatolicum, Hyalomma aegypticum, Hyalomma marginatum, Hyalomma transiens, Rhipicephalus evertsi, Ixodes ricinus, Ixodes hexagonus, Ixodes can
  • Acarapis spp. Cheyletiella spp., OrnitACHeyletia 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., Laminosioptes spp.; particular examples are: Cheyletiella yasguri, Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Ps
  • the active compounds according to the invention are also suitable for controlling arthropods, helminths and protozoae, which attack animals.
  • Animals include agricultural livestock such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, cultured fish, honeybees.
  • animals include domestic animals - also referred to as companion animals - such as, for example, dogs, cats, cage birds, aquarium fish and what are known as experimental animals such as, for example, hamsters, guinea pigs, rats and mice.
  • arthropods By controlling these arthropods, helminths and/or protozoae, it is intended to reduce deaths and improve performance (in the case of meat, milk, wool, hides, eggs, honey and the like) and health of the host animal, so that more economical and simpler animal keeping is made possible by the use of the active compounds according to the invention.
  • controlling the parasites may help to prevent the transmittance of infectious agents.
  • controlling means that the active compounds are effective in reducing the incidence of the respective parasite in an animal infected with such parasites to innocuous levels. More specifically, “controlling”, as used herein, means that the active compound is effective in killing the respective parasite, inhibiting its growth, or inhibiting its proliferation.
  • the compounds of the present invention are used in the control of ectoparasitic arthropods (as mentioned above) on animals, namely on agricultural livestock or on domestic animals.
  • the active compounds according to the invention when used for the treatment of animals can be applied directly.
  • they are applied as pharmaceutical compositions which may contain pharmaceutically acceptable excipients and/or auxiliaries which are known in the art.
  • the active compounds may be formulated as shampoo or as suitable formulations usable in aerosols, unpressurized sprays, for example pump sprays and atomizer sprays.
  • the active compounds according to the invention can be applied as formulations (for example powders, wettable powders ["WP”], emulsions, emulsifiable concentrates ["EC”], flowables, homogeneous solutions, and suspension concentrates ["SC”]) which comprise the active compounds in an amount of from 1 to 80% by weight, either directly or after dilution (e.g. 100- to 10 000-fold dilution), or else as a chemical bath.
  • formulations for example powders, wettable powders ["WP"], emulsions, emulsifiable concentrates ["EC”], flowables, homogeneous solutions, and suspension concentrates ["SC”]
  • the active compounds according to the invention may be used in combination with suitable synergists or other active compounds, such as for example, acaricides, insecticides, anthelmintics, anti-protozoal drugs.
  • suitable synergists or other active compounds such as for example, acaricides, insecticides, anthelmintics, anti-protozoal drugs.
  • a substance having an insecticidal action against pests including all of these is referred to as an insecticide.
  • An active compound of the present invention can be prepared in conventional formulation forms, when used as an insecticide.
  • the formulation forms include solutions, emulsions, wettable powders, water dispersible granules, suspensions, powders, foams, pastes, tablets, granules, aerosols, active compound-infiltrated natural and synthetic materials, microcapsules, seed coating agents, formulations used with a combustion apparatus (for example, fumigation and smoking cartridges, cans, coils or the like as the combustion apparatus), ULV (cold mist, warm mist), and the like.
  • a combustion apparatus for example, fumigation and smoking cartridges, cans, coils or the like as the combustion apparatus
  • ULV cold mist, warm mist
  • formulations can be produced by methods that are known per se.
  • a formulation can be produced by mixing the active compound with a developer, that is, a liquid diluent or carrier; a liquefied gas diluent or carrier; a solid diluent or carrier, and optionally with a surfactant, that is, an emulsifier and/or dispersant and/or foaming agent.
  • an organic solvent can also be used as an auxiliary solvent.
  • liquid diluent or carrier examples include aromatic hydrocarbons (for example, xylene, toluene, alkylnaphthalene and the like), chlorinated aromatic or chlorinated aliphatic hydrocarbons (for example, chlorobenzenes, ethylene chlorides, methylene chlorides), aliphatic hydrocarbons (for example, cyclohexanes), paraffins (for example, mineral oil fractions), alcohols (for example, butanol, glycols and their ethers, esters and the like), ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like), strongly polar solvents (for example, dimethylformamide, dimethylsulfoxide and the like), water and the like.
  • aromatic hydrocarbons for example, xylene, toluene, alkylnaphthalene and the like
  • the liquefied gas diluent or carrier may be those which are gaseous at normal temperature and normal pressure, for example, aerosol propellants such as butane, propane, nitrogen gas, carbon dioxide and halogenated hydrocarbons.
  • solid diluent examples include pulverized natural minerals (for example, kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth, and the like), pulverized synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates and the like), and the like.
  • pulverized natural minerals for example, kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth, and the like
  • pulverized synthetic minerals for example, highly dispersed silicic acid, alumina, silicates and the like
  • solid carrier for granules examples include pulverized and screened rocks (for example, calcite, marble, pumice, sepiolite, dolomite and the like), synthetic granules of inorganic and organic powder, fine particles of organic materials (for example, sawdust, coconut shells, maize cobs, tobacco stalk and the like), and the like.
  • emulsifier and/or foaming agent examples include nonionic and anionic emulsif ⁇ ers [for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (for example, alkylaryl polyglycol ether), alkylsulfonates, alkylsulfates, arylsulfonates and the like], albumin hydrolyzate, and the like.
  • nonionic and anionic emulsif ⁇ ers for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (for example, alkylaryl polyglycol ether), alkylsulfonates, alkylsulfates, arylsulfonates and the like]
  • albumin hydrolyzate and the like.
  • dispersant examples include lignin sulfite waste liquor and methylcellulose.
  • Fixing agents can also be used in the formulations (powders, granules, emulsions), and examples of the fixing agent include carboxymethylcellulose, natural and synthetic polymers (for example, gum arabic, polyvinyl alcohol, polyvinyl acetate, and the like) and the like.
  • Colorants can also be used, and examples of the colorants include inorganic pigments (for example, iron oxide, titanium oxide, Prussian Blue and the like), organic dyes such as alizarin dyes, azo dyes or metal phthalocyanine dyes, and in addition, trace elements such as the 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 such as alizarin dyes, azo dyes or metal phthalocyanine dyes
  • trace elements such as the salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • the formulations in general can contain the active ingredient in an amount ranging from 0.1 to 95% by weight, and preferably 0.5 to 90% by weight.
  • the compound according to the present invention can also exist as an admixture with other active compounds, for example, insecticides, poisonous baits, bactericides, miticides, nematicides, fungicides, growth regulators, herbicides and the like, in the form of their commercially useful formulation forms and in the application forms prepared from those formulations.
  • active compounds for example, insecticides, poisonous baits, bactericides, miticides, nematicides, fungicides, growth regulators, herbicides and the like, in the form of their commercially useful formulation forms and in the application forms prepared from those formulations.
  • the content of the compound according to the present invention in a commercially useful application form can be varied within a wide range.
  • the concentration of the active compound according to the present invention in actual usage can be, for example, in the range of 0.0000001 to 100% by weight, and preferably 0.00001 to 1% by weight.
  • the compounds according to the present invention can be used through conventional methods that are appropriate for the usage form.
  • the active compound of the present invention have, when used against hygiene pests and pests associated with stored products, stability effective against alkali on lime materials, and also shows excellent residual effectiveness on wood and soil.
  • room temperature means temperatures of about 18 to about 30° C.
  • Methyl 2-[(acetyloxy)methyl]-4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro- isoxazol-3-yl]benzoate (851 mg) and sodium methoxide (9 mg) were stirred in methanol (10 ml) at room temperature for 30 min. Under a reduced pressure, the solvent was removed by distillation.
  • Step 4 Synthesis of N-IYlEVS-rS- ⁇ .S-dicMorophenviyS- ⁇ rifluoromethyl) ⁇ - dihvdro- isoxazol-3-yll-2-(pyridin-2-ylmethyl ' )-2.3-dihvdro-lH-isoindol-l-ylindenlacetamide (Compound No. 1-235)
  • Step 1 Synthesis of 3-[3 ⁇ -bis(bromomethyl)phenyll-5-(3.5-dicMorophenyl)-5-(trifluoromethyl) -4,5-dihydroisoxazole.
  • a dichloroethane solution (38 ml) of 5-(3,5-dichlorophenyl)-3-(3,4-dimethylphenyl) ⁇ 5-(trifluoromethyl)-4,5-dihydroisoxazole (1.0 g), N-bromosuccinimide (1.1 g) and a catalytic amount of 2,2'-azobisisobutyronitrile (AIBN) was heated and refluxed for 3 hours. After the solution was cooled to room temperature, insoluble matters were filtered out and the solvent was distilled off under a reduced pressure. The residue was dissolved in t-butyl methyl ether, then washed with water, and dried over magnesium sulfate.
  • AIBN 2,2'-azobisisobutyronitrile
  • the crude product thus obtained was dissolved in methanol (10 ml), sodium methoxide (0.05 g) was added thereto and the mixture was stirred for 1 hour at room temperature.
  • the reaction solution was diluted with t-butyl methyl ether, then washed with water and a saturated saline solution, and the organic layer was dried over magnesium sulfate.
  • the solvent was distilled off under a reduced pressure to obtain l,3-dihydro-2-benzofuran-5-ylmethanol as a crude product.
  • the crude product thus obtained was dissolved in methylene chloride (20 ml), activated manganese (IV) oxide (2.3 g) was added thereto and the mixture was heated and refluxed for 5 hours.
  • reaction solution was filtered using Celite and the filtered solution was concentrated under a reduced pressure.
  • resulting residue was purified with silica gel chromatography to obtain l,3-dihydro-2-benzofuran-5-carbaldehyde (0.35 g).
  • Step 2 Synthesis of l-oxo-2.3-dihvdro-lH-inden-5-carbaldehvde.
  • Step 4 Synthesis of 5-[5-(3.5-dicMorophenyl)-5-(trifluoromethyl)-4.5-dihydroisoxazol -3-vH-2.3-dihvdro-lH-inden-l-one.
  • Step 6 Synthesis of 2- ⁇ 5-[5-(3,5-dicMorophenyl)-5-(trifluorornethyl)-4,5-dihvdroisoxazol -3-yll-2.3-dihvdro-lH-inden-l-vn-lH-isoindol-1.3(2HVdione.
  • Step 1 Synthesis of 5-oxo-5,6,7,8-tetrahvdronaphthalen-2-yl trifluoromethane sulfonate.
  • 6-hydroxy3,4-dihydro-l(2H)-naphthalenone (10.30 g) and 2,6-lutidine (14.80 ml) were dissolved in methylene chloride (150 ml), and anhydrous trifluoromethane sulfonic acid (25 g) was added thereto at 0 0 C.
  • the reaction solution was stirred overnight at room temperature.
  • Dilute hydrochloric acid was added for the extraction.
  • the organic layer was dried over magnesium sulfate and the solvent was removed by distillation. After the purification with silica gel chromatography, the title compound was obtained (17.00 g, 91%).
  • Step 4 Synthesis of 6-r(E)-(hvdroxyimino ' )methvn-3,4-dihvdronaphthalen-l(2H)-one.
  • Step 5 Synthesis of 6-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol -3-yl " l-3,4-dihvdronaphthalen-l(2HVone.
  • the reaction solution was stirred for 4 hours. While keeping the temperature of the reaction solution at 0 0 C, l,3-dichloro-5-(3,3,3-trifluoroprop-l-en-2-yl)benzene (3.74 g) and potassium hydrocarbonate (1.70 g) were added thereto. The reaction solution was stirred for 3 hours. Water and ethyl acetate were added for the extraction. The organic layer was dried over magnesium sulfate and the solvent was removed by distillation. After the purification with silica gel chromatography, the title compound was obtained (3.60 g, 60%).
  • Step 6 Synthesis of 6-[5-f3.5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol -3-yl]-l ,2,3 ,4-tetrahvdronaphthalen-l -amine.
  • the acidic aqueous layer was neutralized with sodium carbonate and extracted with tert-butylmethyl ether.
  • the organic layer was dried over magnesium sulfate and the solvent was removed by distillation.
  • the title compound was obtained as a crude product (1.15 g).
  • Step 1 Synthesis of tert-butyl 5-fbrmyl-lH-indol-l-carboxyate.
  • Step 2 Synthesis of tert-butyl 5-(hvdroxymethyl)-2,3-dihvdro-lH-indol-l-carboxvate.
  • Step 3 Synthesis of tert-butyl 5-formyl-2.3-dihydro-lH-indol-l-carboxyate.
  • Step 4 Synthesis of tert-butyl 5-r(E)-(hvdroxyimino)methvn-2.3-dihvdro-lH-indol-l- carboxyate.
  • Step 5 Synthesis of tert-butyl 5-[5-(3,5-dicMorophenyl)-5-(trifluoromethyl)-4.5- dihvdro- isoxazol-3-yll-2,3-dihydro-lH-indol-l-carboxvate.
  • Step 6 Synthesis of 5-f5-(3.5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihvdroisoxazol -3-vn-2.3-dihvdro-lH-indole.
  • Step 7 Synthesis of 5-[5-(3.5-dicMorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol -3 -yll -N-ethyl-2,3 -dihydro- 1 H-indol- 1 -carboxamide.
  • Step 2 Synthesis of 6-r5-(3,5-dicMorophenyl)-5-(trifluoromethvD-4.5-dihvdroisoxazol -3-vnquinoline.
  • Step 3 Synthesis of 6-[5-(3.5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihvdroisoxazol -3-yll-l,2,3,4-tetrahydroquinoline.
  • Step 1 Synthesis of l-oxo-23 -dihvdro-lH-inden-5-carbonitrile.
  • Step 2 Synthesis of l-oxo-2,3-dihvdro-lH-inden-5-carboxyic acid.
  • Step 3 Synthesis of l-oxo-N-rftrimethylsilylmethyli ⁇ -dihydro-lHinden-S-carboxyamide.
  • N,N-dimethylaminopyridine (0.01 g)
  • N-(3-dimethylaminopropyl) ⁇ N'-ethylcarbodiimide hydrochloride (0.12 g) were dissolved in methylene chloride (5 ml), and the resulting mixture was stirred for 5 hours at room temperature. After adding water, the reaction solution was stirred and the organic layer was dried over anhydrous magnesium sulfate.
  • Step 4 Synthesis of tert-butyl(5-f[(trimethylsilyl)methyl1carbamoyl)-2,3-dihydro-lH-inden -l-yl)carbamate.
  • Step 5 Synthesis of tert-butyl(5- ⁇ [(trimethylsilyl)methyllcarbamothiovU-2,3-dihvdro - 1 H-inden- 1 -vDcarbamate.
  • Step 6 Synthesis of methyl l-fdert-butoxycarbonvDaminoi-N-fdrimethylsilylimethyl] -2,3-dihydro-lH-inden-5-carboimide thioate.
  • the reaction solution was diluted by adding t-butyl methyl ether, and then washed with water and saturated brine. The organic layer was dried over anhydrous magnesium sulfate.
  • Step 7 Synthesis of tert-butyl (5-[3-(3,5-dicmorophenyl)-3-(trifluoromethyl)-3,4 -dihvdro-2H-pyrrol-5 -yll -2 ,3 -dihydro- 1 H-inden- 1 -yl ) carbamate.
  • tetrahydrofuran solution (10 ml) of methyl l-[(tert-butoxycarbonyl)amino]-N-[(trimethylsilyl)methyl]-2,3-dihydro-lH-inden-5-carboimide thioate (0.25 g) and l,3-dichloro-5-(3,3,3-trifluoropro-l-pene-2-yl)benzene (0.15 g) was cooled to -5°C, and then IM tetrahydrofuran solution of tetrabutylammonium fluoride (0.2 ml) was slowly added dropwise thereto.
  • reaction solution was stirred at room temperature for 20 hours, and then diluted with tert-butyl methyl ether and washed with water and saturated brine.
  • the organic layer was dried over anhydrous magnesium sulfate and the solvent was removed by distillation under reduced pressure.
  • the residues were purified by silica gel chromatography to obtain tert-butyl ⁇ 5-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-
  • Step 8 Synthesis of 5-f3-(3.5-dichlorophenyl)-3-(trifluoromethyl)-3,4-dihvdro-2H-pyrrol-5-yll -2.3 -dihydro- 1 H-inden- 1 -amine.
  • Step 9 Synthesis of l-(5-[3-(3.5-dichlorophenyl ' )-3-(trifluoromethyl)-3.4-dihvdro-2H-pyrrol - -S-yll ⁇ J-dihvdro-lH-inden-l-vU-S-ethylurea.
  • Step 1 Synthesis of 6-r5-(3.5-dicMorophenyl)-5-(trifluoromethyl)A5-dihvdroisoxazol-3-yl1 Quinoline 1 -oxide.
  • Trimethylsilylcyanide (0.30 g) and triethylamine (0.20 g) were added to acetonitrile (10 ml) solution of 6-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]quinoline 1 -oxide, and then the reaction solution was refluxed for 6 hours. After adding ethyl acetate and water to the reaction solution, the organic layer was separated and washed with brine. The organic layer was dried over magnesium sulfate. After the filtration, it was concentrated under reduced pressure.
  • Emulsif ⁇ er Polyoxyethylene alkylphenyl ether, 1 part by weight
  • test solution 1 part by weight of the active compound is mixed with the above-described amount of the solvent which contains the above-described amount of emulsifier. The resulting mixture is diluted with water to a predetermined concentration.
  • Leaves of sweet potato were immersed in the test solution. The leaves are air-dried and placed in a petri dish (9 cm diameter). 10 Spodoptera litura third instar larvae were released in the petri dish, which was then stored in a constant temperature room (25 0 C). More sweet potato leaves were added after 2 and 4 days. 7 days after the release of the larvae mortality was calculated by counting the number of dead larvae. 100 % means that all the larvae have been killed; 0 % means that none of the larvae have been killed. In the present test, an average value was taken from the results obtained from 2 petri dishes for 1 group.
  • test solution has been prepared as described in biological test example 1.
  • acaricidal ratio was calculated. 100 % means that all the mites have been killed; 0 % means that none of the mites have been killed.
  • the compound having the example no. 1-58 known from WO2005/085216, showed a control efficacy with at least 98% mortality at an active compound concentration of 100 ppm.
  • test solution has been prepared as described in biological test example 1.
  • Cucumber leaves were immersed in a test solution that had been diluted to a predetermined concentration with water. The leaves were air-dried and then put in a plastic cup containing sterilized black soil. 5 Aulacophora femoralis second instar larvae were released in the cup. 7 days later, mortality was calculated by counting the number of dead larvae. 100 % means that all larvae have been killed; 0 % means that none of the larvae 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.
  • a piece or kitchen sponge Prior to the assay, a piece or 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.

Abstract

Condensed-ring aryl compounds of formula (I) and use of the same as a agrochemical for controlling noxious organisms wherein (X)mQ, A, R1, (Y)n and the grouping -W1-W2-W3-W4- are as defined herein.

Description

PESTICIDAL CONDENSED-RING ARYL COMPOUNDS
The present invention relates to novel condensed-ring aryl compounds and use of the same as a agrochemical for controlling noxious organisms.
From Japanese Patent Application Laid-open No. 2007-91708 it it known that dihydroazole-substituted benzamide compounds may be used as noxious organism control agent. The same is true for the 5-membered heterocyclic compounds as described in WO2007/12 3853 and for the pyrazoline compounds as described in WO2007/12 3855.
It is also known that certain isoxazoline derivatives can be used as noxious organisms control agent (e.g. WO2005/085216, WO2007/026965, WO2007/074789, WO2007/070606, WO2007/075459, WO2007/079162, WO2007/105814, WO2007/12 5984, Japanese Patent Application Laid-open No. 2007-16017, Japanese Patent Application Laid-open No. 2007-106756, and Japanese Patent Application Laid-open No. 2007-308471, WO2007/026965, and WO2007/105814).
WO2005/085216 and its English equivalent EP-A-I 731 512 discloses certain arylisoxazoline compounds having condensed rings and which are supposed to exhibit insecticidal action.
Inventors of the present invention intensively studied to develop a novel pesticidal compound which exhibits a excellent pesticidal effect and has a broad spectrum. As a result, the inventors found novel condensed-ring aryl compounds, which have high activity, a broad spectrum and safety and also are effective against pests that are resistant to an organic phosphorous agent or a carbamate agent. Thus, this invention is directed to condensed-ring aryl compounds of formula (I)
Figure imgf000003_0001
wherein
X represents halogen; nitro; cyano; hydroxy; thiol; amino; Ci.i2 alkyl, Ci.i2haloalkyl, Ci.i2 alkoxy, C1-12 haloalkoxy, CM2 alkylsulfenyl, CM2 alkylsulfinyl, Ci-I2 alkyl- sulfonyl, Ci_i2haloalkylsulfenyl, C]-I2 haloalkylsulfinyl, Ci_i2haloalkylsulfonyl, Cj-J2 alkylamino,
C2-24 dialkylamino, Cj-J2 acylamino, Cj-J2 alkoxy-carbonylamino, Cj-J2 haloalkoxy-carbonylamino,
Cj-J2 alkylsulfonylamino, or Cj-J2 haloalkylsulfonylamino; preferably chloro, bromo, iodo, fluoro; nitro; cyano; hydroxy; thiol; amino; Ci-6alkyl, Cj.6haloalkyl, Cj-6 alkoxy, Cj-6 haloalkoxy, Cj-6 alkylsulfenyl, Cj-6 alkylsulfinyl, Ci-6 alkylsulfonyl, Ct.6 haloalkylsulfenyl, C]-6 haloalkylsulfinyl,
Ci-6haloalkylsulfonyl, Ci-6 alkylamino, C2-J2 (total carbon number) dialkylamino, Cj-6 acylamino,
Ci-6 alkoxy-carbonylamino, Ci-6 haloalkoxy-carbonylamino, Ci-6 alkylsulfonylamino, or
C)-6 haloalkylsulfonylamino;
Q represents substitutable phenyl, substitutable naphtyl or a substitutable 5- or 6- membered heterocyclic group; preferably represents a optionally substituted group selected among Q-I to Q-54
Figure imgf000003_0002
Figure imgf000004_0001
Figure imgf000005_0001
Y represents halogen; nitro; cyano; hydroxy; thiol; amino; C1-12 alkyl,
Ci.i2haloalkyl, C3.8 cycloalkyl, C3.8 cyclohaloalkyl, C1-12 alkenyl, C2_i2haloalkenyl, C1-12 alkoxy, Ci.i2haloalkoxy, C1-12 alkylsulfenyl, C1.12 alkylsulfinyl, Q-I2 alkylsulfonyl, Ci-I2 haloalkylsulfenyl, C1-12 haloalkylsulfmyl, C1-12 haloalkylsulfonyl, C1-12 alkylamino, C2.24 (total carbon number) dialkyl- amino, C1-12 aminocarbonyl, C1-12 alkylamino-carbonyl, C2-24 (total carbon number) dialkylamino- -carbonyl, C1-12 acylamino, C1-12 alkoxy-carbonylamino, benzyloxy-carbonylamino, C1-12 (haloalkoxy)-carbonylamino, C1-12 alkylsulfonylamino, C1-I2 haloalkylsulfonylamino, or C3-36 (total carbon number) trialkylsilyl; preferably represents chloro, bromo, iodo, fluoro; nitro; cyano; hydroxy; thiol; amino; C1-6alkyl, C1-6haloalkyl, C3-6 cycloalkyl, C3-6 cyclohaloalkyl, C1-6 alkenyl, haloalkenyl, C1-6 alkoxy, C1-6haloalkoxy, C1-6 alkylsulfenyl, C1-6 alkylsulfinyl, C1-6 alkylsulfonyl, C1-6 haloalkylsulfenyl, C1-6 haloalkylsulfmyl, C1-6 haloalkylsulfonyl, Ci-6 alkylamino, C2-12 (total carbon number) dialkylamino, aminocarbonyl, C1-6 alkylamino-carbonyl, C2-12 (total carbon number) dialkylamino-carbonyl, Q-6 acylamino, Cj-6 alkoxy-carbonylamino, benzyloxy-carbonylamino, C1-6 (haloalkoxy)-carbonylamino, C1-6 alkylsulfonylamino, C1-6 haloalkylsulfonylamino, or C3-Ig (total carbon number) trialkylsilyl; more preferably represents chloro, bromo, iodo, fluoro; nitro; cyano; hydroxy; thiol; amino; Chalky., Ci-6haloalkyl, C3-6 cycloalkyl, C3-6 cyclohaloalkyl, C1-6 alkenyl, haloalkenyl, C1-6 alkoxy, C1-6haloalkoxy, C1-6 alkylsulfenyl, C1-6 alkylsulfinyl, C ]-6 alkylsulfonyl, C1-6 haloalkylsulfenyl, C1-6 haloalkylsulfmyl, C1-6 haloalkylsulfonyl, Ci-6 alkylamino, C2-12 (total carbon number) dialkylamino; most preferably represents chloro, bromo, iodo, fluoro, cyano, amino, CM2 alkylamino, Ci.πhaloalkylsulfenyl,
Ci.i2haloalkyl;
R1 represents cyano; C1.12 alkyl, C3.8 cycloalkyl, C4-2o (total carbon number) alkyl- cycloalkyl, C4.2o (total carbon number) cycloalkylalkyl, C2-12 alkenyl, C2-12 alkynyl, Ci.i2haloalkyl, or C3-8 halocycloalkyl; preferably cyano; Ci-6 alkyl, C3-6 cycloalkyl, C4-I2 (total carbon number) alkylcycloalkyl, C4-12 (total carbon number) cycloalkylalkyl, C2-6 alkenyl, C2-6 alkynyl,
C1-6 haloalkyl, or C3-6 halocycloalkyl; preferably represents Ci-6haloalkyl, most preferably CF3>
m represents 0, 1, 2, 3, 4 or 5;
n represents 0, 1, 2 or 3;
A represents O, S, CH2 or N-R2; preferably O;
R2 represents hydrogen; cyano; formyl; Q-I2 alkyl, C2-I2 alkenyl, C2-I2 alkynyl, C3-8 cycloalkyl, C4-20 (total carbon number) alkylcycloalkyl, C4-20 (total carbon number) cycloalkylalkyl, CM2 haloalkyl, Ci-I2 alkylsulfonyl, Ci.i2haloalkylsulfonyl, phenyl, C1-I2 alkyl-carbonyl, Ci-I2 alkoxy-carbonyl, CM2 alkylamino-carbonyl, or C2-24 dialkylamino-carbonyl; preferably represents hydrogen; cyano; formyl; Ci-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, C3-6 CyClOaIlCyI, C4-I2 (total carbon number) alkylcycloalkyl, C4-I2 (total curbon number) cycloalkylalkyl, C ]-6 haloalkyl, Ci-6 alkylsulfonyl, Ci-6haloalkylsulfonyl, phenyl, Ci-6 alkyl-carbonyl, Ci-6 alkoxy-carbonyl, Ci-6 alkylamino-carbonyl, or C2-I2 (total carbon number) dialkylamino-carbonyl;
W1, W2, W3 and W4 each independently may be omitted to yield a 4- or 5-membered ring, and/or each independently represents a single bond, CH2, CH, N, -N+(O")-, -S(O)-, -S(O)2-, -O-S(O)-, O, S, C(R3)-R3, C-R3, C-R4, C(R3)-R4, C(R4)-R4, C-N(R3)-R3, C(R3)-N(R3)-N(R3)-R3, C-N(R3)-N(R3)-R3, C(R3)-N(R4)-N(R3)-R3, C-N(R4)-N(R3)-R3, C(R3)-N(R3)-OR3, C-N(R3)-OR3, C(R3)-OR3, C-OR3, C(R3)-SR\ C-SR3, C-N3, N-R3, N-OR3, N-N(R3)-R3, N-R4, or C=U under the prerequisite that (i) not more than two of W1, W2, W3 and W4 are simultaneously omitted, and/or (ii) not more than two of W1, W2, W3 and W4 represent O, S, N-R3 or N-R4, C-N(R3)-R3,
C-N(R3)-N(R3)-R3, C-N(R4)-N(R3)-R3, C(R3)-N(R3)-OR3, C-N(R3)-OR3, C-SR3, N-R3, N-OR3 or N-N(R3)-R3 at the same time; and/or (iii) not more than two of W1, W2, W3 and W4 represent C=U at the same time, and /or (iv) if two of W1, W2, W3 and W4 represent O and/or S than least one carbon atom is present between them, and/or (v) when one of W1, W2, W3 and W4 represent CH, N, C - R3 or C - R4, C-N(R3)-R3, C-N(R3)-N(R3)-R3, C-N(R4)-N(R3)-R3, C-N(R3)-OR3, C-OR3, C-SR3, N-R3, N-OR3, N-N(R3)-R3 a double bond is formed within the condensed ring; and
U represents CH2, O, S, or N-R3 or N-R4;
R3 each independently represents hydrogen; hydroxy; thiol; amino; cyano; formyl; halogen; nitro; Ci-6alkyl, C2-I2 (total carbon number) alkoxyalkyl, C2.]2 (total carbon number) haloalkoxyalkyl, C2-6 alkenyl, C2-I2 alkynyl, C3-8 cycloalkyl, C4-12 (total carbon number) alkylcyclo- alkyl, C4-I2 (total carbon number) cycloalkylalkyl, Cj^haloalkyl, C^alkylcarbonyl, C1-6 alkyl- carbonyl-Ci.6alkyl, Ci^alkylcarbonyl-C^alkylcarbonyl, C1-6haloalkylcarbonyl, C1-6 alkoxy- carbonyl, Ci^alkylsulfenylcarbonyl, Ci^haloalkylsulfenylcarbonyl, aminocarbonyl, C1-6alkyl- aminocarbonyl, Ci^haloalkylaminocarbonyl, Q-ehydroxyalkylaminocarbonyl, C2-I2 (total carbon number)dialkylamino-carbonyl, C2-6 (total carbon number) di(haloalkyl)aminocarbonyl, C2-6 alkenylaminocarbonyl, C2-6 alkynylaminocarbonyl, Ci-6alkyl-thiocarbonyl, C3-6 cycloalkyl- carbonyl, C4-]2 (total carbon number) cycloalkylalkyl-carbonyl, C3-6 cycloalkyl-thiocarbonyl, C4-I2 (total carbon number) cycloalkylalkyl-thiocarbonyl, Ci-6 haloalkyl-thiocarbonyl, Ci-6alkyl- amino-thiocarbonyl, C3-6cycloalkylamino-carbonyl, C4-I2 (total carbon number) cycloalkylalkyl- amino-carbonyl, C3-6cycloalkylamino-thiocarbonyl, C4-I2 (total carbon number) cycloalkylalkyl- aminothiocarbonyl, Ci-6haloalkylamino-thiocarbonyl, C2-12 (total carbon number) dialkylamino- -thiocarbonyl, C3-6 cycloalkyloxy-carbonyl, C4-I2 (total carbon number) cycloalkylalkyl- oxy-carbonyl, C1-6haloalkoxy-carbonyl, Ci-6 alkylsulfonyl, C1-6haloalkylsulfonyl, phenylsulfonyl, R4-Ci-6alkyl, R4-carbonyl, R4-thiocarbonyl, R4-C1-6 alkylcarbonyl, R4-C1-6 alkyl-thiocarbonyl, R4-oxycarbonyl, R4-Ci-6 alkyloxy-carbonyl, R4-aminocarbonyl, R4-amino-thiocarbonyl,
R4-Ci_6alkylamino-carbonyl, or R^Ci^alkylarnino-thiocarbonyl; and
R4 represents phenyl or 5- or 6-membered saturated or unsaturated heterocyclic ring, preferably is selected among the groups R4-l to R4-83
Figure imgf000008_0001
Figure imgf000009_0001
wherein
G represents O, S or N, and wherein each group R4-l to R4-83 may be substituted with at least one group selected among hydrogen; halogen; cyano, nitro; Ci-6alkyl, Ci.6haloalkyl, C3-6 cycloalkyl, C3-6 halocycloalkyl, Ci-6 alkoxy, Ci.6haloalkoxy, Ci-6alkylsulfenyl, Ci-6haloalkyl- sulfenyl, Ci-6alkylsulfinyl, Ci-6haloalkylsulfmyl, Ci-6 alkylsulfonyl, Ci-6haloalkylsulfonyl,
Ci_6alkylamino, Ci.6haloalkylamino, aminocarbonyl, Ci-6 alkylamino-carbonyl, C2-12 dialkylamino- -carbonyl, Ci_6 alkoxycarbonyl, phenyl,or pyridyl;
preferably the group -W1-W2-W3-W4- is selected among the 4- 5- or 6-membered groups W-I to W-580
Figure imgf000010_0001
Figure imgf000011_0001
Figure imgf000012_0001
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000017_0001
W
Figure imgf000018_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
wherein
U represents CH2, O, S, N-R3 or N-R4, preferably represents CH2, O, S, N-R3,
N-R4, wherein R3 and R4 are selected among hydroxy, Ci-6alkoxy, Ci-6haloalkoxy, Ci.6haloalkyl, alkyl Q-6 alkyl, Ci-6alkylamino, C2-I2 dialkylamino, pyridin-2-yl-Ci-6alkyl, pyridin-2-yl-Ci-6alkoxy, C1-6 alkylcarbonyl, Ci-6 alkyl-carbonylamino and Ci-6 haloalkylamino.
k stands for 0, 1 or 2,
W represents O" , R3, OR3, SR3, NHR3, N(R3)2, N(R3)N(R3)R3, N(R4)N(R3)R3,
N(R3)OR3, R4, NR4, or N3;
W preferably represents CT R3, OR3, SR3, NHR3, N(R3)2, N(R3)N(R3)R3, N(R4)N(R3)R3, N(R3)OR3, R4, NR4, or N3 wherein R3 and R4 are selected among hydrogen, formyl, Ci-6 alkyl, C2-I2 alkoxyalkyl, C2-12 haloalkoxyalkyl, C2-6alkenyl, C2-6alkynyl, C3-8 cycloalkyl, C4-I2 alkylcycloalkyl, C4-I2 cycloalkylalkyl, Q^haloalkyl, Ci-6alkylimino, Ci-6haloalkylimino, Ci^alkenyl-carbonyl, Ci-6alkynyl-carbonyl, Ci-6haloalkyl-carbonyl, Cj.ehydroxyalkyl-carbonyl, Ci-6alkoxy-carbonyl, Ci-ehaloalkoxy-carbonyl, aminocarbonyl, C^ealkylamino-carbonyl, Ci^haloalkylamino-carbonyl, d-βhydroxyalkylamino-carbonyl, C2-I2 dialkylamino-carbonyl, C2-6 di(haloalkyl)aminocarbonyl, C2-6alkenylamino-carbonyl, C2-6alkynylamino-carbonyl, C3-6 cycloalkyl-carbonyl, C4-π cycloalkylalkyl-carbonyl, C3-6 cycloalkylamino-carbonyl, C4-I2 cyclo- alkylalkylamino-carbonyl, C3-6 cycloalkyloxy-carbonyl, C4-I2 cycloalkylalkyloxy-carbonyl, Ci-6haloalkoxy-carbonyl, phenyl-Ci-6alkyl, 2-pyridyl-Ci-6alkyl, 3-pyridyl-Ci-6alkyl, 4-pyridyl- -Ci-6alkyl, phenylcarbonyl, 2-pyridylcarbonyl, 3-pyridylcarbonyl, 4-pyridylcarbonyl, phenyl- -Ci-6alkylcarbonyl, 2-pyridyl-C1-6alkylcarbonyl, 3-pyridyl-Ci.βalkylcarbonyl, 4-pyridyl-Ci-6alkyl- carbony, phenyloxy-carbonyl, 2-pyridyloxy-carbonyl, 3-pyridyloxy-carbonyl,
4-pyridyloxy-carbonyl, phenyl-C^βalkyloxy-carbonyl, 2-pyridyl-Ci-6alkyloxy-carbonyl, 3-pyridyl- -Ci-6alkyloxy-carbonyl, 4-pyridyl-Ci-6alkyloxy-carbonyl, phenyl-aminocarbonyl, 2-pyridyl-amino- carbonyl, 3-pyridyl-aminocarbonyl, 4-pyridyl-aminocarbonyl, phenyl-Ci-βalkylamino-carbonyl,
2-pyridyl-Ci.6alkylamino-carbonyl, S-pyridyl-Ci^alkylamino-carbonyl or 4-pyridyl-C]-6alkyl- amino-carbonylcarbonyl, Ci-6alkylcarbonyl, Ci-6haloalkylcarbonyl, Ci^alkenylcarbonyl, Ci-6haloalkenylcarbonyl, Ci.6alkynylcarbonyl, Ci-6haloalkynylcarbonyl, Ci-6alkoxycarbonyl, aminocarbonyl, Ci-βalkylaminocarbonyl, C1-6haloalkylaminocarbonyl, Ci-6 hydroxyalkylamino- carbonyl, C2-12 dialkylamino-carbonyl, C2-6 di(haloalkyl)aminocarbonyl, C2-6alkenylaminocarbonyl, C2-6alkynylaminocarbonyl, C1-6alkyl-thiocarbonyl, C3-6 cycloalkylcarbonyl, C4-I2 cycloalkylalkyl- -carbonyl, C3-6 cycloalkyl-thiocarbonyl, C4-I2 (total carbon number) cycloalkylalkyl-thiocarbonyl, Ci-6 haloalkyl-thiocarbonyl, Ci-6 alkylamino-thiocarbonyl, C3-6 cycloalkylamino-carbonyl, C4.i2 cycloalkylalkylamino-carbonyl, C3-6cycloalkylamino-thiocarbonyl, C4-J2 cycloalkylalkyl- aminothiocarbonyl, Ci-6 haloalkylamino-thiocarbonyl, C2-I2 dialkylamino-thiocarbonyl, C3-6 cyclo- alkyloxy-carbonyl, C4-I2 cycloalkylalkyloxy-carbonyl, Ci-6haloalkoxy-carbonyl, Ci-6alkylsulfonyl, Ci.6haloalkylsulfonyl, phenylsulfonyl, phenyl-Ci-6alkyl, 2-pyridyl-Ci-6alkyl, 3-pyridyl-Ci-6alkyl, 4-pyridyl-Ci-6alkyl, phenylcarbonyl, 2-pyridylcarbonyl, 3-pyridylcarbonyl, 4-pyridylcarbonyl, phenyl-tbiocarbonyl, 2-pyridyl-thiocarbonyl, 3-pyridyl-thiocarbonyl, 4-pyridyl-thiocarbonyl, phenyl-C1-6alkylcarbonyl, 2-pyridyl-Ci-6alkylcarbonyl, 3-pyridyl-Ci-6aikyicarbonyl, 4-pyridyl- -Ci-6alkylcarbony, phenyl-Ci-βalkyl-thiocarbonyl, l-pyridyl-Ci-βalkyl-thiocarbonyl, 3-pyridyl- -Ci-6alkyl-thiocarbonyl, 4-pyridyl-Ci-6alkyl-thiocarbonyl, phenyl-oxycarbonyl,
2-pyridyloxycarbonyl, 3-pyridyl- oxycarbonyl, 4-pyridyloxycarbonyl, pb.enyl-Ci-6alkyl- oxy-carbonyl, 2-pyridyl-Ci-6alkyloxy-carbonyl, S-pyridyl-Ci-βalkyloxy-carbonyl, 4-pyridyl- -Ci-6alkyloxy-carbonyl, phenyl-aminocarbonyl, 2-pyridyl-aminocarbonyl, 3-pyridyl-aminocarbonyl, 4-pyridyl-aminocarbonyl, phenyl-amino-thiocarbonyl, 2-pyridylamino-thiocarbonyl, 3-pyridyl- amino-thiocarbonyl, 4-pyridylamino-thiocarbonyl, phenyl-Ci^alkylamino-carbonyl, 2-pyridyl- -C^ealkylamino-carbonyl, 3-pyridyl-Ci.δalkylamino-carbonyl, 4-pyridyl-Ci-6alkylamino-carbonyl, phenyl-Ci^alkylaminothiocarbonyl, 2-pyridyl-Ci-6alkylamino-thiocarbonyl, 3-pyridyl-Cj-6alkyl- amino-thiocarbonyl or 4-pyridyl-Ci-6alkylamino-thiocarbonyl, preferably R3 and R4 are selected among hydrogen, formyl, Ci.ghydroxyalkyl-carbonyl, Ci-6alkoxy-carbonyl, Ci-6alkylamino-
-carbonyl, Ci^haloalkylamino-carbonyl, C2-12 dialkylamino-carbonyl, Ci-6alkylcarbonyl, Ci-ehaloalkylcarbonyl, Ci^alkyl-thiocarbonyl, Ci-6 alkylamino-thiocarbonyl, Ci-6alkylsulfonyl, pyrimidinyl, and pyridyl.
The present invention does not include the following compounds, which are known from WO 2005/085216, namely
(i) compounds of formula (J), wherein the group (X)m-Q stands for 3,5-dichlorophenyl, n stands for 0, A is oxygen, R1 stands for CF3, and the group -W'-W^W^W4- stands for the group W-376 with U standing for oxygen and wherein W which is bound to the nitrogen atom adjacent to the carbonyl group either represents hydrogen or CH2-2 -pyridyl; and
(ii) compounds of formula (I), wherein the group (X)m-Q stands for 3,5-dichlorophenyl, n stands for 0, A is oxygen, R1 stands for CF3, and the group -W'-W^W^W4- stands for the group W-23 with U standing for oxygen and wherein W which is bound to the nitrogen atom is either hydrogen, methyl or CH2-2 -pyridyl; and (iii) compounds of formula (I), wherein the group (X)m-Q stands for 3,5-dichlorophenyl, n stands for 0, A is oxygen, R1 stands for CF3, and wherein W1 is omitted, W2 stands for a group C=CH2, W3 stands for N-CH2-CF3 and W4 stands for a group C=O.
hi another aspect, the invention is directed to compounds of formula (I) wherein
X represents halogen, Ci_i2 alkyl, Ci-J2 haloalkyl, nitro, cyano, Ci-J2 alkoxy, Cj.12 haloalkoxy, CM2 alkylthio, CM2 alkylsulfinyl, Cj.^ alkylsulfonyl, Ci.]2 haloalkylthio, Ci-I2 haloalkylsulfmyl, C].i2haloalkylsulfonyl, hydroxy, mercapto, amino, CM2 alkylamino, C2-24 (total carbon number) dialkylamino, CM2 (total carbon number) acylamino, CM2 alkoxy-carbonyl- amino, Ci-I2 haloalkoxy-carbonylamino, Ci.^alkyl-sulfonylamino group, or Cj.nhaloalkyl- -sulfonylamino; Q represents a group selected among Q-I to Q-54;
Y represents halogen, Q-12 alkyl, C1-I2 haloalkyl, C3.12 cycloalkyl, C3-12 cyclo- haloalkyl, nitro, cyano, C2-I2 alkenyl, C2-I2 haloalkenyl, Cμ2 alkoxy, CM2 haloalkoxy, Ci-]2 alkylthio, Ci-I2 alkylsulfinyl, Q-12 alkylsulfonyl, Ci-I2 haloalkylthio, Ci-I2 haloalkylsulfinyl, CM2 haloalkyl- sulfonyl, hydroxy, mercapto, amino, Ci-I2 alkylamino, C2-24 (total carbon number) dialkylamino, aminocarbonyl, Ci-I2 alkylaminocarbonyl, C2-24 (total carbon number) dialkylaminocarbonyl, C2-I2 (total carbon number) acylamino, Ci-I2 alkoxy-carbonylamino benzyloxy-carbonylamino CM2 haloalkoxy-carbonylamino, CM2 alkylsulfonylamino, CM2 haloalkylsulfonylamino or C3-26 (total carbon number) trialkylsilyl;
R1 represents C^2 alkyl, C3-J2 (total carbon number) cycloalkyl, C4-I2 (total carbon number) alkylcycloalkyl, C4-I2 (total carbon number) cycloalkylalkyl, C2-I2 alkenyl, C2-I2 alkynyl, Ci-I2 haloalkyl, C3-I2 (total carbon number) halocycloalkyl, or cyano;
m represents 0, 1, 2, 3, 4 or 5;
n represents 0, 1, 2 or 3;
A represents O, CH2 or N-Rx,
Rx independently represents hydrogen, cyano, formyl, Cj-I2 alkyl, C2.]2 alkenyl,
C2-12 alkynyl, C3-I2 (total carbon number) cycloalkyl, C4-I2 (total carbon number) alkylcycloalkyl,
C4-I2 (total carbon number) cycloalkylalkyl, Ci-12 haloalkyl, phenyl, Q.^ alkyl-carbonyl,
Ci-I2 alkoxy-carbonyl, Ci-I2 alkyl-aminocarbonyl, C2-24 (total carbon number) dialkyl-amino- carbonyl;
W1, W2, W3 and W4 independently represents a single bond, CH2, CH, N, CH -Rx, C(RX)2, C=U, O, S, N-Ry or N-R2 under the prerequisite that a) two or more of W1, W2, W3 and W4 are not simultaneously a single bond, b) three or more of W1, W2, W3 and W4 are not simultaneously O, S or N— Ry, c) three or more of W1, W2, W3 and W4 are not simultaneously
C=U, d) when two of W1, W2, W3 and W4 simultaneously represent O and/or S, at least one carbon atom is present between them, and, e) when at least one of W1, W2, W3 and W4 is CH or N, at least one of adjacent W1, W2, W3 and W4 is CH or N and forms a double bond.
U represents CH2, O, S, N-Ry or N-Rz;
Ry independently represents hydrogen, hydroxy, amino, Ci.i2 alkyl, C2-I2 alkenyl, C2-J2 alkenyloxy, C2-J2 alkynyl, C2-]2 alkynyloxy, C3-I2 cycloalkyl, C4-I2 (total carbon number) alkyl- cycloalkyl, C4-I2 (total carbon number) cycloalkylalkyl, Ci-I2 haloalkyl, CM2 alkylamino, C2-24 (total carbon number) dialkyl-amino, Cj-I2 alkoxy, Ci-J2 haloalkoxy, formyl, Cj-J2 alkyl-carbonyl, Ci-J2 haloalkyl-carbonyl, Cj-J2 alkyl-carbonylamino, CM2 haloalkyl-carbonylamino, Ci.i2alkyl- sulfonyl, Ci.πhaloalkyl-sulfonyl, phenylsulfonyl, and said substituents other than hydrogen and a formyl group may be substituted with Rz;
Rz is selected among the groups R4-l to R4-83 wherein G represents O, S or N, and which may be substituted with at least one group selected among hydrogen, halogen, Cj-J2 alkyl Ci-I2 haloalkyl, C3_i2 cycloalkyl, C3_i2 halocycloalkyl, CJ.J2 alkoxy, Cj-J2 haloalkoxy, Ci-J2 alkylthio, Cj-J2 haloalkylthio, CM2 alkylsulfinyl, Ci-I2 haloalkylsulfinyl, CM2 alkylsulfonyl, Cj.πhaloalkyl- sulfonyl, CM2 alkylamino, Ci-I2 haloalkylamino, cyano, nitro, aminocarbonyl, CM2 alkyl-amino- carbonyl, C2-24 (total carbon number) dialkyl-aminocarbonyl, CM2 alkoxy-carbonyl phenyl or pyridyl;
In a further aspect, the invention is also directed to compounds of formula (I) wherein
X independently represents halogen, CM2 alkyl, CM2 haloalkyl, nitro, cyano,
CM2 alkoxy, CM2 haloalkoxy, CM2 alkylthio, CM2 alkylsulfinyl, CM2 alkylsulfonyl, CM2 haloalkylthio, CM2 haloalkylsulfinyl, CM2 haloalkylsulfonyl, hydroxy, mercapto, amino, Ci-I2 alkylamino, C2 _24 (total carbon number), dialkylamino, CM2 (total carbon number) acylamino, C2-]3 (total carbon number) alkoxy-carbonylamino, C2-i3 (total carbon number) haloalkoxy-carbonylamino, Ci-I2 alkyl- sulfonylamino, a C1-I2 haloalkylsulfonylamino;
Q is selected among Q-I to Q-54;
Y independently represents halogen, Ci-12 alkyl, Ci-I2 haloalkyl, C3_i2 cycloalkyl, C3 _ J2 cyclohaloalkyl, nitro, cyano, C2-I2 alkenyl, C2-I2 haloalkenyl, Ci.i2 alkoxy, CM2 haloalkoxy,
Ci-I2 alkylthio, CM2 alkylsulfinyl, CM2 alkylsulfonyl, Ci-I2 haloalkylthio, C1-I2 haloalkylsulfϊnyl,
Ci-I2 haloalkylsulfonyl, hydroxy, mercapto, amino, CM2 alkylamino, C2-24 (total carbon number) dialkylamino, aminocarbonyl, C2-13 (total carbon number) alkylaminocarbonyl, C3-2S (total carbon number) dialkylaminocarbonyl, CM2 (total carbon number) acylamino, C2-13 (total carbon number) alkoxy-carbonylamino, benzyloxy-carbonylamino, C2-I3 haloalkoxy-carbonylamino, Ci-12 alkyl- sulfonylamino, CM2 haloalkylsulfonylamino, a C3-2^ (total carbon number) trialkylsilyl;
R1 represents C]-12 alkyl , C3_12 (total carbon number) cycloalkyl, C4-24 (total carbon number) alkylcycloalkyl, C4-24 (total carbon number) cycloalkylalkyl, C2.12 alkenyl, C2-I2 alkynyl, Ci-12 haloalkyl, C3-12 (total carbon number) halocycloalkyl, cyano;
m represents 0, 1, 2, 3, 4 or 5,
n represents 0, 1, 2 or 3,
A represents O, CH2 or N— Rx;
Rx independently represents hydrogen, cyano, formyl, CM2 alkyl, C2-I2 alkenyl,
C2-I2 alkynyl, C3-12 (total carbon number) cycloalkyl, C4-12 (total carbon number) alkylcycloalkyl, C4-24 (total carbon number) cycloalkylalkyl, C1-12 haloalkyl, phenyl, C2-I3 (total carbon number) alkylcarbonyl, C2-13(total carbon number) alkoxycarbonyl, C2-13 (total carbon number) alkylaminocarbonyl or C3-25 (total carbon number) dialkylaminocarbonyl,
W1, W2, W3 and W4 independently represent a single bond, CH2, CH, N, O, S, CH-Ry, C-Ry, C(R^2, N-Rz, N-R**, CH-R1", C-R"" or C=U; under the prerequisite that a) two or more of W1, W2, W3 and W4 are not simultaneously a single bond, b) three or more of W1, W2, W3 and W4 are not simultaneously O, S, N— Rzor N-R1", c) three or more of W1, W2, W3 and W4 are not simultaneously C=U, d) when two of W1, W2, W3 and W4 simultaneously represent O and/or S, at least one carbon atom is present between them, and, e) when one of W1, W2, W3 and W4Is CH, N, C— Ry or C— Rπ, a double bond is formed within the condensed ring;
Ry independently represents hydroxy, amino, cyano, formyl, halogen, nitro,
Ci-I2 alkyl, C2-I2 alkenyl, C2-I2 alkynyl, C3-I2 cycloalkyl, C4-24 alkylcycloalkyl, C4-24 cycloalkylalkyl, Ci-I2 haloalkyl, C2-B (total carbon number) alkylcarbonyl, C2-J3 (total carbon number) alkoxycarbonyl, C2-I3 (total carbon number) alkylaminocarbonyl, C3-I3 (total carbon number) dialkylaminocarbonyl, C2.j3 (total carbon number) alkyl-carbonylamino, C2-I3 (total carbon number) alkylthiocarbonylamino, C4-I3 (total carbon number) cycloalkyl-carbonylamino, Cs-2S (total carbon number) cycloalkylalkyl-carbonylamino, C4-I3 (total carbon number) cycloalkyl- thiocarbonylamino, Cs-25 (total carbon number) cycloalkylalkylthiocarbonylamino, C2-I3 (total carbon number) haloalkyl-carbonylamino, C2-I3 (total carbon number) haloalkylthiocarbonylamino, C2-I3 (total carbon number) alkylamino-carbonylamino, C2-I3 (total carbon number) alkylamino- thiocarbonylamino, C4-I3 (total carbon number) cycloalkylamino-carbonylamino, C5-25 (total carbon number) cycloalkylalkylamino-carbonylamino, C4-I3 (total carbon number) cycloalkylamino- thiocarbonylamino, C5-25 (total carbon number) cycloalkylalkylaminothiocarbonylamino, C2-I3 (total carbon number) haloalkylamino-carbonylamino, C2-I3 (total carbon number) haloalkylamino- thiocarbonylamino, C3-25 (total carbon number) dialkylamino-carbonylamino, C2-25 (total carbon number) dialkylaminothiocarbonylamino, C2-]3 (total carbon number) alkylaminocarbonyloxy, C2-I3 (total carbon number) alkylaminocarbonylthio, C4-I3 (total carbon number) cycloalkylamino- carbonyloxy, C5-25 (total carbon number) cycloalkylalkylaminocarbonyloxy, C4-I3 (total carbon number) cycloalkylaminocarbonylthio, C5-25 (total carbon number) cycloalkylalkylaminocarbonyl- thio, C2-I3 (total carbon number) haloalkylaminocarbonyloxy, C2-I3 (total carbon number) haloalkyl- aminocarbonylthio, C3.25 (total carbon number) dialkylaminocarbonyloxy, C3.25 (total carbon number) dialkylaminocarbonylthio, C2-I3 (total carbon number) alkoxy-carbonylamino, C4-I3 (total carbon number) cycloalkyloxy-carbonylamino, C5-25 (total carbon number) cycloalkylalkyl- oxy-carbonylamino, C2-B (total carbon number) haloalkoxy-carbonylamino, Ci-I2 alkyl- sulfonylamino, Ci-I2 haloalkylsulfonylamino, and said substituents other than cyano, formyl, halogen and nitro may be substituted with R**;
U represents CH2, O, S, N-Rz or N-R**;
Rz represents hydrogen, hydroxy, amino, Ci-I2 alkyl, Ci-I2 haloalkyl, C2-I2 alkenyl,
C2.]2 alkenyloxy, C2-I2 alkynyl, C2-I2 alkynyloxy, C3-I2 cycloalkyl, C4-24 alkylcycloalkyl, C4-24 cyclo- alkylalkyl, Ci-I2 alkylamino, C2-24 (total carbon number) dialkylamino, Ci.i2 alkoxy, Ci-I2 haloalkoxy, formyl group, a C2-I3 (total carbon number) alkylcarbonyl, C2-I3 (total carbon number) haloalkylcarbonyl, C2-I3 (total carbon number) alkoxycarbonyl, C2-I3 (total carbon number) alkylaminocarbonyl, C2-I3 (total carbon number) alkyl-carbonylamino, C2-I3 (total carbon number) haloalkyl-carbonylamino, C2-I3 (total carbon number) alkoxy-carbonylamino, C2-I3 (total carbon number) alkylamino-carbonylamino, Ci-I2 (total carbon number) alkylsulfonyl, Ci-12 (total carbon number) haloalkylsulfonyl, phenylsulfonyl, C2-I3 (total carbon number) alkylaminocarbonyl group which may be substituted or a C2-]3 (total carbon number) haloalkylaminocarbonyl, and said substituents other than hydrogen and formyl may be substituted with R1";
R*" is selected among the groups R4-l to R4-83 wherein G represents O, S or N, and which may be substituted with at least one group selected among hydrogen, halogen, Ci-)2 alkyl, Ci-J2 haloalkyl, C3-I2 cycloalkyl, C3-I2 halocycloalkyl, Ci_i2 alkoxy, CM2 haloalkoxy, CM2 alkylthio, CM2 haloalkylthio, Q-I2 alkylsulfinyl, CM2 haloalkylsulfinyl, CM2 alkylsulfonyl, Ci-]2 haloalkylsulfonyl, CM2 alkylamino, CM2 haloalkylamino, cyano, nitro, aminocarbonyl,
Figure imgf000030_0001
alkyl-amino- carbonyl, C2-24 (total carbon number) dialkyl-aminocarbonyl, CM2 alkoxy-carbonyl phenyl or pyridyl. The compounds according to the invention have asymmetric carbons, and thus the compounds also include optically active species. Moreover, the present invention also includes N-oxides and salts of the compounds according to the invention.
The present application is further directed to the following embodiments:
Embodiment A: Compounds having the structure (I-a-1) or (I-a-2), wherein the chemical groups A, R1, W1, W2, W3 and W4 are as defined herein, and wherein each X1, X2 and X3 are as defined herein for X, and wherein each Yi, Y2 and Y3 are as defined herein for Y.
Figure imgf000031_0001
Embodiment B: Compounds as defined in embodiment A, wherein the group -W'-W^W^W4- is selected among W-5, W-8, W-12 , W-16, W-17, W-18, W-20, W-22, W-23, W-24, W-30, W-31,
W-33, W-38, W-39, W-40, W-41, W-42, W-44, W-45, W-46, W-53, W-54, W-64, W-76, W-79,
W-86, W-98, W-99, W-114, W-115, W-134, W-157, W-161, W-173, W-223, W-224, W-225, W-241,
W-315, W-337, W-339, W-344, W-345, W-348, W-351 and W-357, preferably W-5, W-7, W-Il,
W-16, W-17, W-20, W-39, W-44, W-45, W-134, W-138, W-158, W-161, W-222, W-225, W-315, W-337, W-340, W-351 and W-357, more preferably W-5 and W-134, or W-16 and W-39.
Embodiment C: Compounds as defined in embodiment A or B, wherein A represents oxygen or CH2, R1 represents CF3, and/or X1, X2, X3 are independently selected among hydrogen, halogen, amino, Ci_6 alkylamino, C2-12 dialkylamino, nitro, Q.6 alkoxy, and Q.6 haloalkyl and Y1 , Y2, Y3 is H.
Embodiment D: Compounds having the structure (I-d-1), wherein the chemical groups A, R1, Q, X, Y, m, n and W are as defined herein and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, C^alkyl, Ci-6haloalkyl, Ci.6 alkoxy, Ci-6alkylsulfenyl, Ci-6alkylsulfinyl,
Ci-6alkylsulfonyl.
Figure imgf000032_0001
Embodiment Dl: Compounds as defined in embodiment D, wherein the group Q is selected among Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Ci^alkylamino, C2-12 dialkylamino, nitro, C]-6alkoxy, and Ci-6haloalkyl.
Embodiment D2: Compounds as defined in embodiment D or Dl, wherein A represents oxygen or CH2, R1 represents CF3, and Y is H.
In these embodiments, W preferably represents amino, hydroxy, carbonylamino Ci-6 alkyl-carbonylamino, C]-6 alkylcarbonyl-Ci_6 alkyl-carbonylamino, Q-6 alkylsulfenyl-Ci-6 alkyl- -carbonylamino, Ci-6 alkylsulfenyl-Ci-6 alkyl-carbonylamino, Ci-6 alkylsulfinyl-Ci-6 alkyl-carbonylamino, C1-6 alkylsulfonyl-Ci-6 alkyl-carbonylamino, Ci^haloalkyl-carbonylamino, cyano-Ci-6 alkyl- -carbonylamino C 1 -6 alkenyl-carbonylamino, C 1 -6 haloalkenyl-carbonylamino, C 1 -6 alkynyl- -carbonylamino, Ci-6haloalkynyl-carbonylamino, Ci-όalkoxy-carbonylamino, Ci-6haloalkoxy- -carbonylamino, cyano-Ci.βalkoxy-carbonylamino, Ci-ealkoxy-Ci^ alkylamino-carbonylamino, Ci-6 alkoxy-C].6 alkoxy-carbonylamino, amino-carbonylamino, C].6 alkylamino-carbonylamino,
Ci-66 h] aloalkylamino-carbonylamino, hydroxyCj.6 alkylamino-carbonylamino, cyano-C].6 alkyl- ami innoo--carbonylamino, C2-12 dialkylamino-carbonylamino, C2-i2 dialkylamino-Ci-6 alkyl-carbonylamino, C2-6 di(haloalkyl)amino-carbonylamino, C2-6 alkenylamino-carbonylamino, C2-6 alkynyl- amino-carbonylamino, Ci.ealkoxy-amino-carbonylamino, Ci-6alkylsulfonylamino, Ci-6 alkenyl- oxy-amino-carbonylamino, Ci-6 alkyl-thiocarbonylamino, C3-6 cycloalkyl-carbonylamino, C3-6halocycloalkyl-carbonylarnino, C4-I2 cycloalkylalkyl-carbonylamino, C3-6 cycloalkyl-
-thiocarbonylamino, C4-12 cycloalkylalkyl-thiocarbonylamino, Ci^haloalkyl-thiocarbonylamino, Q-6 alkylamino-thiocarbonylamino, C3.6 cycloalkylamino-carbonylamino, C3.6 halocycloalkyl- amino-carbonylamino, C4-I2 cycloalkylalkylamino-carbonylamino, C3-6 cycloalkylamino-thio- carbonylamino, C4-I2 cycloalkylalkylaminothiocarbonylamino, Ci^haloalkylamino-thiocarbonyl- amino, C2-I2 dialkylamino-thiocarbonylamino, C3_6cycloalkyloxy-carbonylamino, C4-J2 cycloalkyl- alkyloxy-carbonylamino, Ci^haloallcoxy-carbonylamino, C]-6 alkylsulfonylamino, C]-6 haloalkyl- sulfonylamino, Ci^alkylsulfonylamino, phenylsulfonylamino, phenyl-Ci-6 alkylamino, 2-pyridyl- -Ci-6 alkylamino, 3-pyridyl-Ci.6 alkylamino, 4-pyridyl-Ci_6 alkylamino, phenyl-carbonylamino, halo-phenyl-carbonylamino, azetidine-1-yl-carbonylamino, pyrrolidine- 1-yl-carbonylamino, N-methyl-pyrrolidine-2-yl-carbonylamino, furan-2-yl-carbonylamino, trifluoromethylphenyl- -carbonylamino, phenylamino-carbonylamino, halophenylamino-carbonylamino, trifluoromethyl- phenylamino-carbonylamino, 2-pyridyl-carbonylamino, 3-pyridyl-carbonylamino, 4-pyridyl- -carbonylamino, phenyl-thiocarbonylamino, 2-pyridyl-thiocarbonylamino, 3-pyridyl-thiocarbonyl- amino, 4-pyridyl-thiocarbonylamino, phenyl-Ci^alkyl-carbonylamino, 2-pyridyl-C!.6 alkyl- -carbonylamino, 3-pyridyl-Ci-6alkylcarbonyl, 4-pyridyl-Ci-6alkylcarbony, phenyl-Ci-6 alkyl- -thiocarbonyl, 2-pyridyl-Ci-6alkyl-thiocarbonyl, 3-pyridyl-Ci-6alkyl-thiocarbonylamino, 4-pyridyl- -Ci-6 alkyl-thiocarbonylamino, phenyl-oxy-carbonylamino, 2-pyridyloxy-carbonylamino, 3-pyridyloxy-carbonylamino, 4-pyridyloxy-carbonylamino, phenyl-Ci-6 alkyloxy-carbonylamino, 2-pyridyl-C i-6 alkyloxy-carbonylamino, 3-pyridyl-C]-6 alkyloxy-carbonylamino, 4-pyridyl- -CJ-6 alkyloxy-carbonylamino, phenyl-amino-carbonylamino, 2-pyridyl-amino-carbonylamino, 3-pyridyl-amino-carbonylamino, 4-pyridyl-amino-carbonylamino, phenyl-amino-thiocarbonyl- amino, 2-pyridylamino-thiocarbonylamino, 3-pyridylamino-thiocarbonylamino, 4-pyridylamino- -thiocarbonylamino, phenyl-Ci-6 alkylamino-carbonylamino, 2-pyridyl-C i-6 alkylamino-carbonyl- amino, 3-pyridyl-Ci-6 alkylamino-carbonylamino, 4-pyridyl-Ci-6 alkylamino-carbonylamino, phenyl-C 1.6 alkylamino-thiocarbonylamino, 2-pyridyl-C 1 -6 alkylamino-thiocarbonylamino, 3 -pyridyl-C i -6 alkylamino-thiocarbonylamino or 4-pyridyl-C i .6 alkylamino-thiocarbonylamino, l,2,3-triazole-4-trimethylsilyl-l-yl, 1,2,3-triazole-l-yl, succinimide-1-yl, -N3, phthalimide-2-yl, Ci-6alkylcarbonyloxy, more preferably represents amino, hydroxy, carbonylamino, Ci^alkyl- sulfonylamino, Ci.6alkylamino-carbonylamino, Ci-6 alkylthiocarbonylamino, Ci.6alkyl-carbonyl- amino, Q-6 alkylcarbonyl-Ci-6 alkyl-carbonylamino, Ci-6 alkylsulfenyl-C i-6 alkyl-carbonylamino, Ci-6 alkylsulfenyl-Ci.6 alkyl-carbonylamino, Cj-6 alkylsulfinyl-Ci.6 alkyl-carbonylamino, Ci-6 alkyl- sulfonyl-Ci-6 alkyl-carbonylamino, Ci-6 haloalkyl-carbonylamino, cyano-Ci-6 alkyl-carbonylamino Ci-6 alkenyl-carbonylamino, Ci-6 alkynyl-carbonylamino, Ci-6 alkoxy-carbonylamino,
C]-6 haloalkoxy-carbonylamino, cyano-Ci-6 alkoxy-carbonylamino, Ci-6 alkoxy-Ci-6 alkylamino- -carbonylamino, Ci-6 alkoxy-Ci-6 alkoxy-carbonylamino, amino-carbonylamino, Ci-6alkylamino- -carbonylamino, Ci-6 haloalkylamino-carbonylamino, hydroxyCi-6 alkylamino-carbonylamino, cyano-Ci-6 alkylamino-carbonylamino, C2.i2 dialkylamino-carbonylamino, C2-i2 dialkylamino- -Ci-6 alkyl-carbonylamino, C2-6 alkynylamino-carbonylamino, C2-6 alkenylamino-carbonylamino, Ci-6 alkoxy-amino-carbonylamino, Ci-6 alkenyloxy-amino-carbonylamino, C3-6 cycloalkyl-carbonyl- amino, C3-6halocycloalkyl-carbonylamino, C4-I2 cycloalkylalkyl-carbonylamino, Ci-6 alkylamino- -thiocarbonylamino, C3-6 cycloalkylamino-carbonylamino, C3-6 halocycloalkylamino-carbonyl- amino, C4-I2 cycloalkylalkylamino-carbonylamino, Ci-6haloalkylsulfonylamino, phenyl-carbonyl- amino, halo-phenyl-carbonylamino, azetidine-1-yl-carbonylamino, pyrrolidine- 1 -yl-carbonylamino, N-methyl-pyrrolidine-2-yl-carbonylamino, furan-2 -yl-carbonylamino, tirfluoromethylphenyl- -carbonylamino, phenylamino-carbonylamino, halophenylamino-carbonylamino, trifluoromethyl- phenylamino-carbonylamino, 1 ,2,3-triazole-4-trimethylsilyl-l -yl, 1 ,2,3-triazole-l -yl, succinimide-1-yl, -N3, phthalimide-2-yl, Ci^alkylcarbonyloxy, most preferably represents Ci-6 haloalkyl-carbonylamino, Ci-6 alkylamino-carbonylamino, Ci-6 haloalkylamino-carbonylamino, Ci-6 alkylamino-carbonylamino, Ci-6 alkyl-carbonylamino, and Cj-6 haloalkylamino-carbonylamino.
Embodiment E: Compounds having the structure (I-e-1), wherein the chemical groups A, R1, Q, X, Y, m, n, and W are as defined herein and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, Ci-6alkyl, Ci-βhaloalkyl, Ci.6 alkoxy, Ci-6alkylsulfenyl, Ci-6alkylsulfinyl,
Ci.6alkylsulfonyl.
Figure imgf000035_0001
Embodiment El: Compounds as defined in embodiment E, wherein the group Q is selected among Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, C^alkylamino, C2-12 dialkylamino, nitro, Cj^alkoxy, and Ci_6haloalkyl.
Embodiment E2: Compounds as defined in embodiment E or El, wherein A represents oxygen or CH2, R1 represents CF3, and Y is H.
In these embodiments, W preferably represents hydrogen, Ci-6 alky, C^haloalky, Ci-6alkyl- carbonyl, Ci-6 haloalkylcarbonyl, Ci^alkenylcarbonyl, Ci-6 haloalkenylcarbonyl, Ci-β alkynyl- carbonyl, Ci^haloalkynylcarbonyl, Ci^alkoxycarbonyl, aminocarbonyl, Ci_6alkylaminocarbonyl,
Ci^haloalkylaminocarbonyl, Ci.δhydroxyalkylaminocarbonyl, C2-12 dialkylamino-carbonyl,
C2-6 di(haloalkyl)aminocarbonyl, C2-6 alkenylaminocarbonyl, C2-6 alkynylaminocarbonyl, phenyaminocarbonyl, halophenylaminocarbonyl, Ci-6 alkyl-thiocarbonyl, C3-6 cycloalkylcarbonyl, C4.12 cycloalkylalkyl-carbonyl, C3-6 cycloalkyl-thiocarbonyl, C^π cycloalkylalkyl-thiocarbonyl,
Ci_6 haloalkyl-thiocarbonyl, Q-6 alkylamino-thiocarbonyl, C3-6 cycloalkylamino-carbonyl,
C4.12 cycloalkylalkylamino-carbonyl, C3-6 cycloalkylamino-thiocarbonyl, C4.12 cycloalkylalkyl- aminothiocarbonyl, Ci.δhaloalkylamino-thiocarbonyl, C2-^ dialkylamino-thiocarbonyl, C3-6cyclo- alkyloxy-carbonyl, C^π cycloalkylalkyloxy-carbonyl, Ci^haloalkoxy-carbonyl, Ci^alkylsulfonyl, Ci-6 haloalkylsulfonyl, phenylsulfonyl, phenyl-Ci-6 alkyl, pyridin-2-yl-C1-6 alkyl, 3-pyridyl-
-C1.6 alkyl, 4-pyridyl-C1-6 alkyl, phenylcarbonyl, 2-pyridylcarbonyl, 3-pyridylcarbonyl, 4-pyridyl- carbonyl, phenyl-thiocarbonyl, 2-pyridyl-thiocarbonyl, 3-pyridyl-thiocarbonyl, 4-pyridyl-
-thiocarbonyl, phenyl-Ci-6 alkylcarbonyl, 2-pyridyl-Ci.6alkylcarbonyl, 3-pyridyl-Ci.6 alkylcarbonyl, 4-pyridyl-Ci.6 alkylcarbonyl, phenyl-CVβ alkyl-thiocarbonyl, 2-pyridyl-Ci-6 alkyl-thiocarbonyl, 3-pyridyl-Ci-6 alkyl-thiocarbonyl, 4-pyridyl-Ci.6alkyl-thiocarbonyl, phenyl-oxycarbonyl, 2-pyridyloxycarbonyl, 3-pyridyl- oxycarbonyl, 4-pyridyloxycarbonyl, phenyl-Ci.6 alkyl- oxy-carbonyl, 2-pyridyl-Ci-6 alkyloxy-carbonyl, 3-pyridyl-Ci.6 alkyloxy-carbonyl, 4-pyridyl- -Ci-6 alkyloxy-carbonyl, phenyl-aminocarbonyl, 2-pyridyl-aminocarbonyl, 3-pyridyl-amino- carbonyl, 4-pyridyl-aminocarbonyl, phenyl-amino-thiocarbonyl, 2-pyridylamino-thiocarbonyl, 3-pyridylamino-thiocarbonyl, 4-pyridylamino-thiocarbonyl, phenyl-Ci-6 alkylamino-carbonyl, halophenyl-Ci.6 alkylamino-carbonyl, pyridin-2-yl-Ci_6 alkylamino-carbonyl, 3 -pyridyl-Ci.6 alkylamino-carbonyl, 4-pyridyl-Ci.6 alkylamino-carbonyl, phenyl-Ci^alkylamino-thiocarbonyl, 2-pyridyl-Ci.6alkylamino-thiocarbonyl, S-pyridyl-Ci-ealkylamino-thiocarbonyl or 4-pyridyl- -Ci-6 alkylamino-thiocarbonyl, more preferably represents hydrogen, Ch alky., Ci-6haloalkyl, Ci_6 alkylcarbonyl, C1-6 haloalkylcarbonyl, Ci-6alkoxycarbonylCi-6 alkylaminocarbonyl, C1-6haloalkylaminocarbonyl, C2.12 dialkylaminocarbonyl, C2-6 alkenylaminocarbonyl, C2-6alkynyl- aminocarbonyl, phenylaminocarbonyl, halophenylaminocarbonyl, Ci-6 alkylamino-thiocarbonyl, C3-6 cycloalkylamino-carbonyl, C4.12 cycloalkylalkylamino-carbonyl, phenyl-Ci-6 alkyl, pyridin-2-yl-Ci-6 alkyl, phenyl-Ci.6 alkylamino-carbonyl, halophenyl-C].6 alkylamino-carbonyl, pyridin-2-yl-Ci-6 alkylamino-carbonyl.
Embodiment F: Compounds having the structure (I-f-1), wherein the chemical groups A, R1, Q, X, Y, m, n, and W are as defined herein and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, Ci-6 alkyl, Ci-6haloalkyl, Cj.6alkoxy, Ci-6alkylsulfenyl, C].6alkylsulfinyl, C 1.6alkylsulfonyl.
Figure imgf000037_0001
Embodiment Fl: Compounds as defined in embodiment F, wherein the group Q is selected among Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Ci-6 alkylamino, C2-J2 dialkylamino, nitro, Ci-6alkoxy, and Ci-6haloalkyl.
Embodiment F2: Compounds as defined in embodiment F or Fl, wherein A represents oxygen or CH2, R1 represents CF3, and/or Y is H.
In these embodiments, W preferably represents amino, hydroxy, carbonylamino, C)-6 alkyl- -carbonylamino, Ci-6 alkylcarbonyl-Ci-6 alkyl-carbonylamino, Q-6 alkylsulfenyl-C1-6 alkyl-carbonyl- amino, Ci-6 alkylsulfenyl-Ci-6 alkyl-carbonylamino, Ci-6 alkylsulfϊnyl-Ci-6 alkyl-carbonylamino, Ci-6 alkylsulfonyl-Ci-6 alkyl-carbonylamino, Ci-6haloalkyl-carbonylamino, cyano-Ci-6alkyl- -carbonylamino Ci-6 alkenyl-carbonylamino, Ci-6haloalkenyl-carbonylamino, Ci-6 alkynyl- -carbonylamino, Ci-6haloalkynyl-carbonylamino, Ci.6alkoxy-carbonylamino,
C]-6 haloalkoxy-carbonylamino, cyano-Ci-6 alkoxy-carbonylamino, Ci-6 alkoxy-Ci-6 alkylamino- -carbonylamino, Ci-6 alkoxy-Ci-6 alkoxy-carbonylamino, amino-carbonylamino, Q-6 alkylamino- -carbonylamino, Q^haloalkylamino-carbonylamino, hydroxyQ-ealkylamino-carbonylamino, cyano-Ci-6 alkylamino-carbonylamino, C2-U dialkylamino-carbonylamino, C2-)2 dialkylamino- -Ci-6 alkyl-carbonylamino, C2-6 di(haloalkyl)amino-carbonylamino, C2-6 alkenylamino-carbonyl- amino, C2-6 alkynylamino-carbonylamino, Ci-6 alkoxy-amino-carbonylamino, Q.6alkyl- sulfonylamino, Q-ealkenyloxy-arnino-carbonylamino, Ci^alkyl-thiocarbonylamino, C3-6 cyclo- alkyl-carbonylamino, C3-6 halocycloalkyl-carbonylamino, C4-12 cycloalkylalkyl-carbonylamino,
C3-6 cycloalkyl-thiocarbonylamino, C4-I2 cycloalkylalkyl-thiocarbonylamino, Ci-6 haloalkyl- -thiocarbonylamino, Cj-6 alkylamino-thiocarbonylamino, C3-6 cycloalkylamino-carbonylamino, C3-6 halocycloalkylamino-carbonylamino, C^n cycloalkylalkylamino-carbonylamino, C3.6 cyclo- alkylamino-thiocarbonylamino, C4.12 cycloalkylalkylaminothiocarbonylamino, Ci-6 haloalkylamino- -thiocarbonylamino, C2-^ dialkylamino-thiocarbonylamino, C3-6 cycloalkyloxy-carbonylamino, C4-12 cycloalkylalkyloxy-carbonylamino, Ci-6 haloalkoxy-carbonylamino, Ci-6 alkylsulfonylamino, C]-6 haloalkylsulfonylamino, Ci-6alkylsulfonylamino, phenylsulfonylamino, phenyl-Ci-6 alkylamino, 2-pyridyl-C 1 -6 alkylamino, 3 -pyridyl-C 1 -6 alkylamino, 4-pyridyl-C 1 -6 alkylamino, phenyl-carbonyl- amino, halo-phenyl-carbonylamino, azetidine-1-yl-carbonylamino, pyrrolidine- 1 -yl-carbonylamino, N-methyl-pyrrolidine-2-yl-carbonylamino, furan-2 -yl-carbonylamino, trifluoromethylphenyl- -carbonylamino, phenylamino-carbonylamino, halophenylamino-carbonylamino, trifluoromethylphenylamino-carbonylamino, 2-pyridyl-carbonylamino, 3-pyridyl-carbonylamino, 4-pyridyl-carbonylamino, phenyl-thiocarbonylamino, 2-pyridyl-thiocarbonylamino, 3-pyridyl- -thiocarbonylamino, 4-pyridyl-thiocarbonylamino, phenyl-Ci-6alkyl-carbonylamino, 2-pyridyl- -Ci^alkyl-carbonylamino, 3-pyridyl-Ci.βalkylcarbonyl, 4-pyridyl-Ci-6 alkylcarbony, phenyl- -Cj.6 alkyl-thiocarbonyl, 2-pyridyl-Ci-6 alkyl-thiocarbonyl, 3-pyridyl-Ci-6 alkyl-thiocarbonylamino, 4-pyridyl-C i-6 alkyl-thiocarbonylamino, phenyl-oxy-carbonylamino, 2-pyridyloxy-carbonylamino, 3-pyridyloxy-carbonylamino, 4-pyridyloxy-carbonylamino, phenyl-Ci.6 alkyloxy-carbonylamino, 2-pyridyl-Ci-6 alkyloxy-carbonylamino, 3-pyridyl-Ci.6 alkyloxy-carbonylamino, 4-pyridyl- -Ci-6 alkyloxy-carbonylamino, phenyl-amino-carbonylamino, 2-pyridyl-amino-carbonylamino, 3 -pyridyl-amino-carbonylamino, 4-pyridyl-amino-carbonylamino, phenyl-amino-thiocarbonyl- amino, 2-pyridylamino-thiocarbonylamino, 3-pyridylamino-thiocarbonylamino, 4-pyridylamino- -thiocarbonylamino, phenyl-Ci-6 alkylamino-carbonylamino, 2-pyridyl-Ci-6 alkylamino-carbonyl- amino, 3 -pyridyl-C i-6 alkylamino-carbonylamino, 4-pyridyl-Ci-6 alkylamino-carbonylamino, phenyl-C 1 -6alkylamino-ttoocarbonylarnino, 2-pyridyl-C 1.6 alkylamino-thiocarbonylamino,
3-pyridyl-C).6 alkylamino-thiocarbonylamino or 4-pyridyl-C].6 alkylamino-thiocarbonylamino, l,2,3-triazole-4-trimethylsilyl-l-yl, 1,2,3-triazole-l-yl, succinimide-1-yl, -N3, phthalimide-2-yl, Ci-6 alkylcarbonyloxy, more preferably represents amino, hydroxy, carbonylamino, Ci-6alkyl- sulfonylamino, Q-6 alkylamino-carbonylamino, C^alkyl-thiocarbonylamino, C1-6alkyl-carbonyl- amino, Ci-6 alkylcarbonyl-Ci-6 alkyl-carbonylamino, Ci-6 alkylsulfenyl-Ci-6 alkyl-carbonylamino, Ci-6 alkylsulfenyl-Ci-6 alkyl-carbonylamino, Ci-6 alkylsulfinyl-Ci.6 alkyl-carbonylamino, Ci-6 alkyl- sulfonyl-Ci-6 alkyl-carbonylamino, Cj-6 haloalkyl-carbonylamino, cyano-Ci-6 alkyl-carbonylamino, Ci^alkenyl-carbonylamino, C1-6 alkynyl-carbonylamino, Ci-6 alkoxy-carbonylamino,
Ci-6haloalkoxy-carbonylamino, cyano-Ci-6 alkoxy-carbonylamino, Ci-6alkoxy Q-6 alkylamino- -carbonylamino, Ci-6 alkoxy-Ci-6 alkoxy-carbonylamino, amino-carbonylamino, Q-6 alkylamino- -carbonylamino, Q^haloalkylamino-carbonylamino, hydroxy-Ci-6 -alkylamino-carbonylamino, cyano-Ci-6 alkylamino-carbonylamino, C2-H dialkylamino-carbonylamino, C2-H dialkylamino- -Ci-6 alkyl-carbonylamino, C2-6 alkynylamino-carbonylamino, Q^alkoxy-aπiino-carbonylammo, C1-6 alkenyloxy-amino-carbonylamino, C3-6 cycloalkyl-carbonylamino, C3-6 halocycloalkyl- -carbonylamino, C4-12 cycloalkylalkyl-carbonylamino, C1-6 alkylamino-thiocarbonylamino, C3-6 cycloalkylamino-carbonylamino, C3-6 halocycloalkylamino-carbonylamino, C4-I2 cycloalkyl- alkylamino-carbonylamino, C1-6haloalkylsulfonylamino, phenyl-carbonylamino, halo-phenyl- -carbonylamino, azetidine-1-yl-carbonylamino, pyrrolidine- 1-yl-carbonylamino, N-methyl- -pyrrolidine-2-yl-carbonylamino, furan-2-yl-carbonylamino, tirfluoromethylphenyl-carbonylamino, phenylamino-carbonylamino, halophenylamino-carbonylamino, trifluoromethylphenylamino- -carbonylamino, l,2,3-triazole-4-trimethylsilyl-l-yl, 1,2,3-triazole-l-yl, succinimide-1-yl, -N3, phthalimide-2-yl, C1-6 alkylcarbonyloxy, most preferably represents C!-6 haloalkyl-carbonylamino, C1-6 alkylamino-carbonylamino, Q^haloalkylamino-carbonylamino, C]-6 alkylamino-carbonylamino and Ci-ehaloalkylamino-carbonylamino.
Embodiment G: Compounds having the structure (I-g-1) or (I-g-2), wherein the chemical groups A, R1, Q, X, Y, m, n, and W are as defined herein and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, Ci-6alkyl, Ci-6haloalkyl, C1-6alkoxy, Ci-6alkylsulfenyl, Ci-6alkyl- sulfinyl, Ci-6alkylsulfonyl.
Figure imgf000040_0001
Embodiment Gl: Compounds as defined in embodiment G, wherein the group Q is selected among Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Ci-6 alkylamino, C2-H dialkylamino, nitro, Ci.6alkoxy, and Ci-6haloalkyl.
Embodiment G2: Compounds as defined in embodiment G or Gl, wherein A represents oxygen or CH2, R1 represents CF3, and Y is H.
In these embodiments, W preferably represents hydrogen, Ci^alkyl, Ci-6alkylcarbonyl, Ci-βhaloalkylcarbonyl, Ci-6alkenylcarbonyl, Ci^haloalkenylcarbonyl, Ci-6alkynylcarbonyl, Ci-6haloalkynylcarbonyl, C].6alkoxycarbonyl, aminocarbonyl, Ci-6 alkylaminocarbonyl, Ci^haloalkylaminocarbonyl, Ci-6 hydroxyalkylaminocarbonyl, C2-i2 dialkylamino-carbonyl, C2-6 di(haloalkyl)aminocarbonyl, C2-6 alkenylaminocarbonyl, C2-6 alkynylaminocarbonyl, Ci-6 alkyl- -thiocarbonyl, C3_6 cycloalkylcarbonyl, C4-I2 cycloalkylalkyl-carbonyl, C3-6 cycloalkyl-thiocarbonyl, C4-I2 cycloalkylalkyl-thiocarbonyl, Ci-6 haloalkyl-thiocarbonyl, Ci-6 alkylamino-thiocarbonyl, C3-6 cycloalkylamino-carbonyl, C4-I2 cycloalkylalkylamino-carbonyl, C3-6 cycloalkylamino- -thiocarbonyl, C4-I2 cycloalkylalkylaminothiocarbonyl, Ci^haloalkylamino-thiocarbonyl, C2-I2 dialkylamino-thiocarbonyl, C3-6 cycloalkyloxy-carbonyl, C4-I2 cycloalkylalkyloxy-carbonyl, C1-6haloalkoxy-carbonyl, Ci-6alkylsulfonyl, Ci.6haloalkylsulfonyl, phenylsulfonyl, phenyl- -Ci-6 alkyl, 2-pyridyl-Ci-6alkyl, 3-pyridyl-Ci-6alkyl, 4-pyridyl-Ci-6alkyl, phenylcarbonyl, 2-pyridylcarbonyl, 3-pyridylcarbonyl, 4-pyridylcarbonyl, phenyl-thiocarbonyl, 2-pyridyl- -thiocarbonyl, 3-pyridyl-thiocarbonyl, 4-pyridyl-thiocarbonyl, phenyl-Ci^alkylcarbonyl, 2-pyridyl- -C 1 -6 alkylcarbonyl, 3 -pyridyl-C 1 -6 alkylcarbonyl, 4-pyridyl-C 1 -6 alkylcarbony, phenyl-C 1 -6 alkyl- -thiocarbonyl, 2-pyridyl-Ci-6alkyl-thiocarbonyl, 3-pyridyl-Ci-6alkyl-thiocarbonyl, 4-pyridyl- -Ci-βalkyl-thiocarbonyl, phenyl-oxycarbonyl, 2-pyridyloxycarbonyl, 3-pyridyl- oxycarbonyl,
4-pyridyloxycarbonyl, phenyl-C^alkyloxy-carbonyl, 2-pyridyl-Ci.6alkyloxy-carbonyl, 3-pyridyl- -Ci_6alkyloxy-carbonyl, 4-pyridyl-C]-6alkyloxy-carbonyl, phenyl-aminocarbonyl, 2-pyridyl-amino- carbonyl, 3-pyridyl-aminocarbonyl, 4-pyridyl-aminocarbonyl, phenyl-amino-thiocarbonyl, 2-pyridylamino-thiocarbonyl, 3-pyridylamino-thiocarbonyl, 4-pyridylamino-thiocarbonyl, phenyl- -Ci-6 alkylamino-carbonyl, 2-pyridyl-Ci.g alkylamino-carbonyl, 3-pyridyl-Ci_6 alkylamino-carbonyl, 4-pyridyl-Ci-6 alkylamino-carbonyl, phenyl-Ci-βalkylamino-thiocarbonyl, 2-pyridyl-Ci-6 alkyl- amino-thiocarbonyl, S-pyridyl-Ci^alkylamino-thiocarbonyl or 4-pyridyl-Ci.6alkylamino- -thiocarbonyl, more preferably represents hydrogen, Ci.6 alkyl, Ci-6 alkylcarbonyl, Ci-6alkylamino- carbonyl, Ci-6 haloalkylaminocarbonyl, C2-6 alkenylaminocarbonyl, C2-6 alkynylaminocarbonyl, C3-6 cycloalkylamino-carbonyl, C4-I2 cycloalkylalkylamino-carbonyl.
Embodiment H: Compounds having the following structure (I-h-1) or (I-h-2), wherein the chemical groups A, R1, Q, X, Y, m, n, W and U are as defined herein, and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, Ci-6alkyl, Ci.6haloalkyl, Ci-6alkoxy, Ci-6 alkyl- sulfenyl, Ci-6alkylsulfinyl, Ci-6alkylsulfonyl.
Figure imgf000041_0001
Embodiment Hl : Compounds as defined in embodiment H, wherein the group Q is selected among Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Ci-6alkylamino, C2-I2 dialkylamino, nitro, C]-6 alkoxy, and Ci-6haloalkyl.
Embodiment H2: Compounds as defined in embodiment H or Hl, wherein A represents oxygen or CH2, R1 represents CF3, and Y is H and/or U stands for O, Ci-βalkyl-N, pyridin-2-yl-Ci.6alkyl-N or H-N.
Embodiment I: Compounds having the structure (I-i-1) or (I-i-2) wherein the chemical groups A, R1, Q, X, Y, m, n, W and U are as defined herein, and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, Ci-6alkyl, Ci-6haloalkyl, Ci-6alkoxy, Ci-6 alkylsulfenyl, C)-6alkyl- sulfϊnyl, Ci_6alkylsulfonyl.
Figure imgf000042_0001
Embodiment II: Compounds as defined in embodiment I, wherein the group Q is selected among Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Ci-6 alkylamino, C2-i2 dialkylamino, nitro, Ci-6alkoxy, and Ci-6haloalkyl.
Embodiment 12: Compounds as defined in embodiment I or II, wherein A represents oxygen or CH2, R1 represents CF3, and Y is H and/or U stands for O or Ci-6 alkyl-carbonyl-N.
In these embodiments, W preferably represents hydrogen; formyl; Ci-6alkyl, C2-I2 (total carbon number) alkoxyalkyl, C2-I2 (total carbon number) haloalkoxyalkyl, C2-6alkenyl, C2-6 alkynyl, C3-8 cycloalkyl, C4-I2 (total carbon number) alkylcycloalkyl, C4-J2 (total carbon number) cycloalkylalkyl, phenyl, halophenyl, pyrimidin-2-yl, C1-6haloalkyl, C1-6 alkylimino, Ci-6haloalkylimino, Ci-6alkyl- -carbonyl, Ci-6 alkenyl-carbonyl, Ci-6 alkynyl-carbonyl, Ci-6haloalkyl-carbonyl,
Ci-6 alkoxy-carbonyl, Ci.6haloalkoxy-carbonyl, aminocarbonyl, Ci.6alkylamino-carbonyl, Ci-6haloalkylamino-carbonyl, Ci-6hydroxyalkylamino-carbonyl, C2-J2 (total carbon number)dialkyl- amino-carbonyl, C2-6 (total carbon number) di(haloalkyl)aminocarbonyl, C2-6 alkenylamino- -carbonyl, C2-6 alkynylamino-carbonyl, C3-6 cycloalkyl-carbonyl, C4-]2 (total carbon number) cyclo- alkylalkyl-carbonyl, C3-6 cycloalkylamino-carbonyl, C4-I2 (total carbon number) cycloalkylalkyl- amino-carbonyl, C3-6 cycloalkyloxy-carbonyl, C4-I2 (total carbon number) cycloalkylalkyl- oxy-carbonyl, Cj.ehaloalkoxy-carbonyl, phenyl-C]-6 alkyl, halophenyl-Ci-6 alkyl, 2-pyridyl- -Ci-6alkyl, 3-pyridyl-Ci-6 alkyl, 4-pyridyl-Ci.6 alkyl, phenylcarbonyl, 2-pyridylcarbonyl, 3-pyridyl- carbonyl, 4-pyridylcarbonyl, phenyl-Ci.6alkylcarbonyl, 2-pyridyl-C1-6alkylcarbonyl, 3-pyridyl- -Ci-6 alkylcarbonyl, 4-pyridyl-Ci-6alkylcarbony, phenyloxy-carbonyl, 2-pyridyloxy-carbonyl, 3-pyridyloxy-carbonyl, 4-pyridyloxy-carbonyl, phenyl-Ci^alkyloxy-carbonyl, 2-pyridyl-C i-6 alkyl- oxy-carbonyl, 3-pyridyl-Ci-6 alkyloxy-carbonyl, 4-pyridyl-Ci-6alkyloxy-carbonyl, phenyl-amino- carbonyl, 2-pyridyl-aminocarbonyl, 3-pyridyl-aminocarbonyl, 4-pyridyl-aminocarbonyl, phenyl- -C i .6 alkylamino-carbonyl, 2-pyridyl-C i .6 alkylamino-carbonyl, 3 -pyridyl-C i -6 alkylamino-carbonyl or 4-pyridyl-Ci -6 alkylamino-carbonyl, more preferably represents hydrogen, Ci-6 alkyl, C2.n (total carbon number) alkoxyalkyl, C2-6alkenyl, C3-8 cycloalkyl, phenyl, halophenyl, pyrimidin-2-yl, Ci-6haloalkyl, Ci-6alkyl-carbonyl, phenyl-Ci-6 alkyl, halophenyl-Ci-6 alkyl, 2-pyridyl-C i-6 alkyl.
These embodiments do not include compounds nos. 1-50, 1-52, and 1-52 as defined herein.
Embodiment J: Compounds having the structure (I-j-1), wherein the chemical groups A, R1, Q, X, Y, m, n, W and U are as defined herein, and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, C1-6 alkyl, Ci-6haloalkyl, Ci-6alkoxy, Ci-6 alkylsulfenyl, Ci-6alkylsulfϊnyl, Ci.6alkylsulfonyl.
Figure imgf000043_0001
Embodiment Jl: Compounds as defined in embodiment J, wherein the group Q is selected among
Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Ci-6alkylamino, C2-I2 dialkylamino, nitro, Ci.6alkoxy, and Ci^haloalkyl.
Embodiment J2: Compounds as defined in embodiment J or Jl, wherein A represents oxygen or CH2, R1 represents CF3, and Y is H.
In these embodiments, W preferably represents hydrogen; formyl; C]-6 alkyl, C2.i2 (total carbon number) alkoxyalkyl, C2.12 (total carbon number) haloalkoxyalkyl, C2.6alkenyl, C2-6alkynyl, C3-S cycloalkyl, C4-^ (total carbon number) alkylcycloalkyl, C4-i2 (total carbon number) cycloalkylalkyl, Ci-6haloalkyl, Ci-6alkylimino, Ci.6haloalkylimino, Ci.6alkyl-carbonyl, Ci-6alkenyl-carbonyl, Ci-βalkynyl-carbonyl, C^haloalkyl-carbonyl, Ci-6alkoxy-carbonyl, Ci.6haloalkoxy-carbonyl, aminocarbonyl, Ci^alkylamino-carbonyl, Ci^haloalkylamino-carbonyl, Ci-6hydroxyalkylamino- -carbonyl, C2-12 (total carbon number)dialkylamino-carbonyl, C2-6 (total carbon number) di(haloalkyl)aminocarbonyl, C2.6 alkenylamino-carbonyl, C2-6 alkynylamino-carbonyl, C3-6 cyclo- alkyl-carbonyl, C4-I2 (total carbon number) cycloalkylalkyl-carbonyl, C3-6 cycloalkylamino- -carbonyl, C4-I2 (total carbon number) cycloalkylalkylamino-carbonyl, C3-6 cycloalkyloxy-carbonyl, C4-J2 (total carbon number) cycloalkylalkyloxy-carbonyl, Ci-6haloalkoxy-carbonyl, phenyl- -Ci-6 alkyl, 2-pyridyl-Ci-6 alkyl, 3-pyridyl-Ci-6 alkyl, 4-pyridyl-Ci.6alkyl, phenylcarbonyl, 2-pyridylcarbonyl, 3-pyridylcarbonyl, 4-pyridylcarbonyl, phenyl-Ci_6alkylcarbonyl, 2-pyridyl- -Ci-6 alkylcarbonyl, 3-pyridyl-CI-6alkylcarbonyl, 4-pyridyl-Ci-6alkylcarbony, phenyloxy-carbonyl, 2-pyridyloxy-carbonyl, 3-pyridyloxy-carbonyl, 4-pyridyloxy-carbonyl, phenyl-Ci-6alkyl- oxy-carbonyl, 2-pyridyl-Ci_6 alkyloxy-carbonyl, S-pyridyl-Ci-βalkyloxy-carbonyl, 4-pyridyl- -C!.6alkyloxy-carbonyl, phenyl-aminocarbonyl, 2-pyridyl-aminocarbonyl, 3-pyridyl-amino- carbonyl, 4-pyridyl-aminocarbonyl, phenyl-Ci^alkylamino-carbonyl, 2-pyridyl-Ci.6alkylamino- -carbonyl, 3-pyridyl-C^e alkylamino-carbonyl or 4-pyridyl-Ci-6 alkylamino-carbonyl, more preferably represents hydrogen; Ci-6 alkyl-carbonyl, phenyl-C1-6 alkyl, or 2-pyridyl-Ci-6 alkyl. Embodiment K: Compounds having the structure (I-k-1), wherein the chemical groups A, R1, Q, X,
Y, m, n, W and U are as defined herein, and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, Ci.6alkyl, Ci-6haloalkyl, C^ alkoxy, Ci.6alkylsulfenyl, C]-6alkylsulfinyl, C i .6alky 1 sulfonyl .
Figure imgf000045_0001
Embodiment Kl: Compounds as defined in embodiment K, wherein the group Q is selected among Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Cj.6 alkylamino, C2-12 dialkylamino, nitro, Q-6 alkoxy, and Ci-6 haloalkyl.
Embodiment K2: Compounds as defined in embodiment K or Kl, wherein A represents oxygen or CH2, R1 represents CF3, and Y is H and/or U stands for O, hydroxy-N, Ci-6 alkoxy-N, C^haloalkoxy-N, Ci-6 alkylamino-N, C2-i2 di(alkyl)amino-N, 2-pyridyl-Ci_6 alkoxy-N, Ci-6alkyl- -carbonylamino-N, or Ci.6haloalkylamino-N.
Embodiment L: Compounds having the structure (1-1-1), wherein the chemical groups A, R1, Q, X, Y, m, n, W and U are as defined herein, and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, Ci-6alkyl, C1-6haloalkyl, Ci_6alkoxy, Ci_6alkylsulfenyl, Ci-6alkylsulfϊnyl, Ci_6alkylsulfonyl.
Figure imgf000045_0002
Embodiment Ll : Compounds as defined in embodiment L, wherein the group Q is selected among
Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Q-6 alkylamino, C2.]2 dialkylamino, nitro, C)-6alkoxy, and C1-6haloalkyl.
Embodiment L2: Compounds as defined in embodiment L or Ll, wherein A represents oxygen or CH2, R1 represents CF3, Y is H and/or U stands for O.
In these embodiments, W preferably represents hydrogen; formyl; Q-6 alkyl, C2-12 (total carbon number) alkoxyalkyl, C2-I2 (total carbon number) haloalkoxyalkyl, C2-6alkenyl, C2-6alkynyl, C3-8 cycloalkyl, C4-12 (total carbon number) alkylcycloalkyl, C4-12 (total carbon number) cycloalkylalkyl, Q.6haloalkyl, Q.6alkylimino, Q-6 haloalkylimino, Q-6 alkenyl-carbonyl, Q.6alkynyl-carbonyl, Q^haloalkyl-carbonyl, Q-6 alkoxy-carbonyl, Q-6 haloalkoxy-carbonyl, aminocarbonyl, Q-6alkyl- amino-carbonyl, Q^haloalkylamino-carbonyl, Ci^hydroxyalkylamino-carbonyl, C2-I2 (total carbon number)dialkylamino-carbonyl, C2-6 (total carbon number) di(haloalkyl)aminocarbonyl, C2-6 alkenylamino-carbonyl, C2-6 alkynylamino-carbonyl, C3-6 cycloalkyl-carbonyl, C4-I2 (total carbon number) cycloalkylalkyl-carbonyl, C3-6 cycloalkylamino-carbonyl, C4-I2 (total carbon number) cycloalkylalkylamino-carbonyl, C3-6 cycloalkyloxy-carbonyl, C4-I2 (total carbon number) cycloalkylalkyloxy-carbonyl, Ci-6haloalkoxy-carbonyl, phenyl-C1-6 alkyl, 2-pyridyl-Ci-6 alkyl, 3-pyridyl-Ci.6 alkyl, 4-pyridyl-Ci-6 alkyl, phenylcarbonyl, 2-pyridylcarbonyl, 3-pyridylcarbonyl, 4-pyridylcarbonyl, phenyl-Ci^alkylcarbonyl, 2-pyridyl-Ci-6alkylcarbonyl, 3-pyridyl-Q-6 alkyl- carbonyl, 4-pyridyl-Ci-6alkylcarbony, phenyloxy-carbonyl, 2-pyridyloxy-carbonyl, 3-pyridyloxy-carbonyl, 4-pyridyloxy-carbonyl, phenyl-Q^alkyloxy-carbonyl, 2-pyridyl-Ci-6 alkyl- oxy-carbonyl, 3-pyridyl-Ci.δalkyloxy-carbonyl, 4-pyridyl-Ci-6 alkyloxy-carbonyl, phenyl-amino- carbonyl, 2-pyridyl-aminocarbonyl, 3-pyridyl-aminocarbonyl, 4-pyridyl-aminocarbonyl, phenyl- -Ci-6 alkylamino-carbonyl, 2-pyridyl-Ci-6 alkylamino-carbonyl, 3-pyridyl-Ci.6 alkylamino-carbonyl or 4-pyridyl-Ci-6 alkylamino-carbonyl, more preferably represents hydrogen or Ci-6alkyl
Embodiment M: Compounds having the following structure (I-m-1), wherein the chemical groups A, R1, Q, X, Y, m, n, W and U are as defined herein, and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, Cj-βalkyl, Ci-6haloalkyl, Ci.6 alkoxy, Ci-6alkylsulfenyl, Ci-6alkyl- sulfinyl, Ci-6alkylsulfonyl.
Figure imgf000047_0001
Embodiment Ml: Compounds as defined in embodiment M, wherein the group Q is selected among Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Ci.6alkylamino, C2-i2 dialkylamino, nitro, Ci_6alkoxy, and Ci.6haloalkyl.
Embodiment M2: Compounds as defined in embodiment M or Ml, wherein A represents oxygen or CH2, R1 represents CF3, Y is H and/or U stands for O.
hi these embodiments, W preferably represents hydrogen; formyl; C^ alkyl, C2-I2 (total carbon number) alkoxyalkyl, C2-I2 (total carbon number) haloalkoxyalkyl, C2_6alkenyl, C2_6alkynyl, C3.8 cycloalkyl, C4-I2 (total carbon number) alkylcycloalkyl, C4.12 (total carbon number) cycloalkylalkyl, Ci^haloalkyl, Cj.6 alkylimino, Q-6 haloalkylimino, Q-6 alkenyl-carbonyl, Ci.6alkynyl-carbonyl, Ci^haloalkyl-carbonyl, Q-6 alkoxy-carbonyl, Ci.6haloalkoxy-carbonyl, aminocarbonyl, Ci^alkyl- amino-carbonyl, Ci.6 haloalkylamino-carbonyl, Ci-6 hydroxyalkylamino-carbonyl, C2-I2 (total carbon number)dialkylamino-carbonyl, C2-^ (total carbon number) di(haloalkyl)aminocarbonyl, C2.6 alkenylamino-carbonyl, C2.6 alkynylamino-carbonyl, C3-6 cycloalkyl-carbonyl, C4.12 (total carbon number) cycloalkylalkyl-carbonyl, C3-6 cycloalkylamino-carbonyl, C4-I2 (total carbon number) cycloalkylalkylamino-carbonyl, C3-6 cycloalkyloxy-carbonyl, C4-I2 (total carbon number) cycloalkylalkyloxy-carbonyl, Ci^haloalkoxy-carbonyl, phenyl-Ci-6alkyl, 2-pyridyl-Ci.6 alkyl, 3-pyridyl-Ci-6alkyl, 4-pyridyl-Ci-6 alkyl, phenylcarbonyl, 2-pyridylcarbonyl, 3-pyridylcarbonyl, 4-pyridylcarbonyl, phenyl-Ci-6 alkylcarbonyl, 2-pyridyl-Ci-6alkylcarbonyl, 3-pyridyl-Ci.6alkyl- carbonyl, 4-pyridyl-Ci.6alkylcarbony, phenyloxy-carbonyl, 2-pyridyloxy-carbonyl, 3-pyridyloxy-carbonyl, 4-pyridyloxy-carbonyl, phenyl-Ci^alkyloxy-carbonyl, 2-pyridyl-Ci.6 alkyl- oxy-carbonyl, S-pyridyl-Ci^ alkyloxy-carbonyl, 4-pyridyl-C1-6alkyloxy-carbonyl, phenyl-amino- carbonyl, 2-pyridyl-aminocarbonyl, 3-pyridyl-aminocarbonyl, 4-pyridyl-aminocarbonyl, phenyl- -C i -6 alkylamino-carbonyl, 2-pyridyl-C i -6 alkylamino-carbonyl, 3 -pyridyl-C i -6 alkylamino-carbonyl or 4-pyridyl-C I-6 alkylamino-carbonyl.
Embodiment N: Compounds having the structure (I-n-1), wherein the chemical groups A, R1, Q, X, Y, m, n and W are as defined herein.
Figure imgf000048_0001
Embodiment Nl : Compounds as defined in embodiment N, wherein the group Q is selected among Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Ci^alkylamino, C2-I2 dialkylamino, nitro, C^alkoxy, and C1-6haloalkyl.
Embodiment N2: Compounds as defined in embodiment N or Nl, wherein A represents oxygen or CH2, R1 represents CF3, and Y is H.
hi these embodiments, W preferably represents amino, hydroxy, Ci-βalkyl-carbonylamino, Ci.6 haloalkyl-carbonylamino, C].6 alkenyl-carbonylamino, Ci-6 haloalkenyl-carbonylamino, Ci_6alkynyl-carbonylamino, Ci-ghaloalkynyl-carbonylamino, Q-6 alkoxy-carbonylamino, amino- -carbonylamino, Ci-6 alkylamino-carbonylamino, Ci_6 haloalkylamino-carbonylamino, Ci.ehydroxyalkylamino-carbonylamino, C2-i2 dialkylamino-carbonylamino, C2-6 di(haloalkyl)- amino-carbonylamino, C2.6 alkenylamino-carbonylamino, C2.6 alkynylamino-carbonylamino, Ci-6 alkyl-thiocarbonylamino, C3-6 cycloalkyl-carbonylamino, C4-J2 cycloalkylalkyl-carbonylamino,
C3-6 cycloalkyl-thiocarbonylamino, C4-12 cycloalkylalkyl-thiocarbonylamino, C]-6 haloalkyl- -thiocarbonylamino, Ci-6 alkylamino-thiocarbonylamino, C3-6 cycloalkylamino-carbonylamino, C4.12 cycloalkylalkylamino-carbonylamino, C3-6 cycloalkylamino-thiocarbonylamino, C4-I2 cyclo- alkylalkylaminothiocarbonylamino, Ci-βhaloalkylamino-tbiocarbonylamino, C2.]2 dialkylamino- -thiocarbonylamino, C3-6 cycloalkyloxy-carbonylamino, C4-I2 cycloalkylalkyloxy-carbonylamino, C^ghaloalkoxy-carbonylamino, C].6alkylsulfonylamino, Ci-6 haloalkylsulfonylamino, phenyl- sulfonylamino, phenyl-Ci-6 alkylamino, 2-pyridyl-Ci-6 alkylamino, 3-pyridyl-C].6 alkylamino, 4-pyridyl-Ci.6alkylamino, phenyl-carbonylamino, 2-pyridyl-carbonylamino, 3-pyridyl-carbonyl- amino, 4-pyridyl-carbonylamino, phenyl-thiocarbonylamino, 2-pyridyl-thiocarbonylamino, 3-pyridyl-thiocarbonylamino, 4-pyridyl-thiocarbonylamino, phenyl-Ci-6 alkyl-carbonylamino, 2-pyridyl-Ci-6alkyl-carbonylamino, 3-pyridyl-Ci-6 alkylcarbonyl, 4-pyridyl-Ci-6alkylcarbony, phenyl-Ci-6 alkyl-thiocarbonyl, 2-pyridyl-Ci-6 alkyl-thiocarbonyl, 3-pyridyl-Ci.6 alkyl-thiocarbonylamino, 4-pyridyl-Ci-6 alkyl-thiocarbonylamino, phenyl-oxy-carbonylamino, 2-pyridyloxy-carbonyl- amino, 3-pyridyloxy-carbonylamino, 4-pyridyloxy-carbonylamino, phenyl-Ci-6 alkyloxy-carbonyl- amino, 2-pyridyl-Ci-6alkyloxy-carbonylamino, 3-pyridyl-Ci.δ alkyloxy-carbonylamino, 4-pyridyl- -Ci-6 alkyloxy-carbonylamino, phenyl-amino-carbonylamino, 2-pyridyl-amino-carbonylamino, 3-pyridyl-amino-carbonylamino, 4-pyridyl-amino-carbonylamino, phenyl-amino-thiocarbonyl- amino, 2-pyridylamino-thiocarbonylamino, 3-pyridylamino-thiocarbonylamino, 4-pyridylamino- -thiocarbonylamino, phenyl-Ci.e alkylamino-carbonylamino, 2-pyridyl-Ci-6alkylamino-carbonyl- amino, 3-pyridyl-Ci-6 alkylamino-carbonylamino, 4-pyridyl-C].6 alkylamino-carbonylamino, phenyl-Ci-όalkylamino-thiocarbonylamino, 2-pyridyl-Ci-6 alkylamino-thiocarbonylamino,
3-pyridyl-Ci-6 alkylamino-thiocarbonylamino or 4-pyridyl-Ci-6 alkylamino-thiocarbonylamino, more preferably represents amino, Ci-6 alkyl-carbonylamino, Ci-6alkoxy-carbonylaminoC3-6cyclo- alkyl-carbonylamino.
Embodiment O: Compounds having the structure (I-o-l), wherein the chemical groups A, R1, Q, X, Y, m, W and n are as defined herein, and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, Ci-6alkyl, Ci-6haloalkyl, Ci-6alkoxy, C1-6 alkylsulfenyl, Ci.6alkylsulfmyl, Ci^alkylsulfonyl.
Figure imgf000050_0001
Embodiment Ol : Compounds as defined in embodiment O, wherein the group Q is selected among Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Ci_6 alkylamino, C2-12 dialkylamino, nitro, Ci_6alkoxy, and Ci_6haloalkyl.
Embodiment O2: Compounds as defined in embodiment O or Ol , wherein A represents oxygen or CH2, R1 represents CF3, and Y is H.
In these embodiments, W preferably represents hydrogen; cyano, halogen, formyl; Ci_6alkyl, C2-12 (total carbon number) alkoxyalkyl, C2.12 (total carbon number) haloalkoxyalkyl, C2_6alkenyl, C2-6 alkynyl, C3-8 cycloalkyl, C4.12 (total carbon number) alkylcycloalkyl, C4.12 (total carbon number) cycloalkylalkyl, C].6haloalkyl, Ci.6alkylimino, Ci-6haloalkylimino, Ci^alkenyl-carbonyl, Ci_6 alkynyl-carbonyl, Cj^haloalkyl-carbonyl, Ci-6alkoxy-carbonyl, Ci-6haloalkoxy-carbonyl, aminocarbonyl, Q-6 alkylamino-carbonyl, Ci^haloalkylamino-carbonyl, Ci.6hydroxyalkylamino- -carbonyl, C2-12 (total carbon number)dialkylamino-carbonyl, C2-6 (total carbon number) di(haloalkyl)aminocarbonyl, C2.6 alkenylamino-carbonyl, C2.6 alkynylamino-carbonyl, C3-6 cyclo- alkyl-carbonyl, C4-I2 (total carbon number) cycloalkylalkyl-carbonyl, C3-6 cycloalkylamino- -carbonyl, C4.12 (total carbon number) cycloalkylalkylamino-carbonyl, C3-6 cycloalkyloxy-carbonyl, C4.12 (total carbon number) cycloalkylalkyloxy-carbonyl, Ci_6haloalkoxy-carbonyl, phenyl- -Ci.6 alkyl, 2-pyridyl-Ci.6alkyl, 3-pyridyl-Ci-6 alkyl, 4-pyridyl-Ci-6alkyl, phenylcarbonyl, 2-pyridylcarbonyl, 3-pyridylcarbonyl, 4-pyridylcarbonyl, phenyl-Ci^alkylcarbonyl, 2-pyridyl-
-Ci-βalkylcarbonyl, 3-pyridyl-C1-6alkylcarbonyl, 4-pyridyl-C]-6 alkylcarbony, phenyloxy-carbonyl, 2-pyridyloxy-carbonyl, 3-pyridyloxy-carbonyl, 4-pyridyloxy-carbonyl, phenyl-Q^ alkyl- oxy-carbonyl, 2-pyridyl-C1.6alkyloxy-carbonyl, S-pyridyl-Ci^ alkyloxy-carbonyl, 4-pyridyl- -Ci^alkyloxy-carbonyl, phenyl-aminocarbonyl, 2-pyridyl-aminocarbonyl, 3-pyridyl-amino- carbonyl, 4-pyridyl-aminocarbonyl, phenyl-C]-6 alkylamino-carbonyl, 2-pyridyl-Ci.6alkylamino- -carbonyl, 3-pyridyl-Ci-6 alkylamino-carbonyl or 4-pyridyl-Ci.6 alkylamino-carbonyl.
Embodiment V: Compounds having the structure (I-v-1), wherein the chemical groups A, R1, Q, X, Y, m, n, W, and U are as defined herein, and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, Ci_6alkyl, Ci-6haloalkyl, Ci_6alkoxy, Ci-6alkylsulfenyl, Ci-6alkylsulfmyl, Ci.6alkylsulfonyl.
Figure imgf000051_0001
Embodiment Vl: Compounds as defined in embodiment V, wherein the group Q is selected among Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Ci-6 alkylamino, C2-n dialkylamino, nitro, Ci-6 alkoxy, and Ci-6 haloalkyl.
Embodiment V2: Compounds as defined in embodiment V or Vl, wherein A represents oxygen or CH2, R1 represents CF3, and Y is H.
W preferably represents hydrogen.
Embodiment Z: Compounds having the structure (I-z-1), wherein the chemical groups A, R1, Q, X, Y, m, n, W, and U are as defined herein, and wherein W" is selected among hydrogen, halogen, hydroxy, thiol, cyano, Ci-6alkyl, Ci-6haloalkyl, Ci-6alkoxy, Ci.6alkylsulfenyl, Ci.6alkylsulfinyl,
C i .6alkylsulfonyl.
Figure imgf000052_0001
Embodiment Zl : Compounds as defined in embodiment Z, wherein the group Q is selected among Q-I, Q-2, Q-42 to Q-54 and X is independently selected among hydrogen, halogen, amino, Ci.6alkylamino, C2-I2 dialkylamino, nitro, Ci-6alkoxy, and Ci.6haloalkyl.
Embodiment Z2: Compounds as defined in embodiment Z or Zl, wherein A represents oxygen or CH2, R1 represents CF3, and Y is H and/or U stands for O, hydroxy-N, Ci-6 alkoxy-N, Ci-6 haloalkoxy-N.
As used herein, the term "alkyl" refers to linear or branched CM2 alkyl including, for example, ethyl, methyl, 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, and preferably refers to Ci-6 alkyl. The alkyl moiety in a group having alkyl as a part of its formula may have the same meaning as described for the aforementioned "alkyl". The alkyl group can be unsubstituted or substituted with at least one suitable substituent.
The term "halogen" and a halogen moiety in a group substituted with halogen represents fluorine, chlorine, bromine and iodine. Preferred halogens are fluorine, chlorine and bromine.
The term "haloalkyl" used alone or combined with other terms refers to alkyl groups which are partially or fully substituted with halogen atoms which may be the same or different. Examples of "haloalkyl" includes for example CF3, CH2F, CHF2, CCl3, CH2Cl, CHCl2, CF2CF3, CHFCF3, The haloalkyl group can additionally be unsubstituted or substituted with at least one suitable substituent.
The term "cycloalkyl" refers to C3.s cycloalkyl including, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl, and preferably refers to C3-7 cycloalkyl. The cycloalkyl group can be unsubstituted or substituted with with at least one suitable substituent.
The term "alkenyl" refers to C2-5 alkenyl including, for example, vinyl, allyl, 1-propenyl, l-(or 2- or 3-) butenyl and 1-pentenyl, and preferably refers to C2-4 alkenyl. The alkenyl group can be unsubstituted or substituted with at least one suitable substituent.
The term "alkynyl" used either alone or combined with other terms preferably stands for alkynyl having 2 to 6 or 2 to 5 carbon atoms. Examples include ethynyl, propargyl, 1-propynyl, but-3-ynyl or pent-4-ynyl. More preferred it stands for alkynyl having 2 to 4 carbon atoms. The alkinyl group can be unsubstituted or substituted with at least one suitable substituent.
A "heterocyclic group" preferably refers to a 5- or 6-membered heterocyclic group containing at least one of hetero atoms selected from N, O or S, and said heterocyclic group also refers to a condensed heterocyclic group which may be benzo-condensed. Typically a heterocyclic group contains no more than 4 nitrogens, 2 oxygens and 2 sulfur atoms. The cyclic group can be saturated, unsaturated or partially saturated. If not mentioned otherwise, then a heterocyclic group can be can be attached through any available carbon or heteroatom. Heterocyclic group include for example furyl, thienyl, pyrrolyl, isoxazolyl, pyrazolyl, oxazolyl, oxathiazolyl, imidazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, benzoxazolyl or quinolyl. The heterocyclic group can be unsubstituted or substituted with with at least one suitable substituent.
The term "acylamino" refers to, for example, alkyl-carbonylamino, cycloalkyl-carbonylamino and benzoylamino, wherein the alkyl moiety may the same meaning as described for the aforementioned "alkyl", and cycloalkyl moiety may have the same meaning as described below.
The acylamino group can be unsubstituted or substituted with with at least one suitable substituent.
Suitable substituents include for example the following chemical groups, namely amino, hydroxy, halogen, nitro, cyano, isocyano, mercapto, isothiocyanato, carboxy, carbonamide, SF5, amino- sulfonyl, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkinyl, monoalkyl-amino, dialkyl-amino, N-alkanoyl-amino, alkoxy, alkenyloxy, alkinyloxy, cycloalkoxy, cycloalkenyloxy, alkoxy-carbonyl, alkenyloxy-carbonyl, alkinyloxy-carbonyl, aryloxycarbonyl, alkanoyl, alkenyl-carbonyl, alkinyl-carbonyl, aryl-carbonyl, alkylthio, cycloalkylthio, alkenylthio, cycloalkenylthio, alkinylthio, alkylsulfenyl, alkylsulfϊnyl, including both enantiomeric forms of alkylsulfinyl, alkyl- sulfonyl, monoalkyl-aminosulfonyl, dialkyl-aminosulfonyl, alkylphosphinyl, alkylphosphonyl, including both enantiomeric forms of alkylphosphinyl and alkylphosphonyl, respectively, N-alkyl- -aminocarbonyl, N,N-dialkyl-aminocarbonyl, N-alkanoyl-amino-carbonyl, N-alkanoyl-N-alkyl- -aminocarbonyl, aryl, aryloxy, benzyl, benzyloxy, benzylthio, arylthio, arylamino, benzylamino, heterocyclyl and trialkylsilyl. Substituents which are further substituted, like for example alkoxyalkyl, alkylthioalkyl, alkylthioalkoxy, alkoxyalkoxy, phenethyl, benzyloxy, haloalkyl, haloalkoxy, haloalkylthio, haloalkanoyl, haloalkylcarbonyl, haloalkoxycarbonyl, haloalkoxyalkoxy, haloalkoxyalkylthio, haloalkoxyalkanoyl, haloalkoxyalkyl are also included. Preferred substituents are chloro, fluoro, bromo, iodo, NH2, NO2, CN, OH, SH and COOH.
Compounds according to the invention may be prepared by using generally known methods or by combining known methods with the preparation methods described herein.
For example, preparation method (a-1) and (a-2) can be carried out according to the method described in WO2007/021308. Preparation method Ca-I")
Compounds of formula (I-i-1) as defined in embodiment I, wherein U represents oxygen and W stands for a group T1 can be prepared by preparation methods (a-1), namely by
reacting a compound of the formula (II-a)
Figure imgf000055_0001
wherein L1 stands for halogen, alkylsulfonyloxy (e.g. methanesulfonyloxy), or arylsulfonyloxy (e.g. para-toluenesulfonyloxy), and L2 stands for alkoxy (e.g. methoxy) or aryloxy (e.g. phenoxy), and wherein (X)m, (Y)n, A, R1 and Q have the same meaning as described herein, particulary as described for embodiment I, Il or 12, with a compound of the formula (III):
Figure imgf000055_0002
wherein L3 stands for hydroxy, thiol or amino, and T1 stands for either R3 or R4 ,
if appropriate, in the presence of a diluent and/or a base to yield compounds of formula (I-i-1) as defined in embodiment I, wherein U represents oxygen and W stands for a group T1.
In carrying out preparation method (a-1), 1 mole of a compound of formula (II-a) can be reacted with 1 to 2 moles of a compound of formula (ITT) in a diluent, such as toluene, and in the presence of a base, such as potassium carbonate, to obtain the desired compound.
Known compounds of formula (III) include for example water, hydrogen sulfide, ammonia, methylamine, ethylamine, benzylamine, 2-pyridinomethylamine, acetamide. Compounds of formula (I-i-2) as defined in embodiment I, wherein U represents oxygen and W stands for a group T1 can also be prepared by preparation method (a-1), namely by
reacting a compound of the formula (II-b)
Figure imgf000056_0001
L1 stands for halogen, alkylsulfonyloxy or arylsulfonyloxy, and L2 stands for alkoxy (e.g. methoxy) or aryloxy (e.g. phenoxy), and wherein (X)m, (Y)n, A, R1 and Q have the same meaning as described herein, particulary as described for embodiment I, Il or 12, with a compound of formula (III).
Preparation method (a-2)
Compounds of formula (1-1-1) as defined in embodiment L, wherein U represents oxygen and the two W stand for a group T1 and H, can be prepared by preparation method (a-2), namely by
reacting a compound of the formula (II-a) wherein L1 stands for halogen, alkylsulfonyloxy or arylsulfonyloxy, and L2 stands for alkoxy or aryloxy, and wherein (X)m, (Y)n, A, R1 and Q have the same meaning as described herein, particulary as described for embodiment L, Ll or L2,
with a compound of the formula (IV):
H2NHN-T (IV) wherein T1 stand for either R3 or R4 , and include, among other, methylhydrazine or ethylhydrazine,
if appropriate, in the presence of a diluent and/or a base to yield compounds of formula (1-1-1), wherein U represents oxygen and the one of the two W stands for a group T1 and the other W stands for H.
In carrying out Preparation method (a-2), 1 mole of a compound of formula (II-a) can be reacted with 1 to 2 moles of a compound of formula (IV) in a diluent, such as toluene, and in the presence of a base, such as potassium carbonate to obtain the desired compound.
Preparation method (b)
Compounds of formula (I-i-1) or (I-i-2) as defined in embodiment I, wherein U represents oxygen and the W stands for H can be prepared by preparation method (b ), namely by
reacting a compound of the formula (V-a)
Figure imgf000057_0001
wherein (X)m, (Y)n, A, R1 and Q have the same meaning as described herein, particulary as described for embodiment I, Il or 12, with
(i) a compound of the formula (Vl-a):
L4— T1 (Vl-a) wherein L4 stands for halogen, alkylsulfonyloxy, arylsulfonyloxy or alkylcarbonyloxy, and T1 stand for either R3 or R4 ; or with
(ii) a compound of the formula (VI-b)
T1— O-T1 (VI-b)
wherein T1 stands for R3 or R4 ; in case T1 stands for a carbonyl-containing moiety, formula (VI-b) is an acid anhydride;
if appropriate, in the presence of a diluent and/or a base to yield compounds of formula (I-i-1), wherein U represents oxygen and W stands for a group T1.
Similarly, compounds of formula (I-i-2) can be prepared by reacting a compound of formula (V-b):
Figure imgf000058_0001
wherein (X)m, (Y)n, A, R1 and Q have the same meaning as described herein, particulary as described for embodiment I, Il or 12, with compounds of the formula (VI-a) or (VI-b).
In carrying out preparation method (b), 1 mole of a compound of formula (V-a) or (V-b) can be reacted with 1 to 10 moles of a compound of formula (VI-a) or (VI-b) in a diluent, for example toluene, in the presence of base to obtain the desired compound.
Compounds of formula (VI-a) and (VI-b) include, for example, acetic acid anhydride, acetyl chloride, methyl iodide, and benzyl bromide.
Similar preparation methods are described in WO99/05055, which methods are hereby incoφorated.
Preparation method (c)
Compounds of formula (I-h-1) as defined in embodiment H, wherein U represents N-T1 can be prepared by preparation method (c), namely by
reacting a compound of the formula (VII-a)
Figure imgf000059_0001
wherein (X)n,, (Y)n, A, R1 and Q have the same meaning as described herein, particulary as described for embodiment H, Hl or H2, and wherein T1 stands for either R3 or R4, with alkyl- sulfonyl chloride or phenylsulfonyl chloride, if appropriate, in the presence of a base, and/or in the presence of a diluent.
Compounds of formula (I-h-2) as defined in embodiment H, wherein U represents N-T1, wherein T1 is as defined herein, can be prepared by preparation method (c) by using compounds of the formula (VII-b) as a starting material
Figure imgf000059_0002
wherein (X)m, (Y)n, A, R1 and Q have the same meaning as described herein, particulary as described for embodiment H, Hl or H2, and wherein T1 stands for either R3 or R4.
Preparation method (c) can be carried out according to the method described in Synlett (2006), 801-803 which is hereby incorporated by reference.
hi carrying out Preparation method (c), 1 mole of a compound of formula (VII-a) can be reacted with 1 to 2 moles of methane sulfonyl chloride in a diluent, for example tetrahydrofuran, in the presence of a base to obtain the desired compound.
Preparation method ( d)
Compounds of formula (I-i-1) as defined in embodiment I, wherein U represents N-H and W stands for T1 can be prepared by preparation method (d), namely by
reacting a compound of formula (Vϋl-a)
Figure imgf000060_0001
wherein (X)m, (Y)n, A, R1 and Q have the same meaning as described herein, particulary as described for embodiment I, Il or 12,
with a compound of formula (EX)
H2N-T (IX) wherein T1 stands for either R3 or R4 , if appropriate, in the presence of a base, and/or in the presence of a diluent.
Compounds of formula (I-i-2) as defined in embodiment I, wherein U represents N-H and W stands for T1 can be prepared by preparation method (d), using a compound of formula (VHI-b)
Figure imgf000061_0001
wherein (X)m, (Y)n, A, R1, Q and L1 have the same meaning as described herein as starting material.
Preparation method (d) can be carried out according to the methods described in US 6,376,530, and which preparation methods are hereby incorporated by reference.
In carrying out preparation method (d), 1 to 2 moles of a compound of formula (VIII-a) can be reacted with 1-2 moles of a compound of formula (DC) in a diluent, for example acetonitrile, in the presence of potassium carbonate to obtain the desired compound.
Preparation method (e)
Compounds of formula (I-i-1) as defined in embodiment I, wherein U represents N-T1 and W stands for T1 can be prepared by preparation method (e) namely by
reacting a compound of the formula (X-a)
Figure imgf000061_0002
wherein (X)m, (Y)n, A, R1 and Q have the same meaning as described herein, particulary as described for embodiment I, Il or 12, with a compound of formula (VI-a) or (VI-b), if appropriate, in the presence of a base, and /or in the presence of a diluent.
Compounds of formula (I-i-2) as defined in embodiment I, wherein U represents N-T1 and W stands for T1 can be prepared by preparation method (e) using compounds of the formula (X-b):
Figure imgf000062_0001
wherein (X)m, (Y)n, A, R1 and Q have the same meaning as described herein.
Compounds of formula (X-a) or (X-b) can be synthesized according to preparation method (d).
Compounds of formula (VI-a) or (VI-b) include for example acetic acid anhydride, acetyl chloride, methyl iodide, and benzyl bromide.
Preparation method (e) is a known organic synthetic reaction. In the presence of an appropriate base a substitution reaction can occur.
In carrying out preparation method (e), 1 mole of a compound of formula (X) can be reacted with 1 to 1.5 moles of a compound of formula (VI) in a diluent, for example tetrahydrofuran, in the presence of pyridine to obtain a desired compound.
Preparation method (f)
Compounds of formula (I-j-1) as defined in embodiment J, wherein W stands for T1 can be prepared by preparation method (f), namely by reacting a compound of the formula (XI)
Figure imgf000063_0001
wherein (X)m, (Y)n, A, R1 and Q have the same meaning as described herein, particulary as described for embodiment J, Jl or J2, with a compound of formula (III), if appropriate, in the presence of a base, and /or in the presence of a diluent.
Compounds aof formula (Iu) are for example methylamine, ethylamine, benzylamine, 2-pyridinomethylamine or acetamide.
Preparation method (f) can be carried out according to the methods disclosed in Tetrahedron Lett., 2005, 5927-5930 which are hereby incorporated by reference.
In carrying out preparation method (f), 1 mole of a compound of formula (XI) can be reacted with 1 to 2 moles of a compound of formula (HI) in a diluent, for example tetrahydrofuran, in the presence of 1 to 2 moles of sodium hydride as the base, to obtain the desired product.
Preparation method (s)
Compounds according to the invention wherein A is oxygen can be prepared according to preparation methods (g) and (h), namely by
reacting a compound of the formula (XII)
Figure imgf000064_0001
wherein (X)m, R1 and Q have the same meaning as described herein, particularly as described in the embodiments A, B, C or L, Ll or L2,
with a compound of the following formula (XIII):
Figure imgf000064_0002
wherein W1 to W4 and (Y)n have the same meaning as described herein,
in the presence of inert diluents, and, if appropriate in the presence of a base.
Preparation method (g) can be carried out according to the methods disclosed in WO2004/018410, WO2005/085216, Tetrahedron, 2000, VoI 56, 1057-1064.
In carrying out preparation method (g), 1 mole of a compound of formula (XIII) can be reacted with 1 to 2 moles of a compound of formula (XII) and with 1 mole to a slightly excessive amount of base in a diluent, for example DMF, to obtain the desired compound. Preparation method (h)
Compovmds according to the invention wherein A is nitrogen or oxygen can be prepared according to preparation method (h), namely by
reacting a compound of the formula (XIV)
Figure imgf000065_0001
wherein (X)m, (Y)n, A, R1 and Q have the same meaning as described herein, particularly as described in the embodiments A, B, C, Hl, H2, and H3, and wherein W1 to W4 and (Y)n have the same meaning as described herein, with
(i) a compound of the formula (XV):
Figure imgf000065_0002
or a hydrochloride acid salt thereof, wherein R2 has the same meaning as described herein, to form a pyrazoline ring at the appropriate position; or
(ii) a hydroxyamine or a hydrochloride acid salt thereof to form an isoxazoline ring at the appropriate position;
if appropriate in the presence of a base and optionally in the presence of a diluent.
Examples of the compound of formula (XV) include hydrazine, methylhydrazine and ethylhydrazine. Compounds according to the invention wherein A is CH2 can be prepared according to preparation methods (i) and (j).
Preparation method (ϊ)
Shifting an imino double bond in compounds of formula (XVI):
Figure imgf000066_0001
wherein (X)m, (Y)n, A, R1 and Q have the same meaning as described herein, particularly as described in the embodiments A, B, C, Hl, H2, and H3, and wherein W1 to W4 and (Y)n have the same meaning as described herein,
if appropriate, in the presence of a base, and optionally in the presence of a diluent.
Preparation method (i) can be carried out according to the methods disclosed in Japanese Patent Application Laid-Open 2007-91708 and Chem. Lett., 1985, 1601-1604 which are hereby incorporated by reference.
In carrying out preparation method (i), 1 mole to a slightly excessive amount of base can be reacted with 1 mole of a compound of formula (XVI) in a diluent, for example tetrahydrofuran, to obtain a desired compound of formula (I) .
Preparation method (i)
Reacting a compound of formula (XII) as defined above with a compound of the following formula (XXX):
Figure imgf000067_0001
wherein Ri', R2' and R3' each independently represent Q.^ alkyl, or phenyl; R4' represents hydrogen; or is selected among Ci-I2 alkyl, CM2 alkenyl, Cj-I2 alkynyl and benzyl; and
W1 to W4 and (Y)n have the same meaning as described herein, if appropriate, in the presence of a fluoride reagent, such as potassium fluoride, tetramethylammonium fluoride, tetraethylammonium fluoride, or tetrabutylammonium fluoride.
For carrying out preparation method (j) 1 mole of a compound of formula (XII) relative to 1 mole of compound of formula (XXX) can be reacted with 0.1 mole of a fluoride reagent in a diluent, for example THF, to obtain a desired compound of formula (I).
Preparation method (j) can be carried out according to the methods described in J. Org. Chem., Vol. 52, 1027-1035, 1987 which is hereby incorporated by reference.
The preparation methods can be illustrated by the following reaction schemes, by way of examples.
Reaction scheme 1 - Preparation method (a-1):
Figure imgf000067_0002
Here, methyl 2-(bromomethyl)-4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro-
-isoxazol-3-yl]benzoate and ammonia are used as starting material.
Reaction scheme 2 - Preparation method (a-2):
Figure imgf000068_0001
Here, methyl 2-(bromomethyl)-4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro- -isoxazol-3-yl]benzoate and ethyl hydrazine are used as starting material.
Reaction scheme 3 - Preparation method (b):
Figure imgf000068_0002
Here, 5-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro- isoxazol-3-yl]-2,3-dihydro-lH-isoindol-l-one and an acetic anhydride are used as starting material. Reaction scheme 4 - Preparation method (c):
Figure imgf000069_0001
Here, 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]-2-(hydroxymethyl)- N-methylbenzamide, methanesulfonyl chloride and triethylamine are used as starting material.
Reaction scheme 5 - Preparation method (d):
Figure imgf000069_0002
Here, 2-(bromomethyl)-4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro- isoxazol-3-yl]benzonitrile and l-(pyridin-2-yl)methaneamine are used sarting material.
Reaction scheme 6 - Preparation method Ce):
Figure imgf000069_0003
Here, 5-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro- isoxazol-3-yl]-2-(pyridin-2-ylmethyl)-2,3-dihydro-lH-isoindol-l-imine, acetyl chloride and tiretylamine are used as starting material.
Reaction scheme 7 - Preparation method ffl:
Figure imgf000070_0001
Here, 3-[3,4-bis(bromomethyl)phenyl]-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro- isoxazole, acetamide and sodium hydride are used as starting material.
Reaction scheme 7 - Preparation method (g):
Figure imgf000070_0002
Here, l,3-dichloro-5-(3,3,3-trifluoroprop-l-en-2-yl)benzene and N-hydroxy-l,3-dihydro -2-benzofuran-5-carboxyimidylchloride are used as starting material. Reaction scheme 8 - Preparation method (h):
Figure imgf000071_0001
Here,
5-[3-(3,5-dichlorophenyl)-4,4,4-trifluorobut-2-enoyl]-2-(pyridin-2-ylmethyl)~ 2,3-dihydro-lH-isoindol-l-one and hydroxyamine are used as starting material.
Reaction scheme 9 - Preparation method (ϊ):
Figure imgf000071_0002
Here, 5-[4-(3,5-dichlorophenyl)-4-(trifluoromethyl)~
3,4-dihydro-2H-pyrrol-2-yl]-2-(pyridin-2-ylmethyl)-2,3-dihydro-lH-isoindol-l-one is used as starting material. Reaction scheme 10 - Preparation method (i):
Figure imgf000072_0001
Here, l,3-dichloro-5-(3,3,3-trifluoroprop-l-en-2-yl)benzene and methyl l-[(tert-butoxycarbonyl- )amino]-N-[(trimethylsilyl)methyl]-2,3-dihydro-lH-inden-5-carboimide thioate are used as starting material.
Known compounds of formulae (II-a) and (II-b) can be obtained by reacting compounds of formula (XVII-a) or (XVII-b)
Figure imgf000072_0002
wherein (X)m, (Y)n, A, R1, Q and L2 have the same meaning as described herein, with a halogenating agent, such as chlorine, bromine, iodine, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, l,3-dichloro-5,5-hydantoin, l,3-dibromo-5,5-dimethylhydantoin, benzyl trimethyl ammonium tetrachloroiodate and sodium hypochlorite, if appropriate, in the presence of a catalyst (e.g. AIBN (2,2'-azabisisobutyronitrile) or benzoyl peroxide). Compounds of formulae (II-a) or (II-b) are for example methyl 2-(bromomethyl)~
4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]benzoate, methyl
2-(bromomethyl)-5-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]benzoate, methyl 2-(bromomethyl)-4-[5-(3,5-dichlorophenyl)-l-methyl-5-(trifluoromethyl)-4,5-di- hydro- lH-pyrazol-3-yl]benzoate, and methyl 2-(bromomethyl)-5-[5-(3,5-dichlorophenyl)~ 1 -methyl-5 -(trifluoromethyl)-4,5 -dihydro- 1 H-pyrazol-3 -yl]benzoate.
Compounds of formula (V-a) or (V-b) can be obtained through preparation method (a-1) and include 5-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]-2,3-
-dihydro- 1 H-isoindol- 1 -one, 6-[5 -(3 ,5 -dichlorophenyl)-5 -(trifluoromethyl)-4,5 -dihydro- isoxazol-3-yl]-2,3-dihydro-lH-isoindol-l-one, 5-[5-(3,5-dichlorophenyl)-l-methyl-
-5-(trifluoromethyl)-4,5-dihydro- 1 H-pyrazol-3 -yl]-2,3dihydro- 1 H-isoindol- 1 -one, and
6-[5-(3,5-dichlorophenyl)-l-methyl-5-(trifluoromethyl)-4,5dihydro-lH-pyrazol-3-yl]-2,3~ dihydro- 1 H-isoindol- 1 -one.
Compounds of formula (VII-a) or (VII-b) include for example 4-[5-(3,5-dichlorophenyl)~ 5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]-2-(hydroxymethyl)-N-methylbenzamide,
5-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]-2-(hydroxymethyl)-N- -methylbenzamide, 4-[5-(3,5-dichlorophenyl)-l-methyl-5-(trifluoromethyl)~
4,5-dihydro-lH-pyrazol-3-yl]-2-(hydroxymethyl)-N-methylbenzamide, and 5-[5-(3,5-dichloro- phenyl)-l-methyl-5-(trifluoromethyl)-4,5-dihydro-lH-pyrazol-3-yl]-2-(hydroxymethyl)-N-methyl- benzamide.
Compounds of formula (VII-a) or (VII-b) can be obtained by reacting a compound of formula (XDC-a) or (XlX-b), which can be obtained by using preparation method (a),
Figure imgf000074_0001
Figure imgf000074_0002
wherein (X)m, (Y)n, A, R1 and Q have the same meaning as described herein,
with a compound of formula (DC), if appropriate, in the presence of a base.
Compounds of formula (XIX-a) and (XIX-b) can be obtained according to preparation method (a) and according to the method disclosed in EP-A-I 362 856. For example by reacting compounds of formula (II-a) or (II-b) with sodium acetate to give the compounds of the formula (XX-a) and (XX-b), respectively
Figure imgf000074_0003
Figure imgf000074_0004
wherein (X)m, (Y)n, A, R1, Q and L2 have the same meaning as described herein, following reation with a base in alcohol.
Compounds of formula (XIX-a) or (XDC-b) include for example 5-[5-(3,5-dichlorophenyl)~ 5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]-2-benzofuran-l(3H)-one,
6-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]-2-benzofuran-l(3H)-one,
5-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]-2-benzofuran-l(3H)-one,
6-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]-2-benzofuran-l(3H)-one.
Compounds of formula (XX-a) and (XX-b) include for example Methyl 2-[(acetyloxy)methyl]-4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro- isoxazol-3-yl]benzoate, Methyl 2-[(acetyloxy)methyl]-5-[5-(3,5-dichlorophenyl)~
5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]benzoate, Methyl
2-[(acetyloxy)methyl]-4-[5-(3,5-dichlorophenyl)-l-methyl-5-(trifluoromethyl)~ 4,5-dihydro-lH-pyrazol-3-yl]benzoate, Methyl 2-[(acetyloxy)methyl]-5-[5-(3,5-dichlorophenyl)~ l-methyl-5-(trifluoromethyl)-4,5-dihydro-lH-pyrazol-3-yl]benzoate.
Compounds of formula (VHI-a) or (VIII-b) can be obtained according to the preparation method described herein for the preparation of compounds of formula (II-a).
Compounds of formula (Vπi-a) or (VIII-b) include for example 2-(bromomethyl)~ 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]benzonitrile, 2-(bromomethyl)-5-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro- soxazol-3-yl]benzonitrile, 2-(bromomethyl)-4-[5-(3,5-dichlorophenyl)- 1 -methyl-
-5-(trifluoromethyl)-4,5-dihydro-lH-pyrazol-3-yl]benzonitrile, and 2-(bromomethyl)~
5-[5-(3,5-dichlorophenyl)-l-methyl-5-(trifluoromethyl)-4,5-dihydro-lH-pyrazol-3-yl]benzonitrile.
Compounds of formula (DC) include for example methylamine, ethylamine, benzylamine, 2-pyridinomethylamine, and acetamide.
Compounds of formula (X-a) or (X-b) include for example 5-[5-(3,5-dichlorophenyl)~
5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]-2-(pyridin-2-ylmethyl)--
2,3 -dihydro- 1 H-isoindol- 1 -imine,
6-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]-2-(pyridin-2-ylmethyl)~ 2,3 -dihydro- 1 H-isoindol- 1 -imine,
5 -[5 -(3 ,5 -dichlorophenyl)- 1 -methyl-5 -(trifluoromethyl)-- 4,5-dihydro-lH-pyrazol-3-yl]-2-(pyridin-2-ylmethyl)-2,3-dihydro-lH-isoindol-l -imine, and
6-[5-(3,5-dichlorophenyl)-l-methyl-5-(trifluoromethyl)~ 4,5-dihydro-lH-p3τazol-3-yl]-2-(pyridin-2-ylmethyl)-2,3-dihydro-lH-isoindol-l -imine.
Compounds of formula (XVII-a) and (XVII-b) can be synthesized according to known methods (cf. WO2004/018410, WO2005/085216, Tetrahedron, 2000, VoI 56, 1057-1064, or WO2007/074789) and/or via preparation method (h) by using the compounds of formula (XVIII-a) or (XVIII-b) as starting material
Figure imgf000076_0001
wherein (X)m, (Y)n, R1 and Q have the same meaning as described herein, and reacting these compounds with a compound of formula (XV) or the hydrochloride acid salt therefrom, or, alternatively, with hydroxyamine or the hydrochloride acid salt therefrom, if appropriate, in the presence of a base.
Compounds of formula (XVII-a) or (XVII-b) are for example methyl 2-methyl-4-[5-(3,5-dichloro- phenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]benzoate, methyl 2-methyl-
-5-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]benzoate, methyl
2-methyl-4-[5-(3,5-dichlorophenyl)-l-methyl-5-(trifluoromethyl)~
4,5-dihydro-lH-pyrazol-3-yl]benzoate, and methyl 2-methyl-5-[5-(3,5-dichlorophenyl)-l-methyl- -5-(trifluoromethyl)-4,5-dihydro-lH-pyrazol-3-yl]benzoate.
Compounds of formula (XI) can be synthesized by diluting a compound of the formula (XXI)
Figure imgf000077_0001
wherein (X)n,, (Y)n, A, R1 and Q have the same meaning as described herein, with an appropriate diluent, for example dichloroethane, and then treating the mixture with a halogenating agent such as N-bromosuccinimide.
Compounds of formula (XI) include for example 3-[3,4-bis(bromomethyl)phenyl]- -5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazole, and
3-[3,4-bis(bromomethyl)phenyl]-5-(3,5-dichlorophenyl)-l-methyl-5-(trifluoromethyl)~ 4,5 -dihydro- 1 H-pyrazole. Compounds of formula (XXI) can be obtained based on the synthesizing route described for compounds of formula (XVII-a) or (XVII-b). Compounds of formula (XXI) include for example 5-(3,5-dichlorophenyl)-3-(3,4-dimethylphenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazole, 5-(3,5-dichlorophenyl)-3-(3,4-dimethylphenyl)-l-methyl-5-(trifluoromethyl)— 4,5-dihydro-lH-pyrazole.
Compounds of formula (XlI) are also described in The Journal of Organic Chemistry, 1991, VoI 56, 7336-7340, ibid, 1994, VoI 59, 2898-2901, Journal of Fluorine Chemistry, 1999, VoI 95, 167-170, orWO2005/05085216.
Compounds of formula (XII) include for example [l-(trifluoromethyl)vinyl]benzene, 1,3-difluoro- -5-[l-(trifluoromethyl)vinyl]benzene, l-chloro-3-[l-(trifluoromethyl)vinyl]benzene, 1,3-dichloro- -5-[ 1 -(trifluoromethyl)vinyl]benzene, 1 -trifluoromethyl-3 -[ 1 -(trifluoromethyl)vinyl]benzene,
1 -trifluoromethyl-4-[ 1 -(trifluoromethyl)vinyl]benzene, 1 ,3-bis(trifluoromethyl)-5-[ 1 -(trifluoro- methyl)vinyl]benzene, l,3-dibromo-5-[l-(trifluoromethyl)vinyl]benzene, and l,2,3-trichloro-5-[l- -(trifluoromethyl)vinyl]benzene, 1 -fluoro-2-(trifluoromethyl)-4-[ 1 -(trifluoromethyl)vinyl]benzene.
Compounds of formula (XIII) can be obtained by reacting compounds of formula (XXII)
Figure imgf000078_0001
wherein W1 to W4 and (Y)n have the same meaning as described herein, with a halogenating agent. Compounds of formula (XXII) can be obtained by reacting compounds of the formula (XXIII)
Figure imgf000079_0001
wherein W1 to W4 and (Y)n have the same meaning as described herein, with hydroxyamine or a salt thereof.
Compounds of formula (XXIϋ) include for example lH-indol-5-carbaldehyde,
t-butyl 5-formyl-lH-indol-l-carboxyate, lH-indol-6-carbaldehyde,
t-butyl 6-formyl- 1 H-indol- 1 -carboxyate, 2,3-dihydro- 1 H-indol-5-carbaldehyde,
t-butyl 5-formyl-2,3-dihydro-lH-indol-l-arboxyate, l-oxo-2,3-dihydro-lH-inden-5-carbaldehyde, 5-oxo-5,6,7,8-tetrahydronaphthalen-2-carbaldehyde, 2,3-dihydro-l-benzofuran-5-carbaldehyde, l,3-benzdioxol-5-carbaldehyde, l,4-benzodioxan-6-carbaldehyde, l-oxo-l,3-dihydro-2-benzo- furan-5-carbaldehyde, and 1 -oxo-2-(pyridin-2-ylmethyl)-2,3-dihydro-lH-isoindol-5-carbaldehyde.
Reaction scheme 11 and 12 - Methods for the preparation of compounds of formula (XXIID:
Reaction scheme 11 for synthesizing t-butyl 5-formyl-lH-indol-l-carboxyate (Sl-IT) and t-butyl 5-formyl-2.3-dihvdro-lH-indol-l -carboxyate (S 1 -IV):
Figure imgf000080_0001
(wherein, Boc represents a t-butoxycarbonyl group, MeCN represents acetonitrile, cat.DMAP represents a catalytic amount of 4-dimethylaminopyridine, Pd-C represents palladium charcoal and ETOH represents ethanol).
Reaction scheme 12 for synthesizing l-oxo-2,3-dihvdro-lH-inden-5-carbaldehyde:
Figure imgf000080_0002
(wherein, Ac represents an acetyl group, DPPP represents l,3-bis(diphenylphosphino)propane, Et3N represents triethylamine, DMF represents dimethylformamide, and Me represents a methyl group). 5-Oxo-5,6,7,8-tetrahydronaphthalen-2-carbaldehyde can be synthesized in the same manner as the method of Scheme 12 , by using 6-bromo-3,4-dihydronaphthalen-l(2H)-one as starting material.
Halogenating agents which are suitable for the preparation of compounds of the formula (XIII) include chlorine, bromine, iodine, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, l,3-dichloro-5,5-hydantoin, l,3-dibromo-5,5-dimethylhydantoin, benzyl trimethyl ammonium tetrachloroiodate, and sodium hypochlorite.
Compounds of formula (XXIH) include for example N-hydroxy-lH-indol-5-carboxyimidoyl chloride, t-butyl 5-[chloro(hydroxyimino)methyl]-lH-indol-l-carboxyate, t-butyl-5-[chloro- (hydroxyimino)methyl]-2,3-dihydro-lH-indol-l-carboxyate, N-hydroxy-lH-indol-6-carboxy- imidoyl chloride, N-hydroxy-2,3-dihydro-l-benzofuran-5-carboxyimidoyl chloride, N-hydroxy-l,3-benzodioxol-5-carboxyimidoyl chloride, N-hydroxy-2,3-dihydro-l,4-benzo- dioxin-6-carboxyimidoyl chloride, N-hydroxy-l-oxo-l,3-dihydro-2-benzofuran-5-carboxyimidoyl chloride, N-hydroxy-l-oxo-2-(pyridin-2-ylmethyl)-2,3-dihydro-lH-isoindol-5-carboxyimidoyl chloride and N-hydroxy-l-oxo-2,3-dihydro-lH-inden-5-carboxyimidyl chloride.
With respect to preparation method (g), once an isoxazoline ring is constructed, substitution with various substituents can be made. Reaction scheme 13 and Reaction scheme 14 show synthetic method examples to introduce substituents.
Reaction scheme 13 for synthesizing 2.3-dihydro-lH-indole derivatives:
Figure imgf000082_0001
(wherein, c.HCl represents concentrated hydrochloric acid, Et represents an ethyl group, heat represents a heating treatment and THF represents tetrahydrofuran).
Reaction scheme 14 for synthesizing 2.3-dihvdro-lH-inden-l -amine derivatives:
Figure imgf000083_0001
(wherein, Me represents a methyl group, DEAD represents diethyl azodicarboxyate, Ph represents a phenyl group, Et represents an ethyl group, and THF represents tetrahydrofuran).
Preparation method (g) can be applied to the synthetic method comprising reacting the compounds of formula (XXXI) which fall under the general formula (XXXI-a):
Figure imgf000083_0002
wherein R2, W1 to W4 and (Y)n have the same meaning as described herein, with the compounds of formula (XII) described herein. The invention is further directed to useful intermediate compounds of formula (XXXI-a) for the preparation of compounds according the invention
Figure imgf000084_0001
wherein T2 stands for O, N-OH and N-NH-R2, and W1 to W4 and (Y)n have the same meaning as defined herein.
Compounds of the formula (XXII), (XXIII) and (XXXII), which are useful intermediates for the preparation of compounds according to the invention, are represented by the formula (XXXI-a).
Compounds of formula (XXXI) can be prepared using the same preparation methods as described for compounds of formula (XIII), however, starting with (XXXII).
Figure imgf000084_0002
The compounds of formula (XIV), which are useful intermediates for the preparation of compounds according to the invention, can be obtained by reacting compounds of formula (XXIV)
Figure imgf000084_0003
wherein W1 to W4, (X)m, (Y)n, R1 and Q have the same meaning as described herein
with thionyl chloride.
Compounds of formula (XXIV) are for example 3-(3,5-dichlorophenyl)~ 4,4,4-trifiuoro-3-hydroxy-l -(lH-indol-5-yl)butan-l -one, 5-[3-(3,5-dichlorophenyl)-4,4,4-trifluoro- -3-hydroxybutanoyl]-2-benzofuran-l(3H)-one, 5-[3-(3,5-dichlorophenyl)-4,4,4-trifluoro-
-3-hydroxybutanoyl]-2-(pyridin-2-ylmethyl)-2,3-dihydro-lH-isoindol-l-one, 3-(3,4,5-trichloro- phenyl)-4,4,4-trifluoro-3-hydroxy-l-(lH-indol-5-yl)butan-l-one, 5-[3-(3,4,5-trichlorophenyl)— 4,4,4-trifluoro-3-hydroxybutanoyl]-2-benzofuran-l(3H)-one, 5-[3-(3,4,5-trichlorophenyl)~
4,4,4-trifluoro-3-hydroxybutanoyl]-2-(pyridin-2-ylmethyl)-2,3-dihydro-lH-isoindol-l-one, 3-[3,5-bis(trifluoromethyl)phenyl]-4,4,4-trifluoro-3-hydroxy-l-(lH-indol-5-yl)butan-l-one,
5-{3-[3,5-bis(trifluoromethyl)phenyl]-4,4,4-trifluoro-3-hydroxybutanoyl}-2-benzofuran-l(3H)~ one, 5-{3-[3,5-bis(trifluoromethyl)phenyl]-4,4,4-trifluoro-3-hydroxybutanoyl}-2-(pyridin-2~ ylmethyl)-2,3-dihydro-lH-isoindol-l-one.
Compounds of formula (XXlV) can be synthesized according to a method disclosed in Zhurnal Organicheskoi Khimii, VoI 28 (No. 3), 518-526, namely by reacting the compound represented by the formula (XXV)
Figure imgf000085_0001
(wherein (X)m, Q and R1 have the same meaning as described herein) with the compound represented by the following formula (XXVI):
Figure imgf000086_0001
(wherein W1 to W4 and (Y)n have the same meaning as described herein).
Compounds of formula (XXV) include for example trifluoroacetophenone, 3',5'-dichloro-2,2,2-trifluoroacetophenone, 3',4'-dichloro-2,2,2-trifluoroacetophenone, 3',4',5'- -trichloro-2,2,2-trifluoroacetophenone, 3 '-fluoro-2,2,2-trifiuoroacetophenone, 3 '-chloro— 2,2,2-trifiuoroacetophenone, 3 '-bromo-2,2,2-trifluoroacetophenone, 3 '-iodo-2,2,2-trifluoroaceto- phenone, 3'-nitro-2,2,2-trifluoroacetophenone, 3'-cyano-2,2,2-trifluoroacetophenone, 3'-(trifluoro- methyl)-2,2,2-trifluoroacetophenone, and 3 ',5 '-bis(trifluoromethyl)-2,2,2-trifluoroacetophenone.
Compounds of formula (XXVI) include for example 5-acetylindane, 6-acetyltetraline, 3',4'-(methylenedioxy)acetophenone, 1, 4-benzodioxane-6-yl methyl ketone, 5-acetyl-2,3-dihydro- -1-benzofuran, 5-acetyl-lH-indole, 5-acetyl-2-benzofuran-l(3H)-one, and 5-acetyl-2-(pyridin-2-yl- methyl)-2,3-dihydro- 1 H-isoindol- 1 -one.
Compounds of formula (XlV) include for example 3-(3,5-dichlorophenyl)-4,4,4- -trifluoro-l-(lH-indol-5-yl)but-2-ene-l-one, 5-[3-(3,5-dichlorophenyl)-4,4,4-trifluoro-2-enoyl]-2-
-benzofuran-l(3H)-one, 5-[3-(3,5-dichlorophenyl)-4,4,4-trifluorobut-2-enoyl]-2-(pyridin-
-2-ylmethyl)-2,3-dihydro- 1 H-isoindol- 1 -one, 3 -(3 ,4,5-trichlorophenyl)-4,4,4-trifluoro- 1 -( 1 H-indol-
-5-yl)but-2-ene-l-one, 5-[3-(3,4,5-trichlorophenyl)-4,4,4-trifluoro-2-enoyl]-2-benzofuran-l(3H)-- one, 5-[3-(3,4,5-trichlorophenyl)-4,4,4-trifluorobut-2-enoyl]-2-(pyridin-2-ylmethyl)-2,3-dihydro- -1 H-isoindol- 1 -one, 3-[3,5-bis(trifluoromethyl)phenyl]-4,4,4-trifluoro-l-(lH-indol-5-yl)but-
-2-ene-l-one, 5-{3-[3,5-bis(trifluoromethyl)phenyl]-4,4,4-trifluoro-2-enoyl}-2-benzofuran-l(3H)~ one, and 5- {3-[3,5-bis(trifluoromethyl)phenyl]-4,4,4-trifluorobut-2-enoyl} -2-(pyridin-2-yl- methyl)-2,3-dihydro- 1 H-isoindol- 1 -one.
Preparation method (h) can also be used to prepare compounds of formula (XVII-a) and (XVII-b) from the compounds of formula (XVIU-a) and (XVIII-b).
Compounds of formula (XVI) can be synthesized according to the method disclosed in EP-A- 1 538 138, namely by reacting the compound represented by the formula (XXVII):
Figure imgf000087_0001
(wherein W1 to W4 and (Y)n have the same meaning as described herein).
with the compound of formula (XII), if appropriate, in the presence of a metal catalyst (e.g. copper(II)oxide).
Representative examples of the compound of formula (XVI) include 5-[4-(3,5-dichlorophenyl)~ 4-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-2-yl]-2-(pyridin-2-ylmethyl)~
2,3-dihydro-lH-isoindol-l-one, N-[5-[4-(3,5-dichlorophenyl)-4-(trifluoromethyl)~
3,4-dihydro-2H-pyrrol-2-yl]-2-(pyridin-2-ylmethyl)-2,3-dihydro-lH-isoindol-l-yliden]acetamide, and 4-(3,5-dichlorophenyl)-2-(l,3-dihydro-2-benzofuran-5-yl)-4-(trifluoromethyl)~
3 ,4-dihydro-2H-pyrrole.
The compound of formula (XXVII) can be synthesized according to the method disclosed in Chem. Lett., 1977, 697-698, or by reacting compounds of the formula (XXVIII)
Figure imgf000088_0001
(wherein W1 to W4 and (Y)n have the same meaning as described herein)
with ethyl formate, to obtain the compound of the formula (XXIX):
Figure imgf000088_0002
followed by steps of halogenation and dehydrohalogenation.
Compounds of formula (XXVI) include for example 5-(isocyanomethyl)-2-(pyridin-2-ylmethyl)~ 2,3-dihydro-lH-isoindol-l-one, N-[5-(isocyanomethyl)-2-(pyridin-2-ylmethyl)--
2,3-dihydro-lH-isoindol-l -ylidenjacetamide, and 1 ,3-dihydro-2-benzofuran-5-ylmethylisocyanide.
Reaction Scheme 15 for the preparation of the compounds of formula (XXVIID
Figure imgf000088_0003
(wherein DMF represents N,N-dimethylformamide and dioxane represents 1,4-dioxane).
Compounds of formula (XXIX) include for example N-{[l-oxo-2-(pyridin-2-ylmethyl)- 2,3-dihydro-lH-isoindol-5-yl]methyl}formamide, N-[5-[(formylamino)methyl]-2-(pyridin-2-ylmethyl)-2,3-dihydro-lH-isoindol-l-yliden]acetamide.
Reaction scheme 16 for the preparation of the compounds of formula (XXX):
Figure imgf000089_0001
(wherein, Me stands for methyl, (Ph3P)4Pd stands for tetrakistriphenylphosphine palladium, c.HCl stands for concentrated hydrochloric acid, Ac stands for an acetyl group, reflux stands for a heating treatment, EDC stands for l-ethyl-3-(3-dimethylaminopropyl)-carbodiimide, DMAP stands for dimethylaminopyridine, TMS stands for a trimethylsilyl group, Boc rep stands for a t-butoxycarbonyl group, toluene stands for toluene, Lawesson reagent stands for
2,4-bis(4-methoxyphenyl)-l,3-dithia-2,4-diphosphetane-2,4-disulfϊde, BuO-t represents a t-butoxy group, THF stands for tetrahydrofuran, and t-BuOK stands for t-butoxy potassium). Compounds of formula (XXX) include for example methyl l-[(t-butoxycarbonyl)amino-
]-N-[(trimethylsilyl)methyl]-2,3-dihydro-lH-inden-5-carboimide thioate, methyl
5-[(t-butoxycarbonyl)amino]-N-[(trimethylsilyl)methyl]-5,6,7,8-tetrahydro- naphthalen-2-carboimide thioate, methyl 5-[(t-butoxycarbonyl)amino]-N-[(trimethylsilyl)- methyl]naphthalen-2-carboimide thioate, methyl 6-[(t-butoxycarbonyl)amino]-N-[(trimethylsilyl)- methyl]naphthalen-2-carboimide thioate.
Methyl 5-[(t-butoxycarbonyl)amino]-N-[(trimethylsilyl)methyl]-5,6,7,8-tetrahydronaphthalen-2~ carboimide thioate can be synthesized according to the method shown in reaction scheme 16, by using 6-bromo-3,4-dihydronaphthalen-l(2H)-one as a starting material.
The compounds of formula (XXX) are intermediates for the preparation of compounds according to the invention. Namely, as compounds according to the invention can be prepared by reacting a compound of formula (XII) with compounds of formula (XXX) in the presence of a fluorine reagent if R4' does not stands for H. In case that R4' stands for H, the reaction can be carried out in a one pot reaction by firstly adding an alkylating reagent, such as methyl iodide and then adding an appropriate fluorine reagent.
With respect to preparation method (j), once a pyrroline ring part is constructed, substitution with various substituents can be made.
Reaction scheme 17 shows a synthetic method example for introducing various substituents on condensed-ring moiety. Reaction scheme 17
Figure imgf000091_0001
(wherein, Bu-t represents a t-butyl group, Et represents an ethyl group and THF represents tetrahydrofuran) .
Appropriate diluents for the preparation methods disclosed herein, particularly for preparation methods (a-1), (a-2), (b), (c), (d), (e), (f), (g), (i) include aliphatic, alicyclic, and aromatic hydrocarbons (which may be chlorinated in some cases), for example, pentane, hexane, cyclo- hexane, petroleum ether, ligroin, benzene, toluene, xylene, chlorobenzene, dichlorobenzene and the like; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM) and the like; ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone, methyl isobutyl ketone (MIBK) and the like; nitriles, for example, acetonitrile, propionitrile and the like; esters, for example, ethyl acetate, amyl acetate and the like; acid amides, for example, dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, l,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide (HMPA) and the like; sulfones and sulfoxides, for example, dimethylsulfoxide (DMSO), sulforane and the like; and bases, for example, pyridine and the like. Appropriate diluents for the preparation method (j) include for example aliphatic, alicyclic, and aromatic hydrocarbons (which may be chlorinated in some cases), for example, pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1 ,2-dichloroethane, chlorobenzene, dichlorobenzene and the like; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM) and the like; ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone, methyl isobutyl ketone (MIBK) and the like; nitriles, for example, acetonitrile, propionitrile, acrylonitrile and the like; esters, for example, ethyl acetate, amyl acetate and the like.
Appropriate bases for the preparation methods disclosed herein, particularly for preparation methods (a-1), (a-2), (b), (c), (d), (e), (f), (g) include inorganic bases such as hydrides, hydroxides, carbonates and bicarbonates of alkaline metals and alkaline earth metals, for example, sodium hydride, lithium hydride, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and the like; and organic bases such as alcoholate, tertiary amines, dialkyl- aminoanilines and pyridines, for example, triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP), l,4-diazabicyclo[2,2,2]octane (DABCO), and l,8-diazabicyclo[5,4,0]undec-7-ene (DBU) and the like.
Further appropriate bases, particularly for the preparation methods (i) and (h) are alkaline metal bases, such as for example, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, potassium-tert-butoxide and the like; and an organic base such as triethylamine, diisopropylethylamine, tributylamine, N-methylmorpholine, N,N-dimethylaniline, N,N-diethylaniline, 4-tert-butyl-N,N-dimethylaniline, pyridine, picoline, lutidine, diazabicyclo- undecene, diazabicyclooctane, imidazole and the like.
The preparation methods disclosed herein, particularly the preparation methods (a-1), (a-2), (b), (c), (d), (e), (f), (g), (i) can be carried out within a substantially broad range of temperatures, i.e. in range of -78 0C to about 200 0C. Generally, it can be carried out at a temperature in the range of about 10 to about 1500C, preferably in the range of about 30 to about 12 00C. They can be carried out at any pressure, i.e. at a pressure of about 1013 mbar, at a pressure lower than 1013 mbar and a pressure higher than 1013 mbar. Reaction time may vary from about 0.1 hours to about 72 hours, preferably from 1 to 24 hours.
Preparation method (j) can be carried out within a substantially broad range of temperatures, generally, it can be carried out at a temperature in a range of about -78 and about 1000C, preferably in a range of about -10 and about 500C. In addition, although the above-described reaction is preferably carried out at normal pressure, it can also be carried out under increased or reduced pressure. Reaction time is from 0.1 to 10 hours, and preferably from 1 to 5 hours.
The compounds according to the present invention show a potent insecticidal action and can therefore be used as an insecticide. Furthermore, the compounds according to the present invention exhibit a strong control effect against harmful insects, without imposing any harmful side effects of drug to cultivated plants.
The compounds of the present invention can thus be used for the control of a wide range of pest species, for example, harmful sucking insects, chewing insects, as well as other plant parasitic pests, storage insects, hygiene pests and the like, and can be applied for the purpose of disinfestations and extermination thereof. Harmful animal pest are for example:
As for insects, coleopterans, for example, Callosobruchus cninensis, Sitophilus zeamais, Tribolium castaneum, Epilachna vigintioctomaculata, Agriotes fuscicollis, Anomala rufocuprea, Leptinotarsa decemlineata, Diabrotica spp., Monochamus alternatus, Lissorhoptrus oryzophilus, Lyctus bruneus,
Aulacophora femoralis; lepidopterans, 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, Phyllocnistis citrella; hemipterans, for example, Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki, Unaspis yanonensis, Myzus persicas, Aphis pomi, Aphis gossypii, Rhopalosiphum pseudobrassicas, Stephanitis nashi, Nezara spp., Trialeurodes vaporariorm, Psylla spp.; thysanopterans, for example, Thrips palmi, Franklinella occidental; orthopterans, for example, Blatella germanica, Periplaneta americana, gryllotalpa Africana, Locusta migratoria migratoriodes; isopterans, for example, Reticulitermes speratus, Coptotermes formosanus; dipterans, for example, Musca domestica, Aedes aegypti, Hylemia platura, Culex pipiens, Anopheles sinensis, Culex tritaeniorhynchus, Liriomyza trifolii.
As for acari, for example, Tetranychus cinnabarinus, Tetranychus urticae, Panonychus citri, Aculops pelekassi, Tarsonemus spp.
As for nematodes, for example, Meloidogyne incognita, Bursaphelenchus lignicolus Mamiya et Kiyohara, Aphelenchoides besseyi, Heterodera glycines, Pratylenchus spp..
Additionally, the compounds according to the present invention show a good plant tolerance and favourable toxicity to warm-blooded animals and being tolerated well by the environment, and thus are suitable for protecting plants and plant parts.
Application of the compounds of the invention may result in increasing the harvest yields, improving the quality of the harvested material. Additionally, the compounds can be used for controlling animal pests, in particular insects, arachnids, helminths, nematodes and molluscs, which are encountered in agriculture, in horticulture, the field of veterinary medicine, in forests, in gardens and leisure facilities, in the protection of stored products and of materials, and in the hygiene sector. They may be preferably employed as plant protection agents. They are active against normally sensitive and resistant species and against all or some stages of development. These pests include inter alia:
From the order of the Anoplura (Phthiraptera), for example, Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectes spp.
From the class of the Arachnida, for example, 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, Eutetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans, Metatetranychus spp., Oligonychus spp., Ornithodoros spp., Panonychus spp., Phyllocoptmta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scoφio maurus, Stenotarsonemus spp., Tarsonemus spp., Tetranychus spp., Vasates lycopersici.
From the class of the Bivalva, for example, Dreissena spp.
From the order of the Chilopoda, for example, geophilus spp., Scutigera spp.
From the order of the Coleoptera, for example, Acanthoscelides obtectus, Adoretus spp., Agelastica ami, 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 zealandica, Curculio spp., Cryptorhynchus lapathi, Dermestes spp., Diabrotica spp., Epilachna spp., Faustinus cubae, gibbium psylloides, Heteronychus arator, Hylamoφha 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., Trogo- derma spp., Tychius spp., Xylotrechus spp., Zabrus spp.
From the order of the Collembola, for example, Onychiurus armatus.
From the order of the Dermaptera, for example, Forficula auricularia.
From the order of the Diplopoda, for example, Blaniulus guttulatus.
From the order of the Diptera, for example, 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, Wohlfahrtia spp.
From the class of the gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.
From the class of the helminths, for example, 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 medinensis, Echinococcus granulosus, Echinococcus multilocularis, 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, Wuchereria bancrofti.
It is furthermore possible to control protozoa, such as Eimeria.
From the order of the Heteroptera, for example, 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., Horcias nobilellus, Leptocorisa spp., Leptoglossus phyllopus, Lygus spp.,
Macropes excavatus, Miridae, Nezara spp., Oebalus spp., Pentomidae, Piesma quadrata, Piezodorus spp., Psallus seriatus, Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp.
From the order of the Homoptera, for example, 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 fϊcus, Cicadulina mbila, Coccomytilus halli, Coccus spp., Cryptomyzus 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 fϊmbriolata, Melanaphis sacchari, Metcalfiella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp., Nasonovia ribisnigri, Nephotettix spp., Nilaparvata lugens, Oncometopia spp., Orthezia praelonga, Parabemisia myricae, Paratrioza 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., Quesada 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., Viteus vitifolii.
From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
From the order of the Isopoda, for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber.
From the order of the Isoptera, for example, Reticulitermes spp., Odontotermes spp.
From the order of the Lepidoptera, for example, Acronicta major, Aedia leucomelas, Agrotis spp., Alabama argillacea, Anticarsia spp., Barathra brassicae, Bucculatrix thurberiella, Bupalus piniarius, Cacoecia podana, Capua reticulana, Caφocapsa pomonella, Cheimatobia brumata, Chilo spp., Choristoneura fumiferana, Clysia ambiguella, Cnaphalocerus spp., Earias insulana, Ephestia kuehniella, Euproctis chrysorrhoea, Euxoa spp., Feltia spp., galleria mellonella, Helicoveφa 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, Trichoplusia spp. From the order of the Orthoptera, for example, Acheta domesticus, Blatta orientalis,
Blattella germanica, gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria.
From the order of the Siphonaptera, for example, Ceratophyllus spp., Xenopsylla cheopis.
From the order of the Symphyla, for example, Scutigerella immaculata.
From the order of the Thysanoptera, for example, Baliothrips biformis, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentarus, Scirtothrips spp., Taeniothrips cardamoni, Thrips spp.
From the order of the Thysanura, for example, Lepisma saccharina.
The phytoparasitic nematodes include, for example, 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., Tylenchulus semipenetrans, Xiphinema spp.
All plants and plant parts can be treated in accordance with the invention. Plants are to be understood as meaning in the present context all plants and plant populations such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional plant breeding and optimization methods or by biotechnological and genetic engineering methods or by combinations of these methods, including the transgenic plants and including the plant cultivars protectable or not protectable by plant breeders' rights. Plant parts are to be understood as meaning all parts and organs of plants above and below the ground, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes. The plant parts also include harvested material, and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.
Treatment according to the invention of the plants and plant parts with the active compounds is carried out directly or by allowing the compounds to act on their surroundings, habitat or storage space by the customary treatment methods, for example by immersion, spraying, evaporation, fogging, scattering, painting on, injecting and, in the case of propagation material, in particular in the case of seed, also by applying one or more coats.
As already mentioned above, it is possible to treat all plants and their parts according to the invention. In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and parts thereof, are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering methods, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof, are treated. The terms "parts", "parts of plants" and "plant parts" have been explained above.
Particularly preferably, plants of the plant cultivars which are in each case commercially available or in use are treated according to the invention. Plant cultivars are understood as meaning plants having novel properties ("traits") which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be cultivars, bio- or genotypes.
Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive "synergistic") effects. Thus, for example, reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the substances and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, higher quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products are possible, which exceed the effects which were actually to be expected.
The preferred transgenic plants or plant cultivars (obtained by genetic engineering) which are to be treated according to the invention include all plants which, by virtue of the genetic modification, received genetic material which imparts particularly advantageous, useful traits to these plants. Examples of such traits are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, higher quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products. Further and particularly emphasized examples of such traits are a better defence of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses, and also increased tolerance of the plants to certain herbicidally active compounds. Examples of transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice), maize, soya beans, potatoes, sugar beet, tomatoes, peas and other vegetable varieties, cotton, tobacco, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes), and particular emphasis is given to maize, soya beans, potatoes, cotton, tobacco and oilseed rape. Traits that are emphasized in particular are the increased defence of the plants against insects, arachnids, nematodes and slugs and snails by virtue of toxins formed in the plants, in particular those formed in the plants by the genetic material from Bacillus thuringiensis (for example by the genes CryΙA(a), CryΙA(b), CryΙA(c), CryllA, CrylllA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF and also combinations thereof) (referred to hereinbelow as "Bt plants"). Traits that are also particularly emphasized are the increased defence of the plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. Traits that are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulphonylureas, glyphosate or phosphinotricin (for example the "PAT" gene). The genes which impart the desired traits in question can also be present in combination with one another in the transgenic plants. Examples of "Bt plants" which may be mentioned are maize varieties, cotton varieties, soya bean varieties and potato varieties which are sold under the trade names YIELD gARD® (for example maize, cotton, soya beans), KnockOut® (for example maize), StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants which may be mentioned are maize varieties, cotton varieties and soya bean varieties which are sold under the trade names Roundup Ready® (tolerance to glyphosate, for example maize, cotton, soya beans), Liberty Link® (tolerance to phosphinotricin, for example oilseed rape), IMI® (tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, for example maize). Herbicide-resistant plants (plants bred in a conventional manner for herbicide tolerance) which may be mentioned include the varieties sold under the name Clearfϊeld® (for example maize). Of course, these statements also apply to plant cultivars having these genetic traits or genetic traits still to be developed, which plant cultivars will be developed and/or marketed in the future.
The plants listed can be treated according to the invention in a particularly advantageous manner with the compounds according to the invention at a suitable concentration.
Furthermore, in the field of veterinary medicine, the novel compounds of the present invention can be effectively used against various harmful animal parasitic pests (endoparasites and ectoparasites), for example, insects and helminthes. Examples of such animal parasitic pests include the pests as described below. Examples of the insects include gasterophilus spp., Stomoxys spp., Trichodectes spp., Rhodnius 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 fields, i.e. in the field of veterinary medicine, the active compounds according to the present invention are active against animal parasites, in particular ectoparasites or endoparasites. The term endoparasites includes in particular helminths, such as cestodes, nematodes or trematodes, and protozoae, such as coccidia. Ectoparasites are typically and preferably arthropods, in particular insects such as flies (stinging and licking), parasitic fly larvae, lice, hair lice, bird lice, fleas and the like; or acarids, such as ticks, for examples hard ticks or soft ticks, or mites, such as scab mites, harvest mites, bird mites and the like.
These parasites include:
From the order of the Anoplurida, for example Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.; particular examples are: 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, Solenopotes capillatus;
from the order of the Mallophagida and the suborders Amblycerina and Ischnocerina, for example Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.; particular examples are: Bovicola bovis, Bovicola ovis, Bovicola limbata, Damalina bovis, Trichodectes canis, Felicola subrostratus, Bovicola caprae, Lepikentron ovis, Werneckiella equi;
from the order of the Diptera and the suborders Nematocerina and Brachycerina, for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Odagmia spp., Wilhelmia spp., Hybomitra 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., Tipula spp.; particular examples are: 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 paludosa, 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, Melophagus ovinus, Lipoptena capreoli, Lipoptena cervi, Hippobosca variegata, Hippobosca equina, gasterophilus intestinalis, gasterophilus haemorroidalis, gasterophilus inermis, gasterophilus nasalis, gasterophilus nigricornis, gasterophilus pecorum, Braula coeca;
from the order of the Siphonapterida, for example Pulex spp., Ctenocephalides spp., Tunga spp., Xenopsylla spp., Ceratophyllus spp.; particular examples are: Ctenocephalides cards, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis;
from the order of the Heteropterida, for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.
From the order of the Blattarida, for example Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp. (e.g. Suppella longipalpa); From the subclass of the Acari (Acarina) and the orders of the Meta- and Mesostigmata, for example Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Rhipicephalus (Boophilus) spp Dermacentor spp., Haemophysalis spp., Hyalomma spp., Dermanyssus spp., Rhipicephalus spp. (the original genus of multi host ticks) Ornithonyssus spp., Pneumonyssus spp., Raillietia spp., Pneumonyssus spp., Stemostoma spp., Varroa spp., Acarapis spp.; particular examples are: Argas persicus, Argas reflexus, Ornithodorus moubata, Otobius megnini, Rhipicephalus (Boophilus) microplus, Rhipicephalus (Boophilus) decoloratus, Rhipicephalus (Boophilus) annulatus, Rhipicephalus (Boophilus) calceratus, Hyalomma anatolicum, 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, Varroa jacobsoni;
from the order of the 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., Laminosioptes spp.; particular examples are: Cheyletiella yasguri, Cheyletiella blakei, Demodex canis, Demodex bovis, Demodex ovis, Demodex caprae, Demodex equi, Demodex caballi, Demodex suis, Neotrombicula autumnalis, Neotrombicula desaleri, Neoschδngastia xerothermobia, Trombicula akamushi, Otodectes cynotis,
Notoedres cati, Sarcoptis canis, Sarcoptes bovis, Sarcoptes ovis, Sarcoptes rupicaprae (=S. caprae), Sarcoptes equi, Sarcoptes suis, Psoroptes ovis, Psoroptes cuniculi, Psoroptes equi, Chorioptes bovis, Psoergates ovis, Pneumonyssoidic mange, Pneumonyssoides caninum, Acarapis woodi.
The active compounds according to the invention are also suitable for controlling arthropods, helminths and protozoae, which attack animals. Animals include agricultural livestock such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, cultured fish, honeybees. Moreover, animals include domestic animals - also referred to as companion animals - such as, for example, dogs, cats, cage birds, aquarium fish and what are known as experimental animals such as, for example, hamsters, guinea pigs, rats and mice.
By controlling these arthropods, helminths and/or protozoae, it is intended to reduce deaths and improve performance (in the case of meat, milk, wool, hides, eggs, honey and the like) and health of the host animal, so that more economical and simpler animal keeping is made possible by the use of the active compounds according to the invention.
For example, it is desirable to prevent or interrupt the uptake of blood by the parasites from the hosts (when applicable). Also, controlling the parasites may help to prevent the transmittance of infectious agents.
The term "controlling" as used herein with regard to the veterinary field, means that the active compounds are effective in reducing the incidence of the respective parasite in an animal infected with such parasites to innocuous levels. More specifically, "controlling", as used herein, means that the active compound is effective in killing the respective parasite, inhibiting its growth, or inhibiting its proliferation.
According to a preferred embodiment the compounds of the present invention are used in the control of ectoparasitic arthropods (as mentioned above) on animals, namely on agricultural livestock or on domestic animals.
Generally, when used for the treatment of animals the active compounds according to the invention can be applied directly. Preferably they are applied as pharmaceutical compositions which may contain pharmaceutically acceptable excipients and/or auxiliaries which are known in the art.
In the veterinary field and in animal keeping, the active compounds are applied (= administered) in the known manner by enteral administration in the form of, for example, tablets, capsules, drinks, drenches, granules, pastes, boluses, the feed-through method, suppositories; by parenteral administration, such as, for example, by injections (intramuscular, subcutaneous, intravenous, intraperitoneal and the like), implants, by nasal application, by dermal application in the form of, for example, bathing or dipping, spraying, pouring-on and spotting-on, washing, dusting, and with the aid of active-compound-comprising shaped articles such as collars, ear tags, tail tags, limb bands, halters, marking devices and the like. The active compounds may be formulated as shampoo or as suitable formulations usable in aerosols, unpressurized sprays, for example pump sprays and atomizer sprays.
When used for livestock, poultry, domestic animals and the like, the active compounds according to the invention can be applied as formulations (for example powders, wettable powders ["WP"], emulsions, emulsifiable concentrates ["EC"], flowables, homogeneous solutions, and suspension concentrates ["SC"]) which comprise the active compounds in an amount of from 1 to 80% by weight, either directly or after dilution (e.g. 100- to 10 000-fold dilution), or else as a chemical bath.
When used in the veterinary field the active compounds according to the invention may be used in combination with suitable synergists or other active compounds, such as for example, acaricides, insecticides, anthelmintics, anti-protozoal drugs. In the present invention, a substance having an insecticidal action against pests including all of these is referred to as an insecticide.
An active compound of the present invention can be prepared in conventional formulation forms, when used as an insecticide. Examples of the formulation forms include solutions, emulsions, wettable powders, water dispersible granules, suspensions, powders, foams, pastes, tablets, granules, aerosols, active compound-infiltrated natural and synthetic materials, microcapsules, seed coating agents, formulations used with a combustion apparatus (for example, fumigation and smoking cartridges, cans, coils or the like as the combustion apparatus), ULV (cold mist, warm mist), and the like.
These formulations can be produced by methods that are known per se. For example, a formulation can be produced by mixing the active compound with a developer, that is, a liquid diluent or carrier; a liquefied gas diluent or carrier; a solid diluent or carrier, and optionally with a surfactant, that is, an emulsifier and/or dispersant and/or foaming agent.
In the case where water is used as the developer, for example, an organic solvent can also be used as an auxiliary solvent.
Examples of the liquid diluent or carrier include aromatic hydrocarbons (for example, xylene, toluene, alkylnaphthalene and the like), chlorinated aromatic or chlorinated aliphatic hydrocarbons (for example, chlorobenzenes, ethylene chlorides, methylene chlorides), aliphatic hydrocarbons (for example, cyclohexanes), paraffins (for example, mineral oil fractions), alcohols (for example, butanol, glycols and their ethers, esters and the like), ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like), strongly polar solvents (for example, dimethylformamide, dimethylsulfoxide and the like), water and the like.
The liquefied gas diluent or carrier may be those which are gaseous at normal temperature and normal pressure, for example, aerosol propellants such as butane, propane, nitrogen gas, carbon dioxide and halogenated hydrocarbons.
Examples of the solid diluent include pulverized natural minerals (for example, kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth, and the like), pulverized synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates and the like), and the like.
Examples of the solid carrier for granules include pulverized and screened rocks (for example, calcite, marble, pumice, sepiolite, dolomite and the like), synthetic granules of inorganic and organic powder, fine particles of organic materials (for example, sawdust, coconut shells, maize cobs, tobacco stalk and the like), and the like.
Examples of the emulsifier and/or foaming agent include nonionic and anionic emulsifϊers [for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (for example, alkylaryl polyglycol ether), alkylsulfonates, alkylsulfates, arylsulfonates and the like], albumin hydrolyzate, and the like.
Examples of the dispersant include lignin sulfite waste liquor and methylcellulose.
Fixing agents can also be used in the formulations (powders, granules, emulsions), and examples of the fixing agent include carboxymethylcellulose, natural and synthetic polymers (for example, gum arabic, polyvinyl alcohol, polyvinyl acetate, and the like) and the like.
Colorants can also be used, and examples of the colorants include inorganic pigments (for example, iron oxide, titanium oxide, Prussian Blue and the like), organic dyes such as alizarin dyes, azo dyes or metal phthalocyanine dyes, and in addition, trace elements such as the salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general can contain the active ingredient in an amount ranging from 0.1 to 95% by weight, and preferably 0.5 to 90% by weight.
The compound according to the present invention can also exist as an admixture with other active compounds, for example, insecticides, poisonous baits, bactericides, miticides, nematicides, fungicides, growth regulators, herbicides and the like, in the form of their commercially useful formulation forms and in the application forms prepared from those formulations.
The content of the compound according to the present invention in a commercially useful application form can be varied within a wide range.
The concentration of the active compound according to the present invention in actual usage can be, for example, in the range of 0.0000001 to 100% by weight, and preferably 0.00001 to 1% by weight.
The compounds according to the present invention can be used through conventional methods that are appropriate for the usage form.
The active compound of the present invention have, when used against hygiene pests and pests associated with stored products, stability effective against alkali on lime materials, and also shows excellent residual effectiveness on wood and soil.
Next, the present invention is exemplified by way of the following examples, but the invention is not intended to be limited thereto. References to room temperature means temperatures of about 18 to about 30° C.
A: Synthesis of 2-aceM-5-[5-(3,5-dicMorophenyl)-5-(trifluoromethvI)-4.5-dihvdroisoxazol
-3-vll-2.3-dihvdro-lH-isoindol-l-one (Compound No. 1-221).
Figure imgf000111_0001
5-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]-2,3-dihydro-lH-isoindol- -1-one (100 mg) was heated and refluxed in anhydrous acetic acid (246 mg) for 2 hours. After removing anhydrous acetic acid by distillation under a reduced pressure, the mixture was diluted with an appropriate amount of t-butyl methyl ether, washed with water and a saturated saline solution, and dried over magnesium sulfate. After separation by filtration, the solvent was distilled off under a reduced pressure and the resulting residue was purified with silica gel chromatography to obtain 2-acetyl-5-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-
-yl]-2,3-dihydro-lH-isoindol-l-one (70 mg) in 63% yield.
1H-NMR (CDCl3) δ : 2.70 (3H, s), 3.76 (IH, d, J=17.0 Hz), 4.14 (IH, d, J=17.4 Hz), 4.85 (2H, s), 7.44-7.45 (IH, m), 7.51-7.52 (2H, m), 7.81-7.83 (2H, m), 7.96-7.99 (IH, m).
B: Synthesis of 5-[5-(3,5-dichIorophenvI)-5-(trifluoromethv0-4.5-dihvdroisoxazol
-3-yll-2-benzofuran-l(3H)-one (Compound No. 1-2)
Step 1. Synthesis of methyl 2-[(acetyloxy)methyll-4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl) -4,5 -dihydroisoxazol-3 -ylibenzoate
Figure imgf000112_0001
Methyl 2-(bromomethyl)-4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro- oxazol-3-yl]benzoate (887 mg) and sodium acetate (285 mg) were dissolved in DMF (10 ml) and then stirred at 700C for 5 hours. After cooled to room temperature, the mixture was diluted with an appropriate amount of t-butyla methyl ether, washed with water three times and with a saturated saline solution, and dried over magnesium sulfate. After separation by filtration, the solvent was distilled off under a reduced pressure to obtain methyl 2-[(acetyloxy)methyl]-4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]- benzoate (850 mg) in 99% crude yield.
1H-NMR (CDCl3) δ : 2.17 (3H, s), 3.73 (IH, d), 3.93 (3H, s), 4.12 (IH, d), 5.52 (2H, s), 7.43-7.44 (IH, m), 7.52-7.52 (2H, m), 7.63-7.65 (IH, m), 7.83-7.83 (IH, m), 8.02-8.05 (IH, m). Step 2. Synthesis of 5-r5-(3J-dicMorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol
-3-yll-2-benzofuran-l(3H)-one (Compound No. 1-2)
Figure imgf000113_0001
Methyl 2-[(acetyloxy)methyl]-4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro- isoxazol-3-yl]benzoate (851 mg) and sodium methoxide (9 mg) were stirred in methanol (10 ml) at room temperature for 30 min. Under a reduced pressure, the solvent was removed by distillation.
Then, the residue was diluted with an appropriate amount of t-butyl methyl ether, washed with water and a saturated saline solution, and dried over magnesium sulfate. After separation by filtration, the solvent was distilled off under a reduced pressure and the resulting residue was purified with silica gel chromatography to obtain 5-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)—
4,5-dihydroisoxazol-3-yl]-2-benzofuran-l(3H)-one (140 mg) in 19% yield.
1H-NMR (CDCl3) δ : 3.94 (2H, m), 5.36 (2H, s), 7.44-7.51 (3H, m), 7.78-8.04 (3H, m).
C: Synthesis of N- KlE)-S- [5-(3.5-dichlorophenvD-5-(trifluoromethv0-4,5-dihvdroisoxazol
-3-yll-2-(pyridin-2-ylmethyl)-2.3-dihvdro-lH-isoindol-l-ylindenl acetamide (Compound No. 1-235).
Step 1. Synthesis of 4-f5-(3.5-dichlorophenyl)-5-(trifluoromethyl)-4.5-dihvdroisoxazol -3-yll-2-methylbenzonitrile
Figure imgf000114_0001
3 -(4-bromo-3 -methylphenyl)-5 -(3 ,5 -dichlorophenyl)-5 -(trifluoromethyl)-4,5 -dihydro- isoxazole (5.10 g) was dissolved in DMF (10 ml), and under an argon atmosphere zinc cyanide (0.93 g) and tetrakis(triphenylphosphine)palladium (1.30 g) were added thereto. The mixture was then stirred at 800C for 4 hours. After cooled to room temperature, the mixture was diluted with an appropriate amount of t-butyl methyl ether, washed with water and dried over magnesium sulfate. After separation by filtration, the solvent was distilled off under a reduced pressure and the resulting crystal was washed with hexane to obtain 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)~ 4,5-dihydroisoxazol-3-yl]-2-methylbenzonitrile (3.0 g) in 66% yield.
1H-NMR (CDCl3) δ : 2.59 (3H, s), 3.69 (IH, d), 4.07 (IH, d), 7.43-7.44 (IH, m), 7.50-7.50 (2H, m), 7.56-7.58 (IH, m), 7.63-7.67 (2H, m). Step 2. Synthesis of 2-(bromomethyl)-4-r5-(3.5-dicMorophenyl)-5-(trifluoromethyl)-4.5- dihvdro- isoxazol-3-vHbenzonitrile
Figure imgf000115_0001
A dichloroethane solution (38 ml) of 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)~ 4,5-dihydroisoxazol-3-yl]-2-methylbenzonitrile (1.0 g), N-bromosuccinimide (0.62 g) and a catalytic amount of 2,2'-azobisisobutyronitrile (AIBN) was heated and refiuxed for 3 hours. After the solution was cooled to room temperature, insoluble matters were filtered out and the solvent was distilled off under a reduced pressure. The residue was dissolved in t-butyl methyl ether, then washed with water, and dried over magnesium sulfate. After separation by filtration again, the solvent was distilled off under a reduced pressure to obtain 2-(bromomethyl)~
4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]benzonitrile as a crude product. The crude product thus obtained was used for a further reaction without any purification.
1H-NMR (CDCl3) δ : 3.71 (IH, d), 4.09 (IH, d), 4.64 (2H, s), 7.45-7.48 (3H, m), 7.72-7.73 (2H, m), 7.83-7.86 (IH, m).
Step 3. Synthesis of 5-r5-(3.5-dicmorophenvD-5-(trifluoromethylV4,5-dihvdroisoxazol
-3 -yll -2-(p yridin-2-ylmethyl V 2.3 -dihvdro- 1 H-isoindol- 1 -imine
Figure imgf000116_0001
2-(bromomethyl)-4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro- isoxazol-3-yl]benzonitrile (500 mg), 2-pyridylmethylamine (113 mg) and potassium carbonate (289 mg) in acetonitrile (10 ml) were heated and refluxed for 3 hours. After cooled to room temperature, the mixture was diluted with an appropriate amount of t-butyl methyl ether, washed with water and a saturated saline solution, and dried over magnesium sulfate. After separation by filtration, the solvent was distilled off under a reduced pressure and the resulting residue was purified with silica gel chromatography to obtain 5-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro- isoxazol-3-yl]-2-(pyridin-2-ylmethyl)-2,3-dihydro-lH-isoindol-l-imine (400 mg) in 75% yield.
Step 4. Synthesis of N-IYlEVS-rS-β.S-dicMorophenviyS-αrifluoromethyl)^- dihvdro- isoxazol-3-yll-2-(pyridin-2-ylmethyl')-2.3-dihvdro-lH-isoindol-l-ylindenlacetamide (Compound No. 1-235)
Figure imgf000117_0001
Acetyl chloride (94 mg) and pyridine (119 mg) were added to 5-[5-(3,5-dichlorophenyl)~
5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]-2-(pyridin-2-ylmethyl)~
2,3-dihydro-lH-isoindol-l-imine (505 mg) in tetrahydrofuran (5 ml) and the mixture was stirred at room temperature for 1 hour. Then, the resulting mixture was diluted with an appropriate amount of t-butyl methyl ether, washed with water and a saturated saline solution, and dried over magnesium sulfate. After separation by filtration, the solvent was distilled off under a reduced pressure and the resulting residue was purified with silica gel chromatography to obtain N-[(1E)~ 5-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]-2-(pyridin-2-ylmethyl)~ 2,3-dihydro-lH-isoindol-l-ylinden]acetamide (80 mg) in 15% yield.
1H-NMR (CDCl3) δ : 2.12 -2.24 (3H, m), 3.60-3.68 (IH, m), 4.02-4.08 (IH, m), 4.73-4.82 (4H, m), 7.13-7.73 (9H, m), 8.44-8.61 (IH, m). D; Synthesis of l-{5-[5-(3.5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol
-3-yll-l,3-dihvdro-2H-isoindol-2-vUethanone (Compound No. 1-151).
Step 1. Synthesis of 3-[3Λ-bis(bromomethyl)phenyll-5-(3.5-dicMorophenyl)-5-(trifluoromethyl) -4,5-dihydroisoxazole.
Figure imgf000118_0001
A dichloroethane solution (38 ml) of 5-(3,5-dichlorophenyl)-3-(3,4-dimethylphenyl)~ 5-(trifluoromethyl)-4,5-dihydroisoxazole (1.0 g), N-bromosuccinimide (1.1 g) and a catalytic amount of 2,2'-azobisisobutyronitrile (AIBN) was heated and refluxed for 3 hours. After the solution was cooled to room temperature, insoluble matters were filtered out and the solvent was distilled off under a reduced pressure. The residue was dissolved in t-butyl methyl ether, then washed with water, and dried over magnesium sulfate. After separation by filtration again, the solvent was distilled off under a reduced pressure to obtain 3-[3,4-bis(bromomethyl)phenyl]- -5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazole as a crude product. The crude product thus obtained was used for a further reaction without any purification.
1H-NMR (CDCl3) δ : 3.66-3.71 (IH, m), 4.04-4.11 (IH, m), 4.64 (2H, s), 7.41-7.67 (6H, m). Step 2. Synthesis of l-{5-f5-(3.5-dichlorophenyl)-5-(trifluoromethylV4.5-dihvdroisoxazol
-3-yll-l,3-dihvdro-2H-isoindol-2-vUethanone (Compound No. 1-151).
Figure imgf000119_0001
3-[3,4-bis(bromomethyl)phenyl]-5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro- isoxazole (1.41 g), acetamide (0.15 g) and sodium hydride (0.10 g) were heated and refluxed in tetrahydrofuran solution (30 ml) for 3 hours. After cooled to room temperature, the mixture was diluted with an appropriate amount of t-butyl methyl ether, washed with water and a saturated saline solution, and dried over magnesium sulfate. After separation by filtration, the solvent was distilled off under a reduced pressure and the resulting residue was purified with silica gel chromatography to obtain l-{5-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro- isoxazol-3-yl]-l,3-dihydro-2H-isoindol-2-yl}ethanone (100 mg) in 8.8% yield.
1H-NMR (CDCl3) δ : 2.18 (3H, s), 3.71 (IH, d), 4.10 (IH, d), 4.82-4.85 (4H, m), 7.32-7.39 (IH, m), 7.43-7.43 (IH, m), 7.52-7.65 (4H, m).
E: 5-("3.5-dichlorophenyl)-3-(1.3-dihvdro-2-benzofuran-5-vI)-5-(trifluoromethyl)- 4,5- dihydroisoxazole (Compound No. 1-131)
Step 1. Synthesis of 2.5-dimethylbenzyl acetate
Figure imgf000120_0001
Acetyl chloride (1.5 g) was added to a tetrahydrofuran solution (30 ml) including
2,5-dimethylbenzyl alcohol and triethylamine (2.4 g) under ice cooling. After stirring at room temperature for 1 hour, the reaction solution was diluted with t-butyl methyl ether. The solution was then washed with water and a saturated saline solution, and the organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure to obtain 2,5-dimethylbenzyl acetate (2.8 g).
1H-NMR (CDCl3) δ : 2.09 (3H, s), 2.31 (6H, d), 5.09 (2H, s), 7.08-7.12 (3H, m).
Step 2. Synthesis of 5-(bromomethyl)-l,3-dihvdro-2-benzofuran
Figure imgf000120_0002
A dichloroethane solution (30 ml) of 2,5-dimethylbenzyl acetate (3 g), 2,2'-azobisisobutyronitrile (AffiN)(0.2 g) and N-bromosuccinimide (6.8 g) was stirred at 900C for 3 hours. Under a reduced pressure, the reaction solution was concentrated, t-butyl methyl ether was added to the residue, and separation was carried out by filtration. The filtered solution was washed with water and a saturated saline solution, and the organic layer was dried over magnesium sulfate. The solvent was distilled off under a reduced pressure and the resulting residue was purified with silica gel chromatography to obtain 2,5-bis(bromomethyl)benzyl acetate (2.0 g), to which ethanol
(10 ml) and water (5 ml) were added followed by the addition of sodium hydroxide (0.5 g). The mixture was stirred at room temperature for 1 hour. The reaction solution was then diluted with t-butyl methyl ether, washed with water and a saturated saline solution, and then the organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure and the resulting residue was purified with silica gel chromatography to obtain 5-(bromomethyl)-l,3-dihydro-2-benzofuran (0.65 g).
1H-NMR (CDCl3) δ : 4.52 (2H, s), 5.10 (4H, s), 7.19-7.31 (3H, m).
Step 3. Synthesis of L3-dihydro-2-benzofuran-5-carbaldehyde
Figure imgf000121_0001
A N,N-dimethylformamide solution (10 ml) of 5-(bromomethyl)— l,3-dihydro-2-benzofuran (0.7 g) and sodium acetate (0.54 g) was stirred at 700C for 3 hours. The reaction solution was diluted with t-butyl methyl ether, then washed with water and a saturated saline solution, and the organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure to obtain l,3-dihydro-2-benzofuran-5-ylmethyl acetate as a crude product. The crude product thus obtained was dissolved in methanol (10 ml), sodium methoxide (0.05 g) was added thereto and the mixture was stirred for 1 hour at room temperature. The reaction solution was diluted with t-butyl methyl ether, then washed with water and a saturated saline solution, and the organic layer was dried over magnesium sulfate. The solvent was distilled off under a reduced pressure to obtain l,3-dihydro-2-benzofuran-5-ylmethanol as a crude product. The crude product thus obtained was dissolved in methylene chloride (20 ml), activated manganese (IV) oxide (2.3 g) was added thereto and the mixture was heated and refluxed for 5 hours. The reaction solution was filtered using Celite and the filtered solution was concentrated under a reduced pressure. The resulting residue was purified with silica gel chromatography to obtain l,3-dihydro-2-benzofuran-5-carbaldehyde (0.35 g).
1H-NMR (CDCl3) δ : 5.16 (4H, s), 7.39-7.41 (IH, m), 7.78-7.80 (2H, m), 10.02 (IH, s).
Step 4. Synthesis of 5-(3,5-dichlorophenyl)-3-(13-dihvdro-2-benzofuran-5-yl)-5-
(trifluoromethyl)-4,5-dihvdroisoxazole (Compound No. 1-131)
Figure imgf000122_0001
Ethanol (10 ml) and water (6 ml) solution including 1 ,3-dihydro-2-benzofuran- -5-carbaldehyde (0.4 g), hydroxyamine hydrochloride (0.28 g) and sodium acetate (0.45 g) was stirred at room temperature for 1 hour. The reaction solution was diluted with t-butyl methyl ether, then washed with water and a saturated saline solution, and then the organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled off under a reduced pressure to obtain l-(l,3-dihydro-2-benzofuran-5-yl)-N-hydroxymethanimine (0.2 g) as a crude product. The crude product thus obtained was dissolved in N,N-dimethylformamide (10 ml), N-chlorosuccinimide (0.18 g) was added thereto, and the mixture was stirred at room temperature for 2 hours. To the reaction solution, l,3-dichloro-5-[l-(trifluoromethyl)vinyl]benzene (0.2 g) was added. After cooled to 00C, potassium hydrogen carbonate (0.1 g) was added thereto and the mixture was stirred at room temperature for 8 hours. After adding water, extraction was carried out using t-butyl methyl ether. The organic layer was washed with a saturated saline solution, and then dried over magnesium sulfate. The solvent was distilled off under a reduced pressure and the resulting residue was purified with silica gel chromatography to obtain 5-(3,5-dichlorophenyl)— 3-(l ,3-dihydro-2-benzofuran-5-yl)-5-(trifluoromethyl)-4,5-dihydroisoxazole (0.14 g).
1H-NMR (CDCl3) δ : 3.72 (IH, d), 4.11 (IH, d), 5.11 (4H, s), 7.27-7.30 (IH, m), 7.41-7.41 (IH, m), 7.51-7.57 (4H, m).
F: Synthesis of 5-[5-(3,5-dichIorophenyl)-5-(trif1uoromethvO-4,5-dihvdiOisoxazol -3-yll-2-benzofuran-l(3H)-imine (Compound No. 1-232)
Step 1. Synthesis of 2-cyano-5-f5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4.5- dihvdro- isoxazol-3-yllbenzyl acetate
Figure imgf000123_0001
2-(bromomethyl)-4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro- isoxazol-3-yl]benzonitrile (900 mg) and sodium acetate (300 mg) were dissolved in N,N-dimethylformamide (10 ml) and the mixture was stirred at 700C for 5 hours. After cooled to room temperature, the mixture was diluted with an appropriate amount of t-butyl methyl ether, washed with water three times and with a saturated saline solution, and dried over magnesium sulfate. After separation by filtration, the solvent was distilled off under a reduced pressure and the resulting residue was purified with silica gel chromatography to obtain 2-cyano- -5-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]benzyl acetate (250 mg) in 30% yield.
1H-NMR (CDCl3) δ : 2.16 (3H, s), 3.72 (IH, d), 4.10 (IH, d), 5.30 (2H, s), 7.44-7.44 (IH, m), 7.48-7.52 (2H, m), 7.72-7.78 (2H, m), 7.81-7.84 (IH, m). Step 2. Synthesis of 5-[5-(3.5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol
-3-yl1-2-benzofuran-l(3H)-imine (Compound No. 1-232)
Figure imgf000124_0001
2-cyano-5-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]benzyl acetate (300 mg) and sodium methoxide (10 mg) in methanol (10 ml) was stirred at room temperature for 30 min. After removing the solvent by distillation under a reduced pressure, the mixture was diluted with an appropriate amount of t-butyl methyl ether, washed with water and a saturated saline solution, and dried over magnesium sulfate. After separation by filtration, the solvent was distilled off under a reduced pressure to obtain 5-[5-(3,5-dichlorophenyl)-- 5-(trifluoromethyl)-4,5-dmydroisoxazol-3-yl]-2-benzofuran-l(3H)-imine (200 mg) in 74% yield.
1H-NMR (CDCl3) δ : 3.74 (IH, d), 4.12 (IH, d), 5.34 (2H, s), 7.44-7.44 (IH, m), 7.49-7.52 (2H, m), 7.71-7.73 (IH, m), 7.76-7.79 (IH, m), 7.92-7.95 (IH, m).
G: Synthesis of N-{5-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihvdroisoxazol-3-yll -2.3-dihydro-lH-inden-l-vUacetamide (No. 3-3)
Step 1. Synthesis of methyl (2E)-3-(l-oxo-2,3-dihydro-lH-inden-5-yl)prop-2-enoate.
Figure imgf000124_0002
5-bromoindanone (10 g), methyl acrylate (8.56 ml), and 1 ,3-bis(diphenyl- phosphino)propane (1.17 g) were dissolved in triethylamine (100 ml)-acetonitrile (100 ml), and palladium acetic acid (0.53 g) was added thereto under argon atmosphere. The reaction solution was heated at 800C for 8 hours. After the cooling, methyl acrylate (4.28 ml) was further added to the mixture. It was again heated at 800C for 8 hours, and the solvent was distilled off under reduced pressure. Dilute hydrochloric acid and methylene chloride were added for the extraction. The organic layer was dried over magnesium sulfate and the solvent was removed by distillation. After the purification with silica gel chromatography, the title compound was obtained (5.36 g, 52%).
1H-NMR (CDCl3) δ : 2.73 (t, 2H), 3.17 (t, 2H), 3.83 (s, 3H), 6.55 (d, IH), 7.50-7.82 (m, 4H).
Step 2. Synthesis of l-oxo-2.3-dihvdro-lH-inden-5-carbaldehvde.
Figure imgf000125_0001
Methyl (2E)-3-(l-oxo-2,3-dihydro-lH-inden-5-yl)prop-2-enoate was dissolved in
1 ,2-dichloroethane (70 ml) - water (70 ml), and sodium periodate (13.25 g) and ruthenium trichloride hydrates (0.18 g) were added thereto at room temperature. The reaction solution was stirred for 4 hours. Sodium thiosulfate and ethyl acetate were added for the extraction. The organic layer was dried over magnesium sulfate and the solvent was removed by distillation. After the purification with silica gel chromatography, the title compound was obtained (1.92 g, 50%).
1H-NMR (CDCl3) δ : 2.78 (t, 2H), 3.25 (t, 2H), 7.90 (s, 2H), 8.00 (s, IH), 10.14 (s, IH).
Step 3. Synthesis of 5-r(E)-(hvdroxyimino)methyll-2,3-dihydro-lH-inden-l-one.
Figure imgf000125_0002
l-oxo-2,3-dihydro-lH-inden-5-carbaldehyde (2.0O g) and sodium hydrocarbonate (1.36 g) were suspended in ethanol, and hydroxyamine hydrochloride (0.87 g) was added thereto at
00C. After stirring for 1 hour, the solvent was removed by distillation. Water and ethyl acetate were added for the extraction. The organic layer was dried over magnesium sulfate and the solvent was removed by distillation. The title compound was obtained as a crude product (1.92 g).
1H-NMR (CDCl3) δ : 2.73 (t, 2H), 3.17 (t, 2H), 7.61 (d, IH), 7.68 (s, IH), 7.77 (d, IH), 8.19 (s, IH).
Step 4. Synthesis of 5-[5-(3.5-dicMorophenyl)-5-(trifluoromethyl)-4.5-dihydroisoxazol -3-vH-2.3-dihvdro-lH-inden-l-one.
Figure imgf000126_0001
5-[(E)-(hydroxyimino)methyl]-2,3-dihydro-lH-inden-l-one (1.92 g) was dissolved in
N,N-dimethylformamide (40 ml), and then N-chlorosuccinimide (1.47 g) was added thereto at O0C. The reaction solution was stirred for 4 hours. After cooling down the mixture to -100C, l,3-dichloro-5-(3,3,3-trifluoroprop-l-en-2-yl)benzene (2.91 g) and potassium hydrocarbonate (1.32 g) were added thereto. The reaction solution was stirred for 4 hours. Water and ethyl acetate were added for the extraction. The organic layer was dried over magnesium sulfate and the solvent was removed by distillation. After the purification with silica gel chromatography, the title compound was obtained (2.85 g, 63%).
IH-NMR (CDC13) δ : 1H-NMR (CDCl3) δ :2.75 (t, 2H), 3.19 (t, 2H), 3.74 (d, IH), 4.12 (d, IH), 7.44 (s, IH), 7.51 (s, 2H), 7.67 (d, IH), 7.77-7.83 (m, 2H). Step 5. Synthesis of 5-r5-(3.5-dicMorophenyl)-5-(trifluoromethyl)-4.5-dihvdroisoxazol
^-yll^J-dihvdro-lH-inden-l-ol.
Figure imgf000127_0001
5-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro- isoxazol-3-yl]-2,3-dihydro-lH-inden-l-ol (0.83 g) was dissolved in methanol (10 ml) and sodium borohydride (0.11 g) was added thereto at room temperature. After stirring the reaction solution overnight, the solvent was removed by distillation. Water and ethyl acetate were added for the extraction. The organic layer was dried over magnesium sulfate and the solvent was removed by distillation. The title compound was obtained as a crude product (0.77 g).
IH-NMR (CDC13) δ : 1.90-2.03 (m, IH), 2.48-2.60 (m, IH), 2.48-2.60 (m, IH), 2.77-2.90 (m, IH), 3.00-3.13 (m, IH), 3.70 (d, IH), 4.09 (d, IH), 5.27 (t, IH), 7.40-7.59 (m, 6H).
Step 6. Synthesis of 2-{5-[5-(3,5-dicMorophenyl)-5-(trifluorornethyl)-4,5-dihvdroisoxazol -3-yll-2.3-dihvdro-lH-inden-l-vn-lH-isoindol-1.3(2HVdione.
Figure imgf000127_0002
5 -[5 -(3 ,5 -dichlorophenyl)-5 -(trifluoromethyl)-4,5 -dihydroisoxazol-3 -yl] -2 ,3 -dihydro— lH-inden-1-ol (0.80 g), phthalimide (0.31 g) and triphenylphophine (0.71 g) were dissolved in tetrahydrofuran (10 ml), and then diethyl azodicarboxyic acid (40%/toluene, 1.32 ml) was added thereto at room temperature. The reaction solution was stirred for 3 hours. The solvent was removed by distillation. After the purification with silica gel chromatography, the title compound was obtained (0.58 g, 55%).
IH-NMR (CDC13) δ : 2.42-2.66 (m, 2H), 2.95-3.09 (m, IH), 3.31-3.43 (m, IH), 3.68 (d, IH), 4.07 (m, IH), 5.89 (t, IH), 7.15 (s, IH), 7.42 (s, IH), 7.45 (d, IH), 7.50 (s, 2H), 7.61 (d, IH), 7.70-7.78 (m, 2H), 7.80-7.90 (m, 2H).
Step 7. Synthesis of 5-r5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4.5-dihvdroisoxazol
-3-V-1-2 .3 -dihydro- 1 H-inden- 1 -amine.
Figure imgf000128_0001
2- {5-[5 -(3 ,5 -dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro- isoxazol-3-yl]-2,3-dihydro-lH-inden-l-yl}-lH-isoindol-l,3(2H)-dione (0.58 g) was dissolved in ethanol (10 ml), and then hydrazine hydrate (0.10 ml) was added thereto. The reaction solution was heated at 800C for 5 hours. The solvent was removed by distillation and ethyl acetate was added. Precipitates were removed by filtration, and the filtrate was concentrated. The title compound was obtained as a crude product (0.39 g).
IH-NMR (CDC13) δ : 1.64-1.80 (m, IH), 2.10 (bs, 2H), 2.47-2.61 (m, IH), 2.75-2.90 (m, IH), 2.90-3.05 (m, IH), 3.69 (d, IH), 4.08 (d, IH), 4.38 (t, IH), 7.35-7.44 (m, 2H), 7.46-7.57 (m, 4H). Step 8. Synthesis of N-(5-r5-(3.5-dicMorophenyl)-5-(trifluoromethyl)-4,5-dihvdroisoxazol
-S-yli^J-dihydro-lH-inden-l-vUacetarnide.
Figure imgf000129_0001
5-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro- isoxazol-3-yl]-2,3-dihydro-lH-inden-l-amine (0.10 g) was dissolved in tetrahydrofuran (2 ml), and then anhydrous acetic acid (0.028 ml) was added thereto at room temperature. After stirring overnight, the solvent was removed by distillation. After the purification with silica gel chromatography, the title compound was obtained (0.086 g, 75%).
IH-NMR (CDC13) δ : 1.74-1.91 (m, IH), 2.06 (s, 3H), 2.57-2.70 (m, IH), 2.82-3.07 (m, 2H), 3.69 (d, IH), 4.07 (d, IH), 5.52 (q, IH), 5.60-5.67 (d, IH), 7.34 (d, IH), 7.40-7.61 (m, 5H).
H: Synthesis of 6-[5-(3,5-dichlorophenvD-5-(trifluoromethvI)-4,5-dihvdroisoxazol -3-vn-l,2,3,4-tetrahvdronaphthalen-l-amine (No. 3-211).
Step 1. Synthesis of 5-oxo-5,6,7,8-tetrahvdronaphthalen-2-yl trifluoromethane sulfonate.
Figure imgf000129_0002
6-hydroxy3,4-dihydro-l(2H)-naphthalenone (10.30 g) and 2,6-lutidine (14.80 ml) were dissolved in methylene chloride (150 ml), and anhydrous trifluoromethane sulfonic acid (25 g) was added thereto at 00C. The reaction solution was stirred overnight at room temperature. Dilute hydrochloric acid was added for the extraction. The organic layer was dried over magnesium sulfate and the solvent was removed by distillation. After the purification with silica gel chromatography, the title compound was obtained (17.00 g, 91%).
IH-NMR (CDCB) δ : 2.12 -2.24 (m, 2H), 2.69 (t, 2H), 3.02 (t, 2H), 7.18-7.23 (m, 2H), 8.14 (d, IH).
Step 2. Synthesis of methyl (2E)-3-(5-oxo-5.6J,8-tetrahydronaphthalen-2-yI)prop-2-enoate.
Figure imgf000130_0001
5-oxo-5,6,7,8-tetrahydronaphthalen-2-yl trifluoromethane sulfonate (7.1O g), methyl acrylate (13.0 ml), l,3-bis(diphenylphosphino)propane (0.60 g) and triethylamine (10.1 ml) were dissolved in N,N-dimethylformamide (80 ml), and the resulting mixture was stirred under argon atmosphere for 10 min. To the reaction solution, palladium acetic acid (0.27 g) was added and the reaction solution was heated at 800C for 10 hours. Water and ethyl acetate were added for the extraction. The organic layer was dried over magnesium sulfate and the solvent was removed by distillation. After the purification with silica gel chromatography, the title compound was obtained (4.1O g, 74%).
IH-NMR (CDC13) δ : 2.09-2.21 (m, IH), 2.67 (t, IH), 2.98 (t, IH), 3.82(s, 3H), 6.51 (d, IH), 7.39 (s, IH), 7.46 (d, IH), 7.68 (d, IH), 8.04 (d, IH).
Step 3. Synthesis of 5-oxo-5.6,7,8-tetrahvdronaphthalen-2-carbaldehvde.
Figure imgf000130_0002
Methyl (2E)-3-(5-oxo-5,6,7,8-tetrahydronaphthalen-2-yl)prop-2-enoate was dissolved in 1,2-dichloroethane (70 ml) - water (70 ml), and sodium periodate (13.25 g) and ruthenium trichloride hydrate (0.18 g) were added thereto at room temperature. The reaction solution was stirred for 4 hours. Sodium thiosulfate and ethyl acetate were added for the extraction. The organic layer was dried over magnesium sulfate and the solvent was removed by distillation. After the purification with silica gel chromatography, the title compound was obtained (1.92 g, 50%).
IH-NMR (CDC13) δ : 2.10-2.25 (m, 2H), 2.72 (t, 2H), 3.07 (t, 2H), 7.72-7.83 (m, 2H), 8.18 (d, IH), 10.08 (s, IH).
Step 4. Synthesis of 6-r(E)-(hvdroxyimino')methvn-3,4-dihvdronaphthalen-l(2H)-one.
Figure imgf000131_0001
l-oxo-2,3-dihydro-lH-inden-5-carbaldehyde (2.46 g) and sodium hydrocarbonate (1.42 g) were suspended in ethanol (70 ml), and hydroxyamine hydrochloride (0.98 g) was added thereto at 00C. After stirring for 1 hour, the solvent was removed by distillation. Water and ethyl acetate were added for the extraction. The organic layer was dried over magnesium sulfate and the solvent was removed by distillation. The title compound was obtained as a crude product (2.60 g).
IH-NMR (CDC13) δ : 2.10-2.21 (m, 2H), 2.68 (t, 2H), 2.99 (t, 2H), 7.47 (s, IH), 7.52 (d, IH), 7.75 (bs, IH), 8.05 (d, IH), 8.14 (s, IH).
Step 5. Synthesis of 6-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol -3-yl"l-3,4-dihvdronaphthalen-l(2HVone.
Figure imgf000131_0002
6-[(E)-(hydroxyimino)methyl]-3,4-dihydronaphthalen-l(2H)-one (2.67 g) was dissolved in N,N-dimethylformamide (50 ml), and then N-chlorosuccinimide (1.89 g) was added thereto at
00C. The reaction solution was stirred for 4 hours. While keeping the temperature of the reaction solution at 00C, l,3-dichloro-5-(3,3,3-trifluoroprop-l-en-2-yl)benzene (3.74 g) and potassium hydrocarbonate (1.70 g) were added thereto. The reaction solution was stirred for 3 hours. Water and ethyl acetate were added for the extraction. The organic layer was dried over magnesium sulfate and the solvent was removed by distillation. After the purification with silica gel chromatography, the title compound was obtained (3.60 g, 60%).
IH-NMR (CDC13) δ : 2.11-2.22 (m, 2H), 2.69 (t, 2H), 3.00 (t, 2H), 3.71 (d, IH), 4.10 (d, IH), 7.41-7.59 (m, 5H), 8.08 (d, IH).
Step 6. Synthesis of 6-[5-f3.5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol -3-yl]-l ,2,3 ,4-tetrahvdronaphthalen-l -amine.
Figure imgf000132_0001
6-[5 -(3 ,5 -dichlorophenyl)-5 -(trifluoromethyl)-4,5 -dihydro- isoxazol-3-yl]-3,4-dihydronaphthalen-l(2H)-one (1.56 g) and ammonium acetate (4.2I g) were dissolved in methanol (40 ml), and then sodium cyanotrihydro borate (0.69 g) was added thereto at room temperature. The reaction solution was heated at 700C for 8 hours. The solvent was removed by distillation, and water and tert-butylmethyl ether were added thereto. The aqueous layer was separated off and the organic layer was extracted with concentrated hydrochloric acid. The acidic aqueous layer was neutralized with sodium carbonate and extracted with tert-butylmethyl ether. The organic layer was dried over magnesium sulfate and the solvent was removed by distillation. The title compound was obtained as a crude product (1.15 g).
IH-NMR (CDC13) δ : 1.47-2.11 (m, 6H), 2.68-2.90 (m, 2H), 3.68 (d, IH), 3.98 (t, IH), 4.07 (d, IH), 7.37 (s, IH), 7.42 (t, IH), 7.48 (s, 2H), 7.51 (s, 2H).
I: Synthesis of 5-[5-(3.5-dichIorophenvO-5-(trifluoromethyI)-4,5-dihvdroisoxazol O-yll-N-ethvI-Z.S-dihvdro-lH-indoI-l-carboxamide (No. 3-638)
Step 1. Synthesis of tert-butyl 5-fbrmyl-lH-indol-l-carboxyate.
Figure imgf000133_0001
Indol-5-carboxyaldehyde (8.00 g) and 4-dimethylaminopyridine (0.67 g) were dissolved in acetonitrile (200 ml), and di-tert-butyl bicarbonate (15.6 g) was added thereto at room temperature. After stirring overnight, the solvent was removed by distillation. After the dilution with ethyl acetate, the mixture was washed with dilute hydrochloric acid and an aqueous solution of sodium carbonate. After drying over magnesium sulfate, the solvent was removed by distillation. The title compound was obtained as a crude product (13.5 g).
IH-NMR (CDC13) δ : 1.69 (s, 9H), 6.69 (d, IH), 7.69 (d, IH), 7.86 (d, IH), 8.10 (s, IH), 8.29 (d, IH), 10.07 (s, IH).
Step 2. Synthesis of tert-butyl 5-(hvdroxymethyl)-2,3-dihvdro-lH-indol-l-carboxvate.
Figure imgf000133_0002
Tert-butyl 5-formyl-lH-indol-l-carboxyate (13.5 g) and triethylamine (7.67 ml) were dissolved in ethanol (150 ml), and then palladium-activated charcoal (10%, 1.33 g) was added thereto at room temperature. Hydrogen gas was introduced thereto using a balloon and the mixture was stirred for 4 days. The catalyst was removed by filtration, and the filtrate was concentrated under reduced pressure. After the purification with silica gel chromatography, the title compound was obtained (2.91 g, 52%, 21%).
IH-NMR (CDC13) δ : 1.52-1.62 (m, 10H), 3.08 (t, 2H), 3.98 (t, 2H), 4.61 (d, 2H), 7.10-7.25 (m, 2H), 7.66-7.92 (m, IH).
Step 3. Synthesis of tert-butyl 5-formyl-2.3-dihydro-lH-indol-l-carboxyate.
Figure imgf000134_0001
Tert-butyl 5-(hydroxymethyl)-2,3-dihydro-lH-indol-l-carboxyate (2.91 g) was dissolved in methylene chloride (50 ml), and then activated manganese dioxide (10.1 g) was added thereto at room temperature. The mixture was stirred overnight. The solids were removed by filtration, and the filtrate was concentrated under reduced pressure. As a result, the title compound was obtained as a crude product (2.73 g).
IH-NMR (CDC13) δ : 1.58 (s, 9H), 3.15 (t, 2H), 4.05 (t, 2H), 7.62-7.73 (m, 2H), 7.80-8.01 (m, IH), 9.86 (s, IH).
Step 4. Synthesis of tert-butyl 5-r(E)-(hvdroxyimino)methvn-2.3-dihvdro-lH-indol-l- carboxyate.
Figure imgf000134_0002
Tert-butyl 5-formyl-2,3-dihydro-lH-indol-l-carboxyate (2.73 g) and sodium hydrocarbonate (1.39 g) were suspended in ethanol, and then hydroxyamine hydrochloride salt
(0.92 g) was added thereto at room temperature. The reaction solution was stirred overnight and the solvent was removed by distillation. Water and ethyl acetate were added for the extraction. The organic layer was dried over magnesium sulfate and the solvent was removed by distillation. As a result, the title compound was obtained as a crude product (2.50 g).
IH-NMR (CDC13) δ : 1.57 (s, 9H), 3.10 (t, 2H), 4.00(t, 2H), 7.24-7.48 (m, 2H), 7.62-7.92 (m, IH), 8.07 (s, IH).
Step 5. Synthesis of tert-butyl 5-[5-(3,5-dicMorophenyl)-5-(trifluoromethyl)-4.5- dihvdro- isoxazol-3-yll-2,3-dihydro-lH-indol-l-carboxvate.
Figure imgf000135_0001
Tert-butyl 5-[(E)-(hydroxyimino)methyl]-2,3-dihydro-lH-indol-l-carboxyate (2.50 g) was dissolved in N,N-dimethylformamide (50 ml), and then N-chlorosuccinimide (1.27 g) was added thereto at room temperature. The reaction solution was then stirred for 4 hours. After cooling the solution to 00C, l,3-dichloro-5-(3,3,3-trifluoroprop-l-ene-2-yl)benzene (2.53 g) and potassium hydrocarbonate (1.15 g) were added thereto. The reaction solution was stirred overnight at room temperature. Water and ethyl acetate were added for the extraction. The organic layer was dried over magnesium sulfate and the solvent was removed by distillation. As a result, the title compound was obtained as a crude product (4.78 g).
IH-NMR (CDC13) δ : 1.57 (s, 9H), 3.11 (t, 2H), 3.67 (d, IH), 3.94-4.06 (m, 3H), 7.30-7.59 (m, 6H).
Step 6. Synthesis of 5-f5-(3.5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihvdroisoxazol -3-vn-2.3-dihvdro-lH-indole.
Figure imgf000136_0001
Tert-butyl 5-[5-(3,5-dicmorophenyl)-5-(trifluoromethyl)-4,5-dihydro- isoxazol-3-yl]-2,3-dihydro-lH-indol-l-carboxyate (4.78 g), concentrated hydrochloric acid (20 ml) and ethanol (75 ml) were mixed and the resulting mixture was heated at 800C for 8 hours. Solvent was removed by distillation, and water and ethyl acetate were added. The resulting mixture was neutralized by adding sodium carbonate, and then extracted. The organic layer was dried over magnesium sulfate and the solvent was removed by distillation. After the purification with silica gel chromatography, the title compound was obtained (3.37 g, 88%).
IH-NMR (CDC13) δ : 1.58(bs, IH), 3.05 (t, 2H), 3.57-3.69 (m, 3H), 4.04 (d, IH), 6.56 (d, IH), 7.23 (d, IH), 7.40 (s, IH), 7.47 (s, IH), 7.51 (s, 2H).
Step 7. Synthesis of 5-[5-(3.5-dicMorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol -3 -yll -N-ethyl-2,3 -dihydro- 1 H-indol- 1 -carboxamide.
Figure imgf000136_0002
5-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro- isoxazol-3-yl]-2,3-dihydro-lH-indole (0.12 g) and triethylamine (0.042 ml) were dissolved in tetrahydrofuran (2 ml), and ethyl isocyanate (0.047 ml) was added thereto at room temperature. After stirring the mixture overnight, the solvent was removed by distillation. After the purification with silica gel chromatography, the title compound was obtained (0.104 g, 74%). IH-NMR (CDCB) δ : 1.22 (t, 3H), 3.20 (t, 2H), 3.39 (quintet, 2H), 3.68 (d, IH), 3.93 (t, 2H), 4.07
(d, IH), 4.57-4.66 (m, IH), 7.31 (d, IH), 7.41 (s, IH), 7.51 (s, 2H), 7.58 (s, IH), 7.98 (d, IH).
J: Synthesis of 6-[5-(3,5-dichlorophenvI)-5-ftrifluoromethyl)-4,5-dihydroisoxazol-3-yll -N-ethyl-3.4-dihvdroquinolin-l(2Eπ-carboxamide (No. 3-638).
Step 1. Synthesis of (E)-N-hvdroxyl-(quinolin-6-yl)methaneimine.
Figure imgf000137_0001
Quinolin-6-carbaldehyde (1.01 g) and triethylamine (1.34 ml) were dissolved in ethanol
(70 ml), and hydroxyamine hydrochloride (0.54 g) was added thereto at room temperature. After stirring the mixture overnight, the solvent was removed by distillation. Water and ethyl acetate were added thereto for extraction. The organic layer was dried over magnesium sulfate and the solvent was removed by distillation. The title compound was obtained as a crude product (1.00 g).
IH-NMR (CDC13) δ : 1.57 (bs, IH), 7.41-7.49 (m, IH), 7.89 (s, IH), 8.06-8.23 (m, 3H), 8.32 (s, IH), 8.90-8.97(m, IH).
Step 2. Synthesis of 6-r5-(3,5-dicMorophenyl)-5-(trifluoromethvD-4.5-dihvdroisoxazol -3-vnquinoline.
Figure imgf000137_0002
(E)-N-hydroxyl-(quinolin-6-yl)methaneimine (0.98 g) was dissolved in N,N-dimethylformamide (50 ml), and then N-chlorosuccinimide (0.83 g) was added thereto at room temperature. The reaction solution was stirred for 1 hour at 500C. After cooling the reaction solution to O0C5 l,3-dichloro-5-(3,3,3-trifluoroprop-l-ene-2-yl)benzene (1.5O g) and potassium hydrocarbonate (0.68 g) were added thereto. The reaction solution was stirred overnight at room temperature. Water and ethyl acetate were added for the extraction. The organic layer was dried over magnesium sulfate and the solvent was removed by distillation. After washing with a small amount of hexane for purification, the title compound was obtained (0.88 g, 38%).
IH-NMR (CDC13) δ : 3.83 (d, IH), 4.23 (d, IH), 7.41-7.59 (m, 4H), 7.95 (s, IH), 8.13-8.22 (m, 3H), 8.95-9.00 (m, IH).
Step 3. Synthesis of 6-[5-(3.5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihvdroisoxazol -3-yll-l,2,3,4-tetrahydroquinoline.
Figure imgf000138_0001
6-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]quinoline (0.76 g) and sodium cyanotrihydroborate (0.23 g) were dissolved in methanol (20 ml), and then boron trifluoro diethyl ether complex (0.58 ml) was added thereto. The reaction solution was refluxed for
6 hours under heating. The solvent was removed by distillation. After the purification with silica gel chromatography, the title compound was obtained (0.52 g).
1H-NMR (CDCl3) δ : 1.91-1.93 (2H, m), 2.73-2.75 (2H, m), 3.33-3.35 (2H, m), 3.62 (IH, d), 4.02 (IH), 4.21 (IH, s), 6.41 (IH, d), 7.24-7.25 (2H, m), 7.39 (IH, t), 7.51 (2H, s). Step 4. Synthesis of 6-r5-(3,5-dicMorophenyl)-5-(trifluoromethyl)-4,5-dihvdroisoxazol
-3-yll-N-ethyl-3,4-dihvdroquinolin-l(2H)-carboxamide.
Figure imgf000139_0001
To the ethyl acetate solution (5 ml) of 6-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)~ 4,5-dihydroisoxazol-3-yl]-l,2,3,4-tetrahydroquinoline (0.163 g), diisopropylethylamine (82 mg) and bis(trichloromethyl)carbonate (64 mg) were added under ice cooling. The reaction solution was stirred for 90 min under ice cooling. After adding an aqueous solution of 70% ethylamine (0.16 ml) to the reaction solution under ice cooling, the reaction solution was stirred at room temperature for 2 hours. Ethyl acetate and water were added to the reaction solution to separate the organic layer, which was then washed with brine and dried over magnesium sulfate. After the filtration, the solution was concentrated under reduced pressure. Residues were purified by silica gel chromatography using a solvent of n-hexane/ethyl acetate (1:2) to obtain the desired compound of 6-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro- isoxazol-3-yl]-N-ethyl-3,4-dihydroquinolin-l(2H)-carboxamide (150 mg).
IH-NMR (CDC13) δ : 1.15 (3H, t), 1.89-1.98 (2H, m), 2.76 (2H, t), 3.28-3.38 (2H, m), 3.64-3.75 (3H, m), 4.06 (IH, d), 5.02 (IH, t), 7.44-7.48 (7H, m).
K: Synthesis of l-IS-β-te.S-dichlorophenvD-S^trifluoromethvQ-S.-l-dihvdro-ZH-pyrrol-S- yll
-Z^-dihydro-lH-inden-l-vn-S-ethylurea (No. 3-112 ).
Step 1. Synthesis of l-oxo-23 -dihvdro-lH-inden-5-carbonitrile.
Figure imgf000140_0001
Under the argon atmosphere, N,N-dimethylformamide solution (50 ml) of
5-bromo-l-indane (5 g), zinc cyanide (1.9 g), and palladium tetrakistriphenylphosphine (2.7 g) was stirred for 1 hour at 85°C. After cooling, the reaction solution was diluted with tert-butylmethylether and washed twice with water. The organic layer was dried over anhydrous magnesium sulfate and then the solvent was removed by distillation under reduced pressure. Thus obtained crystals were washed with tert-butylmethylether to obtain l-oxo-2,3-dihydro-lH-inden- -5-carbonitrile (3.0 g).
1H-NMR (CDCl3) δ : 2.76-2.80 (2H, m), 3.21-3.24 (2H, m), 7.65-7.67 (IH, m), 7.82-7.85 (2H, m).
Step 2. Synthesis of l-oxo-2,3-dihvdro-lH-inden-5-carboxyic acid.
Figure imgf000140_0002
l-oxo-2,3-dihydro-lH-inden-5-carbonitrile (1.0 g) was suspended in a solution of concentrated hydrochloric acid (10 ml) and acetic acid (20 ml), and stirred at 12 00C for 16 hours. After cooling, the reaction solution was concentrated under reduced pressure, tert-butyl methyl ether and water was added and then stirred. The organic layer was dried over anhydrous magnesium sulfate. After removing the solvent by distillation under reduced pressure, l-oxo-2,3-dihydro-lH-inden-5-carboxyic acid (0.7 g) was obtained. 1H-NMR (acetone-^) δ : 2.69-2.75 (3H, m), 3.23-3.25 (3H, m), 7.74(1H, d), 8.04 (IH, d), 8.19
(IH, s).
Step 3. Synthesis of l-oxo-N-rftrimethylsilylmethyli^^-dihydro-lHinden-S-carboxyamide.
Figure imgf000141_0001
l-oxo-2,3-dihydro-lH-inden-5-carboxyic acid (0.1 g), (triniethylsilyl)methylamine
(0.06 g), N,N-dimethylaminopyridine (0.01 g) and N-(3-dimethylaminopropyl)~ N'-ethylcarbodiimide hydrochloride (0.12 g) were dissolved in methylene chloride (5 ml), and the resulting mixture was stirred for 5 hours at room temperature. After adding water, the reaction solution was stirred and the organic layer was dried over anhydrous magnesium sulfate. After removing the solvent by distillation under reduced pressure, and the resulting residues were purified with silica gel chromatography, l-oxo-N-[(trimethylsilylmethyl]-2,3-dihydro-lHinden- -5-carboxyamide was obtained (0.11 g).
1H-NMR (CDCl3) δ : 0.15 (9H, s), 2.72-2.76 (2H, m), 2.99 (2H, d, J = 5.9 Hz), 3.18-3.20 (2H, m), 6.05 (IH, br s), 7.66 (IH, d), 7.79 (IH, d), 7.87 (IH, s).
Step 4. Synthesis of tert-butyl(5-f[(trimethylsilyl)methyl1carbamoyl)-2,3-dihydro-lH-inden -l-yl)carbamate.
Figure imgf000141_0002
l-oxo-N-[(trimethylsilylmethyl]-2,3-dihydro-lHinden-5-carboxyamide (1.0 g), ammonium acetate (3.2 g) and sodium cyanoborohydride (0.4 g) were dissolved in methanol (30 ml), refluxed for 6 hours under the argon atmosphere, and stirred further at room temperature for 5 hours. The solvent was removed by distillation under reduced pressure, and tert-butyl methyl ether and water were added to the residues and stirred. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed by distillation under reduced pressure. The residues were dissolved in toluene (30 ml), di-tert-butyl bicarbonate (1.0 g) was added thereto, and the resulting mixture was heated under stirring for 30 min at 1000C. After cooling, the solvent was removed by distillation and the residues were purified by silica gel chromatography to obtain tert-butyl(5-{[(trimethylsilyl)methyl]carbamoyl}-2,3-dihydro-lH-inden-l-yl)carbamate (0.25 g).
1H-NMR (CDCl3) δ : 0.13 (9H,s), 1.49 (9H, s), 1.78-1.84 (IH, m), 2.56-2.66 (IH, m), 2.85-2.98 (4H, m), 4.74-4.77 (IH, m), 5.18-5.21 (IH, m), 5.93-5.96 (IH, m), 7.35 (IH, d), 7.55-7.58 (2H, m).
Step 5. Synthesis of tert-butyl(5-{[(trimethylsilyl)methyllcarbamothiovU-2,3-dihvdro - 1 H-inden- 1 -vDcarbamate.
Figure imgf000142_0001
Tert-butyl(5- { [(trimethylsilyl)methyl]carbamoyl} -2,3-dihydro- 1 H-inden- 1 -yl)carbamate (0.25 g) and Lawesson's reagent (0.2 g) were suspended in toluene (10 ml), and the resulting mixture was refluxed under heating for 1 hour. After cooling down to room temperature, the reaction solution was washed with water and saturated brine. The organic layer was dried over anhydrous magnesium sulfate. After removing the solvent under reduced pressure, and the residues were purified by silica gel chromatography, tert-butyl(5-{[(trimethylsilyl)methyl]carbamothioyl}-2,3-dihydro-lH-inden-l-yl)carbamate was obtained(0.25 g).
1H-NMR (CDCl3) δ : 0.18 (9H, s), 1.46 (9H, s), 1.69-1.77 (IH, m), 2.46-2.56 (IH, m), 2.71-2.97 (2H, m), 3.52 (2H, d), 4.76-4.79 (IH, m), 4.98-5.01 (IH, m), 7.23 (IH, d), 7.45 (IH, d), 7.57 (IH, s), 7.96 (lH, br s).
Step 6. Synthesis of methyl l-fdert-butoxycarbonvDaminoi-N-fdrimethylsilylimethyl] -2,3-dihydro-lH-inden-5-carboimide thioate.
Figure imgf000143_0001
Tetrahydrofuran (10 ml) solution of methyl iodide (0.1 g), potassium tert-butoxide (0.09 g) and tert-butyl(5- { [(trimethylsilyl)methyl]carbamothioyl} -2,3-dihydro- 1 H-inden- 1 -yl)carbamate (0.25 g) was stirred for 2 hours at room temperature. The reaction solution was diluted by adding t-butyl methyl ether, and then washed with water and saturated brine. The organic layer was dried over anhydrous magnesium sulfate. After removing the solvent by distillation, residues were simply purified by silica gel chromatography to obtain methyl 1 -[(tert-butoxycarbonyl)amino- ]-N-[(trimethylsilyl)methyl]-2,3-dihydro-lH-inden-5-carboimide thioate (0.25 g).
Step 7. Synthesis of tert-butyl (5-[3-(3,5-dicmorophenyl)-3-(trifluoromethyl)-3,4 -dihvdro-2H-pyrrol-5 -yll -2 ,3 -dihydro- 1 H-inden- 1 -yl ) carbamate.
Figure imgf000143_0002
Under the argon atmosphere, tetrahydrofuran solution (10 ml) of methyl l-[(tert-butoxycarbonyl)amino]-N-[(trimethylsilyl)methyl]-2,3-dihydro-lH-inden-5-carboimide thioate (0.25 g) and l,3-dichloro-5-(3,3,3-trifluoropro-l-pene-2-yl)benzene (0.15 g) was cooled to -5°C, and then IM tetrahydrofuran solution of tetrabutylammonium fluoride (0.2 ml) was slowly added dropwise thereto. The reaction solution was stirred at room temperature for 20 hours, and then diluted with tert-butyl methyl ether and washed with water and saturated brine. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed by distillation under reduced pressure. The residues were purified by silica gel chromatography to obtain tert-butyl {5-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-
-5-yl]-2,3-dihydro-lH-inden-l-yl}carbamate (0.23 g).
1H-NMR (CDCl3) δ : 1.49 (9H, s), 1.78-1.88 (IH, m), 2.59-2.62 (IH, m), 2.80-3.02 (2H, m), 3.44 (IH, d), 3.79 (IH, d), 4.41 (IH, d), 4.83-4.89 (2H, m), 5.19-5.22 (IH, m), 7.26-7.29 (2H, m), 7.36-7.39 (2H, m), 7.66-7.73 (2H, m).
Step 8. Synthesis of 5-f3-(3.5-dichlorophenyl)-3-(trifluoromethyl)-3,4-dihvdro-2H-pyrrol-5-yll -2.3 -dihydro- 1 H-inden- 1 -amine.
Figure imgf000144_0001
To the methylenechloride solution (10 ml) of tert-butyl {5-[3-(3,5-dichlorophenyl)~ 3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]-2,3-dihydro-lH-inden-l-yl}carbamate (0.23 g), trifluoroacetic acid (0.5 g) was added and then the resulting mixture was stirred at room temperature for 2 hours. Under reduced pressure, the solvent was removed by distillation, and tert-butyl methyl ether and a saturated aqueous solution of sodium hydrocarbonate were added to the residues and stirred. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed by distillation under reduced pressure to obtain 5-[3-(3,5-dichlorophenyl)~
3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]-2,3-dihydro-lH-inden-l -amine (0.17 g).
1H-NMR (CDCl3) δ : 1.85-1.95 (IH, m), 2.51-2.55 (IH, m), 2.82-3.46 (5H, m), 3.77 (IH, d), 4.36-4.52 (2H, m), 4.80-4.85 (IH, m), 7.24-7.28 (2H, m), 7.36-7.37 (IH, m), 7.45 (IH, d, J = 7.9
Hz), 7.69-7.72 (2H, m).
Step 9. Synthesis of l-(5-[3-(3.5-dichlorophenyl')-3-(trifluoromethyl)-3.4-dihvdro-2H-pyrrol - -S-yll^J-dihvdro-lH-inden-l-vU-S-ethylurea.
Figure imgf000145_0001
After stirring the tetrahydrofuran solution (5 ml) of 5-[3-(3,5-dichlorophenyl)~
3-(trifluoromethyl)-3,4-dihydro-2H-pyrrol-5-yl]-2,3-dihydro-lH-inden-l -amine (0.09 g) and ethyl isocyanate (0.02 g) for 16 hours, the solvent was removed by distillation. With the purification based on silica gel chromatography, l-{5-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)~ 3,4-dihydro-2H-pyrrol-5-yl]-2,3-dihydro-lH-inden-l-yl}-3-ethylurea was obtained (0.06 g).
1H-NMR (CDCl3) δ : 1.11 (3H, t), 1.65-1.82 (IH, m), 2.51-2.56 (IH, m), 2.77-2.89 (2H, m), 3.17-3.22 (2H, m), 3.42 (IH, d), 3.77 (IH, d), 4.40 (IH, d), 4.81-4.86 (2H, m), 4.98 (IH, d), 5.25-5.28 (IH, m), 7.27-7.37 (4H, m), 7.62-7.68 (2H, m).
L: Synthesis of 6-[5-(3.5-dichlorophenyr)-5-(trifluoromethyr)-4,5-dihvdroisoxazol -3-vU quinolin-2-carbonitriIe (No. 1-255).
Step 1. Synthesis of 6-r5-(3.5-dicMorophenyl)-5-(trifluoromethyl)A5-dihvdroisoxazol-3-yl1 Quinoline 1 -oxide.
Figure imgf000146_0001
6-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]quinoline (0.30 g) was dissolved in methylene chloride (15 ml), and then 3-chloroperbenzoic acid (0.21 g) was added thereto at room temperature. After stirring the mixture for 5 hours, an aqueous solution of sodium thiosulfate was added thereto. The organic layer was separated and washed with an aqueous solution of sodium carbonate. After drying over magnesium sulfate, the title compound was obtained as a crude product (0.24 g).
IH-NMR (CDC13) δ : 3.82 (IH, d), 4.21 (IH, d), 7.37 (IH, dd), 7.44-7.45 (IH, m), 7.53-7.54 (2H, m), 7.74 (IH, d), 8.02-8.02 (IH, m), 8.15 (IH, dd), 8.55 (IH, d), 8.79 (IH, d).
Step 2. Synthesis of 6-r5-(3.5-dichlorophenyl)-5-(trifluoromethyl)-4.5-dihvdroisoxazol-3-yl] quinolin-2-carbonitrile.
Figure imgf000146_0002
Trimethylsilylcyanide (0.30 g) and triethylamine (0.20 g) were added to acetonitrile (10 ml) solution of 6-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]quinoline 1 -oxide, and then the reaction solution was refluxed for 6 hours. After adding ethyl acetate and water to the reaction solution, the organic layer was separated and washed with brine. The organic layer was dried over magnesium sulfate. After the filtration, it was concentrated under reduced pressure. The residues were purified by silica gel chromatography using the solvent of n-hexane/ethyl acetate (3:1) to obtain the title compound of 6-[5-(3,5-dichlorophenyl)~ 5 -(trifluoromethyl)-4,5 -dihydroisoxazol-3 -yl]quinolin-2-carbonitrile (0.30 g) .
1H-NMR (CDCl3) δ : 3.84 (IH, d), 4.22 (IH, d), 7.44 (IH, t), 7.54-7.54 (2H, m), 7.77 (IH, d), 8.00 (IH, d), 8.21 (IH, d Hz), 8.29-8.33 (2H, m).
M: Synthesis of l-chloro-ό-fS-O.S-dichlorophenvD-S-ftrifluoromethvπ^^S-dihydroisoxazol -3-yllαuinoline (No. 3-777) and 4-chloro-6-[5-(3,5-dichlorophenyr>-5-(trifluor()methvI)-4,5- dihydroisoxazoI-3-vn quinoline.
Figure imgf000147_0001
6-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]quinoline 1 -oxide (0.24 g) was dissolved in phosphorus oxychloride (0.60 ml) at room temperature, and stirred for 9 hours. Ethyl acetate and water were added to the reaction solution for extraction. The organic layer was dried over magnesium sulfate, and the solvent was removed by distillation. With the purification based on silica gel chromatography, 4-chloro-6-[5-(3,5-dichlorophenyl)~ 5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]quinoline was obtained (0.083 g, yield 22%), and also 2-chloro-6-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-yl]quinoline was obtained (0.12 g, yield 30%).
IH-NMR(CDCB) δ : 3.81 (d, IH), 4.20 (d, IH), 7.40-7.49 (m, 2H), 7.54 (s, 2H), 7.96 (s, IH), 8.01-8.22 (m, 3H) of 2-chloro-6-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4,5-dihydro- isoxazol-3 -yl] quinoline.
1H-NMR(CDC13) δ : 3.86 (d, IH), 4.25 (d, IH), 7.45 (s, IH), 7.53-7.60 (m, 3H) 8.16 (d, IH), 8.24-8.31 (m, 2H), 8.84 (d, IH) of 4-chloro-6-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)- 4,5-dihydroisoxazol-3-yl]quinoline.
The compounds of the present invention as well as useful intermediates for the manufacturing of the compounds are described in the following tables. In the tables, abbreviations are as follows. Pr: propyl, Bu: butyl, Ph: phenyl, py: pyridyl, n-: normal, iso-: iso, tert-: tertiary, eye-: cyclo, dio: dioxolan, pyrim: pyrimidine, pyra: pyrazole, tria: triazole, thia: thiazole. In addition, symbol (-) described in columns for Wl to W4 indicates a single bond, ie. that W is omitted.
Table 1
Figure imgf000148_0001
Figure imgf000148_0002
Figure imgf000149_0001
Figure imgf000150_0001
Figure imgf000151_0001
Figure imgf000152_0001
Figure imgf000153_0001
Figure imgf000154_0001
Figure imgf000155_0001
Figure imgf000156_0001
Figure imgf000157_0002
Table 2
Figure imgf000157_0001
Figure imgf000157_0003
Figure imgf000158_0001
Figure imgf000159_0001
Figure imgf000160_0001
Figure imgf000161_0001
Figure imgf000162_0001
Figure imgf000163_0001
Figure imgf000163_0002
Figure imgf000164_0001
Figure imgf000165_0001
Figure imgf000166_0001
Figure imgf000167_0001
Figure imgf000168_0001
Figure imgf000169_0001
Figure imgf000170_0001
O
Figure imgf000171_0001
Figure imgf000172_0001
Figure imgf000173_0001
Figure imgf000174_0001
Figure imgf000175_0001
Figure imgf000176_0001
Figure imgf000177_0001
Figure imgf000178_0001
Figure imgf000179_0001
Figure imgf000180_0001
Figure imgf000181_0001
Figure imgf000182_0001
Figure imgf000183_0001
Figure imgf000184_0001
Figure imgf000185_0001
Figure imgf000186_0001
Figure imgf000187_0001
Figure imgf000188_0001
Figure imgf000189_0001
Figure imgf000190_0001
Figure imgf000191_0001
Figure imgf000192_0001
Figure imgf000193_0001
Figure imgf000194_0001
Figure imgf000195_0001
Figure imgf000196_0001
Figure imgf000197_0001
Figure imgf000198_0001
Figure imgf000199_0001
Figure imgf000200_0001
Figure imgf000201_0001
Figure imgf000202_0001
Figure imgf000203_0001
Figure imgf000204_0001
Figure imgf000205_0001
Figure imgf000206_0001
Figure imgf000207_0001
Figure imgf000207_0002
Figure imgf000208_0001
Figure imgf000209_0001
Figure imgf000210_0001
Figure imgf000211_0001
Figure imgf000212_0001
Figure imgf000213_0001
Figure imgf000214_0001
Figure imgf000215_0001
Figure imgf000216_0001
Figure imgf000217_0002
Table 5
Figure imgf000217_0001
Figure imgf000217_0003
Figure imgf000218_0001
Figure imgf000219_0001
Figure imgf000220_0001
Figure imgf000221_0001
Figure imgf000222_0001
Figure imgf000223_0001
Table 6
Figure imgf000224_0001
Figure imgf000224_0002
Figure imgf000225_0001
Figure imgf000226_0001
Figure imgf000227_0001
Figure imgf000228_0001
Figure imgf000229_0001
Figure imgf000230_0001
Figure imgf000231_0001
Table 6-1
Figure imgf000232_0001
Figure imgf000232_0002
Figure imgf000233_0001
Figure imgf000234_0001
Figure imgf000235_0001
Figure imgf000236_0001
Figure imgf000237_0001
Figure imgf000238_0001
Figure imgf000239_0001
Table 6-2
Figure imgf000240_0001
Figure imgf000240_0002
Figure imgf000241_0001
Figure imgf000242_0001
Figure imgf000243_0001
Figure imgf000244_0001
Figure imgf000245_0001
Figure imgf000246_0001
Figure imgf000247_0001
Table 7
Figure imgf000248_0001
Figure imgf000248_0002
Figure imgf000249_0001
Figure imgf000250_0001
Figure imgf000251_0001
Figure imgf000252_0001
Figure imgf000253_0001
Figure imgf000254_0001
Figure imgf000255_0001
Figure imgf000256_0001
Figure imgf000257_0001
Figure imgf000258_0001
Figure imgf000259_0001
Figure imgf000260_0001
Figure imgf000261_0001
Figure imgf000262_0001
Figure imgf000263_0002
Table 8
Figure imgf000263_0001
Figure imgf000263_0003
Figure imgf000264_0001
Figure imgf000265_0001
Figure imgf000266_0001
Figure imgf000267_0001
Figure imgf000268_0001
Figure imgf000269_0001
Figure imgf000270_0001
Figure imgf000271_0001
Figure imgf000272_0001
Table 9
Figure imgf000273_0001
Figure imgf000273_0002
Figure imgf000274_0001
Figure imgf000275_0001
Figure imgf000276_0001
Figure imgf000277_0001
Figure imgf000278_0001
Figure imgf000279_0001
Figure imgf000280_0001
Figure imgf000281_0001
Figure imgf000282_0001
Figure imgf000283_0001
Figure imgf000284_0001
Figure imgf000285_0001
Figure imgf000286_0001
Figure imgf000287_0001
Figure imgf000288_0001
Figure imgf000289_0001
Figure imgf000290_0001
Figure imgf000291_0001
Figure imgf000292_0001
Figure imgf000293_0001
Figure imgf000294_0001
Figure imgf000295_0001
Figure imgf000296_0001
Figure imgf000297_0001
Figure imgf000298_0001
Figure imgf000299_0001
Figure imgf000300_0001
Figure imgf000301_0001
Figure imgf000302_0001
Figure imgf000303_0001
Figure imgf000304_0001
Figure imgf000305_0001
Figure imgf000306_0001
Figure imgf000307_0001
Figure imgf000308_0001
Biological test example 1; Test on Spodoptera litura larvae
Solvent: Dimethylformamide, 3 parts by weight
Emulsifϊer: Polyoxyethylene alkylphenyl ether, 1 part by weight
To prepare the test solution 1 part by weight of the active compound is mixed with the above-described amount of the solvent which contains the above-described amount of emulsifier. The resulting mixture is diluted with water to a predetermined concentration.
Leaves of sweet potato were immersed in the test solution. The leaves are air-dried and placed in a petri dish (9 cm diameter). 10 Spodoptera litura third instar larvae were released in the petri dish, which was then stored in a constant temperature room (250C). More sweet potato leaves were added after 2 and 4 days. 7 days after the release of the larvae mortality was calculated by counting the number of dead larvae. 100 % means that all the larvae have been killed; 0 % means that none of the larvae have been killed. In the present test, an average value was taken from the results obtained from 2 petri dishes for 1 group.
Compounds having the example nos. 1-50 and 1-58, known from WO2005/085216, showed a control efficacy with 100% mortality at an active compound concentration of 100 ppm.
The following compounds showed a control efficacy with 100% mortality at an active compound concentration of 100 ppm :
Example Nos.: 1-2, 1-10, 1-38, 1-44, 1-54, 1-56, 1-67, 1-69, 1-79, 1-80, 1-114, 1-12 1, 1-12 5, 1-12 6, 1-12 7, 1-12 9, 1-131, 1-132, 1-150, 1-211, 1-213, 1-223, 1-232, 1-235, 1-250, 1-255, 1-259, 1-264, 1-271, 1-272, 1-273, 1-295, 3-1, 3-3, 3-4, 3-6, 3-7, 3-8, 3-9, 3-23, 3-32, 3-39, 3-40, 3-42, 3-43, 3-44, 3-45, 3-48, 3-55, 3-57, 3-61, 3-73, 3-74, 3-81, 3-82, 3-88, 3-89, 3-90, 3-91, 3-92, 3-93, 3-95, 3-97, 3-98, 3-104, 3-106, 3-112 , 3-140, 3-142, 3-143, 3-145, 3-166, 3-188, 3-191, 3-193, 3-211, 3-213, 3-217, 3-218, 3-219, 3-220, 3-221, 3-230, 3-235, 3-236, 3-238, 3-239, 3-241, 3-251, 3-253, 3-254, 3-256, 3-257, 3-258, 3-259, 3-261, 3-270, 3-302, 3-303, 3-304, 3-305, 3-306, 3-307, 3-320, 3-322, 3-323, 3-326, 3-355, 3-358, 3-361, 3-547, 3-549, 3-551, 3-637, 3-638, 3-641, 3-642, 3-643, 3-644, 3-645, 3-646, 3-649, 3-650, 3-652, 3-656, 3-659,3-661, 3-663, 3-664, 3-782, 3-785, 3-829, 3-831, 3-832, 3-833, 3-835, 3-836, 3-837, 3-838, 3-839, 3-840, 3-841, 3-842, 3-843, 3-844, 3-845, 3-846, 3-847, 3-848, 3-849, 3-850, 3-851, 3-852, 3-853, 3-854, 3-855, 3-856, 3-858, 3-859, 3-862, 3-863, 3-864, 3-865, 3-866, 3-867, 3-868, 3-869, 3-870, 3-871, 3-872, 3-873, 3-874, 3-875, 3-876, 3-877, 3-878, 3-879, 3-880, 3-881, 3-882, 3-883, 3-884, 3-885, 3-886, 3-887, 3-888, 3-889, 3-890, 3-891, 3-892, 3-893, 3-894, 3-896, 3-897, 3-898, 3-899, 3-900, 3-902, 3-904, 3-916, 3-917, 3-918, 3-919.
Biological test example 2: Test on Tetranychus urticae (Spray test)
The test solution has been prepared as described in biological test example 1.
50 to 100 adult Tetranychus urticae were placed on pinto bean leaves at true leaf stage having two main leaves that had been grown in a pot (6 cm diameter). After 1 day, a generous amount of the test solution which has been diluted with water to the predetermined concentration was sprayed thereto using a spray gun.
After keeping the pot in a green house for 7 days, acaricidal ratio was calculated. 100 % means that all the mites have been killed; 0 % means that none of the mites have been killed.
The compound having the example no. 1-58, known from WO2005/085216, showed a control efficacy with at least 98% mortality at an active compound concentration of 100 ppm.
The following compounds showed a control efficacy with at least 98% mortality at an active compound concentration of 100 ppm : Example Nos.: 1-38, 1-44, 1-114, 1-12 7, 1-12 9, 1-132, 1-232, 1-235, 1-259, 1-264, 1-273, 3-3, 3-4, 3-6, 3-7, 3-8, 3-9, 3-23, 3-32, 3-39, 3-40, 3-42, 3-43, 3-44, 3-45, 3-48, 3-55, 3-57, 3-61, 3-70, 3-73, 3-74, 3-81, 3-82, 3-88, 3-89, 3-90, 3-91, 3-92, 3-93, 3-95, 3-97, 3-98, 3-106, 3-112 , 3-142, 3-143, 3-145, 3-166, 3-188, 3-191, 3-193, 3-213, 3-216, 3-217, 3-218, 3-219, 3-220, 3-221, 3-230, 3-235, 3-236, 3-238, 3-239,3-253, 3-254, 3-256, 3-257, 3-258, 3-259, 3-261, 3-270, 3-302, 3-303, 3-304, 3-305, 3-306, 3-307, 3-323, 3-326, 3-355, 3-358, 3-361, 3-549, 3-551, 3-642,3-644, 3-661, 3-829, 3-832, 3-833, 3-835, 3-836, 3-838, 3-839, 3-840, 3-841, 3-842, 3-843, 3-844, 3-845, 3-846, 3-847, 3-848, 3-849, 3-850, 3-851, 3-852, 3-853, 3-854, 3-855, 3-856, 3-859, 3-862, 3-863, 3-864, 3-865, 3-866, 3-867, 3-868, 3-869, 3-870, 3-871, 3-872, 3-873, 3-874, 3-875, 3-876, 3-877, 3-878, 3-880, 3-881, 3-883, 3-884, 3-885, 3-886, 3-887, 3-888, 3-889, 3-890, 3-891, 3-892, 3-893, 3-895, 3-896, 3-897, 3-898, 3-899, 3-900, 3-902, 3-903, 3-917, 3-918, 3-919.
Biological test example 3: Test on Aulacophora femoralis (Spray application)
The test solution has been prepared as described in biological test example 1.
Cucumber leaves were immersed in a test solution that had been diluted to a predetermined concentration with water. The leaves were air-dried and then put in a plastic cup containing sterilized black soil. 5 Aulacophora femoralis second instar larvae were released in the cup. 7 days later, mortality was calculated by counting the number of dead larvae. 100 % means that all larvae have been killed; 0 % means that none of the larvae have been killed.
Compounds having the example nos. 1-50, 1-52, and 1-58, known from WO2005/085216, showed a control efficacy with 100% mortality at an active compound concentration of 100 ppm.
The following compounds showed a control efficacy with 100% mortality at an active compound concentration of 100 ppm :
Example Nos.: 1-2, 1-38, 1-44, 1-54, 1-61, 1-64, 1-80, 1-114, 1-115, 1-12 5, 1-12 7, 1-12 9, 1-131, 1-132, 1-142, 1-150, 1-151, 1-169, 1-221, 1-232, 1-251, 1-259,1-264, 1-272, 1-273, 3-1, 3-3, 3-4, 3-6, 3-7, 3-8, 3-9, 3-23, 3-32,3-39, 3-40, 3-42, 3-43, 3-44, 3-45, 3-48, 3-55, 3-57, 3-61, 3-73, 3-74, 3-81, 3-82, 3-88, 3-89, 3-90, 3-91, 3-92, 3-93, 3-95, 3-97, 3-98, 3-106, 3-112 , 3-142, 3-143, 3-145, 3-166, 3-188, 3-191, 3-193, 3-211, 3-213, 3-217, 3-218, 3-220, 3-221, 3-230, 3-235, 3-236, 3-238, 3-239, 3-241, 3-253, 3-254, 3-256, 3-257, 3-258, 3-259, 3-261, 3-270, 3-302, 3-303, 3-304, 3-305, 3-306, 3-307, 3-323, 3-326, 3-358, 3-361, 3-547, 3-549, 3-551, 3-637, 3-638, 3-640, 3-642, 3-643, 3-644, 3-645, 3-646, 3-651, 3-652, 3-659, 3-663, 3-664, 3-779, 3-785, 3-829, 3-831, 3-832, 3-833, 3-835, 3-836, 3-837, 3-838, 3-839, 3-841, 3-842, 3-843, 3-844, 3-845, 3-846, 3-847, 3-848, 3-849, 3-850, 3-851, 3-852, 3-853, 3-854, 3-855, 3-856, 3-859, 3-862, 3-863, 3-864, 3-865, 3-866, 3-867, 3-868, 3-869, 3-870, 3-871, 3-872, 3-873, 3-874, 3-875, 3-876, 3-877, 3-878, 3-880, 3-881, 3-882, 3-883, 3-884, 3-885, 3-886, 3-887, 3-888, 3-889, 3-890, 3-891, 3-892, 3-893, 3-894, 3-895, 3-896, 3-897, 3-898, 3-899, 3-900, 3-901, 3-902, 3-903, 3-904, 3-917, 3-918, 3-919.
Biological test example 4: Musca domestica - test
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 or 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. Compounds having the example nos. 1-50, 1-52, and 1-58, known from WO2005/085216, showed good acitivity of > 80 % at application rate of 100 ppm.
In this test for example, the following compounds from the preparation examples showed good activity of > 80 % at application rate of 100 ppm:
Example Nos.: 1-2, 1-10, 1-38, 1-44, 1-54, 1-56, 1-61, 1-64, 1-80, 1-114, 1-12 5, 1-126, 1-129, 1-131, 1-132, 1-142, 1-211 , 1-213, 1-232, 1-235, 1-255, 1-264, 1-271, 1-272, 3-3, 3-7, 3-9, 3- 23, 3-32, 3-39, 3-40, 3-42, 3-43, 3-44, 3-45, 3-48, 3-55, 3-90, 3-91, 3-92, 3-93, 3-95, 3-106, 3- 112 , 3-213, 3-217, 3-218, 3-221, 3-230, 3-235, 3-236, 3-239, 3-253, 3-256, 3-257, 3-258, 3- 259, 3-261, 3-270, 3-302, 3-304, 3-305, 3-320, 3-323, 3-326, 3-637, 3-638, 3-640, 3-641, 3- 642, 3-643, 3-644, 3-645, 3-646, 3-651, 3-652, 3-656, 3-785, 3-829, 3-832, 3-833, 3-835, 3- 836, 3-838, 3-844, 3-845, 3-846, 3-307, 3-847, 3-848, 3-851, 3-57, 3-849, 3-89, 3-303, 3-852, 3-4, 3-878, 3-8, 3-859, 3-862, 3-863, 3-864, 3-865, 3-74, 3-254, 3-917, 3-918, 3-880, 3-98, 3- 881, 3-853, 3-868, 3-73, 3-897, 3-898, 3-97, 3-81, 3-872, 3-361, 3-355, 3-358.
Biological test example 5: Lucillia cuprina - test
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. Approximately 20 -30 (Lucilia cuprina larvae) are transferred into a test tube containing lcm3 of minced horse meat and 0.5 ml aqueous dilution of test compound. After 2 days, mortality in % is deteπnined. 100 % means that all the larvae have been killed; 0 % means that none of the larvae have been killed.
Compounds having the example nos. 1-50, 1-52 and 1-58, known from WO2005/085216, showed good activity of > 80 % at application rate of lOOppm.
In this test for example, the following compounds from the preparation examples showed good activity of > 80 % at application rate of lOOppm:
Example Nos.: 1-2, 1-10, 1-38, 1-44, 1-54, 1-56, 1-61, 1-64, 1-67, 1-69, 1-79, 1-80, 1-114, 1- 116, 1-12 1, 1-12 5, 1-12 6, 1-12 9, 1-131 , 1-132, 1-142, 1-150, 1-151, 1-155, 1-164, 1-211, 1- 213, 1-232, 1-235, 1-241, 1-255, 1-264, 1-270, 1-271, 1-272, 3-3, 3-7, 3-9, 3-23, 3-32, 3-39, 3- 40, 3-42, 3-43, 3-44, 3-45, 3-48, 3-55, 3-70, 3-90, 3-91, 3-92, 3-93, 3-95, 3-106, 3-112 , 3-213, 3-216, 3-217, 3-218, 3-219, 3-221, 3-230, 3-235, 3-236, 3-239, 3-241, 3-253, 3-256, 3-257, 3- 258, 3-259, 3-261, 3-270, 3-302, 3-304, 3-305, 3-320, 3-323, 3-326, 3-344, 3-637, 3-638, 3- 640, 3-641, 3-642, 3-643, 3-644, 3-645, 3-646, 3-651, 3-652, 3-656, 3-659, 3-660, 3-661A, 3- 663, 3-664, 3-785, 3-828, 3-829, 3-831, 3-832, 3-833, 3-835, 3-836, 3-838, 3-844, 3-845, 3- 846, 3-307, 3-847, 3-848, 3-851, 3-57, 3-849, 3-89, 3-303, 3-852, 3-4, 3-878, 3-8, 3-859, 3- 862, 3-863, 3-864, 3-865, 3-74, 3-254, 3-917, 3-918, 3-880, 3-98, 3-881, 3-853, 3-868, 3-73, 3- 897, 3-898, 3-97, 3-81, 3-872, 3-361, 3-355, 3-358.
Biological test example 6: Ctenocephalides felis - test
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 10 to 15 adult unfed (Ctenocepahlides felis) are placed in flea chambers. The blood chamber, are 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 0C 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.
Compounds having the example nos. 1-50, 1-52 and 1-58, known from WO2005/085216, showed good activity of > 80 % at application rate of lOOppm.
In this test for example, the following compounds from the preparation examples showed good activity of > 80 % at application rate of lOOppm:
Example Nos.: 1-2, 1-10, 1-38, 1-44, 1-54, 1-56, 1-61, 1-64, 1-67, 1-80, 1-114, 1-115, 1-121, 1- 125, 1-12 6, -129, 1-131, 1-132, 1-150, 1-164, 1-232, 1-235, 1-255,1-264, 1-271, 1-272, 3-3, 3- 7, 3-9, 3-23, 3-32, 3-39, 3-40, 3-42, 3-43, 3-44, 3-45, 3-48, 3-55, 3-90, 3-91, 3-92, 3-93, 3-95, 3-106, 3-112 , 3-213, 3-216, 3-217, 3-218, 3-221, 3-230, 3-235, 3-236, 3-239, 3-241, 3-253, 3- 256, 3-257, 3-258, 3-259, 3-261, 3-270, 3-302, 3-304, 3-305, 3-320, 3-323, 3-326, 3-637, 3- 638, 3-640, 3-641, 3-642, 3-643, 3-644, 3-645, 3-646,3-651, 3-652, 3-656, 3-663, 3-785, 3-829, 3-831, 3-832, 3-833, 3-835, 3-836, 3-838, 3-844, 3-845, 3-846, 1-69, 3-307, 3-847, 3-848, 3- 851, 3-57, 3-849, 3-89, 3-303, 3-852, 3-4, 3-878, 3-8, 3-859, 3-862, 3-863, 3-864, 3-865, 3-74, 3-254, 3-917, 3-918, 3-880, 3-98, 3-881, 3-853, 3-868, 3-73, 3-897, 3-898, 3-97, 3-81, 3-872, 3-361, 3-355, 3-358.
Biological test example 7: Boophilus microplus - test (injection)
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 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.
Compounds having the example nos. 1-50, 1-52 and 1-58, known from WO2005/085216, showed good activity of > 80 % at application rate of 20μg/animal.
In this test for example, the following compounds from the preparation examples showed good activity of > 80 % at application rate of 20μg/animaI:
Example Nos.: 1-2, 1-10, 1-38, 1-44, 1-54, 1-56, 1-61, 1-64, 1-67, 1-69, 1-79, 1-80, 1-114, 1- 115, 1-116, 1-12 1, 1-12 5, 1-12 6, 1-12 9, 1-131, 1-132, 1-142, 1-150, 1-151, 1-164, 1-169, 1-175, 1-211, 1-213, 1-232, 1-235, 1-241 , 1-255, 1-264, 1-270, 1-271, 1-272, 3-3, 3-7, 3-9, 3- 23, 3-32, 3-39, 3-40, 3-42, 3-43, 3-44, 3-45, 3-48, 3-55, 3-70, 3-90, 3-91, 3-92, 3-93, 3-95,3- 106, 3-112 , 3-137, 3-138, 3-211, 3-213, 3-216, 3-217, 3-218,3-219, 3-221, 3-230, 3-235, 3- 236, 3-239, 3-241, 3-253, 3-254, 3-256, 3-257, 3-258, 3-259, 3-261, 3-270, 3-302, 3-304, 3- 305, 3-320, 3-323, 3-326, 3-344, 3-637, 3-638, 3-640, 3-641, 3-642, 3-643, 3-644, 3-645, 3- 646, 3-651, 3-652, 3-656, 3-659, 3-660, 3-661A, 3-663, 3-664, 3-785, 3-828, 3-829, 3-832, 3- 833, 3-835, 3-836, 3-838, 3-844, 3-845, 3-846, 3-307, 3-847, 3-848, 3-851, 3-57, 3-849, 3-89, 3-303, 3-852, 3-4, 3-878, 3-8, 3-859, 3-862, 3-863, 3-864, 3-865, 3-74, 3-254, 3-917, 3-918, 3-
880, 3-98, 3-881, 3-853, 3-868, 3-73, 3-897, 3-898, 3-97, 3-81, 3-872, 3-361, 3-355, 3-358.
Biological test example 8; Boophilus microplus - test (dip)
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 > 80 % at application rate of 100 ppm:
Example Nos.: 1-2, 1-38, 1-1 14, 3-3, 3-4, 3-7, 3-8, 3-9, 3-23, 3-39, 3-40, 3-42, 3-43, 3- 44, 3-45, 3-48, 3-55, 3-57, 3-74, 3-89, 3-90, 3-91, 3-92, 3-93, 3-98, 3-106, 3-112 , 3- 213, 3-217, 3-218, 3-221, 3-235, 3-239, 3-253, 3-254, 3-256, 3-257, 3-258, 3-259, 3- 261, 3-270, 3-305, 3-307, 3-323, 3-326, 3-358, 3-361, 3-785, 3-835, 3-836, 3-838, 3- 844,3-845, 3-846, 3-847, 3-849, 3-851, 3-852, 3-863, 3-864, 3-865, 3-878, 3-880, 3-
881, 3-917, 3-307, 3-847, 3-851, 3-57, 3-849, 3-89, 3-852, 3-4, 3-878, 3-8, 3-863, 3- 864, 3-865, 3-74, 3-254, 3-917, 3-880, 3-98, 3-881, 3-853, 3-868, 3-73, 3-897, 3-898, 3-97, 3-81, 3-872, 3-361, 3-358, 3-870, 3-887, 3-890,3-874, 3-875, 3-876, 3-877, 3- 142, 3-145. Biological test example 9: Amblvomma hebraeum - test
Solvent: dimethyl sulfoxide
To produce a suitable preparation of active compound, 10 mg active compound is mixed with
0,5 ml solvent, and the concentrate is diluted with containing solvent 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 Petri dish and incubated in a climate chamber for 42 days. After the specified period of time, 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 >80 % at application rate of lOO ppm:
Example Nos.: 3-9, 3-39, 3-40, 3-90, 3-91, 3-93, 3-832, 3-833, 3-835, 3-836, 3-838
Biological test example 10; Phaedon cochleariae - test (spray application)
Solvent: 78.0 parts by weight of acetone 1.5 parts by weight of dimethylformamide
Emulsifϊer: 0.5 parts by weight of alkylaryl polyglycolether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and emulsifϊer, and the concentrate is diluted with emulsifϊer-containing water to the desired concentration.Chinese cabbage {Brassica pekinesis) leaf-disks are sprayed with a preparation of the active ingredient of the desired concentration. Once dry, the leaf disks are infested with mustard beetle larvae {Phaedon cochleariae).
After 7 days, mortality in % is determined. 100 % means that all beetle larvae have been killed and 0 % means that none of the beetle larvae have been killed.In this test for example, the following compounds from the preparation examples showed good activity of > 80 % at application rate of 500 g/ha:
Example Nos.: 1-2, 1-209, 1-224, 4-3, 4-6,4-11, 4-17, 4-19, 4-41, 4-44, 4-48, 4-56, 4-57
Biological test example 11: Spodoptera frugiperda -test (spray application)
Solvent: 78.0 parts by weight acetone
1.5 parts by weight dimethylformamide Wetting agent 0.5 parts by weight alkylarylpolyglcolether
To produce a suitable preparation of the active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and emulsifier, and the concentrate is dilutes with emulsifϊer-contammg water to the desired concentration.
Maize (Zea mats) leaf sections are sprayed with a preparation of the active ingredient of the desired concentration. Once dry, the leaf sections are infested with fall armyworm larvae (Spodoptera frugiperda). After 7 days, mortality in % is determined. 100 % means that all caterpillars have been killed and 0 % means that none of the caterpillars have been killed. In this test for example, the following compounds from the preparation examples showed good activity of >80 % at application rate of 500 g/ha:
Example Nos. : 1-2, 1-224, 4-3, 4-6, 4-11, 4-17, 4-19, 4-48
Preparation example 1 (granule formulation)
To a mixture including the compound of the present invention (Compound No. 1-2; 10 parts by weight), bentonite (montmoπlonite; 30 parts by weight), talc (58 parts by weight) and hgnm sulfonate (2 parts by weight), water (25 parts by weight) is added and the resulting mixture is kneaded well. By using an extrusive granulator, granules of 10 to 40 mesh are formed and a granule formulation is obtained after drying at 40 to 500C.
Preparation example 2 (granule formulation)
Clay mineral having a size distribution in the range of 0.2-2 mm (95 parts by weight) is added to a rotary mixer. By spraying the compound of the present invention (Compound No. 1-2; 5 parts by weight) together with a liquid diluent under rotation, the clay is moistened followed by drying at 40 to 500C to obtain a granule formulation.
Preparation example 3 (emulsion)
By mixing the compound of the present invention (Compound No. 1-2; 30 parts by weight), xylene (55 parts by weight), polyoxyethylene alkylphenyl ether (8 parts by weight) and calcium alkylbenzene slufonate (7 parts by weight) with stirring, an emulsion is obtained.
Preparation example 4 (wettable agent)
By mixing the compound of the present invention (Compound No. 1-2; 15 parts by weight), a mixture including white carbon (fine powders of hydrous non-crystalline silicon oxide) and powder clay (1 :5 mixture; 80 parts by weight), and a condensate of sodium alkylnaphthalene sulfonate formalin (3 parts by weight) and sodium alkylbenzene slufonate (2 parts by weight) with pulverization, a wettable agent is obtained.
Preparation example 5 (wettable granules)
The compound of the present invention (Compound No. 1-2; 20 parts by weight), lignin sodium sulfonate (30 parts by weight), bentonite (15 parts by weight) and calcined diatomaceous earth powder (35 parts by weight) are thoroughly mixed. After adding water thereto, the mixture is extruded through 0.3 mm screen followed by drying to obtain wettable granules.
The novel pesticidal condensed-ring aryl derivatives of the present invention have an excellent pesticidal activity as shown in the biological examples.

Claims

Claims:
1. Condensed-ring aryl compounds of formula (I)
Figure imgf000321_0001
wherein
X represents halogen; nitro; cyano; hydroxy; thiol; amino; Ci-12 alkyl,
C1-I2 haloalkyl, C1-12 alkoxy, C1-12 haloalkoxy, C1-12 alkylsulfenyl, C1-12 alkylsulfmyl, C1-12 alkylsulfonyl, C1-i2haloalkylsulfenyl, C1-12 haloalkylsulfinyl, C1-12 haloalkyl- sulfonyl, Ci-12 alkylamino, C2.24 dialkylamino, C].i2 acylamino, C1-12 alkoxy-carbonyl- amino, C1-12 haloalkoxy-carbonylamino, Ci-12 alkylsulfonylamino, or C1-I2 haloalkyl- sulfonylamino; preferably chloro, bromo, iodo, fluoro; nitro; cyano; hydroxy; thiol; amino; Ci-6 alkyl, Ci-6 haloalkyl, C1-6 alkoxy, C1-6 haloalkoxy, Ci-6 alkylsulfenyl, C^ alkylsulfϊnyl, C1-6 alkylsulfonyl, Ci-6haloalkylsulfenyl, Ci-6 haloalkylsulfinyl, Ci-6 haloalkylsulfonyl, C1-6 alkylamino, C2-I2 dialkylamino, Ci-6 acylamino, C1-6 alkoxy-carbonylamino, C1-6 haloalkoxy-carbonylamino, Ci-6 alkylsulfonylamino, or C1-6haloalkylsulfonylamino;
Q represents substitutable phenyl, naphtyl or a substitutable 5- or 6- membered heterocyclic group;
Y represents halogen; nitro; cyano; hydroxy; thiol; amino; CM2 alkyl, C]-12 haloalkyl, C3-8 cycloalkyl, C3-8 cyclohaloalkyl, CM2 alkenyl, C2-12 haloalkenyl, CM2 alkoxy, Ci.^ haloalkoxy, Ci-I2 alkylsulfenyl, Ci-I2 alkylsulfmyl, Ci_i2 alkyl- sulfonyl, Ci.^haloalkylsulfenyl, Ci.i2 haloalkylsulfmyl, Ci.π haloalkylsulfonyl, CM2 alkylamino, C2-24 dialkylamino, C|.,2 aminocarbonyl, Ci.n alkylamino-carbonyl, C2-24 dialkylamino-carbonyl, Ci.i2 acylamino, Ci-)2 alkoxy-carbonylamino, benzyloxy-carbonylamino, C1-I2 haloalkoxy-carbonylamino, Ci-I2 alkylsulfonylamino,
CM2 haloalkylsulfonylamino, or C3.36 trialkylsilyl;
R1 represents cyano; Ci-I2 alkyl, Q-8 cycloalkyl, C4-2O alkylcycloalkyl,
C4.20 cycloalkylalkyl, C2-i2 alkenyl, C2-)2 alkynyl, C]-I2 haloalkyl, or C3-8 halocyclo- alkyl;
m represents 0, 1, 2, 3, 4 or 5;
n represents 0, 1, 2 or 3;
represents O, S, CH2 or N-R2;
R2 represents hydrogen; cyano; formyl; Ci-I2 alkyl, C2-I2 alkenyl,
C2-I2 alkynyl, C3-8 cycloalkyl, C4-20 alkylcycloalkyl, C4-20 cycloalkylalkyl, C1-I2 haloalkyl, CM2 alkyl sulfonyl, Ci.i2haloalkylsulfonyl, phenyl, C]-I2 alkyl-
-carbonyl, Ci-I2 alkoxy-carbonyl, Ci. alkylamino-carbonyl, or C2-24 dialkylamino-
-carbonyl;
W1, W2, W3 and W4 each independently represents a single bond, CH2, CH, N, -N+(O )-, -S(O)-, -S(O)2-, -O-S(O)-, O, S, C(R3)-R3, C-R3, C-R4, C(R3)-R4, C(R4)- R4, C-N(R3)-R3, C(R3)-N(R3)-N(R3)-R3, C-N(R3)-N(R3)-R3, C(R3)-N(R4)-N(R3)-R3,
C-N(R4)-N(R3)-R3, C(R3)-N(R3)-OR3, C-N(R3)-OR3, C(R3)-OR3, C-OR3, C(R3)-SR3, C-SR3, C-N3, N-R3, N-OR3, N-N(R3)-R3, N-R4, or C=U under the prerequisite that (i) not more than two of W1, W2, W3 and W4 are simultaneously omitted, and/or (ii) not more than two of W1, W2, W3 and W4 represent O, S, N-R3 Or N-R4, C-N(R3)-R3, C-N(R3)-N(R3)-R3, C-N(R4)-N(R3)-R3, C(R3)-N(R3)-OR3, C-N(R3)-OR3, C-SR3, N-R3, N-OR3 or N-N(R3)-R3 at the same time; and/or (iii) not more than two of W1, W2, W3 and W4 represent C=U at the same time, and /or (iv) if two of W1, W2, W3 and W4 represent O and/or S than least one carbon atom is present between them, and/or (v) when one of W1, W2, W3 and W4 represent CH, N, C-R3 or C-R4, C-N(R3)-R3, C-N(R3)-N(R3)-R3, C-N(R4)-N(R3)-R3, C-N(R3)-OR3, C-OR3, C-SR3, N-R3, N-OR3, N-N(R3)-R3 a double bond is formed within the condensed ring;
U represents CH2, O, S, or N-R3 or N-R4;
R3 each independently represents hydrogen; hydroxy; thiol; amino; cyano; formyl; halogen; nitro; Ci_6alkyl, C2-12 (total carbon number) alkoxyalkyl, C2_12haloalkoxyalkyl, C2-6alkenyl, C2-I2 alkynyl, C3-8 cycloalkyl, C4-I2 alkylcycloalkyl, C4-I2 cycloalkylalkyl, C^haloalkyl, Ci.6alkylcarbonyl, Q.e alkylcarbonyl-Q.βalkyl, Ci-6 alkylcarbonyl-Ci-6 alkylcarbonyl, C1-6 haloalkylcarbonyl, Ci_6 alkoxycarbonyl, Ci-6 alkylsulfenylcarbonyl, Ci.6haloalkylsulfenylcarbonyl, aminocarbonyl, Ci.6 alkyl- aminocarbonyl, C^6 haloalkylaminocarbonyl, Ci-6 hydroxyalkylaminocarbonyl, C2-I2 dialkylamino-carbonyl, C2_6 di(haloalkyl)aminocarbonyl, C2-6 alkenylamino- carbonyl, C2.6 alkynylaminocarbonyl, Q-βalkyl-thiocarbonyl, C3.6 cycloalkylcarbonyl, C4-I2 cycloalkylalkyl-carbonyl, C3-6 cycloalkyl-thiocarbonyl, C4_i2 cycloalkylalkyl- -thiocarbonyl, Q-βhaloalkyl-thiocarbonyl, C1-6 alkylamino-thiocarbonyl, C3.6 cyclo- alkylamino-carbonyl, C4-I2 cycloalkylalkylamino-carbonyl, C3.6 cycloalkylamino- -thiocarbonyl, C4.12 cycloalkylalkylaminothiocarbonyl, C^haloalkylamino- -thiocarbonyl, C2.]2 dialkylamino-thiocarbonyl, C3.6 cycloalkyloxy-carbonyl, C4-I2 cycloalkylalkyloxy-carbonyl, Ci.6haloalkoxy-carbonyl, C1^ alkylsulfonyl, Ci-βhaloalkylsulfonyl, phenylsulfonyl, R4-Ci-6 alkyl, R4-carbonyl, R4-thiocarbonyl, R4-Ci_6 alkylcarbonyl, R4-C1-6 alkyl-thiocarbonyl, R4-oxycarbonyl, R4-C,.6 alkyl- oxy-carbonyl, R4-aminocarbonyl, R4-amino-thiocarbonyl, R4-Ci.6 alkylamino- -carbonyl, or R4-Ci.6 alkylamino-thiocarbonyl; and
R4 represents phenyl or 5- or 6-membered saturated or unsaturated heterocyclic ring.
2. Compounds according to claim 1, wherein
Q is selected among optionally subsituted Q-I to Q-54
Figure imgf000324_0001
Figure imgf000325_0001
and the grouping -W -W2-WJ-W - is selected among W-I to W-580
Figure imgf000326_0001
Figure imgf000327_0001
Figure imgf000328_0001
Figure imgf000329_0001
Figure imgf000330_0001
Figure imgf000331_0001
Figure imgf000332_0001
Figure imgf000333_0001
Figure imgf000334_0001
Figure imgf000335_0001
Figure imgf000336_0001
Figure imgf000337_0001
Figure imgf000339_0001
Figure imgf000340_0001
wherein
U represents CH2, O, S, N-R3 or N-R4;
k stands for 0, 1 or 2;
W represents O" , R3, OR3, SR3, NHR3, N(R3)2, N(R3)N(R3)R3, N(R4)N(R3)R3, N(R3)OR3, R4, NR4, or N3;
R3 each independently represents hydrogen; hydroxy; thiol; amino; cyano; formyl; halogen; nitro; Ci-6alkyl, C2-12 alkoxyalkyl, C2-I2 haloalkoxyalkyl, C2.6 alkenyl, C2-I2 alkynyl, C3.8 cycloalkyl, C4-I2 alkylcycloalkyl, C4-J2 cycloalkylalkyl, C1-6haloalkyl, C1-6 alkylcarbonyl, C^alkylcarbonyl-Q-ealkyl, Q-6 alkylcarbonyl- -Ci-6 alkylcarbonyl, Ci^haloalkylcarbonyl, Ci-6 alkoxycarbonyl, Ci-6 alkyl- sulfenylcarbonyl, Ci^haloalkylsulfenylcarbonyl, aminocarbonyl, C].6alkylamino- carbonyl, Ci-βhaloalkylaminocarbonyl, Ci^hydroxyalkylaminocarbonyl, C2-12 dialkyl- amino-carbonyl, C2-6 di(haloalkyl)aminocarbonyl, C2-6 alkenylaminocarbonyl, C2-6 alkynylaminocarbonyl, Ci-6 alkyl-thiocarbonyl, C3-6 cycloalkylcarbonyl, C4-I2 cycloalkylalkyl-carbonyl, C3-6 cycloalkyl-thiocarbonyl, C4-12 cycloalkylalkyl-
-thiocarbonyl, Q^haloalkyl-thiocarbonyl, Ci-6 alkylamino-thiocarbonyl, C3-6cyclo- alkylamino-carbonyl, C4-I2 cycloalkylalkylamino-carbonyl, C3-6 cycloalkylamino- -thiocarbonyl, C4.]2 cycloalkylalkylaminothiocarbonyl, C1-6haloalkylamino- -thiocarbonyl, C2-12 dialkylamino-thiocarbonyl, C3-6 cycloalkyloxy-carbonyl, C4-I2 cycloalkylalkyloxy-carbonyl, C1-6haloalkoxy-carbonyl, C1-6 alkylsulfonyl,
Ci-6haloalkylsulfonyl, phenylsulfonyl, R4-Ci-6 alkyl, R4-carbonyl, R4-thiocarbonyl, R4-C1-6 alkylcarbonyl, R4-Ci-6 alkyl-thiocarbonyl, R4-oxycarbonyl, R4-Ci-6alkyl- oxy-carbonyl, R4-aminocarbonyl, R4-amino-thiocarbonyl, R4-Ci-6alkylamino- -carbonyl, or R4-Ci-6 alkylamino-thiocarbonyl; and R4 represents phenyl or 5- or 6-membered saturated or unsaturated heterocyclic ring;
3. Compounds according to claim 2, wherein R4 is selected among the groups R4-l to
R4-83
Figure imgf000342_0001
Figure imgf000343_0001
wherein
G represents 0, S or N, and wherein each group R4-l to R4-83 may be substituted with at least one group selected among hydrogen; halogen; cyano, nitro; Ci-6alkyl, Ci-6haloalkyl, C3.6cycloalkyl, C3-6 halocycloalkyl, Ci-6 alkoxy, C^haloalkoxy, Ci.6 alkylsulfenyl, Ci.6haloalkylsulfenyl, Ci-6 alkylsulfinyl, Ci.6 haloalkylsulfϊnyl, Ci.6 alkylsulfonyl, Ci.6 haloalkylsulfonyl, Ci-6 alkylamino, Ci-6haloalkylamino, aminocarbonyl, C1-6 alkylamino-carbonyl, C2.n dialkylamino- -carbonyl, Ci^ alkoxycarbonyl, phenyl, or pyridyl.
4. A pesticide containing as an active ingredient one or more compounds selected from the compounds according to any one of claims 1 to 3.
5. Method for controlling animal pests characterized in that an active ingredient which is selected from one or more compounds according to any one of claims 1 to 3 is applied to animal pests and/or their habitat.
6. Use of an active ingredient which is selected from one or more compounds according to any one of claims 1 to 3 for treating seed of conventional or transgenic plants.
7. Pharmaceutical containing as an active ingredient one or more compounds selected from the compounds according to any one of claims 1 to 3.
8. Use of an active ingredient which is selected from one or more compounds according to any one of claims 1 to 3 for the preparation of pharmaceutical compositions for controlling parasites in or on animals.
PCT/EP2009/001841 2008-03-14 2009-03-13 Pesticidal condensed - ring aryl compounds WO2009112275A1 (en)

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DOP2010000271A (en) 2010-10-15
MX2010009904A (en) 2010-09-30
US20110071141A1 (en) 2011-03-24
TW200950703A (en) 2009-12-16
JP2009286773A (en) 2009-12-10
AU2009224896A1 (en) 2009-09-17
JP2011517663A (en) 2011-06-16
EP2254863A1 (en) 2010-12-01
PE20091619A1 (en) 2009-11-05
KR101349629B1 (en) 2014-02-06
KR20100138987A (en) 2010-12-31
ZA201006502B (en) 2011-11-30
CR11672A (en) 2011-02-24

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