WO2013027660A1 - Pesticide - Google Patents

Pesticide Download PDF

Info

Publication number
WO2013027660A1
WO2013027660A1 PCT/JP2012/070874 JP2012070874W WO2013027660A1 WO 2013027660 A1 WO2013027660 A1 WO 2013027660A1 JP 2012070874 W JP2012070874 W JP 2012070874W WO 2013027660 A1 WO2013027660 A1 WO 2013027660A1
Authority
WO
WIPO (PCT)
Prior art keywords
oil
compound
formula
compounds
salt
Prior art date
Application number
PCT/JP2012/070874
Other languages
French (fr)
Inventor
Kenichi Nakamoto
Hidemasa Kominami
Masakazu SERIZAWA
Yuko Nishihama
Tatsuya Kani
Tatsuya Shimada
Original Assignee
Ishihara Sangyo Kaisha, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ishihara Sangyo Kaisha, Ltd. filed Critical Ishihara Sangyo Kaisha, Ltd.
Publication of WO2013027660A1 publication Critical patent/WO2013027660A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/34—One oxygen atom
    • 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
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • 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
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • A01N31/14—Ethers
    • 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
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
    • A01N33/18—Nitro compounds
    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/10—Sulfones; Sulfoxides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—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
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/14—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C317/22—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/01—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton
    • C07C323/09—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and halogen atoms, or nitro or nitroso groups bound to the same carbon skeleton having sulfur atoms of thio groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/18—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/19—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton with singly-bound oxygen atoms bound to acyclic carbon atoms of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/64—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton
    • C07C323/65—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton containing sulfur atoms of sulfone or sulfoxide groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/65—One oxygen atom attached in position 3 or 5
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/68—One oxygen atom attached in position 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/84—Nitriles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D237/14—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D237/18—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/38—One sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/096—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings

Definitions

  • the alkyi or alkyi moiety in the formula (I) may be linear or branched.
  • d -6 alkyi such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec- butyl, tert-butyl, pentyl or hexyl may be mentioned.
  • the pyridyl which is represented by Q in the formula (I) may, for example, be 2- pyridyl, 3-pyridyl or 4-pyridyl.
  • the number of substituents is from 1 to 4. Further, when it is substituted with a plurality of
  • R 4 the number of substituents is from 1 to 5. Further, when it is substituted with a plurality of R 4 , the plurality of R 4 may be the same or different.
  • the transition metal catalyst may be used in an amount of from 0.001 to 1 time by mol, preferably from 0.01 to 0.1 time by mol, to the compound of the formula (II) or the formula (V).
  • the reaction temperature is usually from -50 to 200°C, preferably from 20 to 150°C.
  • the base may, for example, be the same one as used in the above process [1].
  • the base may be used in an amount of from 1 to 5 times by mol, preferably from 1.5 to 3 times by mol, to the compound of the formula (X).
  • the compound of the formula (XI) may be a known product or may be produced by reacting the corresponding magnesium reagent or lithium reagent with trimethyl borate.
  • the solvent may, for example, be the same one as used in the above process
  • the process [6] can be carried out by reacting the compound of the formula (XII) and the compound of the formula (VII) in the presence of a base in a solvent.
  • This reaction may be carried out, if necessary, in the presence of a radical initiator.
  • the radical initiator may, for example, be the same one as used in the above process [3]. In a case where a radical initiator is used, it may be used in an amount of from 0.1 to 5 times by mol, preferably from 0.5 to 2 times by mol, to the compound of the formula (XII).
  • W, A 1 , A 2 , A 3 , A 4 , A 5 , B 1 , B , R , R 2 , R 3 , n, y, V and T" are as defined above.
  • the solvent may, for example, be the same one as used in the above process
  • hydrocarbon such as chlorobenzene or dichlorobenzene
  • an aliphatic hydrocarbon such as pentane, hexane, heptane, octane or cyclohexane
  • organic acid such as acetic acid or propionic acid
  • the reaction temperature is usually from 0°C to 200°C, preferably from 0°C to 150°C.
  • the reaction time is usually from 1 to 48 hours, preferably from 1 to 24 hours.
  • the base may, for example, be the same one as in the above process [1].
  • the base may be used in an amount of from 1 to 10 times by mol, preferably from 1 to 5 times by mol, to the compound of the formula (XV).
  • the solvent may, for example, be the same one as in the above process [1].
  • the reaction temperature is usually from -50 to 150°C, preferably from 0 to 50°C.
  • a compound of the formula (111-1) can be produced, for example, by the following reaction.
  • T R 1 , R 2 , R 3 and n are as defined above.
  • the reaction is carried out usually in an inert gas atmosphere such as nitrogen gas or argon gas.
  • the transition metal catalyst may, for example, be the same one as in the above process [1].
  • the transition metal catalyst may be used in an amount of from 0.001 to 1 time by mol, preferably from 0.01 to 0.1 time by mol, to the compound of the formula (V).
  • insects e.g. aphids such as green peach aphid (Myzus persicae) and cotton aphid (Aphis gossvpii); agricultural insect pests such as diamondback moth (Plutella xylostella), cabbage armyworm (Mamestra brassjcae), common cutworm (Spodoptera litura), codling moth (Cvdia pomonella), bollworm(Heliothis zea), tobacco budworm (Heliothis virescens), gypsy moth (Lymantria dispar), rice leafroller
  • plant parasitic mites such as two-spotted spider mite (Tetranvchus urticae), carmine spider mite (Tetranvchus cinnabarinus), kanzawa spider mite (Tetranvchus kanzawai), citrus red mite (Panonvchus citri). European red mite (Panonvchus ulmi), broad mite
  • plant parasitic nematodes such as root-knot nematodes, cyst nematodes, root-lesion nematodes, white-tip nematode (Aphelenchoides bessevi), strawberry bud nematode (Nothotylenchus acris), and pine wood nematode (Bursaphelenchus xylophilus); and soil pests, e.g. isopods such as pillbugs (Armadillidium vulgare) and pillbugs (Porcellio scaber).
  • isopods such as pillbugs (Armadillidium vulgare) and pillbugs (Porcellio scaber).
  • insecticide, miticide, nematicide or soil pesticide containing the compound of the present invention may be agricultural and horticultural insecticides, miticides, nematicides or soil pesticides which collectively control the above-mentioned plant parasitic mites, agricultural insect pests, plant parasitic nematodes, gastropods and soil pests.
  • pyridaphenthion pirimiphos-methyl, propaphos, phosalone, formothion, malathion, tetrachlorvinphos, chlorfenvinphos, cyanophos, trichlorfon, methidathion, phenthoate, ESP, azinphos-methyl, fenthion, heptenophos, methoxychlor, parathion, phosphocarb, demeton-S-methyl, monocrotophos, methamidophos, imicyafos, parathion-methyl, terbufos, phosphamidon, phosmet, phorate, phoxim and triazophos;
  • organic chlorine compounds such as dicofol, tetradifon, endosulfan, dienochlor and dieldrin;
  • organic metal compounds such as fenbutatin oxide and cyhexatin
  • pyridazinone compounds such as pridaben
  • pyridine compounds such as pyridalyl and flonicamid
  • the active ingredient compounds of the fungicide in the above-mentioned other agricultural chemicals include, for example, (by common names, some of them are still in an application stage, or test codes of Japan Plant Protection Association):
  • dithiocarbamate compounds such as maneb, zineb, mancozeb, polycarbamate, metiram, propineb and thiram;
  • anilide compounds such as metalaxyl, metalaxyl-M, mefenoxam, oxadixyl, ofurace, benalaxyl, benalaxyl-M (another name: kiralaxyl, chiralaxyl), furalaxyl, cyprofuram, carboxin, oxycarboxin, thifluzamide, boscalid, bixafen, isotianil, tiadinil and sedaxane;
  • sulfamide compounds such as dichlofluanid
  • phthalimide compounds such as captan, captafol and folpet;
  • morpholine compounds such as fenpropimorph and tridemorph
  • organotin compounds such as fentin hydroxide and fentin acetate
  • urea compounds such as pencycuron
  • phenylcarbamate compounds such as diethofencarb
  • cyanopyrrole compounds such as fludioxonil and fenpiclonil
  • oxazolidinone compounds such as famoxadone
  • thiazolecarboxamide compounds such as ethaboxam
  • benzenesulfonamide compounds such as flusulfamide
  • the pesticides against parasites on animals are effective for controlling e.g.
  • Schistosoma japonicum and Fasciola hepatica and protozoa such as coccidia, malaria parasites (Plasmodium malariae), intestinal sarcocyst, toxoplasma, and
  • the present invention also includes a method for controlling a pest by the above- mentioned administration method or by the above-mentioned dose, particularly a method for controlling external parasites or internal parasites.
  • the present invention by controlling pests parasitic on animals as described above, it is possible to prevent or cure various diseases of the host animal thereby caused in some cases.
  • the present invention also includes a
  • preventive or therapeutic agent for an animal disease caused by parasites containing the compound of the present invention as an active ingredient, and a method for preventing or curing an animal disease caused by parasites.
  • the present invention includes such a mixed pesticidal composition having the above-mentioned various components mixed or combined for use, and further a method for controlling a pest by using it, particularly a method for controlling external parasites or internal parasites.
  • 0.12 g of m-chloroperbenzoic acid was added to a mixed solution comprising 0.19 g of 2-(benzyloxy)-4-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)pyridine and 3 mL of chloroform, followed by a reaction at room temperature for 3 hours.
  • Water was added to the reaction solution, followed by extraction with ethyl acetate. Then, the organic layer was washed with an aqueous sodium bicarbonate solution, water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying.
  • R 5 is substituted at the position corresponding to the number allotted to the chemical structural formula in each Table.
  • a compound identified with "-" indicates that R 5 is a hydrogen atom.
  • R 5 is other than a hydrogen atom, for example, in the case of a compound identified with "4-F", it is meant that the 4-position is substituted with a fluorine atom.
  • the numerical value shown in the column for the physical properties is a melting point (°C).
  • 1 H-NMR data [measured by 1 H-Nuclear magnetic resonance spectroscopy, ⁇ is a chemical shift value] are shown in Tables 24 and 25.

Abstract

A novel pesticide is provided. The present invention provides a compound represented by the formula (I) or its salt: wherein Q is phenyl or pyridyl which may be substituted; W is an oxygen atom or S(O)m; each of A1 to A5 is -C(R5)= or a nitrogen atom, provided that among A1 to A5, the number of groups which may be nitrogen atoms, is from 0 to 2; each of B1 to B4 is a hydrogen atom, a halogen atom, alkyl or haloalkyl; each of R1 and R2 is a hydrogen atom, a halogen atom, alkyl, haloalkyl, alkoxy, haloalkoxy or cyano; and R3 is alkyl or haloalkyl.

Description

DESCRIPTION
TITLE OF INVENTION: PESTICIDE TECHNICAL FIELD
The present invention relates to an insecticide, miticide, nematicide or soil pesticide containing, as an active ingredient, the after-described novel compound represented by the formula (I) or its salt, i.e. a phenyl sulfide derivative or its salt. BACKGROUND ART
Patent Document 1 discloses a 3-arylphenyl sulfide derivative useful as an insecticide or miticide. However, the compound of the present invention is not disclosed. PRIOR ART DOCUMENT PATENT DOCUMENT
Patent Document 1 : WO99/55668
DISCLOSURE OF INVENTION TECHNICAL PROBLEM
For many years, many pesticides have been used, but many of them have various problems such that the effects are inadequate, and their use is restricted as insects, etc. have acquired resistance thereto. Accordingly, it is desired to develop a novel pesticide substantially free from such problems.
SOLUTION TO PROBLEM
The present inventors have conducted various studies on phenyl sulfide derivatives in an effort to find a superior pesticide. As a result, they have found that a novel phenyl sulfide derivative has a very high controlling effect against pests at a low dose and at the same time has safety to crop plants, and have accomplished the present invention.
That is, the present invention provides a compound represented by the formula (I) or its salt:
Figure imgf000002_0001
wherein Q is phenyl which may be substituted by R4 , or pyridyl which may be substituted by R4 ; W is an oxygen atom or S(O)m ; each of A1 to A5 is -C(R5 )= or a nitrogen atom, provided that among A1 to A5 , the number of groups which may be nitrogen atoms, is from 0 to 2; each of B1 to B4 is a hydrogen atom, a halogen atom, alkyi or haloalkyl; each of R1 and R2 is a hydrogen atom, a halogen atom, alkyi, haloalkyl, alkoxy, haloalkoxy or cyano; R3 is alkyi or haloalkyl; R4 is a halogen atom, alkyi, haloalkyl, alkoxy, haloalkoxy, cyano, nitro, COR6 , C02 R6 , N(R7 )COR6 ,
N(R7)CO2 R6 , NR8 R9 , CONR8 R9 , alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl or haloalkylsulfonyl; R5 is a hydrogen atom, a halogen atom, alkyi, haloalkyl, alkoxy, haloalkoxy, cyano, nitro, COR6 , CO2 R6 , N(R7)COR6 , N(R7 )CO2 R6 , NR8 R9 , CONR8 R9 , alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl or haloalkylsulfonyl; R6 is a hydrogen atom, alkyi or haloalkyl; R7 is a hydrogen atom or alkyi; each of R8 and R9 is a hydrogen atom or alkyi; when R8 and R9 are alkyi, R8 and R9 may form, together with the nitrogen atom to which they are bonded, a 5- or 6- membered ring; n is an integer of 0 or 1 ; m is an integer of 0, 1 or 2; x is an integer of 0 or 1 ; and y is an integer of 0 or 1 , provided that the sum of x and y is not 2.
Further, the present invention provides a pesticide containing the above
compound of the formula (I) or its salt as an active ingredient, and a method for controlling pests, which comprises applying such a compound or its salt thereto.
ADVANTAGEOUS EFFECTS OF INVENTION
A pesticide containing the above compound of the formula (I) or its salt as an active ingredient has a very high controlling effect against pests at a low dose and at the same time has safety to crop plants.
DESCRIPTION OF EMBODIMENTS
As the halogen atom in the formula (I) or the halogen atom as a substituent, an atom of fluorine, chlorine, bromine or iodine may be mentioned. The number of the halogen atoms as the substituents may be one or more, and if more, the respective halogen atoms may be the same or different. Further, the positions for substitution with such halogen atoms may be any positions.
The alkyi or alkyi moiety in the formula (I) may be linear or branched. As its specific example, d-6 alkyi such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec- butyl, tert-butyl, pentyl or hexyl may be mentioned.
The pyridyl which is represented by Q in the formula (I) may, for example, be 2- pyridyl, 3-pyridyl or 4-pyridyl. When the pyridyl is substituted with substituent R4, the number of substituents is from 1 to 4. Further, when it is substituted with a plurality of
R4, the plurality of R4 may be the same or different.
When the phenyl which is represented by Q in the formula (I) is substituted with
R4, the number of substituents is from 1 to 5. Further, when it is substituted with a plurality of R4, the plurality of R4 may be the same or different.
The salt of the compound of the above formula (I) includes all kinds so long as they are acceptable in this technical field. For example, an ammonium salt such as a dimethyl ammonium salt or a triethyl ammonium salt; an inorganic acid salt such as a hydrochloride, a perchlorate, a sulfate or a nitrate; or an organic acid salt such as an acetate or a methane sulfonate, may be mentioned.
The compound of the above formula (I) may have isomers such as optical isomers, and such isomers and mixtures thereof are both included in the present invention. In this specification, isomers are in the form of a mixture, unless otherwise specified. Further, in the present invention, various isomers other than those
mentioned above, may be included within the scope of the common knowledge in this technical field. Further, depending upon the type of the isomer, it may have a chemical structure different from the above formula (I), but for those skilled in the art, it can sufficiently be recognized that it is in an isomeric relationship and falls within the scope of the present invention.
The compound of the above formula (I) or its salt (hereinafter referred to simply as the compound of the present invention) and its raw material compound can be produced by the following processes [1] to [7], [Process 1 for intermediate] to [Process 4 for intermediate] and in accordance with a usual process for producing a salt.
However, the present invention is by no means limited to such processes.
PROCESS [1]
Figure imgf000004_0001
In the process [1], Q, W, A1 , A2 , A3 , A4 , A5 , B , B2 , B3 , B4 , R1 , R2 , R3 , n, x and y are as defined above. T is -B(OH)2 or pinacolatoboranyl, and T" is a bromine atom.
Route A in the process [1] can be carried out by reacting the compound of the formula (II) and the compound of the formula (III) in the presence of a base and a transition metal catalyst in a solvent.
Route B in the process [1] can be carried out by reacting the compound of the formula (IV) and a compound of the formula (V) in the presence of a base and a transition metal catalyst in a solvent.
The compounds of the formulae (III) and (V) include novel compounds and can be produced by a method disclosed in WO2007/034755.
The compound of the formula (IV) may be a known product or may be produced by reacting the corresponding magnesium reagent or lithium reagent with trimethyl borate.
The transition metal catalyst may suitably be selected for use from e.g. a palladium compound such as palladium-activated carbon, palladium acetate, dichlorobis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)palladium or tris(dibenzalacetone)palladium; and a nickel compound such as
bis(triphenylphosphine)nickel chloride or tetrakis(triphenylphosphine)nickel. The transition metal catalyst may be used in an amount of from 0.001 to 1 time by mol, preferably from 0.01 to 0.1 time by mol, to the compound of the formula (II) or the formula (V).
As the base, one or more may suitably be selected for use from e.g. an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; an alkaline earth metal hydroxide such as calcium hydroxide or magnesium hydroxide; an alkali metal carbonate such as sodium carbonate or potassium carbonate; an alkali metal bicarbonate such as sodium hydrogen carbonate or potassium hydrogen carbonate; a metal hydride such as sodium hydride or potassium hydride; a metal alkoxide such as sodium methoxide, sodium ethoxide or potassium tert-butoxide; and an organic base such as triethylamine, Ν,Ν-dimethylaniline, pyridine, 4-N,N-dimethylamino pyridine or 1 ,8-diazabicyclo[5.4.0]-7-undecene. The base may be used in an amount of from 1 to 5 times by mol, preferably from 1.5 to 3 times by mol, to the compound of the formula (II) or (V).
The solvent may be any solvent so long as it is inert to the reaction. For example, one or more may suitably be selected for use from e.g. an ether such as diethyl ether, butyl methyl ether, tetrahydrofuran, 1 ,4-dioxane or dimethoxy ethane; an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; an aprotic polar solvent such as N,N-dimethylformamide, Ν,Ν-dimethylacetamide, N-methyl-2- pyrolidone, dimethylsulfoxide or sulforane; a nitrile such as acetonitrile or propionitrile; an ester such as ethyl acetate or ethyl propionate; an aliphatic hydrocarbon such as pentane, hexane, heptane, octane or cyclohexane; and a protonic solvent such as water, methanol or ethanol.
The reaction temperature is usually from -50 to 200°C, preferably from 20 to 150°C.
The reaction time is usually from 0.5 to 48 hours, preferably from 1 to 24 hours.
Figure imgf000005_0001
(I-a) (I-b)
In the process [2], Q, W, A , A2 , A3 , A4 , A5 , B , B2 B3 , B4 R\ R2 , R3 , x and y are as defined above. This reaction can be carried out by reacting the compound of the formula (l-a) in the presence of an oxidizing agent in a solvent.
The oxidizing agent may suitably be selected for use from e.g. an aqueous hydrogen peroxide solution, m-chloroperbenzoic acid, perbenzoic acid, sodium periodide, OXONE (tradename of E.I. du Pont; containing potassium hydrogen peroxosulfate), N-chlorosuccinimide, N-bromosuccinimide, tert-butyl hypochlorite and sodium hypochlorite. The oxidizing agent may be used in an amount of from 1 to 5 times by mol, preferably from 1 to 2 times by mol, to the compound of the formula (l-a).
This reaction may be carried out, if necessary, in the presence of a catalyst.
The catalyst may be selected for use from e.g. sodium tungstate and flavin. The catalyst may be used in an amount of from 0.0001 to 1 time by mol, preferably from 0.001 to 0.05 time by mol, to the compound of the formula (l-a).
The solvent may be any solvent so long as it is inert to the reaction. For example, one or more may suitably be selected for use from e.g. a halogenated alkane such as chloroform, dichloromethane or dichloroethane; an aromatic hydrocarbon such as chlorobenzene or dichlorobenzene; an ester such as ethyl acetate or ethyl propionate; and acetic acid.
The reaction temperature is usually from -50 to 150°C, preferably from 0 to 50°C.
The reaction time is usually from 0.5 to 48 hours, preferably from 1 to 30 hours. PROCESS [3]
Figure imgf000006_0001
In the process [3], Q, W, A1 , A2 , A3 , A4 , A5 , B1 , B2 , B3 , B4 , x, y and T" are as defined above. J represents a leaving group. The leaving group is not particularly limited so long as the reaction proceeds, and, for example, a halogen atom may be mentioned.
Route A in the process [3] can be carried out by reacting the compound of the formula (VI) and the compound of the formula (VII) in the presence of a base in a solvent.
Route B in the process [3] can be carried out by reacting the compound of the formula (VIII) and a compound of the formula (IX) in the presence of a base in a solvent.
The base may, for example, be the same one as used in the above process [1]. The base may be used in an amount of from 1 to 10 times by mol, preferably from 1 to 5 times by mol, to the compound of the formula (VI) or (VIII).
This reaction may be carried out, if necessary, in the presence of a radical initiator. The radical initiator may be suitably selected from e.g. sulfurous acid, a sulfite and a sulfite adduct such as Rongalite (tradename of Kanto Kagaku, sodium/formaldehyde/sulfoxylate). In a case where a radical initiator is used, it may be used in an amount of from 0.1 to 5 times by mol, preferably from 0.5 to 2 times by mol, to the compound of the formula (VI) or (VIII).
The solvent may, for example, be the same one as used in the above process
[1]·
The reaction temperature is usually from -50 to 200°C, preferably from 0 to 150°C.
The reaction time is usually from 0.5 to 48 hours, preferably from 1 to 24 hours.
Figure imgf000006_0002
In the process [4], Q, W, A1 , A2 , A3 , A4 , A5 , B1 , B2 , B3 , B4 , R1 , R2 , R3 , n, x, y and J are as defined above. The process [4] can be carried out by reacting the compound of the formula (X) and the compound of the formula (IX) in the presence of a base in a solvent.
The base may, for example, be the same one as used in the above process [1]. The base may be used in an amount of from 1 to 5 times by mol, preferably from 1.5 to 3 times by mol, to the compound of the formula (X).
This reaction may be carried out, if necessary, in the presence of a radical initiator. The radical initiator may, for example, be the same one as used in the above process [3]. In a case where a radical initiator is used, it may be used in an amount of from 0.5 to 5 times by mol, preferably from 0.5 to 2 times by mol, to the compound of the formula (X).
The solvent may, for example, be the same one as used in the above process
[1]·
The reaction temperature is usually from -50 to 200°C, preferably from 0 to 150°C.
The reaction time is usually from 0.5 to 48 hours, preferably from 1 to 24 hours.
PROCESS [5]
Figure imgf000007_0001
(XI) (V)
In the process [5], A1 , A2 , A3 , A4 , A5 , B1 , B2 , R1 , R2 , R3 , n, y, T', T" and J are as defined above.
Route A in the process [5] can be carried out by reacting the compound of the formula (VIII) and the compound of the formula (III) in the presence of a base and a transition metal catalyst in a solvent.
Route B in the process [5] can be carried out by reacting the compound of the formula (XI) and the compound of the formula (V) in the presence of a base and a transition metal catalyst in a solvent.
The compound of the formula (XI) may be a known product or may be produced by reacting the corresponding magnesium reagent or lithium reagent with trimethyl borate.
The transition metal catalyst may, for example, be the same one as used in the above process [1]. The transition metal catalyst may be used in an amount of from 0.001 to 1 time by mol, preferably from 0.01 to 0.1 time by mol, to the compound of the formula (VIII) or (V).
The base may, for example, be the same one as used in the above process [1]. The base may be used in an amount of from 1 to 5 times by mol, preferably from 1.5 to 3 times by mol, to the compound of the formula (VIII) or (V).
The solvent may, for example, be the same one as used in the above process
[1]·
The reaction temperature is usually from -50 to 200°C, preferably from 20 to
150°C.
The reaction time is usually from 0.5 to 48 hours, preferably from 1 to 24 hours.
Figure imgf000008_0001
In the process [6], Q, W, A1 , A2 , A3 , A , A5 , B1 , B2 , B3 , B4 , R1 , R2 , R3 , n, x, y and J are as defined above.
The process [6] can be carried out by reacting the compound of the formula (XII) and the compound of the formula (VII) in the presence of a base in a solvent.
The base may, for example, be the same one as used in the above process [1 ]. The base may be used in an amount of from 1 to 5 times by mol, preferably from 1.5 to 3 times by mol, to the compound of the formula (XII).
This reaction may be carried out, if necessary, in the presence of a radical initiator. The radical initiator may, for example, be the same one as used in the above process [3]. In a case where a radical initiator is used, it may be used in an amount of from 0.1 to 5 times by mol, preferably from 0.5 to 2 times by mol, to the compound of the formula (XII).
The solvent may, for example, be the same one as used in the above process
[1]-
The reaction temperature is usually from -50 to 200°C, preferably from 0 to 150°C.
The reaction time is usually from 0.5 to 48 hours, preferably from 1 to 24 hours.
Figure imgf000008_0002
(VI) (III) (XII)
In the process [7], W, A1 , A2 , A3 , A4 , A5 , B1 , B , R , R2 , R3 , n, y, V and T" are as defined above.
The process [7] can be carried out by reacting the compound of the formula (VI) and the compound of the formula (III) in the presence of a base and a transition metal catalyst in a solvent.
The transition metal catalyst may, for example, be the same one as used in the above process [1]. The transition metal catalyst may be used in an amount of from 0.001 to 1 time by mol, preferably from 0.01 to 0.1 time by mol, to the compound of the formula (VI).
The base may, for example, be the same one as used in the above process [1]. The base may be used in an amount of from 1 to 5 times by mol, preferably from 1.5 to 3 times by mol, to the compound of the formula (VI).
The solvent may, for example, be the same one as used in the above process
[1]·
The reaction temperature is usually from -50 to 200°C, preferably from 20 to 150°C.
The reaction time is usually from 0.5 to 48 hours, preferably from 1 to 24 hours. [Process 1 for intermediate]
Among compounds included in the formula (V) for the starting material in the process [1], a compound of the formula (V-1) may be produced, for example, by the reactions of the following (1 ) to (4).
(1 ) A first stage of halosulfonylating a compound of the formula (XIII) to obtain a compound of the formula (XIV).
(2) A second stage of reducing the compound of the formula (XIV) to obtain a compound of the formula (XV).
(3) A third stage of hydrolyzing the compound of the formula (XV) to obtain a compound of the formula (XVI) or (XVII).
(4) A fourth stage of reacting the compound of the formula (XVI) or (XVII) with a compound of the formula (XVIII) to obtain a compound of the formula (V-1).
Now, (1) to (4) will be described in detail. In the following formulae, T", R1, R2 and R3 are as defined above, G is a halogen atom, and L is a halogen atom, a mesyl group or a tosyl group.
Figure imgf000009_0001
(1) The first stage can be carried out in the presence of a halosulfonylation agent. The halosulfonylation agent may suitably be selected from e.g. a halosulfonic acid compound such as chlorosulfonic acid or bromosulfonic acid. The
halosulfonylation agent may be used in an amount of from 1 to 100 times by mol, preferably from 1 to 10 times by mol, to the compound of the formula (XIII).
This reaction may be carried out in the presence of a solvent, as the case requires. The solvent may be any solvent so long as it is inert to the reaction, and one or more may suitably be selected for use from e.g. an ether such as diethyl ether, butyl methyl ether, tetrahydrofuran, 1 ,4-dioxane or dimethoxyethane; a halogenated alkane such as chloroform, dichloromethane or dichloroethane; an aromatic
hydrocarbon such as chlorobenzene or dichlorobenzene; an aliphatic hydrocarbon such as pentane, hexane, heptane, octane or cyclohexane; and an organic acid such as acetic acid or propionic acid.
The reaction temperature is usually from -10°C to 200°C, preferably from 10°C to 150°C.
The reaction time is usually from about 0.2 to 48 hours, preferably from 0.5 to 24 hours.
(2) The second stage can be carried out by the reaction in the presence of a reducing agent in acetic acid. As the reducing agent, one or more may suitably be selected for use from e.g. a phosphorus compound such as red phosphorus or triphenyl phosphine; and a halogenated compound such as potassium iodide or iodine. The reducing agent may be used in an amount of from 1 to 100 times by mol, preferably from 1 to 10 times by mol, to the compound of the formula (XIV).
The reaction temperature is usually from 0°C to 200°C, preferably from 0°C to 150°C. The reaction time is usually from 1 to 48 hours, preferably from 1 to 24 hours.
(3) The third stage can be carried out by the reaction in the presence of water and a base in a solvent.
The base may, for example, be the same one as in the above process [1]. The base may be used in an amount of from 1 to 10 times by mol, preferably from 1 to 5 times by mol, to the compound of the formula (XV). The solvent may, for example, be the same one as in the above process [1].
The reaction temperature is usually from -20 to 150°C, preferably from 0°C to
100°C.
The reaction time is usually from 1 to 48 hours, preferably from 1 to 24 hours.
(4) The fourth stage can be carried out usually by reacting the compound of the formula (XVI) or (XVII)with the compound of the formula (XVIII) in the presence of a base in a solvent.
The base may, for example, be the same one as in the above process [1]. The base may be used in an amount of from 1 to 10 times by mol, preferably from 1 to 5 times by mol, to the compound of the formula (XVI) or (XVII).
This reaction may be carried out, as the case requires, in the presence of a radical initiator. The radical initiator may be suitably selected for use from e.g.
sulfurous acid, a sulfite, or a sulfurous acid adduct such as Rongalite (tradename of Kanto Kagaku, sodium/formaldehyde sulfoxylate). The radical initiator may be used in an amount of from 0 to 5 times by mol, preferably from 0.1 to 2 times by mol, to the compound of the formula (XVI) or (XVII).
The solvent may, for example, be the same one as in the above process [1].
The reaction temperature is usually from -50 to 200°C, preferably from 0 to 150°C.
The reaction time is usually from 0.5 to 72 hours, preferably from 1 to 48 hours. [Process 2 for intermediate]
Among compounds included in the formula (V) for the starting material in the process [1], a compound of the formula (V-2) can be produced, for example, by the following reaction. In the formulae, T", R1, R2 and R3 are as defined above.
Figure imgf000011_0001
This reaction can be carried out by reacting a compound of the formula (V-1) in the presence of an oxidizing agent in a solvent.
The oxidizing agent may, for example, be the same one as in the above process [2]. The oxidizing agent may be used in an amount of from 1 to 5 times by mol, preferably from 1 to 2 times by mol, to the compound of the formula (V-1).
This reaction may be carried out, as the case requires, in the presence of a catalyst. The catalyst may be selected for use from e.g. sodium tungstate, flavin, etc. The catalyst may be used in an amount of from 0.0001 to 1 time by mol, preferably from 0.001 to 0.05 time by mol, to the compound of the formula (V-1).
The solvent may be any solvent so long as it is inert to the reaction, and for example, one or more may suitably be selected for use from e.g. a halogenated alkane such as chloroform, dichloromethane or dichloroethane; an aromatic hydrocarbon such as chlorobenzene or dichlorobenzene; an ester such as ethyl acetate or ethyl propionate; and acetic acid.
The reaction temperature is usually from -50 to 150°C, preferably from 0 to 50°C.
The reaction time is usually from 0.5 to 48 hours, preferably from 1 to 30 hours. [Process 3 for intermediate]
Among compounds included in the formula (III) for the starting material in the process [1], a compound of the formula (111-1) can be produced, for example, by the following reaction. In the following formula, T", R1, R2, R3 and n are as defined above.
Figure imgf000011_0002
The compound of the formula (V) is reacted with a metal reagent, then reacted with a trialkylborane and finally hydrolyzed with an acid.
As the metal reagent, one or more may suitably be selected for use from e.g. a magnesium compound such as magnesium or isopropyl magnesium chloride; and a lithium compound such as lithium chloride or n-butyl lithium. The metal reagent may be used in an amount of from 0.3 to 5 times by mol, preferably from 0.5 to 3 times by mol, to the compound of the formula (V). As the trialkylborane, one or more may suitably be selected for use from e.g. trimethylborane, triethylborane,
triisopropylborane, etc. The trialkylborane may be used in an amount of from 0.3 to 5 times by mol, preferably from 0.5 to 2 times by mol, to the compound of the formula (V).
As the acid, one or more may suitably be selected for use from e.g. acetic acid, hydrochloric acid, sulfuric acid, etc. The acid may be used in an amount of from 0.3 to 5 times by mol, preferably from 0.5 to 3 times by mol, to the compound of the formula (V).
As the solvent, one or more may suitably be selected for use from e.g. an ether such as diethyl ether, butyl methyl ether, tetrahydrofuran, 1 ,4-dioxane or
dimethoxyethane; an aromatic hydrocarbon such as benzene, toluene, xylene or chlorobenzene; and an aliphatic hydrocarbon such as pentane, hexane, heptane, octane or cyclohexane.
The reaction is carried out usually in an inert gas atmosphere such as nitrogen gas or argon gas.
The temperature for the reaction is usually from -150°C to 150°C, preferably from -100°C to 100°C.
The reaction time is usually from about 0.5 to 48 hours, preferably from 1 to 24 hours.
[Process 4 for intermediate]
Among compounds included in the formula (III) for the starting material in the process [1], the compound of the formula (III-2) can be produced, for example, by the following reaction. In the following formulae, T", R1, R2, R3 and n are as defined above.
Figure imgf000012_0001
The compound of the formula (V) and compound of the formula (XIX) are reacted in the presence of a base and a transition metal catalyst in a solvent.
The transition metal catalyst may, for example, be the same one as in the above process [1]. The transition metal catalyst may be used in an amount of from 0.001 to 1 time by mol, preferably from 0.01 to 0.1 time by mol, to the compound of the formula (V).
The base may, for example, be the same one as in the above process [1].
The solvent may, for example, be the same one as in the above process [1]. The reaction is carried out usually in an inert gas atmosphere such as nitrogen gas or argon gas.
The temperature for the reaction is usually from -20°C to 150°C, preferably from
0°C to 100°C.
The reaction time is usually from about 1 to 48 hours, preferably from 1 to 24 hours.
Preferred embodiments of the pesticide containing the compound of the present invention will be described below. The pesticide containing the compound of the present invention is useful, for example, as an agent to control insects, mites, nematodes or soil pests which become problematic in the agricultural and horticultural fields, i.e. as an agricultural and horticultural insecticide, miticide, nematicide or soil pesticide or as an agent to control insects or mites parasitic on animals i.e. as an agent to control parasites on animals.
The compound of the present invention is useful as an agricultural and
horticultural insecticide, miticide, nematicide or soil pesticide. Specifically, it is effective to control insects, e.g. aphids such as green peach aphid (Myzus persicae) and cotton aphid (Aphis gossvpii); agricultural insect pests such as diamondback moth (Plutella xylostella), cabbage armyworm (Mamestra brassjcae), common cutworm (Spodoptera litura), codling moth (Cvdia pomonella), bollworm(Heliothis zea), tobacco budworm (Heliothis virescens), gypsy moth (Lymantria dispar), rice leafroller
(Cnaphalocrocis medinalis), smaller tea tortrix (Adoxophyes sp.), Colorado potato beetle (Leptinotarsa decemlineata), cucurbit leaf beetle (Aulacophora femoralis), boll weevil (Anthonomus qrandis), planthoppers, leafhoppers, scales, bugs, whiteflies, thrips, grasshoppers, anthomyiid flies, scarabs, black cutworm (Aqrotis ipsilon), cutworm (Agrotis segetum) and ants; gastropods such as slugs and snails; hygienic insect pests such as tropical rat mite (Ornithonyssus bacoti), cockroaches, housefly (Musca domestica) and house mosquito (Culex pipiens); stored grain insect such as angoumois grain moth (Sitotroga cerealella), adzuki bean weevil (Callosobruchus chinensis), red flour beetle (Tribolium castaneum) and mealworms; and household goods insect pests such as casemaking clothes moth (Tinea pellionella), black carpet beetle (Attagenus japonicus) and subterranean termites; mites, e.g. plant parasitic mites such as two-spotted spider mite (Tetranvchus urticae), carmine spider mite (Tetranvchus cinnabarinus), kanzawa spider mite (Tetranvchus kanzawai), citrus red mite (Panonvchus citri). European red mite (Panonvchus ulmi), broad mite
(Polyphaqotarsonemus latus), pink citrus rust mite (Aculops pelekassi) and bulb mite (Rhizoglvphus echinopus); and domestic mites such as mold mite (Tyrophagus putrescentiae), Dermatophaqoides farinae, Chelacaropsis moorei; nematodes, e.g. plant parasitic nematodes such as root-knot nematodes, cyst nematodes, root-lesion nematodes, white-tip nematode (Aphelenchoides bessevi), strawberry bud nematode (Nothotylenchus acris), and pine wood nematode (Bursaphelenchus xylophilus); and soil pests, e.g. isopods such as pillbugs (Armadillidium vulgare) and pillbugs (Porcellio scaber). Among them, the agricultural and horticultural insecticide, miticide, nematicide or soil pesticide containing the compound of the present invention is particularly effective for controlling plant parasitic mites, agricultural insect pests, plant parasitic nematodes or the like. Particularly, it is more effective for controlling plant parasitic mites and agricultural insect pests, and accordingly it is useful as an
insecticide or miticide. Further, it is effective against insect pests having acquired resistance to organophosphorus, carbamate, synthetic pyrethroid and/or neonicotinoid insecticides. Moreover, the compound of the present invention has excellent systemic properties, and by the application of the agricultural and horticultural insecticide, miticide, nematicide or soil pesticide containing the compound of the present invention to soil treatment, not only noxious insects, noxious mites, noxious nematodes, noxious gastropods and noxious isopods in soil but also foliage pests can be controlled.
Another preferred embodiments of the insecticide, miticide, nematicide or soil pesticide containing the compound of the present invention may be agricultural and horticultural insecticides, miticides, nematicides or soil pesticides which collectively control the above-mentioned plant parasitic mites, agricultural insect pests, plant parasitic nematodes, gastropods and soil pests.
The agricultural and horticultural insecticide, miticide, nematicide or soil pesticide containing the compound of the present invention, is usually formulated by mixing the compound with various agricultural adjuvants and used in the form of a formulation such as a dust, granules, water-dispersible granules, a wettable powder, a water- based suspension concentrate, an oil-based suspension concentrate, water soluble granules, a water soluble powder, an emulsif'iable concentrate, a soluble concentrate, a paste, an aerosol or an ultra low-volume formulation. However, so long as it is suitable for the purpose of the present invention, it may be formulated into any type of formulation which is commonly used in this field. Such agricultural adjuvants include solid carriers such as diatomaceous earth, slaked lime, calcium carbonate, talc, white carbon, kaoline, bentonite, kaolinite, sericite, clay, sodium carbonate, sodium
bicarbonate, mirabilite, zeolite and starch; solvents such as water, toluene, xylene, solvent naphtha, dioxane, acetone, isophorone, methyl isobutyl ketone,
chlorobenzene, cyclohexane, dimethylsulf oxide, Ν,Ν-dimethylformamide, N,N- dimethylacetamide, N-methyl-2-pyrrolidone, and alcohol; anionic surfactants such as a salt of fatty acid, a benzoate, an alkylsulfosuccinate, a dialkylsulfosuccinate, a polycarboxylate, a salt of alkylsulfuric acid ester, an alkyl sulfate, an alkylaryl sulfate, an alkyl diglycol ether sulfate, a salt of alcohol sulfuric acid ester, an alkyl sulfonate, an alkylaryl sulfonate, an aryl sulfonate, a lignin sulfonate, an alkyldiphenyl ether disulfonate, a polystyrene sulfonate, a salt of alkylphosphoric acid ester, an alkylaryl phosphate, a styrylaryl phosphate, a salt of polyoxyethylene alkyl ether sulfuric acid ester, a polyoxyethylene alkylaryl ether sulfate, a salt of polyoxyethylene alkylaryl ether sulfuric acid ester, a polyoxyethylene alkyl ether phosphate, a salt of polyoxyethylene alkylaryl phosphoric acid ester, and a salt of a condensate of naphthalene sulfonate with formaldehyde; nonionic surfactants such as a sorbitan fatty acid ester, a glycerin fatty acid ester, a fatty acid polyglyceride, a fatty acid alcohol polyglycol ether, acetylene glycol, acetylene alcohol, an oxyalkylene block polymer, a polyoxyethylene alkyl ether, a polyoxyethylene alkylaryl ether, a polyoxyethylene styrylaryl ether, a polyoxyethylene glycol alkyl ether, a polyethylene glycol, a polyoxyethylene fatty acid ester, a polyoxyethylene sorbitan fatty acid ester, a polyoxyethylene glycerin fatty acid ester, a polyoxyethylene hydrogenated castor oil, and a polyoxypropylene fatty acid ester; vegetable and mineral oils such as olive oil, kapok oil, castor oil, palm oil, camellia oil, coconut oil, sesame oil, corn oil, rice bran oil, peanut oil, cottonseed oil, soybean oil, rapeseed oil, linseed oil, tung oil, and liquid paraffins; and so on. Each of the components as such adjuvants may be one or more suitably selected for use, so long as the purpose of the present invention can thereby be accomplished. Further, other than the above-mentioned adjuvants, some among those known in this field may suitably be selected for use. For example, various adjuvants which are commonly used, such as a filler, a thickener, an anti-settling agent, an anti-freezing agent, a dispersion stabilizer, a phytotoxicity reducing agent, an anti-mold agent, and so on, may also be employed.
The weight ratio of the compound of the present invention to the various agricultural adjuvants is usually from 0.001 :99.999 to 95:5, preferably from
0.005:99.995 to 90:10.
In the actual application of such a formulation, it may be used as it is, or may be diluted to a predetermined concentration with a diluent such as water, and various spreaders e.g. surfactants, vegetable oils or mineral oils may be added thereto, as the case requires.
The application of the agricultural and horticultural insecticide, miticide, nematicide or soil pesticide containing the compound of the present invention cannot generally be defined, as it varies depending upon the weather conditions, the type of the formulation, the application season, the application site or the types or degree of outbreak of the pest insects. However, it is usually applied in a concentration of the active ingredient being from 0.05 to 800,000 ppm, preferably from 0.5 to 500,000 ppm, and the dose per unit area is such that the compound of the present invention is from 0.05 to 50,000 g, preferably from 1 to 30,000 g, per hectare. Further, the present invention includes such a method for controlling insects, mites, nematodes or soil pests, particularly for controlling plant parasitic mites, agricultural insect pests or plant parasitic nematodes by such applications.
Various formulations of the agricultural and horticultural insecticide, miticide, nematicide or soil pesticide containing the compound of the present invention or their diluted compositions may be applied by conventional methods for application which are commonly employed, such as spraying (e.g. jetting, misting, atomizing, powder or grain scattering or dispersing in water), soil application (e.g. mixing or drenching), surface application (e.g. coating, powdering or covering) or impregnation to obtain poisonous feed. Further, it is possible to feed domestic animals with a food
containing the above active ingredient and to control the outbreak or growth of pests, particularly insect pests, with their excrements. Furthermore, the active ingredient may also be applied by a so-called ultra low-volume application method. In this method, the composition may be composed of 100% of the active ingredient.
Further, the agricultural and horticultural insecticide, miticide, nematicide or soil pesticide containing the compound of the present invention may be mixed with or may be used in combination with other agricultural chemicals, fertilizers or phytotoxicity- reducing agents, whereby synergistic effects or activities may sometimes be obtained. Such other agricultural chemicals include, for example, a herbicide, an insecticide, a miticide, a nematicide, a soil pesticide, a fungicide, an antivirus agent, an attractant, an antibiotic, a plant hormone, a plant growth regulating agent, and so on. Especially, with an insecticidal, miticidal, nematicidal or soil pesticidal composition having a compound of the present invention mixed with or used in combination with one or more active compounds of other agricultural chemicals, the application range, the application time, the pesticidal activities, etc. may be improved to preferred directions. The compound of the present invention and the active compounds of other agricultural chemicals may separately be formulated so that they may be mixed for use at the time of application, or they may be formulated together. The present invention includes such an insecticidal, miticidal, nematicidal or soil pesticidal composition.
The mixing ratio of the compound of the present invention to the active
compounds of other agricultural chemicals can not generally be defined, since it varies depending upon the weather conditions, the types of formulations, the application time, the application site, the types or degree of outbreak of insect pests, etc., but it is usually within a range of from 1 :300 to 300: 1 , preferably from 1 : 100 to 100: 1 , by weight. Further, the dose for the application is such that the total amount of the active compounds is from 0.1 to 50,000 g, preferably from 1 to 30,000 g, per hectare. The present invention includes a method for controlling insects, mites, nematodes or soil pests by an application of such an insecticidal, miticidal, nematicidal or soil pesticidal composition.
The active ingredient compounds of an insect pest control agents, such as the insecticide, the miticide, the nematicide or the soil insect pesticide in the above- mentioned other agricultural chemicals, include, for example, (by common names, some of them are still in an application stage, or test codes of Japan Plant Protection Association):
organic phosphate compounds, such as profenofos, dichlorvos, fenamiphos, fenitrothion, EPN, diazinon, chlorpyrifos, chlorpyrifos-methyl, acephate, prothiofos, fosthiazate, cadusafos, disulfoton, isoxathion, isofenphos, ethion, etrimfos, quinalphos, dimethylvinphos, dimethoate, sulprofos, thiometon, vamidothion, pyraclofos,
pyridaphenthion, pirimiphos-methyl, propaphos, phosalone, formothion, malathion, tetrachlorvinphos, chlorfenvinphos, cyanophos, trichlorfon, methidathion, phenthoate, ESP, azinphos-methyl, fenthion, heptenophos, methoxychlor, parathion, phosphocarb, demeton-S-methyl, monocrotophos, methamidophos, imicyafos, parathion-methyl, terbufos, phosphamidon, phosmet, phorate, phoxim and triazophos;
carbamate compounds, such as carbaryl, propoxur, aldicarb, carbofuran, thiodicarb, methomyl, oxamyl, ethiofencarb, pirimicarb, fenobucarb, carbosulfan, benfuracarb, bendiocarb, furathiocarb, isoprocarb, metolcarb, xylylcarb, XMC and fenothiocarb;
nereistoxin derivatives, such as cartap, thiocyclam, bensultap, thiosultap-sodium, thiosultap-disodium, monosultap, bisultap and thiocyclam hydrogen oxalate;
organic chlorine compounds, such as dicofol, tetradifon, endosulfan, dienochlor and dieldrin;
organic metal compounds, such as fenbutatin oxide and cyhexatin;
pyrethroid compounds, such as fenvalerate, permethrin, cypermethrin,
deltamethrin, cyhalothrin, tefluthrin, ethofenprox, flufenprox, cyfluthrin, fenpropathrin, flucythrinate, fluvalinate, cycloprothrin, lambda-cyhalothrin, pyrethrins, esfenvalerate, tetramethrin, resmethrin, protrifenbute, bifenthrin, zeta-cypermethrin, acrinathrin, alpha-cypermethrin, allethrin, gamma-cyhalothrin, theta-cypermethrin, tau-fluvalinate, tralomethrin, profluthrin, beta-cypermethrin, beta-cyfluthrin, metofluthrin, phenothrin, flumethrin and decamethrin;
benzoylurea compounds, such as diflubenzuron, chlorfluazuron, teflubenzuron, flufenoxuron, lufenuron, novaluron, triflumuron, hexaflumuron, bistrifluron,
noviflumuron and fluazuron;
juvenile hormone-like compounds, such as methoprene, pyriproxyfen, fenoxycarb and diofenolan;
pyridazinone compounds, such as pridaben;
pyrazole compounds, such as fenpyroximate, fipronil, tebufenpyrad, ethiprole, tolfenpyrad, acetoprole, pyrafluprole and pyriprole;
neonicotinoids, such as imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, nidinotefuran, dinotefuran and nithiazine;
hydrazine compounds, such as tebufenozide, methoxyfenozide, chromafenozide and halofenozide;
pyridine compounds, such as pyridalyl and flonicamid;
cyclic keto-enol compounds, such as spirodiclofen; spiromesifen and
spirotetramat;
strobilurin compounds, such as fluacrypyrim; pyrimidinamine compounds, such as flufenerim;
dinitro compounds; organic sulfur compounds; urea compounds; triazine compounds; hydrazone compounds;
other compounds, such as flupyradifurone, NNI-0711 (pyflubumide), flometoquin, buprofezin, hexythiazox, amitraz, chlordimeform, silafluofen, triazamate, pymetrozine, pyrimidifen, chlorfenapyr, indoxacarb, acequinocyl, etoxazole, cyromazine, 1 ,3- dichloropropene, diafenthiuron, benclothiaz, bifenazate, propargite, clofentezine, metaflumizone, flubendiamide, cyflumetofen, chlorantraniliprole, cyantraniliprole, cyenopyrafen, pyrifluquinazon, fenazaquin, amidoflumet, sulfluramid, hydramethylnon, metaldehyde, HGW-86, ryanodine, verbutin, AKD-1022, chlorobenzoate,
thiazolylcinnanonitrile, sulfoxaflor, fluensulfone, 3-bromo-N-(2-bromo-4-chloro-6-(1- cyclopropylethylcarbamoyl)phenyl)-1-(3-chloropyridin-2-yl)-1 H-pyrazole-5- carboxyamide, 3-bromo-N-(4-chloro-2-(1-cyclopropylethylcarbamoyl)-6-methylphenyl)- 1 -(3-chloropyridin-2-yl)-1 H-pyrazole-5-carboxyamide, 3-bromo-N-(2-bromo-4-chloro-6- (cyclopropylmethylcarbamoyl)phenyl)-1-(3-chloropyridin-2-yl)-1 H-pyrazole-5- carboxyamide, 3-bromo-N-(4-chloro-2-methyl-6-(methylcarbamoyl)phenyl)-1-(3- chloropyridin-2-yl)-1 H-pyrazole-5-carboxyamide and 3-bromo-1-(3-chloropyridin-2-yl)- N-(4-cyano-2-methyl-6-(methylcarbamoyl)phenyl)-1 H-pyrazole-5-carboxyamide; and the like. Further, it may be used in combination with or together with microbial agricultural chemicals, such as insecticidal crystal proteins produced by Bacillus thuringiensis aizawai, Bacillus thuringiensis kurstaki, Bacillus thuringiensis israelensis, Bacillus thuringiensis japonensis, Bacillus thuringiensis tenebrionis or Bacillus thuringiensis, insect viruses, etomopathogenic fungi, and nematophagous fungi;
antibiotics or semisynthetic antibiotics, such as avermectin, emamectin benzoate, milbemectin, milbemycin, spinosad, ivermectin, lepimectin, DE-175, abamectin, emamectin and spinetoram; natural products, such as azadirachtin and rotenone; and repellents, such as deet.
The active ingredient compounds of the fungicide in the above-mentioned other agricultural chemicals include, for example, (by common names, some of them are still in an application stage, or test codes of Japan Plant Protection Association):
anilinopyrimidine compounds, such as mepanipyrim, pyrimethanil, cyprodinil and ferimzone;
triazoropyrimidine compounds, such as 5-chloro-7-(4-methylpiperidin-1-yl)-6- (2,4,6-trifluorophenyl)[1 ,2,4]triazolo[1 ,5-a]pyrimidine;
pyridinamine compounds, such as fluazinam;
azole compounds, such as triadimefon, bitertanol, triflumizole, etaconazole, propiconazole, penconazole, flusilazole, myclobutanil, cyproconazole, tebuconazole, hexaconazole, furconazole-cis, prochloraz, metconazole, epoxiconazole,
tetraconazole, oxpoconazole fumarate, sipconazole, prothioconazole, triadimenol, flutriafol, difenoconazole, fluquinconazole, fenbuconazole, bromuconazole,
diniconazole, tricyclazole, probenazole, simeconazole, pefurazoate, ipconazole and imibenconazole;
quinoxaline compounds, such as quinomethionate;
dithiocarbamate compounds, such as maneb, zineb, mancozeb, polycarbamate, metiram, propineb and thiram;
organic chlorine compounds, such as fthalide, chlorothalonil and quintozene; imidazole compounds, such as benomyl, cyazofamid, thiophanate-methyl, carbendazim, thiabendazole and fuberiazole; cyanoacetamide compounds, such as cymoxanil;
anilide compounds, such as metalaxyl, metalaxyl-M, mefenoxam, oxadixyl, ofurace, benalaxyl, benalaxyl-M (another name: kiralaxyl, chiralaxyl), furalaxyl, cyprofuram, carboxin, oxycarboxin, thifluzamide, boscalid, bixafen, isotianil, tiadinil and sedaxane;
sulfamide compounds, such as dichlofluanid;
copper compounds, such as cupric hydroxide and oxine copper;
isoxazole compounds, such as hymexazol;
organophosphorus compounds, such as fosetyl-AI, tolclofos-methyl, S-benzyl Ο,Ο-diisopropylphosphorothioate, O-ethyl S,S-diphenylphosphorodithioate, aluminum ethylhydrogen phosphonate, edifenphos, and iprobenfos;
phthalimide compounds, such as captan, captafol and folpet;
dicarboximide compounds, such as procymidone, iprodione and vinclozolin; benzanilide compounds, such as flutolanil and mepronil;
amide compounds, such as penthiopyrad, mixture of 3-(difluoromethyl)-1 -methyl- N[(1 RS,4SR,9SR)-1 ,2,3,4-tetrahydro-9-isopropyl-1 ,4-methanonaphthalen-5- yl]pyrazole-4-carboxamide and 3-(difluoromethyl)-1-methyl-N-[(1 RS,4SR,9SR)-1 ,2,3,4- tetrahydro-9-isopropyl-1 ,4-methanonaphthalen-5-yl]pyrazole-4-carboxamide
(isopyrazam), silthiopham, fenoxanil and furametpyr;
benzamide compounds, such as fluopyram and zoxamide;
piperazine compounds, such as triforine;
pyridine compounds, such as pyrifenox;
carbinol compounds, such as fenarimol;
piperidine compounds, such as fenpropidin;
morpholine compounds, such as fenpropimorph and tridemorph;
organotin compounds, such as fentin hydroxide and fentin acetate;
urea compounds, such as pencycuron;
cinnamic acid compounds, such as dimethomorph and flumorph;
phenylcarbamate compounds, such as diethofencarb;
cyanopyrrole compounds, such as fludioxonil and fenpiclonil;
strobilurin compounds, such as azoxystrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, picoxystrobin, oryzastrobin, dimoxystrobin, pyraclostrobin, and fluoxastrobin;
oxazolidinone compounds, such as famoxadone;
thiazolecarboxamide compounds, such as ethaboxam;
valinamide compounds, such as iprovalicarb and benthiavalicarb-isopropyl;
acylamino acid compounds, such as methyl N-(isopropoxycarbonyl)-L-valyl- (3RS)-3-(4-chlorophenyl)-p-alaninate (valiphenalate);
imidazolinone compounds, such as fenamidone;
hydroxyanilide compounds, such as fenhexamid;
benzenesulfonamide compounds, such as flusulfamide;
oxime ether compounds, such as cyflufenamid;
anthraquinone compounds;
crotonic compounds;
antibiotics, such as validamycin, kasugamycin and polyoxins;
guanidine compounds, such as iminoctadine and dodine;
quinoline compounds, such as 6-tert-butyl-8-fluoro-2,3-dimethylquinolin- 4-yl acetate (tebufloquin); thiazolidine compounds, such as (z)-2-(2-fluoro-5-(trifluromethyl)phenylthio)-2-(3- (2-methoxyphenyl)thiazolidin-2-yliden)acetonitrile (flutianil);
and other compounds, such as pyribencarb, isoprothiolane, pyroquilon, diclomezine, quinoxyfen, propamocarb hydrochloride, chloropicrin, dazomet, metam- sodium, nicobifen, metrafenone, UBF-307, diclocymet, proquinazid, amisulbrom
(another name: amibromdole), 3-(2,3,4-trimethoxy-6-methylbenzoyl)-5-chloro-2- methoxy-4-methylpyridine, 4-(2,3,4-trimethoxy-6-methylbenzoyl)-2,5-dichloro-3- trifluoromethylpyridine, pyriofenone, mandipropamid, fluopicolide, carpropamid, meptyldinocap, N-[(3',4'-dichloro-1 , 1 -dimethyl)phenacyl]-3-trifluoromethyl-2- pyridinecarboxyamide, N-[(3',4'-dichloro-1 ,1 -dimethyl)phenacyl]-3-methyl-2- thiophencarboxyamide, N-[(3' ,4'-dichloro- 1 , 1 -dimethyl)phenacyl]- 1 -methyl-3- trif luoromethyl-4-pyrazolecarb0xyamide, N-[[2'-methyl-4'-(2-propyloxy)-1 , 1 - dimethyl]phenacyl]-3-trifluoromethyl-2-pyridinecarboxyamide, N-[[2'-methyl-4'-(2- propyloxy)-1 ,1 -dimethyl]phenacyl]-3-methyl-2-thiophencarboxyamide, N-[[2'-methyl-4'- (2-propyloxy)-1 ,1 -dimethyl]phenacyl]-1 -methyl-3-trifluoromethyl-4- pyrazolecarboxyamide, N-[[4'-(2-propyloxy)-1 ,1 -dimethyl]phenacyl]-3-trifluoromethyl-2- pyridinecarboxyamide, N-[[4'-(2-propyloxy)-1 ,1 -dimethyl]phenacyl]-3-methyl-2- thiophencarboxyamide, N-[[4'-(2-propyloxy)-1 , 1 -dimethyl]phenacyl]-1 -methyl-3- trifluoromethyl-4-pyrazolecarboxyamide, N-[[2'-methyl-4'-(2-pentyloxy)-1 , 1 - dimethyl]phenacyl]-3-trifluoromethyl-2-pyridinecarboxyamide, N-[[4'-(2-pentyloxy)-1 ,1 - dimethyl]phenacyl]-3-trifluoromethyl-2-pyridinecarboxyamide, spiroxamine, S-2188 (fenpyrazamine), S-2200, ZF-9646, BCF-051 , BCM-061 and BCM-062.
Further, agricultural chemicals which may be used in admixture with or in combination with the compounds of the present invention, may , for example, be the active ingredient compounds in the herbicides as disclosed in The Pesticide
Manual(15th edition), particularly those of soil treatment type.
The pesticides against parasites on animals are effective for controlling e.g.
harmful external parasites which are parasitic on the body surface of host animals (such as the back, the axilla, the lower abdomen or inside of the thigh) or harmful internal parasites which are parasitic in the body of host animals (such as the stomach, the intestinal tract, the lung, the heart, the liver, the blood vessels, the subcutis or lymphatic tissues), but they are particularly effective for controlling the external parasites.
The external parasites may, for example, be animal parasitic acarus or fleas. Their species are so many that it is difficult to list all of them, and therefore, their typical examples will be given.
The animal parasitic acarus may, for example, be ticks such as Boophilus microplus, Rhipicephalus sanguineus, Haemaphvsalis lonqicornis, Haemaphvsalis flava, Haemaphvsalis campanulata, Haemaphvsalis concinna, Haemaphvsalis iaponica, Haemaphvsalis kitaokai, Haemaphvsalis ias, Ixodes ovatus, Ixodes
nipponensis, Ixodes persulcatus, Amblvomma testudinarium, Haemaphvsalis
meqaspinosa, Dermacentor reticulatus, and Dermacentor taiwanesis; red mite
(Dermanvssus qallinae); northern fowl mites such as Ornithonvssus sylviarum, and Ornithonvssus bursa; trombiculidae such as Eutrombicula wichmanni,
Leptotrombidium akamushi, Leptotrombidium pallidum, Leptotrombidium fuji,
Leptotrombidium tosa, Neotrombicula autumnalis, Eutrombicula alfredduqesi, and
Helenicula mivaqawai; cheyletidae such as Cheyletiella vasquri, Cheyletiella
parasitivorax, and Cheyletiella blakei; sarcoptic mange mites such as Psoroptes cuniculi, Chorioptes bovis, Otodectes cynotis, Sarcoptes scabiei, and Notoedres cati; and Demodicidae such as Demodex canis. The pesticides against parasites on animals, containing the compounds of the present invention, are particularly effective for the control of ticks among them.
The animal parasitic fleas may, for example, be externally parasitic wingless insects belonging to Siphonaptera, more specifically, fleas belonging to Pulicidae,
Ceratephyllus, etc. Fleas belonging to Pulicidae may for example, be
Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Echidnophaqa qallinacea, Xenopsylla cheopis, Leptopsylla seqnis, Nosopsyllus fasciatus, and Monopsyllus anisus. The pesticides against parasites on animals, containing the compounds of · the present invention, are particularly effective for the control of fleas belonging to
Pulicidae, particularly Ctenocephalides canis and Ctenocephalides felis, among them.
Other external parasites may, for example, be sucking lice (Anoplura) such as shortnosed cattle louse (Haematopinus eurvsternus), horse sucking louse
(Haematopinus asini), sheep louse, longnosed cattle louse (Linoqnathus yjtuli), and head louse (Pediculus capitis); biting lice such as dog biting louse (Trichodectes canis); and blood-sucking dipterous insects such as horsefly (Tabanus triqonus), biting midges (Culicoides schultzei), and blackfly (Simulium ornatum). Further, the internal parasites may, for example, be nematodes such as lung worms, whipworms
(Trichuris), tuberous worms, gastric parasites, ascaris, and filarioidea; cestoda such as Spirometra erinacei, Diphyllobothrium latum, Dipylidium caninum, Taenia multiceps, Echinococcus granulosus, and Echinococcus multilocularis; trematoda such as
Schistosoma japonicum and Fasciola hepatica; and protozoa such as coccidia, malaria parasites (Plasmodium malariae), intestinal sarcocyst, toxoplasma, and
Cryptosporidium.
The host animals may, for example, be pet animals, domestic animals, and poultry, such as dogs, cats, mice, rats, hamsters, guinea pigs, squirrels, rabbits, ferrets, birds (such as pigeons, parrots, hill mynas, Java sparrows, honey parrots, lovebirds and canaries), cows, horses, pigs, sheep, ducks and chickens. The pesticides against parasites on animals, containing the compounds of the present invention, are particularly effective for the control of pests parasitic on pet animals or domestic animals, especially for the control of external parasites, among them.
Among pet animals or domestic animals, they are effective particularly for dogs and cats, cows and horses.
When the compound of the present invention is used as a pesticide against parasites on animals, it may be used as it is or may be used together with suitable adjuvants, as formulated into various formulations such as a dust, granules, tablets, a powder, capsules, a soluble concentrate, an emulsifiable concentrate, a water-based suspension concentrate and an oil-based suspension concentrate. In addition to such formulations, it may be formulated into any type of formulation which is commonly used in this field, so long as it is suitable for the purpose of the present invention. The adjuvants to be used for formulations may, for example, be anionic surfactants or nonionic surfactants exemplified above as adjuvants for formulation of agricultural and horticultural insecticide, miticide, nematicide or soil pesticides; a cationic surfactant such as cetyl trimethylammonium bromide; a solvent such as water, acetone, acetonitrile, N-methylacetamide, Ν,Ν-dimethylacetamide, N,N-dimethylformamide, 2- pyrrolidone, N-methyl-2-pyrrolidone, kerosene, triacetin, methanol, ethanol,
isopropanol, benzyl alcohol, ethylene glycol, propylene glycol, polyethylene glycol, liquid polyoxyethylene glycol, butyl diglycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol n-butyl ether, dipropylene glycol monomethyl ether, or dipropylene glycol n-butyl ether; an antioxidant such as butylhydroxyanisole, butylhydroxytoluene, ascorbic acid, sodium hydrogenmetasulfite, propyl gallate or sodium thiosulfate; a coating film- forming agent such as polyvinylpyrrolidone, polyvinyl alcohol, or a copolymer of vinyl acetate and vinyl pyrrolidone; the vegetable oils and mineral oils as exemplified above as adjuvants for formulation of agricultural and horticultural insecticide, miticide, nematicide or soil pesticides; a carrier such as lactose, sucrose, glucose, starch, wheat flour, corn powder, soybean cake and meal, defatted rice bran, calcium carbonate or other commercially available feed materials; and so on. One or more of the
respective components of these adjuvants may be suitably selected for use, so long as such will not depart from the purpose of the present invention. Further, other than the above-mentioned adjuvants, some among those known in this field may suitably be selected for use, and still further, some among the above-mentioned various adjuvants to be used in the agricultural and horticultural field may suitably be selected for use.
The blend ratio of the compound of the present invention to various adjuvants is usually from 0.1 :99.9 to 90:10, by weight. In the actual use of such a formulation, it may be used as it is, or may be diluted to a predetermined concentration with a diluent such as water, and various spreaders (e.g. surfactants, vegetable oils or mineral oils) may be added thereto, as the case requires.
Administration of the compound of the present invention to a host animal is carried out orally or parenterally. As an oral administration method, a method of administering a tablet, a liquid agent, a capsule, a wafer, a biscuit, a minced meat or other feed, containing the compound of the present invention, may be mentioned. As a parenteral administration method, there may, for example, be mentioned a method wherein the compound of the present invention is formulated into a suitable formulation and then taken into the body by e.g. intravenous administration, intramuscular administration, intradermal administration, hypodermic administration, etc.; a method wherein it is administered on the body surface by spot-on treatment, pour-on treatment or spray treatment; or a method of embedding a resin fragment or the like containing the compound of the present invention under the skin of the host animal.
The dose of the compound of the present invention to a host animal varies depending upon the administration method, the purpose of administration, the deceased symptom, etc., but it is usually administered in a proportion of from 0.01 mg to 100 g, preferably from 0.1 mg to 10 g, per 1 kg of the body weight of the host animal.
The present invention also includes a method for controlling a pest by the above- mentioned administration method or by the above-mentioned dose, particularly a method for controlling external parasites or internal parasites.
Further, in the present invention, by controlling pests parasitic on animals as described above, it is possible to prevent or cure various diseases of the host animal thereby caused in some cases. Thus, the present invention also includes a
preventive or therapeutic agent for an animal disease caused by parasites, containing the compound of the present invention as an active ingredient, and a method for preventing or curing an animal disease caused by parasites.
When the compound of the present invention is used as a pesticide against parasites on animals, various vitamins, minerals, amino acids, nutrients, enzymes, antipyretics, sedatives, antiphlogistics, fungicides, colorants, aromatic substances, preservatives, etc., may be used in admixture with or in combination with the
adjuvants. Further, as the case requires, other animal drugs or agricultural
chemicals, such as vermicides, anti-coccidium agents, insecticides, miticides, pulicides, nematicides, bactericides or antibacterial agents, may be mixed or combined for use, whereby improved effects may sometimes be obtained. The present invention includes such a mixed pesticidal composition having the above-mentioned various components mixed or combined for use, and further a method for controlling a pest by using it, particularly a method for controlling external parasites or internal parasites.
Preferred embodiments of the compound of the above formula (I) are as follows, however, it should be understood that the present invention is by no means limited to such preferred embodiments.
(1) The compound of the above formula (I) or its salt.
(2) The compound or its salt according to the above (1), wherein W is an oxygen atom; x is 0; and y is 1.
(3) A pesticide containing the compound or its salt as defined in the above (2), as an active ingredient.
(4) The pesticide containing the compound or its salt as an active ingredient, according to the above (3) is an agricultural and horticultural insecticide, miticide, nematicide or soil pesticide.
(5) An agricultural and horticultural insecticide or miticide containing the
compound or its salt as an active ingredient according to the above (4).
EXAMPLES
Now, the present invention will be described in further detail with reference to Examples, but it should be understood that the present invention is by no means thereby restricted. Firstly, Preparation Examples for the compounds of the present invention will be described.
PREPARATION EXAMPLE 1
Preparation of (3'-(benzyloxy)-6-fluoro-4-methyl-[1 ,1 '-biphenyl]-3-yl)(2,2,2- trifluoroethyl)sulfane (compound No.2-1)
(1) 0.77 g of benzyl chloride was dropwise added to a mixed solution comprising 1.0 g of 3-bromophenol, 1.6 g of potassium carbonate and 5 mL of N,N- dimethylformamide. After completion of the dropwise addition, a reaction was carried out at 60°C for 2 hours. Water was added to the reaction solution, followed by extraction with ethyl acetate. Then, the organic layer was washed with water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying. The solvent was distilled off under reduced pressure to obtain 1.6 g of oily 1 - (benzyloxy)-3-brornobenzene.
(2) A mixed solution comprising 0.13 g of 1 -(benzyloxy)-3-bromobenzene, 0.13 g of (2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)boronic acid, 0.030 g of tetrakis(triphenylphosphine)palladium, 0.11 g of sodium carbonate, 3 mL of
tetrahydrofuran and 3 mL of water, was heated and refluxed for 5 hours. Water was added to the reaction solution, followed by extraction with ethyl acetate. Then, the organic layer was washed with water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: n-heptane/ethyl acetate=9/1) to obtain 0.11 g of the oily desired product. PREPARATION EXAMPLE 2
Preparation of 3'-(benzyloxy)-2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)sulfinyl)-1 ,1'- biphenyl (compound No.2-2)
0.072 g of m-chloroperbenzoic acid was added to a mixed solution comprising 0.11 g of (3'-(benzyloxy)-6-fluoro-4-methyl-[1 ,1 '-biphenyl]-3-yl)(2,2,2- trifluoroethyl)sulfane and 3 mL of chloroform, followed by a reaction at room
temperature for 2 hours. Water was added to the reaction solution, followed by extraction with ethyl acetate. Then, the organic layer was washed with an aqueous sodium bicarbonate solution, water and an aqueous sodium chloride solution and anhydrous sodium sulfate was added for drying. The solvent was distilled off under reduced pressure to obtain 0.13 g of the desired product (melting point: 84-86°C). PREPARATION EXAMPLE 3
Preparation of benzyl(2'-fluoro-4'-methyl-5'-((2,2,2-trifluoroethyl)thio)-[1 ,1 '-biphenyl]-3- yl)sulfane (compound No.2-557)
(1) 1.5 g of benzyl chloride was dropwise added to a mixed solution comprising 2.0 g of 3-bromothiophenol, 2.9 g of potassium carbonate, 1.6 g of Rongalite and 20 mL of Ν,Ν-dimethylformamide. After completion of the dropwise addition, a reaction was carried out at room temperature for 5 hours. Water was added to the reaction solution, followed by extraction with ethyl acetate. Then, the organic layer was washed with water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying. The solvent was distilled off under reduced pressure to obtain 3.2 g of oily benzyl(3-bromophenyl)sulfane.
(2) A mixed solution comprising 0.14 g of benzyl(3-bromophenyl)sulf ane, 0.13 g of (2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)boronic acid, 0.030 g of tetrakis(triphenylphosphine)palladium, 0.11 g of sodium carbonate, 4 mL of
tetrahydrofuran and 4 mL of water, was heated and refluxed for 15 hours. Water was added to the reaction solution, followed by extraction with ethyl acetate. Then, the organic layer was washed with water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: n-heptane/ethyl acetate=95/5) to obtain 0.13 g of the oily desired product. PREPARATION EXAMPLE 4
Preparation of (6-fluoro-4-methyl-3'-(phenoxymethyl)-[1 ,1 '-biphenyl]-3-yl)(2,2,2- trifluoroethyl)sulfane (compound No.5-1)
(1) A mixed solution comprising 0.56 g of 3-bromobenzylbromide, 0.21 g of phenol, 0.62 g of potassium carbonate and 1 mL of Ν,Ν-dimethylformamide, was reacted at room temperature for 45 hours. Water was added to the reaction solution, followed by extraction with ethyl acetate. Then, the organic layer was washed with water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: n-heptane/ethyl acetate=10/1 ) to obtain 0.59 g of oily 1 -bromo-3-(phenoxymethyl)benzene.
(2) A mixed solution comprising 0.40 g of 1 -bromo-3-(phenoxymethyl)benzene,
0.41 g of (2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)boronic acid, 0.090 g of tetrakis(triphenylphosphine)palladium, 0.42 g of potassium carbonate, 3 mL of 1 ,4- dioxane and 3 mL of water, was heated and refluxed for 6 hours. Water was added to the reaction solution, followed by extraction with ethyl acetate. Then, the organic layer was washed with water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: n- heptane/ethyl acetate=20/1 ) to obtain 0.53 g of the oily desired product.
PREPARATION EXAMPLE 5
Preparation of 2-fluoro-4-methyl-3'-(phenoxymethyl)-5-((2,2,2-trifluoroethyl)sulfinyl)- 1 ,1 '-biphenyl (compound No.5-2)
0.25 g of m-chloroperbenzoic acid was added to a mixed solution comprising 0.38 g of (6-fluoro-4-methyl-3'-(phenoxymethyl)-[1 ,1'-biphenyl]-3-yl)(2,2,2- trifluoroethyl)sulfane and 3 ml_ of chloroform, followed by a reaction at room
temperature for 29 hours. Water was added to the reaction solution, followed by extraction with ethyl acetate. Then, the organic layer was washed with an aqueous sodium bicarbonate solution, water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: n-heptane/ethyl acetate=5/1) to obtain 0.36 g of the desired product (melting point: 88-89°C).
PREPARATION EXAMPLE 6
Preparation of 2-(benzyloxy)-4-(2-fluoro-4-methyl-5-((2,2,2- trifluoroethyl)thio)phenyl)pyridine (compound No.10-1)
(1) 0.37 g of sodium hydride was added to a mixed solution comprising 1.1 g of benzyl alcohol and 3 mL of tetrahydrofuran while cooling with an ice bath, followed by stirring at room temperature for 10 minutes. A mixed solution comprising 0.60 g of 4- bromo-2-chloropyridine and 1 mL of tetrahydrofuran, was added to the reaction solution, followed by heating and refluxing for 3 hours. Water was added to the reaction solution, followed by extraction with ethyl acetate. Then, the organic layer was washed with water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: n- heptane/ethyl acetate=10/1) to obtain 0.71 g of oily 2-(benzyloxy)-4-bromopyridine.
(2) A mixed solution comprising 0.28 g of 2-(benzyloxy)-4-bromopyridine, 0.28 g of (2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)boronic acid, 0.060 g of tetrakis(triphenylphosphine)palladium, 0.29 g of potassium carbonate, 2 mL of 1 ,4- dioxane and 2 mL of water, was heated and refluxed for 6 hours. Water was added to the reaction solution, followed by extraction with ethyl acetate. Then, the organic layer was washed with water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: n- heptane/ethyl acetate=15/1) to obtain 0.30 g of the oily desired product.
PREPARATION EXAMPLE 7
Preparation of 2-(benzyloxy)-4-(2-fluoro-4-methyl-5-((2,2,2- trifluoroethyl)sulfinyl)phenyl)pyridine (compound No.10-2)
0.12 g of m-chloroperbenzoic acid was added to a mixed solution comprising 0.19 g of 2-(benzyloxy)-4-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)pyridine and 3 mL of chloroform, followed by a reaction at room temperature for 3 hours. Water was added to the reaction solution, followed by extraction with ethyl acetate. Then, the organic layer was washed with an aqueous sodium bicarbonate solution, water and an aqueous sodium chloride solution, and anhydrous sodium sulfate was added for drying. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: n-heptane/ethyl acetate=4/1 ) to obtain 0.20 g of the oily desired product.
Typical examples of the compound of the above formula (I) will be given in Tables
1 to 23. These compounds can be prepared based on the above-described
Preparation Examples or the above-described various processes for the production of the compound of the present invention. In Tables 1 to 23, No. represents compound No., Me methyl, Et ethyl, n-Pr n-propyl, i-Pr isopropyl, n-Bu n-butyl, i-Bu isobutyl, s-Bu secondary butyl, t-Bu tert-butyl, Ph phenyl, and Py pyridyl and 2-F-Ph represents phenyl substituted with F at the 2-position, and 3-CF3-2-Py represents 2-pyridyl substituted with CF3 at the 3-position. In the column for Q, a symbol showing a substitution position such as "2-" is allotted on such a basis that with respect to Ph the number of the carbon atom from which a free carbon atomic valence extends is designated to be 1 -position, and with respect to Py, the nitrogen atom is designated to be 1 -position. For example, "2-F-Ph" and "4-CF3 -2-Py" represent the following, respectively:
Figure imgf000025_0001
Further, in the column for R5, it is meant that R5 is substituted at the position corresponding to the number allotted to the chemical structural formula in each Table. A compound identified with "-" indicates that R5 is a hydrogen atom. In a case where R5 is other than a hydrogen atom, for example, in the case of a compound identified with "4-F", it is meant that the 4-position is substituted with a fluorine atom. The numerical value shown in the column for the physical properties is a melting point (°C). Further, with respect to some of the compounds of the above formula (I), 1H-NMR data [measured by 1H-Nuclear magnetic resonance spectroscopy, δ is a chemical shift value] are shown in Tables 24 and 25.
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
TABLE 2 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
2-61 Ph O F Me CH2CF3 3-CN 0 Oil
2-62 Ph O F Me CH2CF3 3-CN 1 Oil
2-63 Ph O F Me CH2CF3 4-CN 0
2-64 Ph O F Me CH2CF3 4-CN 1
2-65 Ph O F Me CH2CF3 3-NO2 0 86-88
2-66 Ph O F Me CH2CF3 3-NO2 1 130-132
2-67 Ph O F Me CH2CF3 4-NO2 0
2-68 Ph O F Me CH2CF3 4-NO2 1
2-69 Ph O F Me CH2CF3 3-COMe 0
2-70 Ph O F Me CH2CF3 3-COMe 1
2-71 Ph O F Me CH2CF3 4-COMe 0
2-72 Ph O F Me CH2CF3 4-COMe 1
2-73 Ph O F Me CH2CF3 3-COCF3 0
2-74 Ph O F Me CH2CF3 3-COCF3 1
2-75 Ph O F Me CH2CF3 4-COCF3 0
2-76 Ph O F Me CH2CF3 4-COCF3 1
2-77 Ph O F Me CH2CF3 3-CO2H 0
2-78 Ph O F Me CH2CF3 3-CO2H 1
2-79 Ph O F Me CH2CF3 4-CO2H 0
2-80 Ph O F Me CH2CF3 4-CO2H 1
2-81 Ph O F Me CH2CF3 3-CO2Me 0
2-82 Ph O F Me CH2CF3 3-CO2Me 1
2-83 Ph O F Me CH2CF3 4-CO2Me 0
2-84 Ph O F Me CH2CF3 4-CO2Me 1
2-85 Ph O F Me CH2CF3 3-NHCOMe 0
2-86 Ph O F Me CH2CF3 3-NHCOMe 1
2-87 Ph O F Me CH2CF3 4-NHCOMe 0
2-88 Ph O F Me CH2CF3 4-NHCOMe 1
2-89 Ph O F Me CH2CF3 5-NHCOMe 0
2-90 Ph O F Me CH2CF3 5-NHCOMe 1
-91 Ph O F Me CH2CF3 3-NHCOCF3 0
2-92 Ph O F Me CH2CF3 3-NHCOCF3 1 TABLE 2 (continued)
Physical
No. Q W R R2 R3 R5 n
properties
2-93 Ph 0 F Me CH2CF3 4-NHCOCF3 0
2-94 Ph 0 F Me CH2CF3 4-NHCOCF3 1
2-95 Ph 0 F Me CH2CF3 5-NHCOCF3 0
2-96 Ph 0 F Me CH2CF3 5-NHCOCF3 1
2-97 Ph 0 F Me CH2CF3 3-NHC02Me 0
2-98 Ph 0 F Me CH2CF3 3-NHC02Me 1
2-99 Ph 0 F Me CH2CF3 4-NHC02Me 0
2-100 Ph 0 F Me CH2CF3 4-NHC02Me 1
2-101 Ph 0 F Me CH2CF3 5-NHC02Me 0
2-102 Ph 0 F Me CH2CF3 5-NHC02Me 1
2-103 Ph 0 F Me CH2CF3 3-NH2 0
2-104 Ph 0 F Me CH2CF3 3-NH2 1
2-105 Ph 0 F Me CH2CF3 4-NH2 0
2-106 Ph 0 F Me CH2CF3 4-NH2 1
2-107 Ph O F Me CH2CF3 5-NH2 0
2-108 Ph 0 F Me CH2CF3 5-NH2 1
2-109 Ph 0 F Me CH2CF3 3-NHMe 0
2-110 Ph 0 F Me CH2CF3 3-NHMe 1
2-111 Ph 0 F Me CH2CF3 4-NHMe 0
2-112 Ph 0 F Me CH2CF3 4-NHMe 1
2-113 Ph O F Me CH2CF3 3-NMe2 0
2-114 Ph 0 F Me CH2CF3 3-NMe2 1
2-1 5 Ph 0 F Me CH2CF3 0
I
2-116 Ph 0 F Me CH2CF3 3- O 1
I
-117 Ph 0 F Me CH2CF3 3-CONH2 0
2-118 Ph 0 F Me CH2CF3 3-CONH2 1
-119 Ph 0 F Me CH2CF3 4-CONH2 0
-120 Ph 0 F Me CH2CF3 4-CONH2 1
-121 Ph 0 F Me CH2CF3 3-CONHMe 0
-122 Ph 0 F Me CH2CF3 3-CONHMe 1
-123 Ph 0 F Me CH2CF3 4-CONHMe 0
-124 Ph 0 F Me CH2CF3 4-CONHMe 1 TABLE 2 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
2-125 Ph 0 F Me CH2CF3 3-CONMe2 0
2-126 Ph 0 F Me CH2CF3 3-CONMe2 1
2-127 Ph 0 F Me CH2CF3 4-CONMe2 0
2-128 Ph 0 F Me CH2CF3 4-CONMe2 1
2-129 Ph 0 F Me CH2CF3 3-SMe 0
2-130 Ph 0 F Me CH2CF3 3-SMe 1
2-131 Ph 0 F Me CH2CF3 4-SMe 0
2-132 Ph 0 F Me CH2CF3 4-SMe 1
2-133 Ph 0 F Me CH2CF3 3-SOMe 0
2-134 Ph 0 F Me CH2CF3 3-SOMe 1
2-135 Ph 0 F Me CH2CF3 4-SOMe 0
2-136 Ph 0 F Me CH2CF3 4-SOMe 1
2-137 Ph 0 F Me CH2CF3 3-S02Me 0
2-138 Ph 0 F Me CH2CF3 3-SO2Me 1
2-139 Ph 0 F Me CH2CF3 4-S02Me 0
2-140 Ph 0 F Me CH2CF3 4-S02Me 1
2-141 Ph 0 F Me CH2CF3 3-SCF3 0
2-142 Ph 0 F Me CH2CF3 3-SCF3 1
2-143 Ph 0 F Me CH2CF3 4-SCF3 0
2-144 Ph 0 F Me CH2CF3 4-SCF3 1
2-145 Ph 0 F Me CH2CF3 3-SOCF3 0
2-146 Ph 0 F Me CH2CF3 3-SOCF3 1
-147 Ph 0 F Me CH2CF3 4-SOCF3 0
2-148 Ph 0 F Me CH2CF3 4-SOCF3 1
-149 Ph 0 F Me CH2CF3 3-SO2CF3 0
-150 Ph 0 F Me CH2CF3 3-SO2CF3 1
-151 Ph 0 F Me CH2CF3 4-SO2CF3 0
-152 Ph 0 F Me CH2CF3 4-SO2CF3 1
-153 2-F-Ph 0 F Me CH2CF3 — 0 Oil -154 2-F-Ph 0 F Me CH2CF3 — 1 Oil -155 3-F-Ph 0 F Me CH2CF3 — 0 Oil -156 3-F-Ph 0 F Me CH2CF3 — 1 Oil
Figure imgf000033_0001
Figure imgf000034_0001
TABLE 2 (continued)
Physical
No. Q W R R2 R3 R5 n
properties
2-221 3-NH2-Ph 0 F Me CH2CF3 — 0
2-222 3-NH2-Ph 0 F Me CH2CF3 — 1
2-223 4-NH2-Ph O F Me CH2CF3 — 0
2-224 4-NH2-Ph 0 F Me CH2CF3 — 1
2-225 3-NMe2-Ph 0 F Me CH2CF3 — 0
2-226 3-NMe2-Ph 0 F Me CH CF3 — 1
2-227 4-NMe2-Ph 0 F Me CH2CF3 — 0
2-228 4-NMe2-Ph 0 F Me CH2CF3 — 1
2-229 3-CONH2-Ph 0 F Me CH2CF3 — 0
2-230 3-CONH2-Ph 0 F Me CH2CF3 — 1
2-231 4-CONH2-Ph 0 F Me CH2CF3 — 0
2-232 4-CONH2-Ph 0 F Me CH2CF3 — 1
2-233 3-SMe-Ph 0 F Me CH2CF3 — 0
2-234 3-SMe-Ph 0 F Me CH2CF3 — 1
2-235 4-SMe-Ph 0 F Me CH2CF3 — 0
2-236 4-SMe-Ph 0 F Me CH2CF3 — 1
2-237 3-SOMe-Ph 0 F Me CH2CF3 — 0
2-238 3-SOMe-Ph 0 F Me CH2CF3 — 1
-239 4-SOMe-Ph 0 F Me CH2CF3 — 0
-240 4-SOMe-Ph 0 F Me CH2CF3 — 1
-241 3-S02Me-Ph 0 F Me CH2CF3 — 0
-242 3-S02Me-Ph 0 F Me CH2CF3 — 1
-243 4-S02Me-Ph 0 F Me CH2CF3 — 0
-244 4-S02Me-Ph 0 F Me CH2CF3 — 1
-245 3-SCF3-Ph 0 F Me CH2CF3 — 0
-246 3-SCF3-Ph 0 F Me CH2CF3 — 1
-247 4-SCF3-Ph 0 F Me CH2CF3 — 0
-248 4-SCF3-Ph 0 F Me CH2CF3 — 1
-249 3-SOCF3-Ph 0 F Me CH2CF3 — 0
-250 3-SOCF3-Ph 0 F Me CH2CF3 — 1
-251 4-SOCF3-Ph 0 F Me CH2CF3 — 0
-252 4-SOCF3-Ph 0 F Me CH2CF3 — 1 TABLE 2 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
2-253 3-S02CF3-Ph 0 F Me CH2CF3 — 0
2-254 3-S02CF3-Ph 0 F Me CH2CF3 — 1
2-255 4-S02CF3-Ph 0 F Me CH2CF3 — 0
2-256 4-S02CF3-Ph 0 F Me CH2CF3 — 1
2-257 2-Py 0 F Me CH2CF3 — 0 Oil
2-258 2-Py 0 F Me CH2CF3 — 1 108-111
2-259 3-Py 0 F Me CH2CF3 — 0 Oil
2-260 3-Py 0 F Me CH2CF3 — 1 Oil
2-261 4-Py 0 F Me CH2CF3 — 0
2-262 4-Py 0 F Me CH2CF3 — 1
2-263 3-CF3-2-Py 0 F Me CH2CF3 — 0 Oil
2-264 3-CF3-2-Py 0 F Me CH2CF3 — 1 59-62
2-265 4-CF3-2-Py 0 F Me CH2CF3 — 0 Oil
2-266 4-CF3-2-Py 0 F Me CH2CF3 — 1 111-113
2-267 5-CF3-2-Py 0 F Me CH2CF3 — 0 Oil
2-268 5-CF3-2-Py 0 F Me CH2CF3 — 1 75-81
2-269 6-CF3-2-Py O F Me CH2CF3 — 0 Oil
2-270 6-CF3-2-Py 0 F Me CH2CF3 — 1 88-92 -271 3-CI-5-CF3-2-Py 0 F Me CH CF3 — 0
2-272 3-CI-5-CF3-2-Py 0 F Me CH2CF3 — 1
-273 4-F-Ph 0 F Me CH2CF3 4-F 0
-274 4-F-Ph 0 F Me CH2CF3 4-F 1
-275 4-CI-Ph 0 F Me CH2CF3 4-F 0
-276 4-CI-Ph 0 F Me CH2CF3 4-F 1
-277 4-Me-Ph 0 F Me CH2CF3 4-F 0
-278 4-Me-Ph 0 F Me CH2CF3 4-F 1
-279 2-CF3-Ph 0 F Me CH2CF3 4-F 0
-280 2-CF3-Ph 0 F Me CH2CF3 4-F 1
-281 3-CF3-Ph 0 F Me CH2CF3 4-F 0
-282 3-CF3-Ph 0 F Me CH2CF3 4-F 1
-283 4-CF3-Ph 0 F Me CH2CF3 4-F 0
-284 4-CF3-Ph O F Me CH CF3 4-F 1 TABLE 2 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
2-285 4-OMe-Ph O F Me CH2CF3 4-F 0
2-286 4-OMe-Ph O F Me CH2CF3 4-F 1
2-287 4-OCF3-Ph O F Me CH2CF3 4-F 0
2-288 4-OCF3-Ph O F Me CH CF3 4-F 1
2-289 4-CN-Ph O F Me CH2CF3 4-F 0
2-290 4-CN-Ph O F Me CH2CF3 4-F 1
2-291 4-N02-Ph O F Me CH2CF3 4-F 0
2-292 4-N02-Ph O F Me CH2CF3 4-F 1
2-293 5-CF3-2-Py O F Me CH2CF3 4-F 0
2-294 5-CF3-2-Py O F Me CH CF3 4-F 1
2-295 3-CI-5-CF3-2-Py O F Me CH2CF3 4-F 0
2-296 3-CI-5-CF3-2-Py O F Me CH CF3 4-F 1
2-297 4-F-Ph O F Me CH2CF3 3-F.4-F 0
2-298 4-F-Ph O F Me CH2CF3 3-F.4-F 1
2-299 4-CI-Ph O F Me CH2CF3 3-F.4-F 0 Oil
2-300 4-CI-Ph O F Me CH2CF3 3-F.4-F 1 96-99
2-301 4-Me-Ph O F Me CH2CF3 3-F.4-F 0 Oil
2-302 4-Me-Ph O F Me CH2CF3 3-F.4-F 1 128-131
2-303 2-CF3-Ph O F Me CH2CF3 3-F.4-F 0 Oil
2-304 2-CF3-Ph O F Me CH2CF3 3-F.4-F 1 84-87
2-305 3-CF3-Ph O F Me CH2CF3 3-F,4-F 0 Oil
2-306 3-CF3-Ph O F Me CH2CF3 3-F.4-F 1 Oil
2-307 4-CF3-Ph O F Me CH2CF3 3-F.4-F 0 Oil
2-308 4-CF3-Ph O F Me CH2CF3 3-F.4-F 1 83-85
2-309 4-OMe-Ph O F Me CH2CF3 3-F.4-F 0 Oil
2-310 4-OMe-Ph O F Me CH2CF3 3-F.4-F 1 99-103
2-311 4-OCF3-Ph O F Me CH2CF3 3-F.4-F 0
2-312 4-OCF3-Ph O F Me CH2CF3 3-F.4-F 1
2-313 4-CN-Ph O F Me CH CF3 3-F.4-F 0 89-95
2-314 4-CN-Ph O F Me CH2CF3 3-F.4-F 1 146-150
2-315 4-NO2-Ph O F Me CH CF3 3-F.4-F 0 147-150
2-316 4-NO2-Ph O F Me CH2CF3 3-F.4-F 1 87-89 TABLE 2 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
2-317 4-C02Me-Ph 0 F Me CH2CF3 3-F.4-F 0
2-318 4-C02Me-Ph 0 F Me CH2CF3 3-F.4-F 1
2-319 4-NHCOMe-Ph 0 F Me CH2CF3 3-F,4-F 0
2-320 4-NHCOMe-Ph 0 F Me CH2CF3 3-F.4-F 1
2-321 4-CONMe2-Ph 0 F Me CH2CF3 3-F,4-F 0
2-322 4-CONMe2-Ph 0 F Me CH2CF3 3-F,4-F 1
2-323 4-SMe-Ph 0 F Me CH2CF3 3-F,4-F 0
2-324 4-SMe-Ph 0 F Me CH2CF3 3-F,4-F 1
2-325 4-S02Me-Ph 0 F Me CH2CF3 3-F.4-F 0
2-326 4-S02Me-Ph 0 F Me CH2CF3 3-F.4-F 1
2-327 2-Py O F Me CH2CF3 3-F.4-F 0
2-328 2-Py 0 F Me CH2CF3 3-F.4-F 1
2-329 3-Py 0 F Me CH2CF3 3-F.4-F 0
2-330 3-Py O F Me CH2CF3 3-F,4-F 1
2-331 4-Py O F Me CH2CF3 3-F.4-F 0
2-332 4-Py O F Me CH2CF3 3-F.4-F 1
2-333 3-CF3-2-Py O F Me CH2CF3 3-F.4-F 0
2-334 3-CF3-2-Py O F Me CH2CF3 3-F.4-F 1
2-335 4-CF3-2-Py O F Me CH2CF3 3-F,4-F 0
2-336 4-CF3-2-Py O F Me CH2CF3 3-F,4-F 1
2-337 5-CF3-2-Py 0 F Me CH2CF3 3-F.4-F 0 Oil
2-338 5-CF3-2-Py 0 F Me CH2CF3 3-F.4-F 1 92-95
2-339 6-CF3-2-Py 0 F Me CH2CF3 3-F,4-F 0
2-340 6-CF3-2-Py 0 F Me CH2CF3 3-F.4-F 1
2-341 3-CI-5-CF3-2-Py 0 F Me CH2CF3 3-F,4-F 0 Oil
2-342 3-CI-5-CF3-2-Py 0 F Me CH2CF3 3-F.4-F 1 102-107
2-343 4-F-Ph 0 F Me CH2CF3 3-CI 0
2-344 4-F-Ph 0 F Me CH2CF3 3-CI 1
2-345 4-CI-Ph 0 F Me CH2CF3 3-CI 0
2-346 4-CI-Ph 0 F . Me CH2CF3 3-CI 1
2-347 4-Me-Ph 0 F Me CH2CF3 3-CI 0 77-80
2-348 4-Me-Ph 0 F Me CH2CF3 3-CI 1 126-128 TABLE 2 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
2-349 2-CF3-Ph O F Me CH2CF3 3-CI 0
2-350 2-CF3-Ph O F Me CH2CF3 3-CI 1
2-351 3-CF3-Ph O F Me CH2CF3 3-CI 0
2-352 3-CF3-Ph O F Me CH2CF3 3-CI 1
2-353 4-CF3-Ph O F Me CH2CF3 3-CI 0 Oil
2-354 4-CF3-Ph O F Me CH2CF3 3-CI 1 103-106
2-355 4-OMe-Ph O F Me CH2CF3 3-CI 0
2-356 4-OMe-Ph O F Me CH2CF3 3-CI 1
2-357 4-OCF3-Ph O F Me CH2CF3 3-CI 0
2-358 4-OCF3-Ph O F Me CH2CF3 3-CI 1
2-359 4-CN-Ph O F Me CH2CF3 3-CI 0
2-360 4-CN-Ph O F Me CH2CF3 3-CI 1
2-361 4-NO2-Ph O F Me CH2CF3 3-CI 0
2-362 4-NOa-P O F Me CH2CF3 3-CI 1
2-363 4-CO2Me-Ph O F Me CH2CF3 3-CI 0
2-364 4-CO2Me-Ph O F Me CH2CF3 3-CI 1
2-365 4-NHCOMe-Ph O F Me CH2CF3 3-CI 0
2-366 4-NHCOMe-Ph O F Me CH2CF3 3-CI 1
2-367 4-CONMe2-Ph O F Me CH2CF3 3-CI 0
2-368 4-CONMe2-Ph O F Me CH2CF3 3-CI 1
2-369 4-SMe-Ph O F Me CH2CF3 3-CI 0
2-370 4-SMe-Ph O F Me CH2CF3 3-CI 1
2-371 4-SO2Me-Ph O F Me CH2CF3 3-CI 0
2-372 4-SO2Me-Ph O F Me CH2CF3 3-CI 1
2-373 2-Py O F Me CH2CF3 3-CI 0
2-374 2-Py O F Me CH2CF3 3-CI 1
2-375 3-Py O F Me CH2CF3 3-CI 0
2-376 3-Py O F Me CH2CF3 3-CI 1
2-377 4-Py O F Me CH2CF3 3-CI 0
2-378 4-Py O F Me CH2CF3 3-CI 1
2-379 3-CF3-2-Py O F Me CH2CF3 3-CI 0 69-73
2-380 3-CF3-2-Py O F Me CH2CF3 3-CI 1 Oil TABLE 2 (continued)
Physical
No. Q W R R2 R3 R5 n
properties
2-381 4-CF3-2-Py 0 F Me CH2CF3 3-CI 0 58-63
2-382 4-CF3-2-Py 0 F Me CH2CF3 3-CI 1 85-88
2-383 5-CF3-2-Py 0 F Me CH2CF03 3-CI 0 74-82
2-384 5-CF3-2-Py 0 F Me CH2CF3 3-CI 1 88-90
2-385 6-CF3-2-Py 0 F Me CH2CF3 3-CI 0 85-89
2-386 6-CF3-2-Py 0 F Me CH2CF3 3-CI 1 84-90
2-387 3-CI-5-CF3-2-Py 0 F Me CH2CF3 3-CI 0 Oil
2-388 3-CI-5-CF3-2-Py 0 F Me CH2CF3 3-CI 1
2-389 4-F-Ph 0 F Me CH2CF3 4-CI 0
2-390 4-F-Ph 0 F Me CH2CF3 4-CI 1
2-391 4-CI-Ph 0 F Me CH2CF3 4-CI 0
2-392 4-CI-Ph 0 F Me CH2CF3 4-CI 1
2-393 4-Me-Ph 0 F Me CH2CF3 4-CI 0
2-394 4-Me-Ph 0 F Me CH2CF3 4-CI 1
2-395 2-CF3-Ph 0 F Me CH2CF3 4-CI 0
2-396 2-CF3-Ph 0 F Me CH2CF3 4-CI 1
2-397 3-CF3-Ph 0 F Me CH2CF3 4-CI 0
2-398 3-CF3-Ph 0 F Me CH2CF3 4-CI 1
2-399 4-CF3-Ph 0 F Me CH2CF3 4-CI 0
2-400 4-CF3-Ph 0 F Me CH2CF3 4-CI 1
2-401 4-OMe-Ph 0 F Me CH2CF3 4-CI 0
2-402 4-OMe-Ph 0 F Me CH2CF3 4-CI 1
2-403 4-OCF3-Ph 0 F Me CH2CF3 4-CI 0
2-404 4-OCF3-Ph 0 F Me CH2CF3 4-CI 1
-405 4-CN-Ph 0 F Me CH2CF3 4-CI 0
2-406 4-CN-Ph 0 F Me CH2CF3 4-CI 1
-407 4-N02-Ph 0 F Me CH2CF3 4-CI 0
-408 4-N02-Ph 0 F Me CH2CF3 4-CI 1
-409 5-CF3-2-Py 0 F Me CH2CF3 4-CI 0
-410 5-CF3-2-Py 0 F Me CH2CF3 4-CI 1
-411 3-CI-5-CF3-2-Py 0 F Me CH2CF3 4-CI 0
-412 3-CI-5-CF3-2-Py 0 F Me CH2CF3 4-CI 1 TABLE 2 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
2-413 Ph 0 H Me CH2CF03 — 0 Oil
2-414 Ph 0 H Me CH CF3 — 1 Oil
2-415 Ph 0 H Me CH2CF3 4-F 0 72.0
2-416 Ph 0 H Me CH2CF3 4-F 1 115.9
2-417 Ph 0 H Me CH2CF3 3-F.4-F 0 68-70
2-418 Ph 0 H Me CH2CF3 3-F.4-F 1 Oil
2-419 Ph 0 H Me CH2CF3 3-CI 0 105.6
2-420 Ph 0 H Me CH2CF3 3-CI 1 121.9
2-421 Ph 0 H Me CH2CF3 4-CI 0
2-422 Ph 0 H Me CHsCF3 4-CI 1
2-423 4-CI-Ph 0 H Me CH2CF3 — 0
2-424 4-CI-Ph 0 H Me CH2CF3 — 1
2-425 4-CI-Ph 0 H Me CH2CF3 4-F 0
2-426 4-CI-Ph 0 H Me CH CF3 4-F 1
2-427 4-CI-Ph 0 H Me CH2CF3 3-F.4-F 0
2-428 4-CI-Ph 0 H Me CH2CF3 3-F.4-F 1
2-429 4-CI-Ph 0 H Me CH2CF3 3-CI 0
2-430 4-CI-Ph 0 H Me CH2CF3 3-CI 1
2-431 4-CI-Ph 0 H Me CH2CF3 4-CI 0
2-432 4-CI-Ph 0 H Me CH2CF05 4-CI 1
2-433 4-CF3-Ph 0 H Me CH2CF3 — 0
2-434 4-CF3-Ph 0 H Me CH2CF3 — 1
2-435 4-CF3-Ph 0 H Me CH CF3 4-F 0
2-436 4-CF3-Ph 0 H Me CH2CF3 4-F 1
2-437 4-CF3-Ph 0 H Me CH2CF3 3-F.4-F 0
2-438 4-CF3-Ph 0 H Me CH2CF3 3-F.4-F 1
2-439 4-CF3-Ph 0 H Me CH2CF3 3-CI 0
2-440 4-CF3-Ph 0 H Me CH2CF0J 3-CI 1
2-441 4-CF3-Ph 0 H Me CH2CF3 4-CI 0
2-442 4-CF3-Ph 0 H Me CH2CF3 4-CI 1
2-443 4-OMe-Ph 0 H Me CH2CF3 — 0
2-444 4-OMe-Ph 0 H Me CH2CF3 — 1
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
TABLE 2 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
2-589 3,4-Me2-Ph O F Me CH2CF3 — 0 Oil
2-590 3,4-Me2-Ph O F Me CH2CF3 — 1 80-84
2-591 3,5-Me2-Ph O F Me CH2CF3 — 0 Oil
2-592 3,5-Me2-Ph O F Me CH2CF3 — 1 Oil
2-593 3,4-CI2-Ph O F Me CH2CF3 — 0 Oil
2-594 3,4-CI2-Ph O F Me CH2CF3 — 1 Oil
2-595 3,5-CI2-Ph O F Me CH2CF3 — 0 Oil
2-596 3,5-CI2-Ph O F Me CH2CF3 — 1 Oil
2-597 3,5-CF3-Ph O F Me CH2CF3 — 0 Oil
2-598 3,5-CF3-Ph O F Me CH2CF3 — 1 101-107
2-599 2-NO2-3-Me-Ph O F Me CH2CF3 — 0 Oil
2-600 2-NO2-3-Me-Ph O F Me CH2CF3 — 1 Oil
2-601 2-NO2-4-Me-Ph O H Me CH2CF3 — 0 Oil
2-602 2-NO2-4-Me-Ph O H Me CH2CF3 — 1 101-108
2-603 4-NO2-3-Me-Ph O H Me CH2CF3 — 0 Oil
2-604 4-NO2-3-Me-Ph O H Me CH2CF3 — 1 131-134
2-605 2-NO2-4-CF3-Ph O H Me CH2CF3 — 0 Oil
2-606 2-NO2-4-CF3-Ph O H Me CH2CF3 — 1 124-128
Figure imgf000048_0001
TABLE 3 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
3-29 Ph 0 F Me CH2CF3 2-CI.5-F 0
3-30 Ph 0 F Me CH2CF3 2-CI.5-F 1
3-31 Ph 0 F Me CH2CF3 2-CI.4-F 0 Oil
3-32 Ph 0 F Me CH2CF3 2-CI.4-F 1 123.2
3-33 Ph 0 F Me CH2CF3 I -NO2 0
3-34 Ph 0 F Me CH2CF3 I -NO2 1
3-35 Ph 0 F Me CH2CF3 2-NO2 0 Oil
3-36 Ph 0 F Me CH2CF3 2-NO2 1
3-37 Ph 0 F Me CH2CF3 1 -CN 0
3-38 Ph 0 F Me CH2CF3 1 -CN 1
3-39 Ph 0 F Me CH2CF3 2-CN 0
3-40 Ph 0 F Me CH2CF3 2-CN 1
3-41 Ph 0 F Me CH2CF3 1 -OMe 0
3-42 Ph 0 F Me CH2CF3 1 -OMe 1
3-43 Ph 0 F Me CH2CF3 2-OMe 0
3-44 Ph 0 F Me CH2CF3 2-OMe 1
3-45 Ph 0 F Me CH2CF3 I -CF3 0
3-46 Ph 0 F Me CH2CF3 I -CF3 1
3-47 Ph 0 F Me CH2CF3 2-CF3 0
3-48 Ph 0 F Me CH2CF3 2-CF3 1
3-49 Ph 0 F Me CH2CF3 I -OCF3 0
3-50 Ph 0 F Me CH2CF3 I -OCF3 1
3-51 Ph 0 F Me CH2CF3 2-OCF3 0
3-52 Ph 0 F Me CH2CF3 2-OCF3 1
3-53 Ph 0 F Me CH2CF3 1 -SMe 0
3-54 Ph 0 F Me CH2CF3 1 -SMe 1
3-55 Ph 0 F Me CH2CF3 2-SMe 0
3-56 Ph 0 F Me CH2CF3 2-SMe 1
3-57 Ph 0 H Me CH2CF3 — 0 Oil
3-58 Ph 0 H Me CH2CF3 — 1 Oil
3-59 Ph 0 H Me CH2CF3 1 -F 0 Oil
3-60 Ph 0 H Me CH2CF3 1 -F 1 Oil TABLE 3 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
3-61 Ph 0 H Me CH2CF3 2-F 0
3-62 Ph 0 H Me CH2CF3 2-F 1
3-63 Ph 0 H Me CH2CF3 1-F.2-F 0
3-64 Ph 0 H Me CH2CF3 1-F.2-F 1
3-65 Ph 0 H Me CH2CF3 1-F.4-F 0
3-66 Ph 0 H Me CH2CF3 1 -F.4-F 1
3-67 Ph 0 H Me CH2CF3 1-F.5-F 0
3-68 Ph 0 H Me CH2CF3 1-F.5-F 1
3-69 Ph 0 H Me CH2CF3 2-F.4-F 0
3-70 Ph 0 H Me CH2CF3 2-F.4-F 1
3-71 Ph 0 H Me CH2CF3 1-CI 0
3-72 Ph O H Me CH2CF3 1-CI 1
3-73 Ph 0 H Me CH2CF3 2-CI 0
3-74 Ph 0 H Me CH2CF3 2-CI 1
3-75 Ph 0 H Me CH2CF3 1 -CI,2-CI 0
3-76 Ph 0 H Me CH2CF3 1-CI,2-CI 1
3-77 Ph 0 H Me CH2CF3 1-CI,4-CI 0
3-78 Ph 0 H Me CH2CF3 1-CI.4-CI 1
3-79 Ph 0 H Me CH2CF3 1-CI,5-CI 0
3-80 Ph 0 H Me CH2CF3 1 -CI.5-CI 1
3-81 Ph 0 H Me CH2CF3 2-CI.4-CI 0
3-82 Ph 0 H Me CH2CF3 2-CI,4-CI 1
3-83 Ph 0 H Me CH2CF3 2-CF3 0
3-84 Ph 0 H Me GH2CF3 2-CF3 1
3-85 3-F-Ph 0 F Me CH2CF3 — 0
3-86 3-F-Ph 0 F Me CH2CF3 — 1
-87 3-F-Ph 0 F Me CH2CF3 1-F 0
-88 3-F-Ph 0 F Me CH2CF3 1-F 1
-89 4-F-Ph 0 F Me CH2CF3 — 0
-90 4-F-Ph 0 F Me CH2CF3 — 1
-91 4-F-Ph 0 F Me CH2CF3 1 -F 0
-92 4-F-Ph 0 F Me CH2CF3 1-F 1
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
TABLE 5 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
5-29 Ph 0 F Me CH2CF3 3-CI.4-F 0
5-30 Ph 0 F Me CH2CF3 3-CI.4-F 1
5-31 Ph 0 F Me CH2CF3 3-CI.5-F 0
5-32 Ph 0 F Me CH2CF3 3-CI.5-F 1
5-33 Ph 0 F Me CH2CF3 3-Br 0
5-34 Ph 0 F Me CH2CF3 3-Br 1
5-35 Ph 0 F Me CH2CF3 4-Br 0 Oil
5-36 Ph 0 F Me CH2CF3 4-Br 1 Oil
5-37 Ph 0 F Me CH2CF3 3-I 0
5-38 Ph 0 F Me CH2CF3 3-I 1
5-39 Ph 0 F Me CH2CF3 4-I 0
5-40 Ph 0 F Me CH2CF3 4-I 1
5-41 Ph 0 F Me CH2CF3 1-Me 0
5-42 Ph 0 F Me CH2CF3 1-Me 1
5-43 Ph 0 F Me CH2CF3 3-Me 0
5-44 Ph O F Me CH2CF3 3-Me 1
5-45 Ph 0 F Me CH2CF3 4-Me 0
5-46 Ph 0 F Me CH2CF3 4-Me 1
5-47 Ph 0 F Me CH2CF3 5-Me 0
5-48 Ph 0 F Me CH2CF3 5-Me 1
5-49 Ph 0 F Me CH2CF3 3-CF3 0
5-50 Ph 0 F Me CH2CF3 3-CF3 1
5-51 Ph 0 F Me CH2CF3 4-CF3 0
5-52 Ph 0 F Me CH2CF3 4-CF3 1
5-53 Ph 0 F Me CH2CF3 3-OMe 0 Oil
5-54 Ph 0 F Me CH2CF3 3-OMe 1 Oil
5-55 Ph 0 F Me CH2CF3 4-OMe 0
5-56 Ph 0 F Me CH2CF3 4-OMe 1
5-57 Ph 0 F Me CH2CF3 3-OCF3 0
5-58 Ph 0 F Me CH2CF3 3-OCF3 1
5-59 Ph 0 F Me CH2CF3 4-OCF3 0
5-60 Ph 0 F Me CH2CF3 4-OCF3 1 TABLE 5 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
5-61 Ph 0 F Me CH2CF3 3-CN 0
5-62 Ph 0 F Me CH2CF3 3-CN 1
5-63 Ph 0 F Me CH2CF3 4-CN 0
5-64 Ph 0 F Me CH2CF3 4-CN 1
5-65 Ph 0 F Me CH2CF3 3-NO2 0
5-66 Ph 0 F Me CH2CF3 3-NO2 1
5-67 Ph 0 F Me CH2CF3 4-NO2 0
5-68 Ph 0 F Me CH2CF3 4-NO2 1
5-69 Ph 0 F Me CH2CF3 3-COMe 0
5-70 Ph 0 F Me CH2CF3 3-COMe 1
5-71 Ph 0 F Me CH2CF3 4-COMe 0
5-72 Ph 0 F Me CH2CF3 4-COMe 1
5-73 Ph 0 F Me CH2CF3 3-COCFg 0
5-74 Ph 0 F Me CH2CF3 3-COCF3 1
5-75 Ph 0 F Me CH2CF3 4-COCF3 0
5-76 Ph 0 F Me CH2CF3 4-COCF3 1
5-77 Ph 0 F Me CH2CF3 3-CO2H 0
5-78 Ph 0 F Me CH2CF3 3-CO2H 1
5-79 Ph 0 F Me CH2CF3 4-CO2H 0
5-80 Ph 0 F Me CH2CF3 4-CO2H 1
5-81 Ph 0 F Me CH2CF3 3-C02Me 0
5-82 Ph 0 F Me CH2CF3 3-C02Me 1
5-83 Ph 0 F Me CH2CF3 4-C02Me 0
5-84 Ph 0 F Me CH2CF3 4-C02Me 1
-85 Ph 0 F Me CH2CF3 3-NHCOMe 0
-86 Ph 0 F Me CH2CF3 3-NHCOMe 1
-87 Ph 0 F Me CH2CF3 4-NHCOMe 0
-88 Ph 0 F Me CH2CF3 4-NHCOMe 1
-89 Ph 0 F Me CH2CF3 5-NHCOMe 0
-90 Ph 0 F Me CH2CF3 5-NHCOMe 1
-91 Ph 0 F Me CH2CF3 3-NHCOCF3 0
-92 Ph 0 F Me CH2CF3 3-NHCOCF3 1 TABLE 5 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
5-93 Ph 0 F Me CH2CF3 4-NHCOCF3 0
5-94 Ph 0 F Me CH2CF3 4-NHCOCF3 1
5-95 Ph 0 F Me CH2CF3 5-NHCOCF3 0
5-96 Ph 0 F Me CH2CF3 5-NHCOCF3 1
5-97 Ph O F Me CH2CF3 3-NHC02Me 0
5-98 Ph 0 F Me CH2CF3 3-NHC02Me 1
5-99 Ph 0 F Me CH2CF3 4-NHC02Me 0
5-100 Ph 0 F Me CH2CF3 4-NHC02Me 1
5-101 Ph 0 F Me CH2CF3 5-NHC02Me 0
5-102 Ph 0 F Me CH2CF3 5-NHC02Me 1
5-103 Ph 0 F Me CH2CF3 3-NH2 0
5-104 Ph 0 F Me CH2CF3 3-NH2 1
5-105 Ph 0 F Me CH2CF3 4-NH2 0
5-106 Ph O F Me CH2CF3 4-NH2 1
5-107 Ph 0 F Me CH2CF3 5-NH2 0
5-108 Ph 0 F Me CH2CF3 5-NH2 1
5-109 Ph 0 F Me CH2CF3 3-NHMe 0
5-110 Ph 0 F Me CH2CF3 3-NHMe 1
5-111 Ph 0 F Me CH2CF3 4-NHMe 0
5-112 Ph 0 F Me CH2CF3 4-NHMe 1
5-113 Ph 0 F Me CH2CF3 3-NMe2 0 Oil
5-114 Ph 0 F Me CH2CF3 3-NMe2 1 Oil
5-115 Ph 0 F Me CH2CF3 4-NMe2 0
5-116 Ph 0 F Me CH2CF3 4-NMe2 1
5-117 Ph 0 F Me CH2CF3 3-CONH2 0
5-118 Ph 0 F Me CH2CF3 3-CONH2 1
5-119 Ph 0 F Me CH2CF3 4-CONH2 0
5-120 Ph 0 F Me CH2CF3 4-CONH2 1
5-121 Ph O F Me CH2CF3 3-CONHMe 0
5-122 Ph 0 F Me CH2CF3 3-CONHMe 1
5-123 Ph 0 F Me CH2CF3 4-CONHMe 0
5-124 Ph 0 F Me CH2CF3 4-CONHMe 1 TABLE 5 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
5-125 Ph 0 F Me CH2CF3 3-CONMe2 0
5-126 Ph 0 F Me CH2CF3 3-CONMe2 1
5-127 Ph 0 F Me CH2CF3 4-CONMe2 0
5-128 Ph 0 F Me CH2CF3 4-CONMe2 1
5-129 Ph 0 F . Me CH2CF3 3-SMe 0 Oil
5-130 Ph 0 F Me CH2CF3 3-SMe 1
5-131 Ph 0 F Me CH2CF3 4-SMe 0
5-132 Ph 0 F Me CH2CF3 4-SMe 1
5-133 Ph 0 F Me CH2CF3 3-SOMe 0 Oil
5-134 Ph 0 F Me CH2CF3 3-SOMe 1 Oil
5-135 Ph 0 F Me CH2CF3 4-SOMe 0
5-136 Ph 0 F Me CH2CF3 4-SOMe 1
5-137 Ph 0 F Me CH2CF3 3-S02Me 0 Oil
5-138 Ph 0 F Me CH2CF3 3-S02Me 1 157-158
5-139 Ph 0 F Me CH2CF3 4-S02Me 0
5-140 Ph 0 F Me CH2CF3 4-S02Me 1
5-141 Ph 0 F Me CH2CF3 3-SCF3 0
5-142 Ph 0 F Me CH2CF3 3-SCF3 1
5-143 Ph 0 F Me CH2CF3 4-SCF3 0
5-144 Ph 0 F Me CH2CF3 4-SCF3 1
5-145 Ph 0 F Me CH2CF3 3-SOCF3 0
5-146 Ph 0 F Me CH2CF3 3-SOCF3 1
5-147 Ph 0 F Me CH2CF3 4-SOCF3 0
5-148 Ph 0 F Me CH2CF3 4-SOCF3 1
5-149 Ph 0 F Me CH2CF3 3-SO2CF3 0
5-150 Ph 0 F Me CH2CF3 3-S02CF3 1
-151 Ph 0 F Me CH2CF3 4-S02CF3 0
-152 Ph 0 F Me CH2CF3 4-SO2CF3 1
-153 2-F-Ph 0 F Me CH2CF3 -— 0
-154 2-F-Ph 0 F Me CH2CF3 — 1
-155 3-F-Ph 0 F Me CH2CF3 — 0
-156 3-F-Ph 0 F Me CH2CF3 — 1 TABLE 5 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
5-157 4-F-Ph 0 F Me CH2CF3 — 0 Oil
5-158 4-F-Ph 0 F Me CH2CF3 — 1 72-73
5-159 2-CI-Ph 0 F Me CH2CF3 — 0 Oil
5-160 2-CI-Ph 0 F Me CH2CF3 — 1 Oil
5-161 3-CI-Ph 0 F Me CH2CF3 — 0 Oil
5-162 3-CI-Ph 0 F Me CH2CF3 — 1 Oil
5-163 4-CI-Ph 0 F Me CH CF3 — 0 Oil
5-164 4-CI-Ph 0 F Me CH2CF3 — 1 Oil
5-165 2-Me-Ph 0 F Me CH2CF3 — 0 Oil
5-166 2-Me-Ph 0 F Me CH2CF3 — 1 Oil
5-167 3-Me-Ph 0 F Me CH2CF3 — 0 Oil
5-168 3-Me-Ph 0 F Me CH2CF3 — 1 Oil
5-169 4-Me-Ph 0 F Me CH2CF3 — 0 Oil
5-170 4-Me-Ph 0 F Me CH2CF3 — 1 79-80
5-171 3-t-Bu-Ph 0 F Me CH2CF3 — 0 Oil
5-172 3-t-Bu-Ph 0 F Me CH2CF3 — 1 Oil -173 4-t-Bu-Ph 0 F Me CH2CF3 — 0 Oil
5-174 4-t-Bu-Ph 0 F Me CH2CF3 — 1 Oil -175 2-CF3-Ph 0 F Me CH2CF3 — 0 Oil -176 2-CF3-Ph 0 F Me CH2CF3 — 1 Oil -177 3-CF3-Ph 0 F Me CH2CF3 — 0 Oil -178 3-CF3-Ph O F Me CH2CF3 — 1 Oil -179 4-CF3-Ph 0 F Me CH2CF3 — 0 Oil -180 4-CF3-Ph O F Me CH2CF3 — 1 Oil -181 2-OMe-Ph 0 F Me CH2CF3 — 0 Oil -182 2-OMe-Ph 0 F Me CH2CF3 — 1 Oil -183 3-OMe-Ph 0 F Me CH2CF3 — 0 Oil -184 3-OMe-Ph 0 F Me CH2CF3 — 1 Oil - 85 4-OMe-Ph 0 F Me CH2CF3 — 0
-186 4-OMe-Ph 0 F Me CH2CF3 — 1
-187 2-OCF3-Ph 0 F Me CH2CF3 — 0
-188 2-OCF3-Ph 0 F Me CH2CF3 — 1 TABLE 5 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
5-189 3-OCF3-Ph 0 F Me CH2CF3 — 0
5-190 3-OCF3-Ph 0 F Me CH2CF3 — 1
5-191 4-OCF3-Ph 0 F Me CH CF3 — 0
5-192 4-OCF3-Ph 0 F Me CH2CF3 — 1
5-193 2-CN-Ph 0 F Me CH2CF3 — 0
5-194 2-CN-Ph 0 F Me CH2CF3 — 1
5-195 3-CN-Ph 0 F Me CH2CF3 — 0
5-196 3-CN-Ph 0 F Me CH2CF3 — 1
5-197 4-CN-Ph 0 F Me CH2CF3 — 0
5-198 4-CN-Ph 0 F Me CH2CF3 — 1
5-199 2-N02-Ph 0 F Me CH2CF3 — 0 Oil
5-200 2-N02-P 0 F Me CH2CF3 — 1 Oil
5-201 3-N02-Ph 0 F Me CH2CF3 — 0 Oil
5-202 3-N02-Ph 0 F Me CH CF3 — 1 Oil
5-203 4-N02-Ph 0 F Me CH2CF3 — 0
5-204 4-N02-Ph 0 F Me CH2CF3 — 1
5-205 3-COMe-Ph 0 F Me CH2CF3 — 0
5-206 3-COMe-Ph 0 F Me CH2CF3 — 1
5-207 4-COMe-Ph 0 F Me CH2CF3 — 0
5-208 4-COMe-Ph 0 F Me CH2CF3 — 1
5-209 3-C02Me-Ph 0 F Me CH2CF3 — 0
5-210 3-C02Me-Ph 0 F Me CH2CF3 — 1
5-211 4-C02Me-Ph 0 F Me CH2CF3 — 0
5-212 4-C02Me-Ph 0 F Me CH2CF3 — 1
5-213 3-NHCOMe-Ph 0 F Me CH2CF3 — 0
5-214 3-NHCOMe-Ph 0 F Me CH2CF3 — 1
5-215 4-NHCOMe-Ph 0 F Me CH2CF3 — 0
5-216 4-NHCOMe-Ph 0 F Me CH2CF3 — 1
5-217 3-NHC02Me-Ph 0 F Me CH2CF3 — 0
5-218 3-NHC02Me-Ph 0 F Me CH2CF3 — 1
5-219 4-NHC02Me-Ph 0 F Me CH2CF3 — 0
5-220 4-NHC02Me-Ph 0 F Me CH2CF3 — 1 TABLE 5 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
5-221 3-NH2-Ph 0 F Me CH2CF3 — 0
5-222 3-NH2-Ph 0 F Me CH2CF3 — 1
5-223 4-NH2-Ph 0 F Me CH2CF3 — 0
5-224 4-NH2-Ph 0 F Me CH2CF3 —■ 1
5-225 3-NMe2-Ph 0 F Me CH2CF3 — 0
5-226 3-NMe2-Ph 0 F Me CH2CF3 — 1
5-227 4-NMe2-Ph 0 F Me CH2CF3 — 0
5-228 4-NMe2-Ph 0 F Me CH CF3 — 1
5-229 3-CONH2-Ph 0 F Me CH2CF3 — 0
5-230 3-CONH2-Ph 0 F Me CH2CF3 — 1
5-231 4-CONH2-Ph 0 F Me CH CF3 — 0
5-232 4-CONH2-Ph 0 F Me CH CF3 — 1
5-233 3-SMe-Ph 0 F Me CH2CF3 — 0
5-234 3-SMe-Ph 0 F Me CH CF3 — 1
5-235 4-SMe-Ph 0 F Me CH CF3 — 0
5-236 4-SMe-Ph 0 F Me CH2CF3 — 1
5-237 3-SOMe-Ph 0 F Me CH2CF3 — 0
5-238 3-SOMe-Ph 0 F Me CH2CF3 — 1
5-239 4-SOMe-Ph 0 F Me CH2CF3 — 0
5-240 4-SOMe-Ph 0 F Me CH2CF3 — 1
5-241 3-S02Me-Ph 0 F Me CH2CF3 — 0
5-242 3-S02Me-Ph 0 F Me CH2CF3 — 1
-243 4-S02Me-Ph 0 F Me CH2CF3 — 0
-244 4-S02Me-Ph 0 F Me CH2CF3 — 1
-245 3-SCF3-Ph 0 F Me CH2CF3 — 0
-246 3-SCF3-Ph 0 F Me CH2CF3 — 1
-247 4-SCF3-Ph 0 F Me CH2CF3 — 0
-248 4-SCF3-Ph 0 F Me CH2CF3 — 1
-249 3-SOCF3-Ph 0 F Me CH2CF3 — 0
-250 3-SOCF3-Plfi 0 F Me CH2CF3 — 1
-251 4-SOCF3-Ph 0 F Me CH2CF3 — 0
-252 4-SOCF3-Ph 0 F Me CH2CF3 — 1 TABLE 5 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
5-253 3-S02CF3-Ph 0 F Me CH2CF3 — 0
5-254 3-SO2CF3-Ph 0 F Me CH2CF3 — 1
5-255 4-S02CF3-Ph 0 F Me CH2CF3 — 0
5-256 4-S02CF3-Ph 0 F Me CH CF3 — 1
5-257 2-Py 0 F Me CH CF3 — 0 Oil
5-258 2-Py 0 F Me CH2CF3 — 1 Oil
5-259 3-Py 0 F Me CH2CF3 — 0 Oil
5-260 3-Py 0 F Me CH2CF3 — 1 Oil
5-261 4-Py 0 F Me CH2CF3 — 0 Oil
5-262 4-Py 0 F Me CH2CF3 — 1
5-263 3-CF3-2-Py 0 F Me CH2CF3 — 0
5-264 3-CF3-2-Py 0 F Me CH2CF3 — 1
5-265 4-CF3-2-Py 0 F Me CH2CF3 — 0
5-266 4-CF3-2-Py 0 F Me CH2CF3 — 1
5-267 5-CF3-2-Py 0 F Me CH2CF3 — 0 Oil
5-268 5-CF3-2-Py 0 F Me CH2CF3 — 1 Oil
5-269 6-CF3-2-Py 0 F Me CH2CF3 — 0
5-270 6-CF3-2-Py 0 F Me CH2CF3 — 1
5-271 3-CI-2-Py 0 F Me CH2CF3 — 0
5-272 3-CI-2-Py 0 F Me CH2CF3 — 1
5-273 4-CI-2-Py 0 F Me CH2CF3 — ■ 0
5-274 4-CI-2-Py 0 F Me CH2CF3 — 1
5-275 3,5-CI2-Py 0 F Me CH2CF3 — 0
5-276 3,5-CI2-Py 0 F Me CH CF3 — 1
5-277 3-CI-5-CF3-2-Py 0 F Me CH2CF3 — 0 Oil
5-278 3-CI-5-CF3-2-Py 0 F Me CH2CF3 — 1 101-103
5-279 5-CI-3-CF3-2-Py 0 F Me CH2CF3 — 0
5-280 5-CI-3-CF3-2-Py 0 F Me CH2CF3 — 1
5-281 5-CF3-3-Py 0 F Me CH2CF3 — 0
5-282 5-CF3-3-Py 0 F Me CH2CF3 — 1
5-283 6-CF3-3-Py 0 F Me CH2CF3 — 0 Oil
5-284 6-CF3-3-Py 0 F Me CH CF3 — 1 Oil TABLE 5 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
5-285 5-CI-3-Py 0 F Me CH2CF3 — 0
5-286 5-CI-3-Py 0 F Me CHaCF3 — 1
5-287 6-OMe-3-Py 0 F Me CH2CF3 — 0
5-288 6-OMe-3-Py 0 F Me CH2CF3 — 1
5-289 6-CN-3-Py 0 F Me CH2CF3 — 0
5-290 6-CN-3-Py 0 F Me CH2CF3 — 1
5-291 2-CF3-4-Py 0 F Me CH2CF3 — 0
5-292 2-CF3-4-Py 0 F Me CH2CF3 — 1
5-293 3-CF3-4-Py 0 F Me CH2CF3 — 0
5-294 3-CF3-4-Py 0 F Me CH2CF3 — 1
5-295 3-CI-4-Py 0 F Me CH2CF3 — 0
5-296 3-CI-4-Py 0 F Me CH2CF3 — 1
5-297 4-F-Ph 0 F Me CH2CF3 3-F 0
5-298 4-F-Ph 0 F Me CH2CF3 3-F 1
5-299 4-CI-Ph 0 F Me CH2CF3 3-F 0
5-300 4-CI-Ph 0 F Me CH2CF3 3-F 1
5-301 4-Me-Ph 0 F Me CH2CF3 3-F 0
5-302 4-Me-Ph 0 F Me CH2CF3 3-F 1
5-303 2-CF3-Ph 0 F Me CH2CF3 3-F 0
5-304 2-CF3-Ph 0 F Me CH2CF3 3-F 1
5-305 3-CF3-Ph 0 F Me CH2CF3 3-F 0
5-306 3-CF3-Ph 0 F Me CH2CF3 3-F 1
5-307 4-CF3-Ph 0 F Me CH2CF3 3-F 0
-308 4-CF3-Ph 0 F Me CH2CF3 3-F 1
5-309 4-OMe-Ph 0 F Me CH2CF3 3-F 0
5-310 4-OMe-Ph 0 F Me CH2CF3 3-F 1
-311 4-OCF3-Ph 0 F Me CH2CF3 3-F 0
5-312 4-OCF3-Ph 0 F Me CH2CF3 3-F 1
-313 4-CN-Ph 0 F Me CH2CF3 3-F 0
-314 4-CN-Ph 0 F Me CH2CF3 3-F 1
5-315 4-N02-Ph 0 F Me CH2CF3 3-F 0
-316 4-N02-Ph 0 F Me CH2CF3 3-F 1 TABLE 5 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
5-317 4-C02Me-Ph 0 F Me CH2CF3 3-F 0
5-318 4-C02Me-Ph 0 F Me CH2CF3 3-F 1
5-319 4-NHCOMe-Ph 0 F Me CH2CF3 3-F 0
5-320 4-NHCOMe-Ph 0 F Me CH2CF3 3-F 1
5-321 4-CONMe2-Ph 0 F Me CH2CF3 3-F 0
5-322 4-CONMe2-Ph 0 F Me CH2CF3 3-F 1
5-323 4-SMe-Ph 0 F Me CH2CF3 3-F 0
5-324 4-SMe-Ph 0 F Me CH2CF3 3-F 1
5-325 4-S02Me-Ph 0 F Me CH2CF3 3-F 0
5-326 4-S02Me-Ph 0 F Me CH2CF3 3-F 1
5-327 2-Py 0 F Me CH2CF3 3-F 0
5-328 2-Py 0 F Me CH2CF3 3-F 1
5-329 3-Py 0 F Me CH2CF3 3-F 0 Oil
5-330 3-Py 0 F Me CH2CF3 3-F 1 Oil
5-331 4-Py 0 F Me CH2CF3 3-F 0
5-332 4-Py 0 F Me CH2CF3 3-F 1
5-333 3-CF3-2-Py 0 F Me CH2CF3 3-F 0
5-334 3-CF3-2-Py O F Me CH2CF3 3-F 1
5-335 4-CF3-2-Py 0 F Me CH2CF3 3-F 0
5-336 4-CF3-2-Py 0 F Me CH2CF3 3-F 1
5-337 5-CF3-2-Py 0 F Me CH2CF3 3-F 0 Oil
5-338 5-CF3-2-Py 0 F Me CH2CF3 3-F 1 90-92
5-339 6-CF3-2-Py 0 F Me CH2CF3 3-F 0
5-340 6-CF3-2-Py 0 F Me CH2CF3 3-F 1
5-341 3-CI-5-CF3-2-Py 0 F Me CH2CF3 3-F 0
5-342 3-CI-5-CF3-2-Py 0 F Me CH2CF3 3-F 1
5-343 4-F-Ph 0 F Me CH2CF3 3-CI 0
5-344 4-F-Ph 0 F Me CH2CF3 3-CI 1
-345 4-CI-Ph 0 F Me CH2CF3 3-CI 0
-346 4-CI-Ph O F Me CH2CF3 3-CI 1
-347 4-Me-Ph 0 F Me CH CF3 3-CI 0
-348 4-Me-Ph 0 F Me CH2CF3 3-CI 1 TABLE 5 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
5-349 2-CF3-Ph 0 F Me CH CF3 3-CI 0
5-350 2-CF3-Ph 0 F Me CH2CF3 3-CI 1
5-351 3-CF3-Ph 0 F Me CH2CF3 3-CI 0
5-352 3-CF3-Ph 0 F Me CH2CF3 3-CI 1
5-353 4-CF3-Ph 0 F Me CH2CF3 3-CI 0
5-354 4-CF3-Ph 0 F Me CH2CF3 3-CI 1
5-355 4-OMe-Ph 0 F Me CH2CF3 3-CI 0
5-356 4-OMe-Ph 0 F Me CH2CF3 3-CI 1
5-357 4-OCF3-Ph 0 F Me CH2CF3 3-CI 0
5-358 4-OCF3-Ph 0 F Me CH2CF3 3-CI 1
5-359 4-CN-Ph 0 F Me CH2CF3 3-CI 0
5-360 4-CN-Ph 0 F Me CH2CF3 3-CI 1
5-361 4-N02-Ph 0 F Me CH2CF3 3-CI 0
5-362 4-N02-Ph 0 F Me CH2CF3 3-CI 1
5-363 4-C02Me-Ph 0 F Me CH2CF3 3-CI 0
5-364 4-C02Me-Ph 0 F Me CH2CF3 3-CI 1
5-365 4-NHCOMe-Ph 0 F Me CH2CF3 3-CI 0
5-366 4-NHCOMe-Ph 0 F Me CH2CF3 3-CI 1
5-367 4-CONMe2-Ph 0 F Me CH2CF3 3-CI 0
5-368 4-CONMe2-Ph 0 F Me CH2CF3 3-CI 1
5-369 4-SMe-Ph 0 F Me CH2CF3 3-CI 0
5-370 4-SMe-Ph 0 F Me CH2CF3 3-CI 1
5-371 4-S02Me-Ph 0 F Me CH2CF3 3-CI 0
5-372 4-S02Me-Ph 0 F Me CH2CF3 3-CI 1
5-373 2-Py 0 F Me CH2CF3 3-CI 0
5-374 2-Py 0 F Me CH2CF3 3-CI 1
5-375 3-Py 0 F Me CH2CF3 3-CI 0 Oil
5-376 3-Py 0 F Me CH2CF3 3-CI 1
5-377 4-Py 0 F Me CH2CF3 3-CI 0
5-378 4-Py 0 F Me CH2CF3 3-CI 1
5-379 3-CF3-2-Py 0 F Me CH2CF3 3-CI 0
5-380 3-CF3-2-Py 0 F Me CH CF3 3-CI 1 TABLE 5 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
5-381 4-CF3-2-Py 0 F Me CH2CF3 3-CI 0
5-382 4-CF3-2-Py 0 F Me CH2CF3 3-CI 1
5-383 5-CF3-2-Py 0 F Me CH2CF3 3-CI 0 Oil
5-384 5-CF3-2-Py 0 F Me CH2CF3 3-CI 1
5-385 6-CF3-2-Py 0 F Me CH2CF3 3-CI 0
5-386 6-CF3-2-Py 0 F Me CH2CF3 3-CI 1
5-387 3-CI-5-CF3-2-Py 0 F Me CH2CF3 3-CI 0
5-388 3-CI-5-CF3-2-Py 0 F Me CH2CF3 3-CI 1
5-389 4-F-Ph 0 F Me CH2CF3 4-CI 0
5-390 4-F-Ph 0 F Me CH2CF3 4-CI 1
5-391 4-CI-Ph 0 F Me CH2CF3 4-CI 0
5-392 4-CI-Ph 0 F Me CH2CF3 4-CI 1
5-393 4-Me-Ph 0 F Me CH2CF3 4-CI 0
5-394 4-Me-Ph 0 F Me CH2CF3 4-CI 1
5-395 2-CF3-Ph 0 F Me CH2CF3 4-CI 0
5-396 2-CF3-Ph 0 F Me CH2CF3 4-CI 1
5-397 3-CF3-Ph 0 F Me CH2CF3 4-CI 0
5-398 3-CF3-Ph 0 F Me CH2CF3 4-CI 1
5-399 4-CF3-Ph 0 F Me CH2CF3 4-CI 0
5-400 4-CF3-Ph 0 F Me CH2CF3 4-CI 1
5-401 4-OMe-Ph 0 F Me CH2CF3 4-CI 0
5-402 4-OMe-Ph 0 F Me CH2CF3 4-CI 1
5-403 4-OCF3-Ph 0 F Me CH2CF3 4-CI 0
5-404 4-OCF3-Ph 0 F Me CH2CF3 4-CI 1
5-405 4-CN-Ph 0 F Me CH2CF3 4-CI 0
5-406 4-CN-Ph 0 F Me CH2CF3 4-CI 1
5-407 4-N02-Ph 0 F Me CH2CF3 4-CI 0
5-408 4-NO2-Ph 0 F Me CH2CF3 4-CI 1
5-409 5-CF3-2-Py 0 F Me CH2CF3 4-CI 0
5-410 5-CF3-2-Py 0 F Me CH2CF3 4-CI 1
5-411 3-CI-5-CF3-2-Py 0 F Me CH2CF3 4-CI 0
5-412 3-CI-5-CF3-2-Py 0 F Me CH2CF3 4-CI 1 TABLE 5 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
5-413 Ph O H Me CH2CF3 — 0 Oil
5-414 Ph O H Me CH2CF3 — 1 Oil
5-415 Ph O H Me CH2CF3 3-F 0
5-416 Ph O H Me CH2CF3 3-F 1
5-417 Ph O H Me CH2CF3 4-F 0
5-418 Ph O H Me CH2CF3 4-F 1
5-419 Ph O H Me CH2CF3 3-CI 0
5-420 Ph O H Me CH2CF3 3-CI 1
5-421 Ph O H Me CH2CF3 4-CI 0
5-422 Ph O H Me CH2CF3 4-CI 1
5-423 4-CI-Ph O H Me CH2CF3 — 0
5-424 4-CI-Ph O H Me CH2CF3 — 1
5-425 4-CI-Ph O H Me CH2CF3 3-F 0
5-426 4-CI-Ph O H Me CH2CF3 3-F 1
5-427 4-CI-Ph O H Me CH2CF3 4-F 0
5-428 4-CI-Ph O H Me CH2CF3 4-F 1
5-429 4-CI-Ph O H Me CH2CF3 3-CI 0
5-430 4-CI-Ph O H Me CH2CF3 3-CI 1
5-431 4-CI-Ph O H Me CH2CF3 4-CI 0
5-432 4-CI-Ph O H Me CH2CF3 4-CI 1
5-433 4-CFg-Ph O H Me CH2CF3 — 0
5-434 4-CF3-Ph O H Me CH2CF3 — 1
5-435 4-CF3-Ph O H Me CH2CF3 3-F 0
5-436 4-CF3-Ph O H Me CH2CF3 3-F 1
5-437 4-CF3-Ph O H Me CH2CF3 4-F 0
5-438 4-CF3-Ph O H Me CH2CF3 4-F 1
5-439 4-CF3-Ph O H Me CH2CF3 3-CI 0
5-440 4-CF3-Ph O H Me CH2CF3 3-CI 1
5-441 4-CF3-Ph O H Me CH2CF3 4-CI 0
5-442 4-CF3-Ph O H Me CH2CF3 4-CI 1
5-443 4-OMe-Ph O H Me CH2CF3 — 0
5-444 4-OMe-Ph O H Me CH2CF3 — 1 TABLE 5 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
5-445 4-OMe-Ph O H Me CH2CF3 3-F 0
5-446 4-OMe-Ph O H Me CH2CF3 3-F 1
5-447 4-OMe-Ph O H Me CH2CF3 4-F 0
5-448 4-OMe-Ph O H Me CH2CF3 4-F 1
5-449 4-OMe-Ph O H Me CH2CF3 3-CI 0
5-450 4-OMe-Ph O H Me CH2CF3 3-CI 1
5-451 4-OMe-Ph O H Me CH2CF3 4-CI 0
5-452 4-OMe-Ph O H Me CH CF3 4-CI 1
5-453 4-NO2-Ph O H Me CH2CF3 — 0
5-454 4-NO2-Ph O H Me CH2CF3 — 1
5-455 4-NO2-Ph O H Me CH2CF3 3-F 0
5-456 4-NO2-Ph O H Me CH CF3 3-F 1
5-457 4-NO2-Ph O H Me CH2CF3 4-F 0
5-458 4-NO2-Ph O H Me CH2CF3 4-F 1
5-459 4-NO2-Ph O H Me CH2CF3 3-CI 0
5-460 4-NO2-Ph O H Me CH2CF3 3-CI 1
5-461 4-NO2-Ph O H Me CH2CF3 4-CI 0
5-462 4-NO2-Ph O H Me CH2CF3 4-CI 1
5-463 5-CF3-2-Py O H Me CH2CF3 — 0
5-464 5-CF3-2-Py O H Me CH CF3 — 1
5-465 5-CF3-2-Py O H Me CH2CF3 3-F 0
5-466 5-CF3-2-Py O H Me CH2CF3 3-F 1
5-467 5-CF3-2-Py O H Me CH2CF3 4-F 0
5-468 5-CF3-2-Py O H Me CH2CF3 4-F 1
5-469 5-CF3-2-Py O H Me CH2CF3 3-CI 0
5-470 5-CF3-2-Py O H Me CH2CF3 3-CI 1
5-471 5-CF3-2-Py O H Me CH2CF3 4-CI 0
5-472 5-CF3-2-Py O H Me CH2CF3 4-CI 1
5-473 Ph O CI Me CH CF3 — 0 Oil
5-474 Ph O CI Me CH2CF3 — 1 113-114
5-475 Ph O CI Me CH2CF3 3-F 0
5-476 Ph O CI Me CH2CF3 3-F 1 6g
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
TABLE 5 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
5-573 3-CI-Ph S F Me CH2CF3 — 0 Oil
5-574 3-CI-Ph S F Me CH CF3 — 1
5-575 4-CI-Ph S F Me CH2CF3 — 0 Oil
5-576 4-CI-Ph S F Me CH CF3 — 1
5-577 3-t-Bu-Ph S F Me CH2CF3 — 0 Oil
5-578 3-t-Bu-Ph S F Me CH2CF3 — 1
5-579 4-t-Bu-Ph S F Me CH2CF3 — 0 Oil
5-580 4-t-Bu-Ph S F Me CH CF3 — 1
5-581 3-NO2-Ph S F Me CH2CF3 — 0
5-582 3-NO2-P S F Me CH2CF3 — 1
5-583 4-NO2-Ph S F Me CH2CF3 — 0 Oil
5-584 4-NO2-Ph S F Me CH2CF3 — 1
5-585 3-CF3-Ph S F Me CH2CF3 — 0 Oil
5-586 3-CF3-Ph S F Me CH2CF3 — 1
5-587 4-CF3-Ph S F Me CH2CF3 — 0 Oil
5-588 4-CF3-Ph S F Me CH2CF3 — 1
Figure imgf000074_0001
TABLE 5 (continued)
Physical
No. Q W FT R2 R3 R5 n
properties
5-621 3,4-Me2-Ph O F Me CH2CF3 4-F 0 Oil
5-622 3,4-Me2-Ph O F Me CH2CF3 4-F 1 Oil
5-623 4-CI-3-Me-Ph O F Me CH2CF3 4-F 0 Oil
5-624 4-CI-3-Me-Ph O F Me CH2CF3 4-F 1 Oil
5-625 3,4-CI2-Ph O F Me CH2CF3 4-F 0 Oil
5-626 3,4-CI2-Ph O F Me CH2CF3 4-F 1 Oil
5-627 5-CF3-2-Py O F Me CH2CF3 4-F 0 Oil
5-628 5-CF3-2-Py O F Me CH2CF3 4-F 1 104-106
5-629 6-Me-3-Py O F Me CH2CF3 4-F 0 Oil
5-630 6-Me-3-Py O F Me CH2CF3 4-F 1 Oil
5-631 6-Me-3-Py O F Me CH2CF3 5-F 0 Oil
5-632 6-Me-3-Py O F Me CH2CF3 5-F 1 Oil
Q-W
TABLE 6 S(0)nR-
Physical
No. Q W R1 R2 R3 R5 n
properties
6-1 Ph O F Me CH2CF3 — 0 Oil
6-2 Ph O F Me CH2CF3 — 1 Oil
6-3 Ph O F Me CH2CF3 1 -F 0
6-4 Ph O F Me CH2CF3 1 -F 1
6-5 Ph O F Me CH2CF3 2-F 0 Oil
6-6 Ph O F Me CH2CF3 2-F 1 Oil
6-7 Ph O F Me CH2CF3 1-F.2-F 0
6-8 Ph O F Me CH2CF3 1-F.2-F 1
6-9 Ph O F Me CH2CF3 1-F.4-F 0
6-10 Ph O F Me CH2CF3 1-F.4-F 1
6-11 Ph O F Me CH2CF3 1-F,5-F 0
6-12 Ph O F Me CH2CF3 1-F.5-F 1
6-13 Ph O F Me CH2CF3 2-F.4-F 0
6-14 Ph O F Me CH2CF3 2-F.4-F 1
6-15 Ph O F Me CH2CF3 -CI 0
6-16 Ph O F Me CH2CF3 1-CI 1
6-17 Ph O F Me CH2CF3 2-CI 0
6-18 Ph O F Me CH2CF3 2-CI 1
6-19 Ph O F Me CH2CF3 1-CI.2-CI 0
6-20 Ph O F Me CH2CF3 1-CI.2-CI 1
6-21 Ph O F Me CH2CF3 1 -CI,4-CI 0
-22 Ph O F Me CH2CF3 1-CI.4-CI 1
6-23 Ph O F Me CH2CF3 1-CI.5-CI 0
6-24 Ph O F Me CH2CF3 1-CI.5-CI 1
-25 Ph O F Me CH2CF3 2-CI,4-CI 0
-26 Ph O F Me CH2CF3 2-CI.4-CI 1
-27 Ph O F Me CH2CF3 2-CI.1-F 0
-28 Ph O F Me CH2CF3 2-CM-F 1 TABLE 6 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
6-29 Ph 0 F Me CH2CF3 2-CI,5-F 0
6-30 Ph 0 F Me CH2CF3 2-CI,5-F 1
6-31 Ph 0 F Me CH2CF3 2-CI.4-F 0
6-32 Ph 0 F Me CH2CF3 2-CI.4-F 1
6-33 Ph 0 F Me CH2CF3 I-NO2 0
6-34 Ph 0 F Me CH2CF3 I-NO2 1
6-35 Ph 0 F Me CH2CF3 2-NO2 0 Oil
6-36 Ph 0 F Me CH2CF3 2-NO2 1 Oil
6-37 Ph 0 F Me CH2CF3 1-CN 0
6-38 Ph 0 F Me CH2CF3 1 -CN 1
6-39 Ph 0 F Me CH2CF3 2-CN 0
6-40 Ph O F Me CH2CF3 2-CN 1
6-41 Ph 0 F Me CH2CF3 1 -OMe 0
6-42 Ph 0 F Me CH2CF3 1-OMe 1
6-43 Ph 0 F Me CH2CF3 2-OMe 0
6-44 Ph 0 F Me CH2CF3 2-OMe 1
6-45 Ph 0 F Me CH2CF3 I-CF3 0
6-46 Ph 0 F Me CH2CF3 I -CF3 1
6-47 Ph 0 F Me CH2CF3 2-CF3 0
6-48 Ph 0 F Me CH2CF3 2-CF3 1
6-49 Ph 0 F Me CH2CF3 I -OCF3 0
6-50 Ph 0 F Me CH2CF3 I-OCF3 1
6-51 Ph 0 F Me CH2CF3 2-OCF3 0
6-52 Ph 0 F Me CH2CF3 2-OCF3 1
-53 Ph 0 F Me CH2CF3 -SMe 0
6-54 Ph 0 F Me CH2CF3 1 -SMe 1
-55 Ph 0 F Me CH2CF3 2-SMe 0
-56 Ph 0 F Me CH2CF3 2-SMe 1
Figure imgf000078_0001
Figure imgf000079_0001
TABLE 7 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
7-29 5-CF3-2-Py 0 F Me CH2CF3 3-CI 0
7-30 5-CF3-2-Py 0 F Me CH2CF3 3-CI 1
7-31 5-CF3-2-Py 0 F Me CH2CF3 4-CI 0
7-32 5-CF3-2-Py O F Me CH2CF3 4-CI 1
7-33 5-CF3-3-CI-2-Py 0 F Me CH2CF3 — 0 Oil
7-34 5-CF3-3-CI-2-Py 0 F Me CH2CF3 — 1
7-35 5-CF3-3-CI-2-Py 0 F Me CH2CF3 2-F 0
7-36 5-CF3-3-CI-2-Py 0 F Me CH2CF3 2-F 1
7-37 5-CF3-3-CI-2-Py 0 F Me CH2CF3 3-F 0
7-38 5-CF3-3-CI-2-Py 0 F Me CH2CF3 3-F 1
7-39 5-CF3-3-CI-2-Py 0 F Me CH2CF3 4-F 0
7-40 5-CF3-3-CI-2-Py 0 F Me CH2CF3 4-F 1
7-41 5-CF3-3-CI-2-Py 0 F Me CH2CF3 5-F 0
7-42 5-CF3-3-CI-2-Py 0 F Me CH2CF3 5-F 1
7-43 5-CF3-3-CI-2-Py 0 F Me CH2CF3 2-CI 0
7-44 5-CF3-3-CI-2-Py 0 F Me CH2CF3 2-CI 1
7-45 5-CF3-3-CI-2-Py 0 F Me CH2CF3 3-CI 0
7-46 5-CF3-3-CI-2-Py 0 F Me CH2CF3 3-CI 1
7-47 5-CF3-3-CI-2-Py 0 F Me CH2CF3 4-CI 0
7-48 5-CF3-3-CI-2-Py 0 F Me CH2CF3 4-CI 1
7-49 5-CF3-2-Py S F Me CH2CF3 — 0
7-50 5-CF3-2-Py s F Me CH2CF3 — 1
7-51 5-CF3-2-Py so2 F Me CH2CF3 — 0
7-52 5-CF3-2-Py so2 F Me CH2CF3 — 1
-53 5-CF3-3-CI-2-Py s F Me CH2CF3 — 0
7-54 5-CF3-3-CI-2-Py s F Me CH2CF3 — 1
-55 5-CF3-3-CI-2-Py so2 F Me CH2CF3 — 0
-56 5-CF3-3-CI-2-Py so2 F Me CH2CF3 — 1
Figure imgf000081_0001
TABLE 8 (continued)
Physical
No. Q W R1 R2 R3 R5 n
properties
8-29 5-CF3-2-Py O F Me CH2CF3 3-CI 0 Oil
8-30 5-CF3-2-Py O F Me CH2CF3 3-CI 1 Oil
8-31 5-CF3-2-Py O F Me CH2CF3 4-CI 0
8-32 5-CF3-2-Py O F Me CH2CF3 4-CI 1
8-33 5-CF3-3-CI-2-Py O F Me CH2CF3 — 0 Oil
8-34 5-CF3-3-CI-2-Py O F Me CH2CF3 — 1 Oil
8-35 5-CF3-3-CI-2-Py O F Me CH2CF3 1-F 0
8-36 5-CF3-3-CI-2-Py O F Me CH2CF3 1 -F 1
8-37 5-CF3-3-CI-2-Py O F Me CH CF3 3-F 0 Oil
8-38 5-CF3-3-CI-2-Py O F Me CH2CF3 3-F 1 Oil
8-39 5-CF3-3-CI-2-Py O F Me CH2CF3 4-F 0 Oil
8-40 5-CF3-3-CI-2-Py O F Me CH2CF3 4-F 1 112=113
8-41 5-CF3-3-CI-2-Py O F Me CH2CF3 5-F 0
8-42 5-CF3-3-CI-2-Py O F Me CH2CF3 5-F 1
8-43 5-CF3-3-CI-2-Py O F Me CH2CF3 1 -CI 0
8-44 5-CF3-3-CI-2-Py O F Me CH2CF3 1-CI 1
8-45 5-CF3-3-CI-2-Py O F Me CH2CF3 3-CI 0 Oil
8-46 5-CF3-3-CI-2-Py O F Me CH2CF3 3-CI 1 Oil
8-47 5-CF3-3-CI-2-Py O F Me CH CF3 4-CI 0
8-48 5-CF3-3-CI-2-Py O F Me CH2CF3 4-CI 1
8-49 5-CF3-2-Py S F Me CH2CF3 — 0
8-50 5-CF3-2-Py S F Me CH2CF3 — 1
8-51 5-CF3-2-Py SO2 F Me CH2CF3 — 0
8-52 5-CF3-2-Py SO2 F Me CH2CF3 — 1
8-53 5-CF3-3-CI-2-Py s F Me CH2CF3 — 0
8-54 5-CF3-3-CI-2-Py s F Me CH2CF3 — 1
8-55 5-CF3-3-CI-2-Py SO2 F Me CH2CF3 — 0
8-56 5-CF3-3-CI-2-Py SO2 F Me CH2CF3 — 1
TABLE 8 (continued)
Physical
No. Q W Ft1 R2 R3 R5 n
properties
8-57 5-CF3-2-Py O F Me CH2CF3 3-F.4-F 0 Oil
8-58 5-CF3-2-Py O F Me ChfeCFs 3-F.4-F 1 104-106
8-59 5-CF3-3-CI-2-Py O F Me CH2CF3 3-F.4-F 0 Oil
8-60 5-CF3-3-CI-2-Py O F Me ChfeCF;} 3-F.4-F 1 Oil
8-61 3-CF3-2-Py O F Me CH2CF3 3-CI 0 Oil
8-62 3-CF3-2-Py O F Me CH2CF3 3-CI 1 Oil
8-63 3-CF3-2-Py O F Me CH2CF3 3-F.4-F 0 Oil
8-64 3-CF3-2-Py O F Me CH2CF3 3-F.4-F 1 Oil
8-65 5-CF3-2-Py O CI Me CH2CF3 3-CI 0 Oil
8-66 5-CF3-2-Py O CI Me CH2CF3 3-CI 1 Oil
8-67 5-CF3-2-Py O CI Me CH CF3 3-F.4-F 0 Oil
8-68 5-CF3-2-Py O CI Me CH2CF3 3-F.4-F 1 104-106
8-69 5-CF3-3-CI-2-Py O CI Me CH2CF3 3-CI 0 Oil
8-70 5-CF3-3-CI-2-Py O CI Me CH CF3 3-CI 1 125-127
8-71 5-CF3-3-CI-2-Py O CI Me CH2CF3 3-F.4-F 0 Oil
8-72 5-CF3-3-CI-2-Py O CI Me CH2CF3 3-F.4-F 1 168-170
8-73 5-CF3-2-Py O F Me CH2CF3 3-CI.5-F 0
8-74 5-CF3-2-Py O F Me CH2CF3 3-CI.5-F 1
8-75 5-CF3-2-Py O CI Me CH2CF3 3-CI.5-F 0
-76 5-CF3-2-Py O CI Me CH2CF3 3-CI.5-F 1
-77 5-CF3-2-Py O Me Me CH2CF3 3-CI.5-F 0
-78 5-CF3-2-Py O Me Me CH2CF3 3-CI.5-F 1
-79 5-CF3-3-CI-2-Py O F Me CH2CF3 3-CI.5-F 0
-80 5-CF3-3-CI-2-Py O F Me CH2CF3 3-CI.5-F 1
-81 5-CF3-3-CI-2-Py O CI Me CH2CF3 3-CI.5-F 0
-82 5-CF3-3-CI-2-Py O CI Me CH2CF3 3-CI.5-F 1
-83 5-CF3-3-CI-2-Py O Me Me CH2CF3 3-CI.5-F 0
-84 5-CF3-3-CI-2-Py O Me Me CH2CF3 3-CI.5-F 1
Figure imgf000084_0001
TABLE 9 (continued)
Physical
No. Q W R R2 R3 R5 n
properties
9-29 5-CF3-2-Py 0 F Me CH2CF3 2-CI 0
9-30 5-CF3-2-Py 0 F Me CH2CF3 2-CI 1
9-31 5-CF3-2-Py 0 F Me CH2CF3 2-CI.4-CI 0
9-32 5-CF3-2-Py 0 F Me CH2CF3 2-CI.4-CI 1
9-33 5-CF3-3-CI-2-Py 0 F Me CH2CF3 — 0 Oil
9-34 5-CF3-3-CI-2-Py 0 F Me CH2CF3 — 1
9-35 5-CF3-3-CI-2-Py 0 F Me CH2CF3 1-F 0
9-36 5-CF3-3-CI-2-Py 0 F Me CH2CF3 1-F 1
9-37 5-CF3-3-CI-2-Py 0 F Me CH2CF3 2-F 0
9-38 5-CF3-3-CI-2-Py 0 F Me CH2CF3 2-F 1
9-39 5-CF3-3-CI-2-Py 0 F Me CH2CF3 1-F.4-F 0
9-40 5-CF3-3-CI-2-Py 0 F Me CH2CF3 1-F.4-F 1
9-41 5-CF3-3-CI-2-Py 0 F Me CH2CF3 2-F.4-F 0
9-42 5-CF3-3-CI-2-Py 0 F Me CH2CF3 2-F,4-F 1
9-43 5-CF3-3-CI-2-Py 0 F Me CH2CF3 1-CI 0
9-44 5-CF3-3-CI-2-Py 0 F Me CH2CF3 1-CI 1
9-45 5-CF3-3-CI-2-Py 0 F Me CH2CF3 2-CI 0
9-46 5-CF3-3-CI-2-Py 0 F Me CH2CF3 2-CI 1
9-47 5-CF3-3-CI-2-Py 0 F Me CH2CF3 2-CI.4-CI 0
9-48 5-CF3-3-CI-2-Py 0 F Me CH2CF3 2-CI.4-CI 1
9-49 5-CF3-2-Py S F Me CH2CF3 — 0
9-50 5-CF3-2-Py s F Me CH2CF3 — 1
9-51 5-CF3-2-Py so2 F Me CH2CF3 — 0
9-52 5-CF3-2-Py so2 F Me CH2CF3 — 1
-53 5-CF3-3-CI-2-Py s F Me CH2CF3 — 0
-54 5-CF3-3-CI-2-Py s F Me CH2CF3 — 1
-55 5-CF3-3-CI-2-Py SO2 F Me CH2CF3 — 0
-56 5-CF3-3-CI-2-Py so2 F Me CH2CF3 — 1
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
Figure imgf000091_0001
TABLE 16 S(0)nR3
Figure imgf000092_0001
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
Figure imgf000096_0001
TABLE 21 S(0)nR3
Figure imgf000097_0001
TABLE 21 (continued)
Physical
No. Q W B1 B2 R3 R5 n
properties
21-29 Ph O H Me CH2CF3 1-F 0 Oil
21-30 Ph O H Me CH2CF3 1 -F 1 Oil
21 -31 Ph O H Me CH2CF3 3-F 0 Oil
21 -32 Ph O H Me CH2CF3 3-F 1 Oil
21 -33 Ph O H Me CH2CF3 4-F 0 Oil
21-34 Ph O H Me CH2CF3 4-F 1 Oil
21-35 3-Me,4-Me O H Me CH2CF3 4-F 0 Oil
21-36 3-Me,4-Me O H Me CH2CF3 4-F 1 Oil
21-37 4-CI,3-Me O H Me CH2CF3 4-F 0 Oil
21-38 4-CI,3-Me O H Me CH2CF3 4-F 1 Oil
21 -39 3-CI,4-CI O H Me CH2CF3 4-F 0 Oil
21 -40 3-CI,4-CI O H Me CH2CF3 4-F 1 Oil
21-41 6-Me-3-Py O H Me CH2CF3 — 0 Oil
21-42 6-Me-3-Py O H Me CH2CF3 — 1 Oil
21-43 6-Me-3-Py O H Me CH2CF3 4-F 0 Oil
21-44 6-Me-3-Py O H Me CH2CF3 4-F 1 104-106
21-45 6-Me-3-Py O H Me CH2CF3 3-CI 0 Oil
21-46 6-Me-3-Py O H Me CH2CF3 3-CI 1 Oil
21 -47 5-CF3-2-Py O H Me CH2CF3 — 0 Oil
21 -48 5-CF3-2-Py O H Me CH2CF3 — 1 Oil
21-49 5-CF3-2-Py O Me Me CH2CF3 — 0 Oil
21-50 5-CF3-2-Py O Me Me CH2CF3 — 1 Oil
Figure imgf000099_0001
Figure imgf000100_0001
Figure imgf000101_0001
TABLE 24 (continued)
No. 1H-NMR δρρηη (Solvent: CDCI3 /500MHz )
2-153 7.60(1 H,d), 7.52(1 H,t), 7.37-7.29(2H,m), 7.17-6.98(6H,m), 5.16(2H,s), 3.32(2H,q), 2.49(3H,s)
2-154 8.04(1 H,d), 7.38-7.29(2H,m), 7.18-6.93(7H,m), 5.17(2H,s), 3.46(2H,m),
2.42(3H,s)
2-155 7.59(1 H,d), 7.36-7.32(2H,m), 7.21-6.95(7H,m), 5.09(2H,s)( 3.32(2H,q), 2.50(3H,s)
2-156 8.04(1 H,d), 7.38-7.32(2H,m), 7.21-6.97(7H,m), 5.09(2H,s), 3.45(2H,m),
2.42(3H,s)
2-157 7.60-7.34(3H,m), 7.13-6.95(7H,m), 5.05(2H,s), 3.31 (2H,q), 2.50(3H,s)
2-158 8.04(1 H,d), 7.42-7.36(2H,m), 7.17-6.99(7H,m), 5.05(2H,s), 3.45(2H,m),
2.42(3H,s)
2-159 7.61 (1 H,d), 7.58(1 H,dd), 7.42-7.34(2H,m), 7.32-7.25(2H,m), 7.16-7.1 1 ( 2H,m), 7.05(1 H,d), 7.00(1 H,dd), 5.21 (2H,s), 3.33(2H,q), 2.51 (3H,s)
2-160 8.06(1 H,d), 7.58(1 H,dd), 7.42-7.36(2H,m), 7.32-7.24(2H,m), 7.22-7.14( 2H,m), 7.07(1 H,d), 7.02(1 H,dd), 5.21 (2H,s), 3.58-3.38(2H,m), 2.43(3H, s)
2-161 7.61 (1 H,d), 7.46(1 H,s), 7.36(1 H,t), 7.33-7.28(3H,m), 7.14-7.10(2H,m), 7.04(1 H,d), 6.97(1 H,dd), 5.08(2H,s), 3.33(2H,q), 2.51 (3H,s)
2-162 8.06(1 H,d), 7.46(1 H,s), 7.38(1 H,t), 7.34-7.28(3H,m), 7.20-7.15(2H,m), 7.07(1 H,d), 6.99(1 H,dd), 5.08(2H,s), 3.58-3.38(2H,m), 2.43(3H,s)
2-165 7.60(1 H,d), 7.42-7.34(2H,m), 7.25-7.21 (3H,m), 7.13-7.10(2H,m), 7.03(1 H,d), 7.00(1 H,dd), 5.06(2H,s), 3.32(2H,q), 2.50(3H,s), 2.38(3H,s)
2-166 8.05(1 H,d), 7.42-7.35(2H,m), 7.25-7.15(5H,m), 7.06(1 H,d), 7.02(1 H,dd) , 5.06(2H,s), 3.45(2H,m), 2.42(3H,s), 2.38(3H,s)
2-167 7.59(1 H,d), 7.34(1 H,t), 7.26-7.08(6H,m), 7.03(1 H,d), 6.98(1 H.dd), 5.05( 2H,s), 3.32(2H,q), 2.49(3H,s), 2.36(3H,s)
2-168 8.05(1 H,d), 7.34(1 H,t), 7.27-7.12(6H,m), 7.06(1 H,d), 7.00(1 H.dd), 5.05( 2H,s), 3.45(2H,m), 2.42(3H,s), 2.36(3H,s)
2-169 7.59(1 H,d), 7.35-7.32(3H,m), 7.19-7.18(2H,m), 7.12-7.08(2H,m), 7.03(1 H,d), 6.97(1 H,dd), 5.05(2H,s), 3.31 (2H,q), 2.49(3H,s), 2.35(3H,s)
2-170 8.04(1 H,d), 7.36-7.32(3H,m), 7.19-7.13(4H,m), 7.05(1 H,d), 6.99(1 H,dd) , 5.05(2H,s), 3.45(2H,m), 2.42(3H,s), 2.35(3H,s)
2-173 7.60(1 H,d), 7.42-7.33(5H,m), 7.13-7.08(2H,m), 7.03(1 H,d), 6.98(1 H.ddd ), 5.05(2H,s), 3.32(2H,q), 2.49(3H,s), 1.31 (9H,s)
2-174 8.05(1 H,d), 7.42-7.33(5H,m), 7.18-7.14(2H,m), 7.06(1 H,d), 7.01 (1 H,dd) , 5.05(2H,s), 3.45(2H,m), 2.42(3H,s), 1.31 (9H,s)
-175 7.75(1 H,d), 7.68(1 H,d), 7.59-7.55(2H,m), 7.41 (1 H,t), 7.35(1 H,t), 7.14-7.
11 (2H,m), 7.03(1 H,d), 6.96(1 H,dd), 5.31 (2H,s), 3.31 (2H,q), 2.49(3H,s) -176 8.03(1 H,d), 7.75(1 H,d), 7.68(1 H,d), 7.57(1 H.t), 7.41 (1 H,t), 7.36(1 H,t), 7.17-7.16(2H,m), 7.06(1 H,d), 6.98(1 H,ddd), 5.30(2H,s), 3.44(2H,m), 3. 42(3H,s)
-177 7.71 (1 H,s), 7.64-7.57(3H,m), 7.50(1 H,t), 7.36(1 H,t), 7.13-7.12(2H,m), 7 .04(1 H,d), 6.98(1 H,dd), 5.14(2H,s), 3.32(2H,q), 2.50(3H,s)
-178 8.05(1 H,d), 7.71 (1 H,s), 7.63(1 H,d), 7.58(1 H,d), 7.51 (1 H,t), 7.38(1 H,t), 7.19-7.17(2H,m), 7.06(1 H,d), 7.00(1 H,ddd), 5.14(2H,s), 3.45(2H,m), 2. 42(3H,s)
-179 7.65-7.53(5H,m), 7.35(1 H,t), 7.13-7.10(2H,m), 7.03(1 H,d), 6.96(1 H,dd), 5.16(2H,s), 3.31 (2H,q), 2.50(3H,s) TABLE 24 (continued)
No. 'H-NMR 5ppm (Solvent: CDCI3 /500MHz )
2-180 8.05(1 H,d), 7.64(2H,d), 7.56(2H,d), 7.37(1 H,t), 7.18-7.17(2H,m), 7.06(1 H,d) , 6.99(1 H.dd), 5.16(2H,s), 3.45(2H,m), 2.42(3H,s)
2-183 7.59(1 H,d), 7.34(1 H,t), 7.29(1 H,t), 7.12-7.09(2H,m), 7.04-6.96(4H,m), 6.85( 1 H,dd), 5.07(2H,s), 3.81 (3H,s), 3.32(2H,q), 2.49(3H,s)
2-184 8.04(1 H,d), 7.35(1 H,t), 7.29(1 H,t), 7.17-7.14(2H,m), 7.06(1 H,d), 7.02-6.99( 2H,m), 6.85(1 H.dd), 5.07(2H,s), 3.81 (3H,s), 3.45(2H,m), 2.42(3H,s)
2-193 7.71-7.69(2H,m), 7.64-7.59(2H,m), 7.43(1 H,t), 7.37(1 H,t), 7.14-7.13(2H,m),
7.03(1 H,d), 7.00(1 H.ddd), 5.29(2H,s), 3.33(2H,q), 2.50(3H,s)
2-194 8.04(1 H,d), 7.71-7.70(2H,m), 7.63(1 H.dt), 7.43(1 H,t), 7.38(1 H,t), 7.20-7.18( 2H,m), 7.07(1 H,d), 7.03(1 H.ddd), 5.30(2H,s), 3.46(2H,m), 2.42(3H,s)
2-195 7.76(1 H,s), 7.67(1 H,d), 7.61 (1 H,t), 7.50(1 H,t), 7.36(1 H,t), 7.15-6.94(5H,m),
5.12(2H,s), 3.32(2H,q), 2.50(3H,s)
2-196 8.05(1 H,d), 7.76(1 H,s), 7.68(1 H,d), 7.62(1 H,d), 7.50(1 H,t), 7.38(1 H,t), 7.20 -7.15(2H,m), 7.07(1 H,d), 6.98(1 H,dd), 5.12(2H,s), 3.45(2H,m), 2.42(3H,s)
2-197 7.67(2H,d), 7.55(2H,d), 7.36(1 H,m), 7.14-6.93(5H,m), 5.16(2H,s), 3.31 (2H, q), 2.57(3H,s)
2-198 8.05(1 H,d), 7.68(2H,d), 7.56(2H,d), 7.37(1 H,t), 7.19-7.15(2H,m), 7.07(1 H,d) , 6.97(1 H.dd), 5.16(2H,s), 3.45(2H,m), 2.42(3H,s)
2-199 8.16(1 H,dd), 7.91 (1 H,d), 7.68(1 H,dt), 7.60(1 H,d), 7.48(1 H,t), 7.36(1 H,t), 7.
13-7.12(2H,m), 6.98(1 H,ddd), 5.53(2H,s), 3.32(2H,q), 2.50(3H,s)
2-200 8.16(1 H,dd), 8.04(1 H,d), 7.92(1 H,d), 7.69(1 H.dt), 7.49(1 H,t), 7.38(1 H,t), 7.
20-7.18(2H,m), 7.07(1 H,d), 7.01 (1 H.ddd), 5.53(2H,s), 3.46(2H,m), 2.42(3H, s)
2-201 8.33(1 H,s), 8.18(1 H,dd), 7.78(1 H,d), 7.60(1 H,d), 7.57(1 H,t), 7.37(1 H,t), 7.1 4-7.12(2H,m), 7.04(1 H,d), 6.98(1 H,dd), 5.19(2H,s), 3.32(2H,q), 2.50(3H,s)
2-202 8.33(1 H,s), 8.18(1 H,dd), 8.05(1 H,d), 7.78(1 H,d), 7.57(1 H,t), 7.38(1 H,t), 7.2 0-7.17(2H,m), 7.07(1 H,d), 7.01 (1 H,ddd), 5.19(2H,s), 3.45(2H,m), 2.42(3H,s
)
2-203 8.26-8.23(2H,m), 7.62-7.59(3H,m), 7.36(1 H,t), 7.14-7.10(2H,m), 7.03(1 H,d),
6.96(1 H.ddd), 5.20(2H,s), 3.31 (2H,q), 2.50(3H,s)
2-204 8.26-8.24(2H,m), 8.05(1 H,d), 7.62(2H,d), 7.38(1 H,t), 7.20-7.15(2H,m), 7.07 (1 H,d), 6.98(1 H.ddd), 5.21 (2H,s), 3.45(2H,m), 2.42(3H,s)
2-257 8.63(1 H,d), 7.95-7.87(1 H,m), 7.71 (1 H,d), 7.60(1 H,d), 7.41-7.32(2H,m), 7.2 0-7.11 (2H,m), 7.08-7.00(2H,m), 5.42(2H,s), 3.34(2H,q), 2.50(3H,s)
2-259 8.87(1 H,s), 8.68(1 H,m), 8.25(1 H,d), 7.74(1 H,dd), 7.60(1 H,d), 7.38(1 H,t), 7.
17-7.11 (2H,m), 7.04(1 H,d), 6.97(1 H.dd), 5.25(2H,s), 3.32(2H,q), 2.50(3H,s)
2-260 8.98(1 H,s), 8.75(1 H,d), 8.53(1 H,d), 8.04(1 H,d), 7.98(1 H.dd), 7.42(1 H,t), 7.
26(1 H,d), 7.16(1 H,s), 7.09(1 H,d), 7.02(1 H.dd), 5.35(2H,s), 3.48(2H,m), 2.4 3(3H,s)
2-263 8.87(1 H,d), 8.60(1 H,d), 7.60(1 H,d), 7.54-7.49(1 H,m), 7.36(1 H,t), 7.17-7.13( 2H,m), 7.06-7.02(2H,m), 5.42(2H,s), 3.34(2H,q), 2.50(3H,s)
2-265 8.81 (1H,d), 7.95(1 H,s), 7.65-7.57(2H,m), 7.40(1 H,t), 7.21 -7.15(2H,m), 7.08- 7.04(2H,m), 5.42(2H,s), 3.34(2H,q), 2.51 (3H,s)
2-267 8.87(1 H,s), 8.01 (1 H,d), 7.76(1 H,d), 7.60(1 H,d), 7.38(1 H,t), 7.18-6.95(4H,m) , 5.35(2H,s), 3.33(2H,q), 2.51 (3H,s)
2-269 7.95-7.79(2H,m), 7.62(2H,t), 7.37(1 H,t), 7.18-6.89(4H,m), 5.32(2H,s), 3.33( 2H,q), 2.51 (3H,s)
Figure imgf000104_0001
Figure imgf000105_0001
Figure imgf000106_0001
Figure imgf000107_0001
Figure imgf000108_0001
Figure imgf000109_0001
Figure imgf000110_0001
Figure imgf000111_0001
Figure imgf000112_0001
Figure imgf000113_0001
Figure imgf000114_0001
Figure imgf000115_0001
TABLE 24 (continued)
No. 1H-NMR δρρι-τι (Solvent: CDCI3 /500MHz )
21-40 8.03(1 H,d), 7.29(1 H,s), 7.23-7.18(2H,m), 7.09-7.07(2H,m), 6.97(1 H,d), 6.69(1 H,dd), 5.27(1 H,q), 3.46(2H,m), 2.42(3H,s), 1.64(3H,d)
21-41 8.15(1 H,d), 7.56(1 H,d), 7.47(1 H,s), 7.39-7.33(3H,m), 7.05-7.01 (2H)m), 6.95(1 H,d), 5.31 (1 H,q), 3.32(2H,q), 2.49(3H,s), 2.41 (3H,s), 1.67(3H,d)
21-42 8.15(1 H,s), 8.01 (1 H,dd), 7.52-7.33(4H,m), 7.07-7.01 (2H,m), 6.95(1 H,d),
5.31 (1 H,q), 3.45(2H,m), 2.42(3H,s), 2.41 (3H,s), 1.67(3H,d)
21-43 8.14(1 H,d), 7.55(1 H,d), 7.25(1 H,d), 7.1 1-6.93(5H,m), 5.29(1 H,q), 3.32( 2H,q), 2.50(3H,s), 2.42(3H,s), 1.66(3H,d)
21-45 8.11 (1 H,d), 7.57(1 H,t), 7.45(1 H,d), 7.41 (1 H,d), 7.32(1 H,dt), 7.01 -6.95(3 H,m), 5.69(1 H,q), 3.29(2H,q), 2.47(3H,s), 2.41 (3H,s), 1.65(3H,d)
21 -46 8.11 (1 H,d), 7.94-7.93(2H,m), 7.63(1 H,s), 7.45-7.38(2H,m), 7.04-6.96(2 H,m), 5.70(1 H,q), 3.41 (2H,m), 2.40(3H,s), 1.66(3H,d)
21 -47 8.37(1 H,s), 7.73(1 H,m), 7.59(1 H,d), 7.55(1 H,s), 7.42-7.31 (3H,m), 7.03( 1 H,d), 6.83(1 H,d), 6.31 (1 H,q), 3.32(2H,q), 2.50(3H,s), 1.68(3H,d)
21 -48 8.37(1 H,s), 8.05(1 H,dd), 7.73(1 H,dt), 7.61 (1 H,s), 7.48-7.41 (3H,m), 7.0 6(1 H,d), 6.84(1 H,dd), 6.30(1 H,q), 3.44(2H,m), 2.42(3H,s), 1.68(3H,d)
21 -49 8.20(1 H,s), 7.68(1 H,m), 7.53-7.49(2H,m), 7.37-7.34(3H,m), 7.01 (1 H,d),
6.77(1 H,d), 3.30(2H,q), 2.48(3H,s), 1.92(6H,s)
21 -50 8.19(1 H,s), 7.99(1 H,d), 7.68(1 H,dd), 7.42-7.37(3H,m), 7.04(1 H,d), 6.78 (1 H,d), 3.46(2H,m), 2.41 (3H,s), 1.93(3H,s), 1.91 (3H,s)
22-1 8.37-6.93(1 OH.m), 5.17(2H,s), 4.05(2H,q), 2.52(3H,s)
TABLE 25
No. 1H-NMR 5ppm (Solvent: CD3COCD3 /500MHz )
5-375 8.39(1 H,d), 8.19(1 H,dd), 7.83(1 H,s), 7.73(1 H,d), 7.59(2H,m), 7.46(1 H,d dd), 7.31 (1 H,m), 7.21 (1 H,d), 5.32(2H,s), 3.77(2H,q), 2.50(3H,s)
5-599 8.22(1 H,d), 7.72(1 H,d), 7.66(1 H,s), 7.51-7.48(3H,m), 7.31 -7.28(1 H,m), 7.19(1 H,d), 7.11 (1 H,d), 5.22(2H,s), 3.77(2H,q), 2.81 (3H,s), 2.37(3H,s)
15-1 8.66(1 H,d), 7.82(1 H,d), 7.76(1 H,s), 7.52(1 H,d), 7.31-7.28(3H,m), 7.06-7 .04(2H,m), 6.95(1 H,t), 5.24(2H,s), 3.82(2H,q), 2.53(3H,s)
Now, Test Examples will be described.
TEST EXAMPLE 1
Test on adults of two-spotted spider mite ( Tetranvchus urticae )
An insecticidal solution was prepared to bring the concentration of the compound of the present invention to 50 ppm. A kidney bean having only one primordial leaf left, was transplanted to a pot (diameter: 8 cm, height: 7 cm), and 20 adults of two-spotted spider mite were released thereon. Together with the kidney bean leaf, they were dipped in the above insecticidal solution for about 5 seconds, dried in air and then left in a constant temperature chamber at 25°C with lightening. On the second or third day after the treatment, the number of dead adults were counted, and the mortality of adults was calculated by the following equation. Adults that dropped from the leaf or were moribund were included in the number of dead. The test was carried out with respect to the above-mentioned Compound Nos. 1-1 , 1 -5, 1 -6, 1-7, 1-15, 1 -43, 2-1 , 2-2, 2-3, 2-4, 2-5, 2-7, 2-8, 2-9, 2-10, 2-11 , 2-12, 2-19, 2-20, 2-21 , 2-22, 2-35, 2-36, 2-53, 2- 54, 2-61 , 2-62, 2-65, 2-66, 2-153, 2-154, 2-155, 2-156, 2-157, 2-158, 2-159, 2-160, 2- 161 , 2-162, 2-163, 2-164, 2-165, 2-166, 2-167, 2-168, 2-169, 2-170, 2-173, 2-174, 2- 175, 2-176, 2-177, 2-178, 2-179, 2-180, 2-183, 2-184, 2-185, 2-186, 2-193, 2-194, 2- 195, 2-196, 2-197, 2-198, 2-199, 2-200, 2-201 , 2-202, 2-203, 2-204, 2-257, 2-258, 2- 259, 2-260, 2-263, 2-264, 2-265, 2-266, 2-267, 2-268, 2-269, 2-270, 2-299, 2-300, 2- 301 , 2-302, 2-303, 2-304, 2-305, 2-306, 2-307, 2-308, 2-309, 2-310, 2-313, 2-314, 2- 315, 2-316, 2-337, 2-338, 2-341 , 2-342, 2-347, 2-348, 2-353, 2-354, 2-379, 2-380, 2- 381 , 2-382, 2-383, 2-384, 2-385, 2-386, 2-387, 2-413, 2-414, 2-415, 2-416, 2-417, 2- 418, 2-419, 2-420, 2-479, 2-480, 2-521 , 2-522, 2-533, 2-557, 2-585, 2-589, 2-590, 2- 591 , 2-592, 2-593, 2-594, 2-595, 2-596, 2-597, 2-603, 2-604, 3-1 , 3-3, 3-4, 3-5, 3-7, 3- 8, 3-9, 3-10, 3-11 , 3-12, 3-13, 3-17, 3-25, 3-26, 3-31 , 3-32, 3-35, 3-57, 3-59, 3-60, 3- 125, 3-127, 3-129, 3-131 , 3-135, 3-136, 3-137, 3-139, 5-1 , 5-2, 5-3, 5-4, 5-5, 5-6, 5-7, 5-8, 5-10, 5-15, 5-16, 5-19, 5-20, 5-21 , 5-22, 5-25, 5-26, 5-35, 5-36, 5-53, 5-54, 5-113, 5-114, 5-129, 5-133, 5-134, 5-137, 5-138, 5-157, 5-158, 5-159, 5-161 , 5-162, 5-163, 5- 164, 5-165, 5-166, 5-167, 5-168, 5-169, 5-170, 5-171 , 5-172, 5-173, 5-174, 5-175, 5- 176, 5-177, 5-178, 5-179, 5-180, 5-181 , 5-183, 5-184, 5-201 , 5-202, 5-257, 5-258, 5- 259, 5-260, 5-267, 5-268, 5-277, 5-283, 5-284, 5-329, 5-330, 5-337, 5-338, 5-375, 5- 383, 5-413, 5-473, 5-510, 5-557, 5-561 , 5-569, 5-573, 5-575, 5-577, 5-579, 5-585, 5- 587, 5-593, 5-595, 5-596, 5-597, 5-598, 5-599, 5-600, 5-601 , 5-602, 5-603, 5-604, 5- 605, 5-606, 5-607, 5-608, 5-609, 5-610, 5-611 , 5-612, 5-613, 5-614, 5-615, 5-616, 5- 617, 5-618, 5-619, 5-620, 5-621 , 5-622, 5-623, 5-624, 5-625, 5-626, 5-627, 5-628, 5- 629, 5-631 , 5-632, 6-1 , 6-2, 6-5, 6-6, 6-35, 6-36, 6-57, 6-63, 6-69, 6-70, 7-33, 8-17, 8- 18, 8-29, 8-30, 8-33, 8-34, 8-37, 8-38, 8-39, 8-40, 8-45, 8-46, 8-57, 8-58, 8-59, 8-60, 8- 61 , 8-62, 8-63, 8-64, 8-69, 8-70, 8-71 , 8-72, 9-17, 9-33, 10-1 , 10-2, 11-1 , 11 -2, 12-1 , 12-2, 13-1 , 14-1 , 15-1 , 15-2, 20-1 , 20-2, 21 -1 , 21 -2, 21-3, 21-4, 21-29, 21 -30, 21-31 , 21-32, 21-33, 21-34, 21-35, 21-36, 21-37, 21 -38, 21-39, 21-40, 21-41 , 21-43, 21-44, 21-45, 21 -46, 21-47, 21 -48, 21 -49, 21-50, 22-1 , 23-1 , whereby all compounds showed a mortality of adults of at least 90%.
Mortality of adults (%) = (The number of dead two-spotted spider mites/
The number of treated two-spotted spider mites ) x 100
TEST EXAMPLE 2
Test on controlling effects against brown planthopper (Nilaparvata lugens)
Rice seedling was dipped for about 10 seconds in an insecticidal solution adjusted to bring the concentration of the compound of the present invention to 200 ppm and then dried in air, its root was wrapped with a wet absorbent cotton, and the seedling was put into a test tube. Then, 20 second-third instar nymphs of brown planthopper were released therein, and the test tube was covered with a gauze and left in a constant temperature chamber at 25°C with lightening. On the 5th day after the release, the number of dead nymphs were counted, and the mortality was calculated by the following equation.
The test was carried out with respect to the above-mentioned Compound Nos. 2- 174, 2-178, 2-195, 2-268, 5-2, 5-5, 5-6, 5-163, 5-166, 5-168, 5-174, 5-178, 5-267, 5- 338, 5-607, 5-609, 5-611 , 5-612, 5-619, 5-629, 8-17, 8-33, 8-38, 8-63, 8-64, 10-2, whereby all compounds showed a mortality of at least 90%.
Mortality (%)=(The number of dead insects/The number of released insects)x100 Now, Formulation Examples are described below.
FORMULATION EXAMPLE 1
(1 ) Compound of the present invention 20 parts by weight
(2) Clay 70 parts by weight
(3) White carbon 5 parts by weight
(4) Sodium polycarboxylate 3 parts by weight
(5) Sodium alkylnaphthalene sulfonate 2 parts by weight
The above components are uniformly mixed to obtain a wettable powder.
FORMULATION EXAMPLE 2
(1) Compound of the present invention 5 parts by weight
(2) Talc 60 parts by weight
(3) Calcium carbonate 34.5 parts by weight
(4) Liquid paraffin 0.5 part by weight
The above components are uniformly mixed to obtain a dust.
FORMULATION EXAMPLE 3
(1) Compound of the present invention 20 parts by weight
(2) N,N-dimethylacetamide 20 parts by weight
(3) Polyoxyethylene tristyryl phenyl ether 10 parts by weight
(4) Calcium dodecylbenzene sulfonate 2 parts by weight
(5) Xylene 48 parts by weight
The above components are uniformly mixed and dissolved to obtain an
emulsifiable concentrate.
FORMULATION EXAMPLE 4
(1) Clay 68 parts by weight
(2) Sodium lignin sulfonate 2 parts by weight
(3) Polyoxyethylenealkylaryl sulfate 5 parts by weight
(4) White carbon 25 parts by weight
The mixture of the above components is mixed with compound of the present invention in a weight ratio of 4:1 to obtain a wettable powder.
FORMULATION EXAMPLE 5
(1 ) Compound of the present invention 50 parts by weight
(2) Sodium alkylnaphthalene sulfonate condensation product of formaldehyde 2 parts by weight
(3) Silicone oil 0.2 part by weight
(4) Water 47.8 parts by weight
The above components are uniformly mixed and pulverized to obtain a base liquid, and (5) Sodium polycarboxylate 5 parts by weight
(6) Anhydrous sodium sulfate 42.8 parts by weight
are added, and the mixture is uniformly mixed, granulated and dried to obtain water- dispersible granules.
FORMULATION EXAMPLE 6
(1) Compound of the present invention 5 parts by weight
(2) Polyoxyethyleneoctylphenyl ether 1 part by weight
(3) Polyoxyethylene alkyl ether phosphoric acid ester 0.1 part by weight
(4) Granular calcium carbonate 93.9 parts by weight
The above components (1) to (3) are preliminarily uniformly mixed and diluted with a proper amount of acetone, and then the mixture is sprayed onto the component (4), and acetone is removed to obtain granules.
FORMULATION EXAMPLE 7
(1) Compound of the present invention 2.5 parts by weight
(2) N,N-dimethylacetamide 2.5 parts by weight
(3) Soybean oil 95.0 parts by weight
The above components are uniformly mixed and dissolved to obtain an ultra low volume formulation.
FORMULATION EXAMPLE 8
(1) Compound of the present invention 10 parts by weight
(2) Diethylene glycol monoethyl ether 80 parts by weight
(3) Polyoxyethylenealkyl ether 10 parts by weight
The above components are uniformly mixed to obtain a soluble concentrate.
The entire disclosure of Japanese Patent Application No. 2011-181996 filed on August 23, 2011 including specification, claims and abstract is incorporated herein by reference in its entirety.

Claims

A compound represented by the formula (I) or its salt:
Figure imgf000120_0001
wherein Q is phenyl which may be substituted by R4 , or pyridyl which may be
substituted by R4 ; W is an oxygen atom or S(0)m ; each of A1 to A5 is -C(R5 )= or a nitrogen atom, provided that among A1 to A5 , the number of groups which may be nitrogen atoms, is from 0 to 2; each of B to B4 is a hydrogen atom, a halogen atom, alkyi or haloalkyi; each of R1 and R2 is a hydrogen atom, a halogen atom, alkyi, haloalkyi, alkoxy, haloalkoxy or cyano; R3 is alkyi or haloalkyi; R4 is a halogen atom, alkyi, haloalkyi, alkoxy, haloalkoxy, cyano, nitro, COR6 , C02 R6 , N(R7 )COR6 ,
N(R7 )CO2 R6 , NR8 R9 , CONR8 R9 , alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl or haloalkylsulfonyl; R5 is a hydrogen atom, a halogen atom, alkyi, haloalkyi, alkoxy, haloalkoxy, cyano, nitro, COR6 , CO2 R6 , N(R7 )COR6 , N(R7 )CO2 R6 , NR8 R9 , CONR8 R9 , alkylthio, haloalkylthio, alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl or haloalkylsulfonyl; R6 is a hydrogen atom, alkyi or haloalkyi; R7 is a hydrogen atom or alkyi; each of R8 and R9 is a hydrogen atom or alkyi; when R8 and R9 are alkyi, R8 and R9 may form, together with the nitrogen atom to which they are bonded, a 5- or 6- membered ring; n is an integer of 0 or 1 ; m is an integer of 0, 1 or 2; x is an integer of 0 or 1 ; and y is an integer of 0 or 1 , provided that the sum of x and y is not 2.
2. A pesticide containing the compound or its salt as defined in Claim 1 , as an active ingredient.
3. An insecticide, miticide, nematicide or soil pesticide containing the compound or its salt as defined in Claim 1 , as an active ingredient.
4. An insecticide or miticide containing the compound or its salt as defined in Claim 1 , as an active ingredient.
5. A method for controlling pests, which comprises applying an effective amount of the compound or its salt as defined in Claim 1 thereto.
6. A method for controlling insects, mites, nematodes or soil pests, which comprises applying an effective amount of the compound or its salt as defined in Claim 1 thereto.
7. A method for controlling insects or mites, which comprises applying an effective amount of the compound or its salt as defined in Claim 1 thereto.
PCT/JP2012/070874 2011-08-23 2012-08-10 Pesticide WO2013027660A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011181996 2011-08-23
JP2011-181996 2011-08-23

Publications (1)

Publication Number Publication Date
WO2013027660A1 true WO2013027660A1 (en) 2013-02-28

Family

ID=46889399

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/070874 WO2013027660A1 (en) 2011-08-23 2012-08-10 Pesticide

Country Status (4)

Country Link
JP (1) JP2013060420A (en)
AR (1) AR087624A1 (en)
TW (1) TW201321347A (en)
WO (1) WO2013027660A1 (en)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015169718A1 (en) * 2014-05-06 2015-11-12 Bayer Cropscience Ag Aryl sulfide and arly sulfoxide derivatives having c-c linked (aza)uracils as pest control agents
CN105517995A (en) * 2013-07-08 2016-04-20 拜耳作物科学股份公司 Six-membered c-n-linked aryl sulfide derivatives and aryl sulfoxide derivatives as pest control agents
CN107074779A (en) * 2014-10-03 2017-08-18 住友化学株式会社 Pyridazine compound
CN108137502A (en) * 2015-10-21 2018-06-08 住友化学株式会社 Pyridine compounds
CN108349909A (en) * 2015-11-02 2018-07-31 住友化学株式会社 Pyrimidine compound
US10173997B2 (en) 2015-01-30 2019-01-08 Sumitomo Chemical Company, Limited Bipyridine compound and use of same for noxious arthropod control
US10172356B2 (en) 2015-01-30 2019-01-08 Sumitomo Chemical Company, Limited Bipyridine compound and use of same for noxious arthropod control
EP3366672A4 (en) * 2015-10-23 2019-05-15 Shenyang Sinochem Agrochemicals R & D Co., Ltd. Biphenyl compound and application thereof
US10299475B2 (en) 2013-08-23 2019-05-28 Ishihara Sangyo Kaisha, Ltd. Pesticide
US10577343B2 (en) 2015-10-16 2020-03-03 Sumitomo Chemical Company, Limited Pyrazine compound and arthropod pest control agent containing same
WO2020083018A1 (en) * 2018-10-25 2020-04-30 沈阳中化农药化工研发有限公司 Sulfobiphenyl compound, preparation method therefor, and uses thereof
CN113943238A (en) * 2020-07-17 2022-01-18 沈阳中化农药化工研发有限公司 Substituted diphenyl sulfide compound and application thereof
CN114642203A (en) * 2020-12-17 2022-06-21 沈阳中化农药化工研发有限公司 Insecticidal and acaricidal composition
WO2022166737A1 (en) * 2021-02-05 2022-08-11 沈阳化工大学 Biphenyl compound containing sulfide (sulfoxide) substitution and use thereof
CN114957062A (en) * 2022-07-05 2022-08-30 海利尔药业集团股份有限公司 Para-substituted biphenyl thioether compound, composition and application thereof

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105541682B (en) * 2014-10-24 2018-01-16 沈阳中化农药化工研发有限公司 A kind of biphenyl compound and its application
WO2017073733A1 (en) * 2015-10-30 2017-05-04 住友化学株式会社 Pest control composition and use thereof
US9856212B1 (en) 2017-04-18 2018-01-02 Shenyang Sinochem Agrochemicals R&D Co., Ltd. Biphenyl compounds and applications thereof
CN110870476B (en) * 2018-08-30 2021-10-01 沈阳中化农药化工研发有限公司 Liquid preparation containing biphenyl compounds and application thereof
CN111226927B (en) * 2018-11-29 2021-06-01 沈阳中化农药化工研发有限公司 Insecticidal and acaricidal composition containing mite growth inhibitor acaricide
CN114642204B (en) * 2020-12-17 2023-06-13 沈阳中化农药化工研发有限公司 Insecticidal and acaricidal composition containing insect growth regulator insect/acarid agent
WO2023182391A1 (en) * 2022-03-24 2023-09-28 住友化学株式会社 Method for controlling plant diseases
WO2023243677A1 (en) * 2022-06-17 2023-12-21 住友化学株式会社 Plant disease control method

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030069242A1 (en) * 1998-04-07 2003-04-10 Kumiai Chemical Industry Co., Ltd. 3-arylphenyl sulfide derivative and insecticide and miticide
WO2007034755A1 (en) 2005-09-21 2007-03-29 Kumiai Chemical Industry Co., Ltd. Biphenyl sulfide compounds and insecticides and miticides
JP2007145828A (en) * 2005-10-28 2007-06-14 Otsuka Pharmaceut Co Ltd Pharmaceutical composition
US20100210704A1 (en) * 2007-10-18 2010-08-19 Kumiai Chemical Industry Co., Ltd. 3-alkoxy-1-phenylpyrazole derivatives and pesticides
JP2011181996A (en) 2010-02-26 2011-09-15 Casio Computer Co Ltd Display order determination device, image display device, and program

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030069242A1 (en) * 1998-04-07 2003-04-10 Kumiai Chemical Industry Co., Ltd. 3-arylphenyl sulfide derivative and insecticide and miticide
WO2007034755A1 (en) 2005-09-21 2007-03-29 Kumiai Chemical Industry Co., Ltd. Biphenyl sulfide compounds and insecticides and miticides
JP2007145828A (en) * 2005-10-28 2007-06-14 Otsuka Pharmaceut Co Ltd Pharmaceutical composition
US20100210704A1 (en) * 2007-10-18 2010-08-19 Kumiai Chemical Industry Co., Ltd. 3-alkoxy-1-phenylpyrazole derivatives and pesticides
JP2011181996A (en) 2010-02-26 2011-09-15 Casio Computer Co Ltd Display order determination device, image display device, and program

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; KATO, MASAYA ET AL: "Drugs containing aminocyanopyrimidine derivatives having adenosine A2A receptor agonistic effects", XP002686552, retrieved from STN Database accession no. 2007:640321 *
DATABASE REGISTRY [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 16 September 2011 (2011-09-16), "5-chloro-4-[3-(methylthio)phenyl]-2-(phenylmethoxy)-pyridine", XP002686553, retrieved from STN Database accession no. 1332614-75-1 *

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105517995A (en) * 2013-07-08 2016-04-20 拜耳作物科学股份公司 Six-membered c-n-linked aryl sulfide derivatives and aryl sulfoxide derivatives as pest control agents
US20160251321A1 (en) * 2013-07-08 2016-09-01 Bayer Cropscience Aktiengesellschaft Six-membered c-n-linked aryl sulfide derivatives and aryl sulfoxide erivatves as pest conrol agents
US9783509B2 (en) * 2013-07-08 2017-10-10 Bayer Cropscience Aktiengesellschaft Six-membered C-N-linked aryl sulfide derivatives and aryl sulfoxide derivatives as pest conrol agents
CN105517995B (en) * 2013-07-08 2018-10-02 拜耳作物科学股份公司 The aromatic yl sulfide and aryl oxysulfide derivative that hexa-atomic C-N as pesticide is bonded
US10299475B2 (en) 2013-08-23 2019-05-28 Ishihara Sangyo Kaisha, Ltd. Pesticide
WO2015169718A1 (en) * 2014-05-06 2015-11-12 Bayer Cropscience Ag Aryl sulfide and arly sulfoxide derivatives having c-c linked (aza)uracils as pest control agents
CN107074779A (en) * 2014-10-03 2017-08-18 住友化学株式会社 Pyridazine compound
US9924719B2 (en) 2014-10-03 2018-03-27 Sumitomo Chemical Company, Limited Pyridazine compound
CN107074779B (en) * 2014-10-03 2020-05-01 住友化学株式会社 Pyridazine compounds
US10173997B2 (en) 2015-01-30 2019-01-08 Sumitomo Chemical Company, Limited Bipyridine compound and use of same for noxious arthropod control
US10172356B2 (en) 2015-01-30 2019-01-08 Sumitomo Chemical Company, Limited Bipyridine compound and use of same for noxious arthropod control
US11001567B2 (en) 2015-10-16 2021-05-11 Sumitomo Chemical Company, Limited Pyrazine compound
US11905271B2 (en) 2015-10-16 2024-02-20 Sumitomo Chemical Company, Limited Pyrazine compound
US10577343B2 (en) 2015-10-16 2020-03-03 Sumitomo Chemical Company, Limited Pyrazine compound and arthropod pest control agent containing same
US10273210B2 (en) 2015-10-21 2019-04-30 Sumitomo Chemical Company, Limited Pyridine compound
CN108137502B (en) * 2015-10-21 2021-03-16 住友化学株式会社 Pyridine compound
CN108137502A (en) * 2015-10-21 2018-06-08 住友化学株式会社 Pyridine compounds
EP3366672A4 (en) * 2015-10-23 2019-05-15 Shenyang Sinochem Agrochemicals R & D Co., Ltd. Biphenyl compound and application thereof
EP3372588A4 (en) * 2015-11-02 2019-04-24 Sumitomo Chemical Company Limited Pyrimidine compound
CN108349909A (en) * 2015-11-02 2018-07-31 住友化学株式会社 Pyrimidine compound
US10645929B2 (en) 2015-11-02 2020-05-12 Sumitomo Chemical Company, Limited Pyrimidine compound
CN108349909B (en) * 2015-11-02 2021-04-06 住友化学株式会社 Pyrimidine compounds
WO2020083018A1 (en) * 2018-10-25 2020-04-30 沈阳中化农药化工研发有限公司 Sulfobiphenyl compound, preparation method therefor, and uses thereof
WO2022012483A1 (en) 2020-07-17 2022-01-20 沈阳中化农药化工研发有限公司 Substituted phenyl sulfide compound and application thereof
CN113943238B (en) * 2020-07-17 2022-11-01 沈阳中化农药化工研发有限公司 Substituted diphenyl sulfide compound and application thereof
CN113943238A (en) * 2020-07-17 2022-01-18 沈阳中化农药化工研发有限公司 Substituted diphenyl sulfide compound and application thereof
CN114642203A (en) * 2020-12-17 2022-06-21 沈阳中化农药化工研发有限公司 Insecticidal and acaricidal composition
CN114642203B (en) * 2020-12-17 2023-03-24 沈阳中化农药化工研发有限公司 Insecticidal and acaricidal composition
WO2022166737A1 (en) * 2021-02-05 2022-08-11 沈阳化工大学 Biphenyl compound containing sulfide (sulfoxide) substitution and use thereof
CN114957062A (en) * 2022-07-05 2022-08-30 海利尔药业集团股份有限公司 Para-substituted biphenyl thioether compound, composition and application thereof
CN114957062B (en) * 2022-07-05 2023-12-29 海利尔药业集团股份有限公司 Para-substituted biphenyl thioether compound, composition and application thereof

Also Published As

Publication number Publication date
JP2013060420A (en) 2013-04-04
TW201321347A (en) 2013-06-01
AR087624A1 (en) 2014-04-09

Similar Documents

Publication Publication Date Title
WO2013027660A1 (en) Pesticide
RU2721119C2 (en) Containing an oxime group of a condensed heterocyclic compound or a salt thereof, an agricultural and garden insecticide containing said compound, and a method of using said insecticide
EP2242739B1 (en) Insecticidal arylpyrrolines
US9055749B2 (en) Insecticidal arylpyrrolines
US8450483B2 (en) Pesticidal arylpyrrolidines
JP2002145707A (en) Herbicide comprising n-substituted dihydropyrrole derivative
US8211828B2 (en) Fungicidal mixtures of 1-methylpyrazol-4-ylcarboxanilides and azolopyrimidinylamines
US11046659B2 (en) 1,2,3-triazole derivative and insecticide and acaricide containing said derivative as active ingredient
CN109415357B (en) Condensed heterocyclic compound having hydrazone group or salt thereof, agricultural and horticultural insecticide containing the compound, and method for using the same
JPH09176125A (en) 5-pyrazolecarboxylic acid amide derivative and plant blight controlling agent
US9266830B2 (en) Pesticidal arylpyrrolidines
WO1999006380A1 (en) Tetrazole compounds and pest control agent
EP2511255A1 (en) Substituted prop-2-in-1-ol and prop-2-en-1-ol derivatives
WO2023189602A1 (en) Pyridazinone compound or salt thereof and pest control agent containing same
WO2023243678A1 (en) Pyrazole compound, production intermediate thereof, and pest control agent
JP2001026578A (en) N-substituted dihydropyrrole derivative
JP2001316362A (en) N-substituted dihydropyrrole derivative
JP2002145706A (en) Insecticide comprising n-substituted dihydropyrrole derivative

Legal Events

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

Ref document number: 12762410

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

NENP Non-entry into the national phase

Ref country code: JP

122 Ep: pct application non-entry in european phase

Ref document number: 12762410

Country of ref document: EP

Kind code of ref document: A1