WO2012050237A1 - Pyrimidine compounds and their use as pesticides - Google Patents

Pyrimidine compounds and their use as pesticides Download PDF

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Publication number
WO2012050237A1
WO2012050237A1 PCT/JP2011/074232 JP2011074232W WO2012050237A1 WO 2012050237 A1 WO2012050237 A1 WO 2012050237A1 JP 2011074232 W JP2011074232 W JP 2011074232W WO 2012050237 A1 WO2012050237 A1 WO 2012050237A1
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group
optionally substituted
halogens
group optionally
compound
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PCT/JP2011/074232
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French (fr)
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Yoshihiko Nokura
Hiroshi Ikegami
Hiroki Tomioka
Daisuke Takaoka
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Sumitomo Chemical Company, Limited
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Publication of WO2012050237A1 publication Critical patent/WO2012050237A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • the present invention relates to a pyrimidine compound and use thereof for controlling pests.
  • Some compounds exhibiting a pest control activity have been discovered and developed as an active ingredient of a pesticidal agent.
  • some types of pyrimidine compounds are known as an active ingredient thereof (see, for example, Patent References 1 to 3) .
  • the purpose of the present invention is to provide a novel compound having a pest control activity.
  • the present inventors have extensively studied to find a compound exhibiting a pest control activity, and then have found that a pyrimidine compound of the following Formula (1) exhibits an excellent activity in controlling pests. Based upon the new findings, the present invention has been completed.
  • the present inventions are as follows.
  • a pyrimidine compound of Formula (1) [1] A pyrimidine compound of Formula (1) :
  • R 1 is C1-C3 chain hydrocarbon group optionally substituted with one or more halogens, hydrogen, halogen or amino group,
  • R 2 is C1-C3 chain hydrocarbon group optionally substituted with one or more halogens, hydrogen, halogen, hydroxy group, mercapto group or amino group,
  • R 3 is C1-C3 chain hydrocarbon group optionally substituted with one or more halogens, hydrogen, halogen, amino group, nitro group or cyano group,
  • R 4 is C1-C6 chain .
  • hydrocarbon group optionally substituted with one or more halogens, C3-C8 cycloalkyl group optionally substituted with one or more halogens, Cl- C6 alkoxy group .
  • Q is oxygen or -S(0) r - wherein r is 0, 1 or 2,
  • A is a single bond, methylene group optionally substituted with one or more atoms or groups selected from the group consisting of C1-C3 alkyl group and halogen, or ethylene group optionally substituted with one or more atoms or groups selected from the group consisting of C1-C3 alkyl group and halogen, and A is attached to the carbon atom of the ring defined as Cyc,
  • Group a consists of C1-C6 chain hydrocarbon group optionally substituted with one or more halogens, C1-C6 alkoxy group optionally substituted with one or more halogens, C1-C6 alkylthio group optionally substituted with one or more halogens, C1-C6 alkylsulfinyl group optionally substituted with one or more halogens, C1-C6 alkylsulfonyl group optionally substituted with one or more halogens, Cl- C6 alkylamino group optionally substituted with one or more halogens, C2-C8 dialkylamino group optionally substituted with one or more halogens, halogen, hydroxy group, mercapto group, amino group, cyano group and nitro group,
  • Group ⁇ consists of C1-C6 chain hydrocarbon group optionally substituted with one or more halogens, C1-C6 alkoxy group optionally substituted with one or more halogens, C1-C6 alkylthio group optionally substituted with one or more halogens, C1-C6 alkylsulfinyl group optionally substituted with one or more halogens, C1-C6 alkylsulfonyl group optionally substituted with one or more halogens, Cl- C6 alkylamino group optionally substituted with one or more halogens, C2-C8 dialkylamino group optionally substituted with one or more halogens, C2-C6 alkylcarbonylamino group optionally substituted with one or more halogens, C2-C6 alkoxycarbonylamino group optionally substituted with one or more halogens, C2-C6 alkylcarbonyl group optionally substituted with one or more halogens, C2-
  • R 7 is C1-C3 alkyl group optionally substituted with one or more halogens or hydrogen
  • X 1 and X 2 are independently selected from the group consisting of oxygen and sulfur
  • T 1 is methylene group optionally substituted with one or more halogens or ethylene group optionally substituted with one or more halogens
  • Group ⁇ 3 consists of bivalent radicals shown by -T 2 - and -X 3 -T 3 -X 4 - wherein X 3 and X 4 are independently selected from the group consisting of oxygen and sulfur, and T 2 and T 3 are independently selected from the group consisting of methylene group optionally substituted with one or more halogens,
  • R is halogen
  • R 9 and R 10 are independently selected from the group consisting of C1-C3 alkyl group optionally substituted with one or more halogens, and halogen,
  • p is an integer, of 0 to 9, provided , that when p is an integer of 2 to 9, each R 9 may be different from each other, q is an integer of 0 to 8, provided that when q is an integer of 2 to 8, each R 10 may be different from each other, and
  • R 1 , R 2 , R 3 , R 4 and G 1 are as defined above, and Z is halogen .
  • R 1 is hydrogen
  • R 2 is hydrogen or amino group
  • R 3 is hydrogen
  • R 4 is C1-C6 chain hydrocarbon group optionally substituted with one or more halogens, C1-C6 alkoxy group optionally substituted with one or more halogens, hydrogen, or halogen,
  • Cyc may be optionally substituted with one or more atoms or groups selected from the following Groups ⁇ to ⁇ 3,
  • A is a single bond, methylene group optionally substituted with C1-C3 alkyl group, or ethylene group optionally substituted with C1-C3 alkyl group,
  • Group ⁇ consists of C1-C6 chain hydrocarbon group optionally substituted with one or more halogens, C1-C6 alkoxy group optionally substituted with one or more halogens, C2-C6 alkoxycarbonyl group optionally substituted with one or more halogens, halogen, hydroxy group, and cyano group,
  • Group ⁇ 3 consists of a bivalent radical shown by -T 2 - wherein T 2 is methylene group optionally substituted with one or more halogens .
  • R 1 is hydrogen
  • R 2 is hydrogen
  • R 3 is hydrogen
  • R 4 is C1-C6 chain hydrocarbon group, hydrogen, or halogen
  • Cyc may be optionally substituted with one or more atoms or groups selected from the following Groups ⁇ to ⁇ 3,
  • A is a single bond, methylene group optionally substituted with C1-C3 alkyl group, or ethylene group optionally substituted with C1-C3 alkyl group,
  • Group ⁇ consists of C1-C6 chain hydrocarbon group optionally substituted with one or more halogens, C1-C6 alkoxy group, C2-C6 alkoxycarbonyl group, halogen, hydroxy group, and cyano group
  • Group ⁇ 3 consists of a bivalent radical shown by -T 2 - wherein T 2 is methylene group optionally substituted with one or more halogens.
  • a pesticidal composition comprising the pyrimidine compound of any one of [1] to [13] and an inert carrier.
  • a method for controlling pests which comprises a step of applying an effective amount of the pyrimidine compound of any one of [1] to [13] to pests or habitats thereof.
  • the present compound is useful as an active ingredient of a pesticidal agent because the compound has an excellent activity in controlling pests.
  • halogen used herein includes fluorine, chlorine, bromine and iodine.
  • C2-C6 in “C2-C6 alkoxycarbonyl group” means the total number of carbon atoms in the alkoxycarbonyl group.
  • C1-C3 chain hydrocarbon group used herein includes, for example, C1-C3 alkyl group such as methyl group, ethyl group, .propyl group and isopropyl group; C2-C3 alkenyl group such as vinyl group and 2-propenyl group; and C2-C3 alkynyl group such as ethynyl group and 2-propynyl group.
  • C1-C3 chain hydrocarbon group optionally substituted with one or more halogens used herein includes, for example, C1-C3 alkyl group optionally substituted with one or more halogens such as methyl group, ethyl group, propyl group, isopropyl group, difluoromethyl group, trifluoromethyl group, dichloromethyl group, trichloro- methyl group, 2, 2, 2-trifluoroethyl group, 2 , 2 , 2-trichloro- ethyl group, pentafluoroethyl group and perfluoropropyl group; C2-C3 alkenyl group optionally substituted with one or more halogens such as vinyl group, 2-propenyl group, 2 , 2-dichlorovinyl group and 3-chloro-2-propenyl group; and C2-C3 alkynyl group optionally substituted with one or more halogens such as ethynyl group and 2-propyl
  • C1-C6 chain hydrocarbon group used herein includes, for example, C1-C6 alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, 1-methylbutyl group, tert- pentyl group, neopentyl group, hexyl group and isohexyl group; C2-C6 alkenyl group such as vinyl group, 2-propenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-2- propenyl group, 3-methyl-2-butenyl group, 2-pentenyl group and 2-hexenyl group; C2-C6 alkynyl group such as ethynyl group, 2-propynyl group, 2-butynyl group and 3-butynyl group .
  • C1-C6 chain hydrocarbon group optionally substituted with one or more halogens used herein includes, for example, C1-C6 alkyl group optionally substituted with one or more halogens such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, 1-methylbutyl group, tert-pentyl group, neopentyl group, hexyl group, isohexyl group, difluoromethyl group, trifluoromethyl group, dichloromethyl group, trichloro- methyl group, 2 , 2 , 2-trifluoroethyl group, 2 , 2 , 2-trichloro- ethyl group, pentafluoroethyl group, perfluoropropyl group, perfluorobutyl group
  • C3-C8 cycloalkyl group optionally substituted with one or more halogens used herein includes, for example, cyclopropyl group, 2 , 2-difluorocyclopropyl group, 2 , 2-dichlorocyclopropyl group, 2 , 2-dibromocyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group.
  • C1-C6 alkoxy group optionally substituted with one or more halogens used herein includes, for example, methoxy group, trifluoromethoxy group, ethoxy group, 2,2,2- trifluoroethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutyloxy group, sec-butyloxy group, tert- butyloxy group, pentyloxy group and hexyloxy group.
  • C1-C6 alkylthio group optionally substituted with one or more halogens includes, for example, methylthio group, trifluorpmethylthio group, ethylthio group, 2 , 2 , 2-trifluoroethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, pentylthio group and hexylthio group.
  • C1-C6 alkylsulfinyl group optionally substituted with one or more halogens includes, for example, methylsulfinyl group, trifluoromethyl sulfinyl group, ethylsulfinyl group, 2 , 2 , 2-trifluoro ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group, isobutylsulfinyl group, sec- butylsulfinyl group, tert-butylsulfinyl group, pentyl- sulfinyl group and hexylsulfinyl group.
  • C1-C6 alkylsulfonyl group optionally substituted with one or more halogens includes, for example, methylsulfonyl group, trifluoromethyl sulfonyl group and ethylsulfonyl group.
  • C1-C6 alkylamino group optionally substituted with one or more halogens used herein includes, for example, methylamino group, ethylamino group, 2,2,2- trifluoroethylamino group, propylamino group, isopropyl- amino group, butylamino group, pentylamino group and hexylamino group.
  • C2-C8 dialkylamino group optionally substituted with one or more halogens used herein includes, for example, dimethylamino group, diethylamino group, , bis (2, 2, 2-trifluoroethyl ) amino group, and dipropylamino group.
  • C2-C6 alkylcarbonylamino group optionally substituted with one or more halogens used herein includes, for example, acetylamino group, propionylamino group, butanoylamino group, pentanoylamino group, 2,2,2- trifluoroacetylamino group and 2 , 2 , 2-trichloroacetylamino group.
  • C2-C6 alkoxycarbonylamino group optionally substituted with one or more halogens used .herein includes, for example, methoxycarbonylamino group, ethoxycarbonyl- amino group, propoxycarbonylamino group, tert-butoxy- carbonylamino group and 2 , 2 , 2-trichloroethoxycarbonylamino group .
  • C2-C6 alkylcarbamoyl group optionally substituted with one or more halogens used herein includes, for example, methylcarbamoyl group, ethylcarbamoyl group and 2 , 2 , 2-trifluoroethylcarbamoyl group.
  • C2-C8 . dialkylcarbamoyl group optionally substituted with one or more halogens used herein includes, for example, dimethylcarbamoyl group, diethylcarbamoyl group and dipropylcarbamoyl group.
  • methylene group optionally substituted with one or more atoms or groups selected from the group consisting of C1-C3 alkyl group and halogen used herein includes, for example, methylene group, (methyl ) methylene group, (ethyl) methylene group, difluoromethylene group and dichloromethylene group.
  • ethylene group optionally substituted with one or more atoms or groups selected from the group consisting of C1-C3 alkyl group and halogen used herein includes, for example, ethylene group, 1-methylethylene group, 2- methylethylene group, 1 , 1-dimethylethylene group and 2,2- difluoroethylene group.
  • C2-C6 alkylcarbonyl group optionally substituted with one or more halogens used herein includes, for example, acetyl group, propionyl group, butanoyl group, pentanoyl group and 2 , 2 , 2-trifluoroacetyl group.
  • C2-C6 alkoxycarbonyl group optionally substituted with one or more halogens used herein includes, for example, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, 2 , 2 , 2-trifluoroethoxycarbonyl group and tert-butoxycarbonyl group.
  • phenyl group optionally substituted with one or more atoms or groups selected from Group a includes, for example, phenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-aminophenyl group, 3-aminophenyl group, 4-aminophenyl group, 2- cyanophenyl group, 3-cyanophenyl group, -cyanophenyl group, 2-nitrophenyl group, 3-nitrophenyl group, 4-nitrophenyl group, 2-methylphenyl group, 3-methylphenyl group, 4- methylphenyl group, 2- ( trifluoromethyl ) phenyl group, 3- (trifluoromethyl) phenyl group, 4- (trifluoromethyl ) phenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4- methoxyphenyl group, 4- (trifluoromethoxy) phenyl group, 4- (methylthio)
  • the "5- to 6-membered aromatic heterocyclic group" used herein includes, for example, 2-pyrrolyl group, 2- furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 5-pyraz.olyl group, 4-pyrazolyl group, 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, pyrazinyl group, 1-pyrrolyl group and 1-pyrazolyl group.
  • the "5- to 6-membered aromatic heterocyclic group optionally substituted with one or more atoms or groups selected from Group a" used herein includes, for example, l-methyl-2-pyrrolyl group, 2-furyl group, 3-furyl group, 5- bromo-2-furyl group, 5-nitro-2-furyl group, 2-methyl-3- furyl group, 2 , 5-dimethyl-3-furyl group, 2 , 4 -dimethyl-3- furyl group, 2-thienyl group, 3-thienyl group, 5-methyl-2- thienyl group, 3-methyl-2-thienyl group, l-methyl-3- trifluoromethyl-5-pyrazolyl group, 5-chloro-l , 3-dimethyl-4- pyrazolyl group, 2-pyridinyl group, 3-pyridinyl group, 4- pyridinyl group, 2-methyl-3-pyridinyl group, 6-methyl-3- pyridinyl group, 2-chloro-3-pyridin
  • the "3- to 8-membered saturated heterocyclic group containing one atom or group selected from the group consisting of oxygen, -S( 0) n - and -NR 6 - as a .
  • ring component used herein includes, for example, epoxy group, oxetan-2-yl group, oxetan-3-yl group, tetrahydrofuran-2-yl group, tetrahydrofuran-3-yl group,, tetrahydrothiophen-2-yl group, tetrahydrothiophen-3-yl group, tetrahydropyran-2-yl group, tetrahydropyran-3-yl group, tetrahydropyran- -yl group, tetrahydrothiopyran-3-yl group, tetrahydrothiopyran- 4-yl group, l-oxotetrahydrothiophen-4 -yl group, 1,1-dio
  • C3-C8 cycloalkyl group used herein includes, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group.
  • C5-C8 cycloalkenyl group used herein is a 5- to 8-membered unsaturated carbocyclic group having one or more double bonds but less than the maximum allowable double bonds, and specific examples thereof include 1- cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, 3- cyclohexenyl group, 1-cycloheptenyl group, 2-cycloheptenyl group, 3-cycloheptenyl group and 4-cycloheptenyl group.
  • the following structures are examples of a cyclohexyl group substituted with two atoms or groups selected from Group ⁇ .
  • the "5- to 8-membered saturated heterocyclic group containing two atoms or groups selected from the group consisting of oxygen, -S( 0) n - and -NR 6 - as a ring component wherein the 5- to 8-membered saturated heterocyclic group may be optionally substituted with one or more atoms or groups selected from Groups ⁇ to ⁇ 3" used herein includes, for example, 1 , 3-dioxolan-4-yl group and 2 , 2-dimethyl-l , 3-dioxolan-4-yl group..
  • C3-C8 cycloalkyl group optionally substituted with one or more atoms or groups selected from Groups ⁇ to ⁇ 3 used herein includes, for example, C3-C8 cycloalkyl group optionally substituted with one or more atoms or groups selected from Group ⁇ such as cyclopropyl group, 2 , 2-difluorocyclopropyl group, 2 , 2-dichlorocyclopropyl group, 2 , 2-dibromocyclopropyl group, cyclobutyl group, cyclopentyl group, 3 , 3-difluorocyclopentyl group, 3,3- dichlorocyclopentyl group, cyclohexyl group, 3- fluorocyclohexyl group, 3-chlorocyclohexyl group, 3,3- difluorocyclohexyl group, 3 , 3-dichlorocyclohexyl group, 4- fluorocyclohexyl group, 4-
  • C3-C8 cycloalkyl group optionally substituted with one or more groups selected from Group ⁇ 2 such as 4-oxycyclohexyl group, 1,4- dioxaspiro [ 4.5] decan-8-yl group, 1 , 4 -dithiaspiro [ 4.5 ] decan- 8-yl group and 4- (methoxyimino) cyclohexyl group;
  • C3-C8 cycloalkyl group optionally substituted with one or more groups selected from Group ⁇ 3 such as 7 , 7-difluoro- bicyclo [ 4.1.0] heptan-3-yl group and 7 , 7-difluoro- bicyclo [ 4.1.0] heptan-2-yl group.
  • the "C5-C8 cycloalkenyl . group optionally substituted with one or more atoms or groups selected from Groups ⁇ to ⁇ 3" used herein includes, for example, 2-cyclopentenyl group, 3-fluoro-2-cyclopentenyl group, 3-chloro-2- cyclopentenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group, 3-fluoro-2-cyclohexenyl group, 3-chloro-2- cyclohexenyl group, 4-fluoro-3-cyclohexenyl group and 4- chloro-3-cyclohexenyl group.
  • the present compound includes, for example, the following pyrimidine compounds.
  • a pyrimidine compound of Formula (1) wherein R 1 is hydrogen, R 2 is hydrogen or amino group, G 1 is nitrogen or -CR 5 , and R 5 is hydrogen.
  • a pyrimidine compound of Formula (1) wherein R 1 is hydrogen, R 2 is hydrogen, G 1 is nitrogen or -CR 5 , and R 5 is hydrogen.
  • a pyrimidine compound of Formula (1) wherein R 1 is hydrogen, R 2 is hydrogen, G 1 is -CR 5 , and R 5 is hydrogen.
  • a pyrimidine compound of Formula (1) wherein R 4 is methyl group is a pyrimidine compound of Formula (1) wherein R 4 is methyl group .
  • a pyrimidine compound of Formula (1) wherein Cyc is 3- to 8-membered saturated heterocyclic group containing one atom or group selected from the group consisting of oxygen, -S( 0) n - and -NR 6 - as a ring component wherein R 6 is as defined above, and the 3- to 8-membered saturated heterocyclic group may be optionally substituted with one or more atoms or groups selected from Groups ⁇ to ⁇ 3; C3- C8 cycloalkyl group optionally substituted with one or more atoms or groups selected from Groups ⁇ to ⁇ 3; or C5-C8 cycloalkenyl group optionally substituted with one or more atoms or groups selected from Groups ⁇ to ⁇ 3.
  • a pyrimidine compound of Formula (1) wherein Cyc is 3- to 8-membered saturated heterocyclic group containing one atom or group selected from the group consisting of oxygen, -S( 0) n - and -NR 6 - as a ring component wherein R 6 is as defined above, and the 3- to 8-membered saturated heterocyclic group may be optionally substituted with one or more atoms or groups selected from Groups ⁇ to ⁇ 3; C3- C8 cycloalkyl group optionally substituted with one or more atoms or groups selected from Groups ⁇ to ⁇ 3; or C5-C8 cycloalkenyl group optionally substituted with one or more atoms or groups selected from Groups ⁇ to ⁇ 3.
  • a pyrimidine compound of Formula (1) wherein Cyc is 3- to 8-membered saturated heterocyclic group containing one atom or group selected from the group consisting of oxygen, -S( 0) n - and -NR 6 - as a ring component wherein R 6 is as defined above, and the 3- to 8-membered.
  • saturated heterocyclic group may be optionally substituted with one or more atoms or groups selected from the group consisting of C1-C3 alkyl group optionally substituted with one or more halogens, and halogen; C3-C8 cycloalkyl group optionally substituted with one or more halogens; or C5-C8 cycloalkenyl group optionally substituted with one or more halogens.
  • a pyrimidine compound of Formula (1) wherein Cyc is 3- to 6-membered saturated heterocyclic group containing one atom or group selected from the group consisting of oxygen, -S( 0) n - and -NR 6 - as a ring component wherein R 6 is as defined above, and the 3- to 6-membered saturated heterocyclic group may be optionally substituted with one or more atoms or groups selected from the group consisting of C.1-C3 alkyl group optionally substituted with one or more halogens, and halogen; C3-C6 cycloalkyl group optionally substituted with one or more halogens; or C5-C6 cycloalkenyl group optionally substituted with one or more halogens.
  • a pyrimidine compound of Formula (1) wherein Cyc is 3-, to 6-membered saturated heterocyclic group containing one group selected from the group consisting of -S( 0) n - and - NR 6 - as a ring component wherein R 6 is as defined above, and the 3- to 6-membered saturated heterocyclic group may be optionally substituted with one or more atoms or groups selected from the group consisting of C1-C3 alkyl group optionally substituted with one or more halogens, and halogen; C3-C6 cycloalkyl group optionally substituted with one or more halogens; or C5-C6 cycloalkenyl group optionally substituted with one or more halogens.
  • a pyrimidine compound of Formula (1) wherein Cyc is 3- to 6-membered saturated heterocyclic group containing one group selected from the group consisting of -S( 0) n - and - NR 6 - as a ring component wherein R 6 is as defined above, and the 3- to 6-membered saturated heterocyclic group may be optionally substituted with one or more atoms or groups selected from the group consisting of C1-C3 alkyl group optionally substituted with one or more fluorine atoms, fluorine and chlorine; C3-C6 cycloalkyl group optionally substituted with one or more fluorine or chlorine atoms; or C5-C6 cycloalkenyl group optionally substituted with one or more fluorine or chlorine atoms.
  • a pyrimidine compound of .Formula (1) wherein Cyc is 3- to 6-membered saturated heterocyclic group containing one - S( 0) n ⁇ as a ring component wherein the 3- to 6-membered saturated heterocyclic group may be optionally substituted with one or more atoms or groups selected from the group consisting of C1-C3 alkyl group optionally substituted with one or more fluorine atoms, fluorine and chlorine; C3-C6 cycloalkyl group optionally substituted with one or more fluorine or chlorine atoms; or C5-C6 cycloalkenyl group optionally substituted with one or more fluorine or chlorine atoms .
  • a pyrimidine compound of Formula (1) wherein Cyc is a group of Jl, p is 0, and Y is -S( 0) n -.or CR 1:L R 12 wherein n is 0, 1 or 2, R 11 is fluorine or chlorine, and R 12 is hydrogen, fluorine or chlorine.
  • a pyrimidine compound of Formula (1) wherein Cyc is a group of Jl, p is 0, Y is -S( 0) n -, and n is 0, 1 or . 2.
  • a pyrimidine compound of Formula (1) wherein Cyc is a group of Jl, p is 0, Y is -S( 0) n -, and n is 0.
  • a pyrimidine compound of Formula (1) wherein Cyc is a group of Jl, p is 0, Y is -S( 0) n -, and n is 1.
  • a pyrimidine compound of Formula (1) wherein Cyc is a group of Jl, p is 0, Y is -S( 0) n -, and n is 2.
  • a pyrimidine compound of Formula (1) wherein A is a single bond; Cyc is a group of Jl or J2; R 8 is fluorine or chlorine; R 9 and R 10 are independently selected from the group consisting of C1-C3 alkyl group. optionally substituted with fluorine or chlorine, fluorine and chlorine; and is -S( 0) n - or CR R 12 wherein is 0, 1 or 2, R 11 is fluorine or chlorine, and R 12 is hydrogen, fluorine or chlorine.
  • a pyrimidine compound of Formula (1) wherein A is a single bond; Cyc is a group of Jl; R 9 is C1-C3 alkyl group optionally substituted with fluorine or chlorine, fluorine, or chlorine; p is an integer of 0 to 2; and Y is -S( 0) n _ or -CR 1]" R 12 - wherein n is 0, 1 or 2, R 11 is fluorine or chlorine, and R 12 is hydrogen, fluorine or chlorine.
  • a pyrimidine compound of Formula (1) wherein A is a single bond; Cyc is a group of Jl; R 9 is C1-C3 alkyl group optionally substituted with fluorine or fluorine; p is an integer of 0 to 2; and Y is -S( 0) n - or -CR 1:L R 12 - wherein n is 0, 1 or 2, R 11 is fluorine, and R 12 is hydrogen or fluorine .
  • a pyrimidine compound of Formula (1) wherein A is a single bond; Cyc is a group of Jl; R 9 is C1-C3 alkyl group optionally substituted with chlorine or chlorine; p is an integer of 0 to 2; and Y is -S( 0) n - or -CR T - wherein n is 0, 1 or 2, R 11 is chlorine, and R 12 is hydrogen or chlorine.
  • a pyrimidine compound of Formula (1) wherein A is a single bond, Cyc is a group of Jl, p is 0, and Y is - S( 0) n - or CR 1:L R 12 wherein n is 0, 1 or 2, .
  • R 11 is fluorine or chlorine, and R 12 is hydrogen, fluorine or chlorine.
  • a pyrimidine compound of Formula (1) wherein A is a single bond, Cyc is a group of Jl, p is 0, Y is -S ⁇ 0) n - r and n is 0, 1 or 2.
  • R 2 is -hydrogen or amino group
  • R 3 is hydrogen
  • R 4 is C1-C6 alkyl group optionally substituted with one or more halogens, C1-C6 alkoxy group optionally substituted with one or more halogens, hydrogen, halogen, amino group, nitro group or cyano group;
  • a pyrimidine compound of Formula (1) wherein Q is oxygen; R 1 is hydrogen; R 2 is hydrogen or amino group; G 1 is nitrogen or -CR 5 wherein R 5 is hydrogen; R 3 is hydrogen; R 4 is C1-C6 alkyl group optionally substituted with one or more halogens, C1-C6 alkoxy group optionally substituted with one or more halogens, hydrogen, halogen, amino group, nitro group or cyano group; and Cyc is a group of Jl or J2.
  • R 1 is hydrogen
  • R 2 is hydrogen or amino group
  • R 3 is hydrogen
  • R 4 is hydrogen, fluorine, chlorine, bromine, iodine, amino group, methyl group, ethyl group or methoxy group
  • a pyrimidine compound of Formula (1) wherein Q is oxygen; R 1 is hydrogen; R 2 is hydrogen or amino group; G 1 is nitrogen or -CR 5 wherein R 5 is hydrogen; R 3 is hydrogen; R 4 is hydrogen, fluorine, chlorine, bromine, iodine, amino group, methyl group, ethyl group or methoxy group; A is a single bond; and Cyc is a group of Jl or J2.
  • a pyrimidine compound of Formula (1) wherein Q is oxygen; R 1 is hydrogen; R 2 is hydrogen; G 1 is nitrogen; R 3 is hydrogen; R 4 is hydrogen, chlorine or methyl group; A is a single bond; Cyc is a group of Jl; R 9 is C1-C3 alkyl group optionally substituted with fluorine or chlorine, fluorine, or chlorine; p is 0 or 1; and Y is -S( 0) n - or - CR 11 R 12 - wherein n is 0, 1 or 2, R 11 is fluorine or chlorine, and R 12 is hydrogen, fluorine or chlorine.
  • a pyrimidine compound of Formula (1-vi) is a pyrimidine compound of Formula (1-vi) :
  • R 1 , R 2 , R 3 , R 4 , G 1 and Z are as defined above.
  • the present compound can be prepared by, for example, the following Processes A to G.
  • R 1 , R 2 , R 3 , R 4 , A, Cyc and G 1 are as defined above, and Q' is oxygen or sulfur [hereinafter, referred to as the present compound (1-i)]
  • R 1 , R 2 , R 3 , R 4 and G 1 are as defined above
  • solvent used herein includes, example, water; ether such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and tert-butyl methyl ether; halogenated hydrocarbon such as dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, and chlorobenzene ; hydrocarbon such as toluene, benzene, and xylene; nitrile such as acetonitrile; an aprotic polar solvent such as N,N- dimethylformamide, N-methylpyrrolidone (hereinafter, referred to as NMP) , 1 , 3-dimethyl-2-imidazolidinone, and dimethylsulfoxide ; and a mixture thereof.
  • solvent used herein includes, example, water; ether such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and tert-butyl
  • the amount of Compound (3) used herein is generally 1 mol to 2 mol per 1 mol of Compound (2) .
  • the reaction is generally carried out in the presence of a base.
  • the base used herein includes, for example, a nitrogen-containing heterocyclic compound such as pyridine, picoline, 2 , 6-lutidine, 1, 8-diazabicyclo [5.4.0] -undec-7-ene (hereinafter, referred to as DBU) , and 1,5- diazabicyclo [ 4.3.0 ] -non-5-ene ; tertiary amine such as triethylamine and N-ethyldiisopropylamine ; and an inorganic base such as potassium carbonate and sodium hydride.
  • the amount of the base used herein is generally 1 mol or more per 1 mol of Compound (2) .
  • the reaction temperature is generally in the range of
  • reaction time is generally in the range of 0.1 hour to 24 hours.
  • the present compound (1-i) can be isolated by pouring the reaction mixture into water, extracting the organic solvent, and then concentrating the organic layer; or by pouring the reaction mixture into water, and then collecting the resultant solid with a filter; or by collecting the solid generated in the reaction mixture with a filter.
  • the isolated present compound (1-i) can be further purified by, for example, recrystallization and chromatography.
  • the present compound (1-i) can be prepared by reacting a compound of Formula (4) :
  • R 1 , R 2 and G 1 are as defined above [hereinafter, referred to as Compound (5)].
  • the reaction is carried out in the presence or absence of a solvent.
  • the solvent used herein includes, for example, water; ether such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and tert-butyl methyl ether; halogenated hydrocarbon such as dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, and chlorobenzene ; hydrocarbon such as toluene, benzene, and xylene; nitrile such as acetonitrile; an aprotic polar solvent such as N,N- dimethylformamide , NMP, 1, 3-dimethyl-2-imidazolidinone, and dimethylsulfoxide; and a mixture thereof.
  • the amount of Compound (5) used herein is generally 1 mol to 2 mol per 1 mol of Compound (4) .
  • the reaction is generally carried out in the presence of a base.
  • the base used herein includes, for example, a nitrogen-containing heterocyclic compound such as pyridine, picoline, 2, 6-lutidine, DBU, and 1 , 5-diazabicyclo [ 4.3.0] - non-5-ene; tertiary amine such as triethylamine and N- ethyldiisopropylamine; and an inorganic base such as potassium carbonate and sodium hydride.
  • the amount of the base used herein is generally 1 mol or more per 1 mol. of Compound (4) .
  • the reaction temperature is generally in the range of -20°C to 100°C.
  • the reaction time is generally in the range of 0.1 hour to 24 hours.
  • the present compound (1-i) can be isolated by pouring the reaction mixture into water, extracting the organic solvent, and then concentrating the organic layer; or by pouring the reaction mixture into water, and then collecting the resultant solid with a filter; or by collecting the solid generated in the reaction mixture with a filter.
  • the isolated present compound (1-i) can be further purified by, for example, recrystallization and chromatography.
  • the present compound (1-i) can be prepared by reacting a compound of Formula (6) :
  • R 1 , R 2 , R 3 , R 4 and G 1 are as defined above [hereinafter, referred to as Compound (6)]
  • the reaction is carried out in the presence or absence of a solvent.
  • the solvent used herein includes, for example, water; ether such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and tert-butyl methyl ether; halogenated hydrocarbon such as dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, and chlorobenzene ; hydrocarbon such as toluene, benzene, and xylene; nitrile such as acetonitrile; an aprotic polar solvent such as N,.N- dimethylformamide, NMP, 1, 3-dimethyl-2-imidazolidinone, and dimethylsulfoxide ; and a mixture thereof.
  • the amount of Compound (3) used herein is generally 1 mol to 2 mol per 1 mol of Compound (6) .
  • the reaction is generally carried out in the .presence of a base.
  • the base used herein includes, for example, a nitrogen-containing heterocyclic compound such as pyridine, picoline, 2 , 6-lutidine, DBU, and 1 , 5-diazabicyclo [ .3.0 ] - non-5-ene; tertiary amine such as triethylamine and N- ethyldiisopropylamine ; and an inorganic base such as potassium carbonate and sodium hydride.
  • the amount of the base used herein is generally 1 mol or more per 1 mol of Compound (6) .
  • the reaction temperature is generally in the range of -20°C to 100°C.
  • the reaction time is generally in the range of 0.1 hour to 24 hours.
  • the present compound . (1-i) can be isolated by pouring the reaction mixture into water, extracting the organic solvent, and then concentrating the organic layer; or by pouring the reaction mixture into water, and then collecting the resultant solid with a filter; or by collecting the solid generated in the reaction mixture with a filter.
  • the isolated present compound (1-i) can be further purified by, for example, recrystallization and chromatography.
  • the present compound (1-i) can be prepared by reacting a compound of Formula (7) :
  • R 1 , R 2 , R 3 ,. R 4 , G 1 and Q' are as defined above [hereinafter, referred to as Compound (7)] with a compound of Formula (8) :
  • a and Cyc are as defined above, and L is a leaving group such as chlorine, bromine, iodine, p- toluenesulfonyloxy group and methanesulfonyloxy group [hereinafter, referred to as Compound (8)].
  • the reaction is carried out in the presence or absence of a solvent.
  • the solvent used herein includes, for example, water; ether such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and tert-butyl methyl ether; halogenated hydrocarbon such as dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, and chlorobenzene ; hydrocarbon such as toluene, benzene, and xylene; nitrile such as acetonitrile ; an aprotic polar solvent such as N,N- dimethylformamide, NMP, 1, 3-dimethyl-2-imidazolidinone, and dimethylsulfoxide ; and a mixture thereof.
  • the amount of Compound (8) used herein is generally 1 mol to 2 mol per 1 mol of Compound (7) .
  • the reaction is generally carried out in . the presence of a base.
  • the base used herein includes, for example, a nitrogen-containing heterocyclic compound such as pyridine, picoline, 2 , 6-lutidine, DBU, and 1 , 5-diazabicyclo [ 4.3.0 ] - non-5-ene; tertiary amine such as triethylamine and N- ethyldiisopropylamine ; and an inorganic base such, as potassium carbonate and sodium hydride.
  • the amount of the base used herein is generally 1 mol or more per 1 mol of Compound (7) .
  • the reaction temperature is generally in the range of -20°C to 100°C.
  • the reaction time is generally in. the range of 0.1 hour to 24 hours.
  • (1-i) can be isolated by pouring the reaction mixture into water, extracting the organic solvent, and then concentrating the organic layer; or by pouring the reaction mixture into water, and then collecting the resultant solid with a filter; or by collecting the solid generated in the reaction mixture with a filter.
  • the isolated present compound (1-i) can be further purified by, for example, recrystallization and chromatography.
  • R 1 , R 2 , R 3 , R 4 and G 1 are as defined above, and n-1 is 1 or 2 [hereinafter, referred to as the present compound (1-ii)]
  • the reaction is generally carried out in the presence of a solvent.
  • the solvent used herein includes, for example, aliphatic halogenated hydrocarbon such as dichloromethane and chloroform; alcohol such as methanol and ethanol; acetic acid; water; and a mixture thereof.
  • the oxidizing agent used herein includes, for example, hydrogen peroxide solution, sodium periodate and m- chloroperbenzoic acid.
  • the amount of oxidizing agent used herein is generally 1 mol to 1.2 mol per 1 mol of Compound (1-iii) .
  • the amount of oxidizing agent used herein is generally 2 mol to 3 mol per 1 mol of Compound (1-iii) .
  • the reaction temperature is generally in the range of -20°C to 80°C.
  • the reaction time is generally in the range W 201
  • the present compound (1-ii) can be isolated by post treatments such as extracting the reaction mixture with an organic solvent, optionally washing the organic layer with an aqueous solution of a reducing agent (e.g. sodium sulfite and sodium thiosulfate) or a base (e.g. sodium bicarbonate), and then drying and concentrating the resultant mixture.
  • a reducing agent e.g. sodium sulfite and sodium thiosulfate
  • a base e.g. sodium bicarbonate
  • R 1 , R 2 , R 3 , R 4 , Z and G 1 are as defined above [hereinafter, referred to as the present compound (l-vi)] or a compound of Formula (1-vii) :
  • R 1 , R 2 , R 3 , R 4 , Z and G 1 are as defined above [hereinafter, referred to as the present compound (1-vii)] can be prepared by reacting a compound of Formula (1-viii):
  • R 1 , R 2 , R 3 , R 4 and G 1 are as defined above [hereinafter, referred to as the present compound (1-viii)] with a halogenating agent.
  • the halogenating agent used herein is a fluorinating agent, and the fluorinating agent includes, for example, (diethylamino) sulfur trifluoride (hereinafter, referred to as DAST) , bis ( 2-methoxyethyl ) aminosulfur trifluoride and 2 , 2-difluoro-1 , 3-dimethyl-imidazolidine .
  • DAST diethylamino sulfur trifluoride
  • DAST bis ( 2-methoxyethyl ) aminosulfur trifluoride and 2 , 2-difluoro-1 , 3-dimethyl-imidazolidine .
  • the reaction is generally carried out in the presence of a solvent.
  • the solvent used herein includes, for example, ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and tert-butyl methyl ether; halogenated hydrocarbons such as dichloromethane , chloroform, carbon tetrachloride, 1, 2-dichloroethane, and chlorobenzene ; hydrocarbons such as toluene, benzene, and xylene; nitriles such as acetonitrile ; aprotic .
  • polar solvents such as N,N- dimethylformamide, NMP, 1, 3-dimethyl-2-imidazolidinone, and dimethylsulfoxide; and a mixture thereof.
  • the amount of the fluorinating agent used herein is generally 1 mol to 4 mol per 1 mol of the present compound (1-viii) .
  • the reaction temperature is generally in the range of -20°C to 100°C.
  • the reaction time is generally in the range of 0.1 hour to 24 hours.
  • the present compounds (1-vi) and (1-vii) can. be isolated by pouring the reaction mixture into water and then extracting the organic solvent, or by collecting the resultant precipitate with a filter.
  • the isolated present compounds (1-vi) and (1-vii) can be further purified by, for example, recrystallization and chromatography .
  • the halogenating agent used herein is a chlorinating agent, and the chlorinating agent includes, for example, tungsten hexachloride .
  • the reaction is generally carried out in the presence of a solvent.
  • the solvent used herein includes, for example, ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and tert-butyl methyl ether; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, and chlorobenzene ; hydrocarbons such as toluene, benzene, and xylene; nitriles such as acetonitrile; aprotic polar solvents such as N,N- dimethylformamide, NMP, 1, 3-dimethyl-2-imidazolidinone, and dimethylsulfoxide ; and a mixture thereof.
  • the amount of the chlorinating agent used herein is generally 1 mol to 4 mol per 1 mol of the present compound ( 1-viii ) .
  • the reaction temperature is generally in the range of -20°C to 100°C.
  • the reaction time is generally in the range of 0.1 hour to 24 hours.
  • the present compounds (1-vi) and (1-vii) can be isolated by pouring the reaction mixture into water and then extracting the organic solvent, or by collecting the resultant precipitate with a filter.
  • the isolated present compounds (1-vi) and (1-vii) can be further purified by, for example, recrystallization and chromatography.
  • the halogenating agent used herein is a brominating agent, and the brominating agent includes, for example, bromine, boron tribromide, boron pentabromide , and a mixture thereof.
  • Compound (2) can be prepared by reacting a compound of Formula ( 9 ) :
  • the reaction is carried out in the presence or absence of a solvent.
  • the solvent used herein includes, for example, water; ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and tert-butyl methyl ether; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1 , 2-dichloroethane, and chlorobenzene ; hydrocarbons such as toluene, benzene, and xylene; nitriles such as acetonitrile; aprotic polar solvents such as N,N- dimethylformamide, NMP, 1, 3-dimethyl-2-imidazolidinone, and dimethylsulfoxide; and a mixture thereof.
  • the amount of Compound (5) used herein is generally 1 mol to 2 mol per 1 mol of Compound (9) .
  • the reaction is generally carried out in the presence of a base.
  • the base used herein includes, for example, a nitrogen-containing heterocyclic compound such as pyridine, picoline, 2, 6-lutidine, DBU, and 1 , 5-diazabicyclo [ 4.3.0 ] - ⁇ -5-ene; tertiary amine such as triethylamine and N- ethyldiisopropylamine ; and an inorganic base such as potassium carbonate and sodium hydride.
  • the amount of the base used herein is generally 1 mol or more per 1 mol of Compound (9) .
  • the reaction temperature is generally in the range of -20°C to 100°C.
  • the reaction time is generally in the range of 0.1 hour to 24 hours.
  • Compound (2) can be isolated by pouring the reaction mixture into water, extracting the organic solvent, and then concentrating the organic layer; or by pouring the reaction mixture into water, and then collecting the resultant solid with a filter; or by collecting the solid generated in the reaction mixture with a filter.
  • the isolated Compound (2) can be further purified by, for example, recrystallization and chromatography.
  • R 1"1 is C1-C3 chain hydrocarbon group optionally substituted with one or more halogens, or hydrogen; and and R 4 are as defined above [hereinafter, referred to
  • R 29 is C1-C6 alkyl group optionally substituted with one or more halogens, and R 1"1 are as defined above [hereinafter, referred to as Compound (11)].
  • the reaction is carried out in the presence or absence of a solvent.
  • the solvent used herein includes, for example, water; ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and tert-butyl methyl ether; halogenated hydrocarbons such as dichloromethane , chloroform, carbon tetrachloride, 1, 2-dichloroethane, and chlorobenzene ; hydrocarbons such as toluene, benzene, and xylene; nitriles such as acetonitrile; aprotic polar solvents such as N,N- dimethylformamide, NMP, 1 , 3-dimethyl-2-imidazolidinone , and dimethylsulfoxide; and a mixture thereof.
  • the amount of Compound (11) used herein is generally 1 mol to 2 mol per 1 mol of Compound (10) .
  • the reaction temperature is generally in the range of -20°C to 100°C.
  • the reaction time is generally in the range of 0.1 hour to 24 hours.
  • Compound (2-i) can be isolated by pouring the reaction mixture into water, extracting the organic solvent, and then concentrating the organic layer.
  • the isolated Compound (2-i) can be further purified by, for example, chromatography and distillation.
  • Compound (10) can be prepared by reacting Compound (9) with hydrazine.
  • the reaction is carried out in the presence or absence of a solvent.
  • the solvent used herein includes, for example, water; ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and tert-butyl methyl ether; halogenated hydrocarbons such as dichloromethane , chloroform, carbon tetrachloride, 1 , 2-dichloroethane, and chlorobenzene ; hydrocarbons such as toluene, benzene, and xylene; nitriles such as acetonitrile; aprotic polar solvents such as N,N- dimethylformamide, NMP, 1 , 3-dimethyl-2-imidazolidinone , and dimethylsulfoxide ; and a mixture thereof.
  • the hydrazine used herein includes, for example, hydrazine and hydrazine hydrate.
  • the amount of hydrazine used herein is generally 1 mol to 10 mol per 1 mol of Compound (9) .
  • the reaction is generally carried out in the presence of a base.
  • the base used herein includes, for example, a nitrogen-containing heterocyclic compound such as pyridine, picoline, 2 , 6-lutidine, DBU, and 1 , 5-diazabicyclo [ .3.0] - non-5-ene; tertiary amine such as triethylamine and N- ethyldiisopropylamine; and an inorganic base such as potassium carbonate and sodium hydride.
  • the amount of the base used herein is generally 1 mol or more per 1 mol of Compound ( 9 ) .
  • the reaction temperature is generally in the range of 0°C to 100°C.
  • the reaction time is generally in the range of 0.1 hour to 24 hours.
  • Compound (10) can be isolated by pouring the reaction mixture into water, extracting the organic solvent, and then concentrating the organic layer; or by pouring the reaction mixture into water, and then collecting the resultant solid with a filter; or by collecting the solid generated in the reaction mixture with a filter.
  • the isolated Compound (10) can be further purified by, for example, recrystallization and chromatography.
  • Compound (4) can be prepared by reacting Compound (9) and Compound (3) .
  • the reaction is carried out in the presence or absence of a solvent.
  • the solvent used herein includes, for example, water; ethers such as 1,4-dioxane, diethyl ether, tetrahydrof.uran, and tert-butyl methyl ether; .
  • halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, and chlorobenzene
  • hydrocarbons such as toluene, benzene, and xylene
  • nitriles such as acetonitrile
  • aprotic polar -solvents such as N,N- dimethylformamide, NMP, 1 , 3-dimethyl-2-imidazolidinone, and dimethylsulfoxide; and a mixture thereof.
  • the amount of Compound (3) used herein is generally 1 mol to 2 mol per 1 mol of Compound (9) .
  • the reaction is generally carried out in the presence of a base.
  • the base used herein includes, for example, a nitrogen-containing heterocyclic compound such as pyridine, picoline, 2 , 6-lutidine, DBU, and 1 , 5-diazabicyclo [ 4.3.0 ] - non-5-ene; tertiary amine such as triethylamine and N- ethyldiisopropylamine; and an inorganic base such as potassium carbonate and sodium hydride.
  • the amount of the base used herein is generally 1 mol or more per 1 mol of Compound (9) .
  • the reaction temperature is generally in the range of 0°C to 100°C.
  • the reaction time is generally in the range of 0.1 hour to 24 hours *
  • Compound (4) can be isolated by pouring the reaction mixture into water and then extracting the organic solvent.
  • the isolated Compound (4) can be further purified by, for example, chromatography [0069]
  • Compound (6) can be prepared by reacting Compound (9) with Compound (5) .
  • the reaction is carried out in the presence or absence of a solvent.
  • the solvent used herein includes, for example, water; ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and tert-butyl methyl ether; halogenated hydrocarbons .
  • the amount of Compound (5) used herein is generally 2 mol to 3 mol per 1 mol of Compound (9) .
  • the reaction is generally carried out in the presence of a base.
  • the base used herein includes, for example, a nitrogen-containing heterocyclic compound such as pyridine, picoline, 2, 6-lutidine, DBU, and 1 , 5-diazabicyclo [ 4.3.0 ] - non-5-ene; tertiary amine such as triethylamine and N- ethyldiisopropylamine; and an inorganic base such as potassium carbonate and sodium hydride.
  • the amount of the base used herein is generally 2 mol or more per 1 mol of Compound (9) .
  • the reaction temperature is generally in the range of 0°C to 100°C.
  • the reaction time is generally in the range of 0.1 hour to 24 hours.
  • Compound (6) can be isolated by pouring the reaction mixture into water, extracting the organic solvent, and then concentrating the organic layer; or by pouring the reaction mixture into water, and then collecting the resultant solid with a filter; or by collecting the solid generated in the reaction mixture with a filter.
  • the isolated Compound (.6) can be further purified by, for example, recrystallization and chromatography.
  • R 1 , R 2 , R 3 , R 4 and G 1 are as defined above.
  • the reaction is carried out in the presence of water as well as a base or an acid.
  • a solvent is optionally used herein, and the solvent includes, for example, ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran, tert-butyl methyl ether, and diglyme; hydrocarbons such as toluene, benzene, and xylene; and nitriles such as acetonitrile .
  • the base used herein includes, for example, an inorganic base such as potassium carbonate , sodium hydroxide, potassium hydroxide, and sodium hydride; a nitrogen-containing heterocyclic compound such as pyridine, picoline, 2 , 6-lutidine, DBU, and 1 , 5-diazabicyclo [ 4.3.0 ] - non-5-ene; and tertiary amine such as triethylamine and N- ethyldiisopropylamine .
  • the amount of the base used herein is generally 0.1 mol to 4 mol per 1 mol of Compound (6) .
  • the acid used herein includes, for example, an inorganic acid such as hydrochloric acid, hydrobromic acid, and sulfuric acid; and an organic acid such as acetic acid and p-toluenesulfonic acid.
  • an inorganic acid such as hydrochloric acid, hydrobromic acid, and sulfuric acid
  • an organic acid such as acetic acid and p-toluenesulfonic acid.
  • the reaction temperature is generally in the range of 20°C to 120°C.
  • the reaction time is generally in the range of 0.1 hour to 24 hours.
  • Compound (7-i) can be isolated by pouring the reaction mixture into water, extracting the organic solvent, and then concentrating the organic layer; or by pouring the reaction mixture into water, and ⁇ then collecting the resultant solid with a filter; or by collecting the solid generated in the reaction mixture with a filter.
  • the isolated Compound (7- i) can be further purified by, for example, recrystallization and chromatography.
  • the reaction is carried out in the presence or absence of a solvent.
  • the solvent used herein includes, for example, ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran, tert-butyl methyl ether, and diglyme; halogenated hydrocarbons such as dichloromethane , chloroform, carbon tetrachloride, 1 , 2-dichloroethane , and chlorobenzene ; hydrocarbons such as toluene, benzene, and xylene; nitriles such as acetonitrile; pyridine derivatives such as pyridine, picoline, and lutidine; and a mixture thereof.
  • the sulfidizing agent used herein includes, for example, phosphorus pentasulfide and Lawesson's reagent [i.e. 2 , 4-bis- ( 4 -methoxyphenyl ) -1, 3-dithia-2, 4- diphosphetane 2 , 4-disulfide] .
  • the amount of the sulfidizing agent used herein is generally 1 mol or more per 1 mol of Compound (7-i) .
  • the reaction temperature is generally in the range of
  • reaction time is generally in the range of 1 hour to 24 hours.
  • Compound (7-ii) can be. isolated by pouring the reaction mixture into water, extracting the organic solvent, and then concentrating the organic layer; or by pouring the reaction mixture into water, and then collecting the resultant solid with a filter; or by collecting the solid generated in the reaction mixture with a filter.
  • the isolated Compound (7- ii) can be further purified by, for example, recrystallization and chromatography.
  • R 1 and R 3 are hydrogen; Q is oxygen; and Cyc, A, and R 2 are any one of the combinations listed in Tables to 6.
  • R 1 and R 3 are hydrogen; Q is oxygen; and Cyc, A, and R 2 are any one of the combinations listed in Tables to 6.
  • R 1 and R 3 are hydrogen; Q is oxygen; and Cyc, A, G 1 and R 2 are any one of the combinations listed in Tables 1 to 6.
  • R 1 and R 3 are hydrogen; Q is oxygen; and Cyc, A, G 1 and R 2 are any one of the combinations listed in Tables 1 to 6.
  • R 1 and R 3 are hydrogen; Q is oxygen; and Cyc, A, and R are any one of the combinations listed in Tables to 6.
  • R 1 and R 3 are hydrogen; Q is oxygen; and Cyc, A, G 1 and R are any one of the combinations listed in Tables 1 to 6.
  • a compound of Formula (G) W 201
  • R 1 and R 3 are hydrogen; Q is oxygen; and Cyc, A, and R 2 are any one of the combinations listed in Tables to 6.
  • R 1 and R 3 are hydrogen; Q is sulfur; and Cyc, A, G 1 and R 2 are any one of the combinations listed in Tables 1 to 6.
  • R 1 and R 3 are hydrogen; Q is sulfur; and Cyc, A, ... G 1 and R 2 are any one of the combinations listed in Tables 1 to 6. [0088] .
  • R 1 and R 3 are hydrogen; Q is sulfur;, and Cyc, A, G 1 and R 2 are any one of the combinations listed in Tables 1 to 6.
  • the present compounds are effective against pests such as harmful arthropods (e.g. harmful insects and mites), nematodes, and mollusks.
  • pests such as harmful arthropods (e.g. harmful insects and mites), nematodes, and mollusks.
  • harmful arthropods e.g. harmful insects and mites
  • nematodes e.g. nematodes
  • mollusks mollusks
  • Planthoppers such as small brown planthopper (Laodelphax striatellus) , brown rice planthopper ⁇ Nilaparvata lugens) , and white-backed rice planthopper ⁇ Sogatella furcifera) ; leafhoppers
  • ⁇ Deltocephalidae such as green rice leafhopper ⁇ Nephotettix cincticeps) , Taiwan green rice leafhopper (Nephotettix virescens) , and tea green leafhopper (Empoasca onukii) ; aphids (Aphididae) such as cotton aphid ⁇ Aphis gossypii) , green peach aphid ⁇ Myzus persicae) , cabbage aphid ⁇ Brevicoryne brassicae) , spirea aphid (Aphis spiraecola) , potato aphid (Macrosiphum euphorbiae) , foxglove aphid (Aulacorthum solani) , oat bird-cherry aphid (Rhopalosiphum padi) , tropical citrus aphid (Toxoptera citricidus) , and mealy plum a
  • Lepidoptera Pyralid moths (Pyralidae) such as rice stem borer (Chilo suppressalis) , yellow stem borer [Tryporyza incertulas) , rice leafroller [Cnaphalocrocis medinalis) , cotton leafroller (Notarcha derogata) , indian meal moth (Plodia interpunctella) , oriental corn borer ⁇ Ostrinia furnacalis) .
  • cabbage webworm [Hellula undalis) , and bluegrass webworm ⁇ Pediasia teterrellus) ; owlet moths (Noctuidae) such as common cutworm ⁇ Spodoptera litura) , beet armyworm ⁇ Spodoptera exigua) , rice armyworm (Pseudaletia separata) , . cabbage armyworm ⁇ Mamestra brassicae) , black cutworm (Agrotis ipsilon) , beet semi- looper (Plusia nigrisigna) , Thoricoplusia spp.
  • Noctuidae such as common cutworm ⁇ Spodoptera litura) , beet armyworm ⁇ Spodoptera exigua) , rice armyworm (Pseudaletia separata) , . cabbage armyworm ⁇ Mamestra brassicae) , black cutworm (Agrotis ipsilon) , beet semi
  • Carposinidae such as peach fruit moth ⁇ Carposina niponensis) ; lyonetiid moths ⁇ Lyonetiidae) such as Lyonetia spp.; tussock moths ⁇ Lymantriidae) such as Lymantria spp.
  • yponomeutid moths ⁇ Yponomeutidae such as diainondback moths ⁇ Plutella xylostella)
  • gelechiid moths such as pink bollworm (Pectinophora gossypiella) and potato tubeworm ⁇ Phthorimaea operculella)
  • tiger moths ⁇ Arctiidae such as fall webworm ⁇ Hyphantria cunea)
  • tineid moths (Tineidae) such as casemaking clothes moth ⁇ Tinea translucens) and webbing clothes moth (Tineola bisselliella) ; and the like.
  • Thrips ⁇ Thripidae such as yellow citrus thrip ( Frankliniella occidentalis) , melon thrip ⁇ Thrips peri) , yellow tea thrip ⁇ Scirtothrips dorsalis) , onion thrip ⁇ Thrips tabaci) , flower thrip ⁇ Frankliniella intonsa) , and the like.
  • Diptera House mosquitos (Culex) such as common house mosquito ⁇ Culex pipiens pallens) , small house mosquito
  • Anopheles spp. such as Chinese anopheles
  • Chroma tomyia horticola Chroma tomyia horticola
  • frit flies Chloropidae
  • rice stem maggot Chlorops oryzae
  • Tephritidae such as melon fly (Dacus cucurbitae) and Mediterranean fruit fly ⁇ Ceratitis capitata) ; Drosophilidae; humpbacked flies (Phoridae) such as humpbacked flies ⁇ Megaselia spiracularis) ; sand flies
  • Coleoptera Corn root worms (Diabrotica spp.) such as Western corn root worm [Diabrotica virgifera virgifera) and Sourthern corn root worm (Diabrotica undecimpunctata howardi) ; scarabs (Scarabaeidae) such as cupreous chafer (Anomala cuprea) , soybean beetle (Anomala rufocuprea) , and Japanese beetle (Popillia japonica) ; weevils
  • beetles [Bostrichidae) ; spider beetles ⁇ Ptinidae) ; longhorn beetles ⁇ Cerambycidae) such as . white-spotted longicorn beetle ⁇ Anoplophora malasiaca) ; Agriotes spp.; rove beetles (Paederus fuscipes) ; and the like.
  • Orthoptera Asiatic locust (Locusta migratoria) , African mole cricket ⁇ Gryllotalpa africana) , rice grasshopper ⁇ Oxya yezoensis) , rice grasshopper ⁇ Oxya japonica) , cricket [Gry11idae) , and the like.
  • Shiphonaptera Cat flea ⁇ Ctenocephalides felis) , dog flea ⁇ Ctenocephalides canis) , human flea ⁇ Pulex irritans) , oriental rat flea ⁇ Xenopsylla cheopis) , and the like.
  • Anoplura Human body louse ⁇ Pediculus humanus corporis), crab louse ⁇ Phthirus pubis), short-nosed cattle louse ⁇ Haematopinus eurysternus) , sheep louse ⁇ Dalmalinia ovis) , hog louse ⁇ Haematopinus suis), and the like.
  • Hymenoptera Ants ⁇ Formicidae) such as pharaoh ant
  • Termitidae Japanese subterranean termite ⁇ Reticulitermes speratus) , Formosan subterranean termite ⁇ Coptotermes formosanus), western drywood termite ( Incisitermes minor), tropical drywood termite
  • Spider mites ⁇ Tetranychidae such as two- spotted spider mite ⁇ Tetranychus urticae) , Kanzawa spider mite ⁇ Tetranychus kanzawai) , citrus red mite ⁇ Panonychus citri) , European red mite ⁇ Panonychus ulmi) , and Oligonychus spp.
  • eriophyidmites ⁇ Eriophyidae such as pink citrus rust mite ⁇ Aculops pelekassi) , pink citrus rust mite ⁇ Phyllocoptruta citri), tomato rust mite ⁇ Aculops lycopersici) , purple tea mite ⁇ Calacarus carinatus) , tea rust mite (Acaphylla theavagrans) , Japanese pear rust mite (Eriophyes chibaensis) , and apple rust .
  • mite (Aculus pointedendali) ; tarosonemid mites ⁇ Tarsonemidae) such as broad mite ⁇ Polyphagotarsonemus latus) ; false spider mites ⁇ Tenuipalpidae) such as flat mite ⁇ Brevipalpus phoenicis) ; peacock mites ⁇ Tuckerellidae) ; ticks ⁇ Ixodidae) such, as New Zealand cattle tick ⁇ Haemaphysalis .
  • acarid mites ⁇ Acaridae) such as mold mite ⁇ Tyrophagus putrescentiae) and acarid mite ⁇ Tyrophagus similis)
  • house dust mites Pyroglyphidae
  • American house dust mite ⁇ Dermatophagoides farinae and European house dust mite ⁇ Dermatophagoides ptrenyssnus
  • ⁇ Cheyletidae such as cheyletid mite ⁇ Cheyletus eruditus) , Cheyletus malaccensis and Cheyletus moorei; parasitoid mites ⁇ Dermanyssidae) such as tropical rat mite ⁇ Ornithonyssus bacoti) , northern fowl mite ⁇ Ornithonyssus sylviarum) , and poultry redmite ⁇ Dermanyssus gallinae) ; chiggers ⁇ Trombiculidae) such as Le otromj idium akamushi; spiders ⁇ Araneae) such as Japanese foliage spider ⁇ Chiracanthium japonicum) and redback spider ⁇ Latrodectus hasseltii) ; and the like.
  • parasitoid mites ⁇ Dermanyssidae such as tropical rat
  • Chilopoda House centipede ⁇ Thereuonema hilgendorfi) , Vietnam giant centipede (Scolopendra subspinipes) , and the like.
  • Diplopoda Garden millipede ⁇ Oxidus gracilis) , red millipede (Nedyopus tambanus) , and the like.
  • Isopoda Common pill bug (Armadillidium vulgare) and the like.
  • Gastropoda Tree slug (Limax marginatus) , yellow slug (Limax flavus) , and the like.
  • Nematoda Rice white-tip nematode (Aphelenchoides besseyi) , strawberry bud nematode (Nothotylenchus acris) , cotton root-knot nematode (Meloidogyne incognita) , northern root-knot nematode (Meloidogyne hapla) , tropical root-knot nematodes (Meloidogyne javanica) , soybean cyst nematode (Heterodera glycines) , potato cyst nematode (Globodera rostochiensis) , coffee root-lesion nematode (Pratylenchus coffeae) , roOt ⁇ iesion nematode (Pratylenchus neglectus) , and the like.
  • the pesticidal agent of the present invention comprises the present compound and an inert carrier.
  • the pesticidal agent of the present invention is generally formulated into, for example, an emulsion, an oil solution, a powder, a granule, a wettable powder, a flowable formulation, a microcapsule agent, an aerosol, a smoking agent, a toxic bait, or a resin formulation by mixing the present compound and an inert carrier (e.g. solid carrier, liquid carrier, and gas carrier) , and, if necessary, adding a surfactant or other formulation additives.
  • an inert carrier e.g. solid carrier, liquid carrier, and gas carrier
  • the pesticidal agent of the present invention generally contains the present compound in an amount of 0.01 wt% to 95 wt%.
  • the solid carrier used herein includes, for example, fine powders and granular materials made from, for example, clays (e.g.. kaolin clay, diatomaceous earth, bentonite, Fubasami clay, and acid clay) / synthetic hydrated silicon oxide; talc; ceramic; other inorganic minerals (e.g. sericite, quartz, sulfur, activated charcoal, calcium carbonate, and hydrated silica) ; and chemical fertilizers (e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and ammonium chloride) .
  • clays e.g... kaolin clay, diatomaceous earth, bentonite, Fubasami clay, and acid clay
  • synthetic hydrated silicon oxide talc
  • ceramic other inorganic minerals
  • other inorganic minerals e.g. sericite, quartz, sulfur, activated charcoal, calcium carbonate, and hydrated silica
  • chemical fertilizers e.g. ammonium
  • the liquid carrier used herein includes, for example, water; alcohols (e.g. methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol, ethylene glycol, propylene glycol, and phenoxy ethanol); ketones (e.g. acetone, methyl ethyl ketone, and cyclohexanone ) ; aromatic hydrocarbons (e.g. toluene, xylene, ethylbenzene, dodecylbenzene , phenylxylylethane , and methylnaphthalene) ; aliphatic hydrocarbons (e.g.
  • esters e.g.. ethyl acetate, butyl acetate, isopropyl myristate, ethyl oleate, diisopropyl adipate, diisobutyl adipate, and. propylene glycol monomethyl ether acetate
  • nitriles e.g. acetonitrile and isobutyronitrile
  • ethers e.g.
  • acid amides e.g. ⁇ ⁇ : ⁇ N, N-dimethylformamide and N,N- dimethylacetamide
  • halogenated hydrocarbons e.g. dichloromethan
  • the gas carrier used herein includes, for example, fluorocarbon, butane gas, LPG (liquefied petroleum gas), dimethyl ether and carbon dioxide gas.
  • the surfactant used herein includes,- for example, a non-ionic surfactant such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, and polyethylene glycol fatty acid ester; and an anionic surfactant such as alkyl sulfonate, alkylbenzene sulfonate, and alkyl sulfate. - [0111]
  • the other formulation additives used herein include, fixing agents, dispersing agents, colorants, stabilizers, and the like; and more specifically, casein, gelatin, saccharides (e.g. starch, gum arabic, cellulose derivatives, and alginic acid), lignin derivatives, bentonite, synthetic water-soluble polymers (e.g.
  • polyvinyl alcohols polyvinyl pyrrolidones, and polyacrylic acids
  • PAP acidic isopropyl phosphate
  • BHT 2 , 6-di-tert-butyl- -methylphenol
  • BHA a mixture of 2-tert-butyl-4 -methoxyphenol and 3-tert-butyl-4 - methoxyphenol
  • the method for controlling pests in the present invention is performed by applying an effective amount of the present compound to pests directly and/or habitats of pests (e.g. plant body, soil, indoor, and animal body).
  • pests e.g. plant body, soil, indoor, and animal body.
  • the present compound is generally used in the form of a pesticidal agent of the present invention.
  • the habitats of pests include, for example, paddy fields, dry paddy fields, fields, tea fields, orchards, non-crop lands, houses, seedling raising trays, seedling raising boxes, seedling raising soils, seedling raising mats, and water culture solutions in water culture farms.
  • the application amount thereof is 1 g to 10, 000 g of the present compound per 10, 000 m 2 .
  • the pesticidal agent of the present invention is formulated into, for example, emulsions, wettable powders, and flowable formulations, the pesticidal agent is generally diluted with water so that the active ingredient concentration thereof can be 0.01 ppm to 10,000 ppm.
  • the pesticidal agent is formulated into, for example, granules and powders, the pesticidal agent is generally used without dilution.
  • formulations and water dilutions thereof may be directly sprayed to pests or plants (e.g. crops which need to be protected from pests), or may be applied to a soil of a cultivated land in order to control pests which inhabit the soil.
  • the pesticidal agent of the present invention can also be used in the form of a resin preparation which may be, for example, processed into a sheet or a string, and then wound around crops, or put around crops, or laid on the soil surface near the root of crops.
  • the pesticidal agent of the present invention can be used for controlling pests which live in a house. When it is used at a plain surface, the application amount thereof is generally 0.01 mg to 1, 000 mg of the present compound per 1 m 2 of the treatment area; and when it is used in an open space, the application amount thereof is generally 0.01 mg to 500 mg of the present compound per 1 m 3 of the treatment space.
  • the pesticidal agent of the present invention is formulated into, for example, emulsions, wettable powders, and flowable formulations, the pesticidal agent is generally diluted with water so that the active ingredient concentration thereof can be 0.1 ppm to 1,000 ppm.
  • the pesticidal agent is formulated into, for example, oil solution, aerosol, smoking agent and toxic bait, the pesticidal agent is generally used without dilution.
  • the pesticidal agent of the present invention can be used in farmlands where the following "crops" are cultivated.
  • Agricultural crops Corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean, peanut, sarrazin, sugar beet, rapeseed, sunflower, sugar cane, tobacco, and the like.
  • Vegetables Solanaceae vegetables (e.g. eggplant, tomato, green . pepper, hot pepper, and potato) , Cucurbitaceae vegetables (e.g. cucumber, pumpkin, zucchini, watermelon, and melon), Cruciferae vegetables (e.g. Japanese radish, turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, brown mustard, broccoli, and cauliflower) , Compositae vegetables (e.g. burdock, garland chrysanthemum, artichoke, and lettuce), Liliaceae vegetables (e.g. Welsh onion, onion, garlic, and asparagus) , Umbelliferae vegetables (e.g.
  • carrot, parsley, celery, and parsnip Chenopodiaceae vegetables (e.g. spinach and Swiss chard), Labiatae vegetables (e.g. Japanese basil, mint, and basil), strawberry, sweat potato, yam, aroid, and the like.
  • Chenopodiaceae vegetables e.g. spinach and Swiss chard
  • Labiatae vegetables e.g. Japanese basil, mint, and basil
  • strawberry sweat potato, yam, aroid, and the like.
  • Fruit trees Pomaceous fruits (e.g. apple, common pear, Japanese pear, Chinese quince, and quince) , stone fleshy fruits (e.g. peach, plum, nectarine, Japanese plum, cherry, apricot, and prune), citrus plants (e.g. Satsuma mandarin, orange, lemon, lime, and grapefruit), nuts (e.g. chestnut, walnut, hazel nut, almond, pistachio, cashew nut, and macadamia nut), berry fruits (e.g. blueberry, cranberry, blackberry, and raspberry) , grape, persimmon, olive, loquat, 9.7 banana, coffee, date, coconut, oil palm, and the like.
  • Pomaceous fruits e.g. apple, common pear, Japanese pear, Chinese quince, and quince
  • stone fleshy fruits e.g. peach, plum, nectarine, Japanese plum, cherry, apricot, and prune
  • citrus plants e.
  • Trees other than fruit trees Tea, mulberry, flowering trees and shrubs (e.g. Rhododendron indicum, Camellia japonica, Hydrangea, Camellia sasanqua, Illicium anisatum, Prunus subg. Cerasus, - Liriodendron tulipifera, Lagerstroemia indica, and Osmanthus fragrans var. aurantiacus ) , street trees (e.g.
  • ash tree birch, dogwood, eucalyptus, ginkgo, lilac, maple tree, oak, poplar, cercis, Chinese sweet gum, plane tree, zelkova, Japanese arborvitae, fir tree, Japanese hemlock, needle juniper, pine, spruce, yew, elm, and horse-chestnut.) , sweet viburnum, Podocarpus macrophyllus , Japanese cedar, Japanese cypress, croton, spindle tree, Chainese howthorn, and the like.
  • Lawn Zoysia (e.g. Japanese lawn grass and mascarene grass), Bermuda grass (e.g. Cynodon dactylon) , bent grass (e.g. creeping bent grass, Agrostis stolonifera, and Agrostis tenuis), bluegrass (e.g. Kentucky bluegrass and rough bluegrass), fescue (e.g. tall fescue, chewing fescue, and creeping fescue), ryegrass (e.g. darnel and perennial. ryegrass), cocksfoot, timothy grass, and the like.
  • Zoysia e.g. Japanese lawn grass and mascarene grass
  • Bermuda grass e.g. Cynodon dactylon
  • bent grass e.g. creeping bent grass, Agrostis stolonifera, and Agrostis tenuis
  • bluegrass e.g. Kentucky bluegrass and rough bluegrass
  • fescue e.g.
  • the "crops” also include recombinant crops.
  • the pesticidal agent of the present invention can be mixed or used together with other insecticides, acaricides, nematicides, fungicides, plant growth regulators, herbicides and/or synergists.
  • insecticides acaricides, nematicides, fungicides, plant growth regulators, herbicides and/or synergists.
  • examples of the active ingredients of the above-mentioned insecticides, acaricides, nematicides, fungicides, plant growth regulators, herbicides and synergists are illustrated.
  • Methidathion (DMTP ) , Mevinphos, Monocrotophos , Naled (BRP) , Omethoate, Oxydemeton-methyl , Parathion, Parathion-methyl , Phenthoate (PAP), Phorate, Phosalone, Phosmet (PMP), Phosphamidon, Phoxim, Pirimiphos-methyl , Profenofos, Propetamphos, Prothiofos, Pyraclorfos, Pyridafenthion, Quinalphos, Sulfotep, Tebupirimfos , Temephos, Terbufos, Tetrachlorvinphos, Thiometon, Triazophos, Trichlorphon (DEP) , Vamidothion, Aluminium phosphide, Butathiofos, Dichlorodiisopropyl ether, Dichlofenthion (ECP) , Formothion, Hydrogen phosphide, Oxyde
  • Bistrifluron Chlorfluazuron, Diflubenzuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Lufenuron, Novaluron, Noviflumuron, Teflubenzuron, Triflumuron, and Fluazuron.
  • Acetoprole, Ethiprole, Fipronil, Vaniliprole, Pyriprole, and Pyrafluprole are examples of the compounds listed above.
  • Chromafenozide Halofenozide , Methoxyfenozide , and Tebufenozide .
  • R is chlorine atom, bromine atom or trifluoromethyl group
  • R 200 is chlorine atom, bromine atom or methyl group
  • R 300 is chlorine atom, bromine atom or cyano group
  • R is chlorine atom, bromine atom or iodine atom, Metoxadiazone, Sulfluramid, Arsenic acid, Benclothiaz, Calcium cyanamide, Calcium polysulfide, Metarn-ammonium, Metam-sodium, Potassium oleate, Sulfur, and Tralopyril.
  • Methyl bromide, 1 3-Dichloropropene , DCIP, Fosthiazate, Levamisol, Methyisothiocyanate, Morantel tartarate, and Im cyafos .
  • sterol biosynthesis-inhibiting compounds such as Azaconazole, Bitertanol, Bromuconazole , Cyproconazole , Difenoconazole, Diniconazole-M, Epoxiconazole, Fenarimol, Fenbuconazole, Flusilazole, Fluquinconazole , Flutriafol, Hexaconazole, Imazalil, Imibenconazole , Ipconazole, Metconazole, Myclobutanil , Nuarimol, Oxpoconazole , Pefurazoate, Penconazole, Prochloraz, Propiconazole , Prothioconazole, Pyrifenox, Simeconazole , Tebuconazole , Tetraconazole, Triadimefon, Triadimenol, Triflumizole , Trifolin, Txiticonazole, Aldimorph, Dodemorph,
  • cytostatic compounds such as Benomyl,. Carbendezim, Fuberidazole, Thiabendazole, Thiphanate, thiophanate-methyl , Diethofencarb, Zoxamide, Pencycuron, and Fluopicolide;
  • signal inhibiting compounds such as Chlozolinate, Iprodione, Procymidone, Vinclozolin, Quinoxyfen,
  • amino acid biosynthesis-inhibiting compounds such as cyprodinil, pyrimethanil , and Mepanipyrim;
  • nucleic acid biosynthesis-inhibiting compounds such as Metalaxyl, Benalaxyl, and Oxolinic acid;
  • lipid/membrane synthesis-inhibiting compounds such as Isoprothiolane, Iprobenfos, Tolclofos-methyl , Prothiocarb, Dimethomorph, Benthiavalicarb-isopropyl, . Iprovalicarb, and Mandipropamid;
  • melanin biosynthesis-inhibiting compounds such as Diclocymet, Carpropamid, Fenoxanil, Fthalide, Tricyclazole , and Pyroquilon;
  • strobilurin compounds such as Azoxystrobin, Dimoxystrobin, Enestrobin, Fluoxastrobin, Kresoxim-methyl , Metominostrobin, Orysastrobin, Picoxystrobin,
  • anilide compounds such as Carboxin, Oxycarboxin,
  • Mepronil Flutoranil, Furametopyr, Thifluzamide, Boscalid, Penthiopyrad, Fluopyram, Bixafen, Isopyrazam, Penflufen, Sedaxan, and Fluxapyrox.ad;
  • resistance induced compounds such as Acibenzolar-S- methyl, Probenazole, Tiadinil, and Isotianil
  • glucan synthesis-inhibiting compounds such as Validamycin A and Polyoxin B
  • protein biosynthesis-inhibiting compounds such as Blastcidin-S , Kasugamycin, and Streptomycin;
  • Fluometuron Isouron, Tebuthiuron, Methabenzthiazuron, Cumyluron, Daimuron, and Methyl-daimuron.
  • Atrazine Ametoryn, Cyanazine, Simazine, Propazine, Simetryn, Dimethametryn, Prometryn, Metribuzin, Triaziflam, W
  • Amiprofos-methyl Butamifos, Bensulide, Piperophos, Anilofos, Glyphosate, Glufosinate, Glufosinate-P, and Bialaphos.
  • Clodinafop-propargyl Cyhalofop-butyl , Diclofop-methyl , Fenoxaprop-ethyl , Fluazifop-butyl, Haloxyfop-methyl ,
  • Imazapyr Imazaquin
  • Imazethapyr Imazethapyr
  • a compound of Formula (1) A compound of Formula (1) :
  • Gyc-A-Q group, R 1 , R 2 , R 3 , R 4 and G 1 are defined in Tables 7 to 15.

Abstract

Pyrimidine compound of Formula (1): (1) wherein R1 is C1-C3 chain hydrocarbon group optionally substituted with one or more halogens, etc.; R2 is C1-C3 chain hydrocarbon group optionally substituted with one or more halogens, etc.; G1 is nitrogen or -CR5=, etc.; R3 is C1-C3 chain hydrocarbon group optionally substituted with one or more halogens, etc.; R4 is C1-C6 chain hydrocarbon group optionally substituted with one or more halogens, etc.; Q is oxygen, etc., Cyc is C3-C8 cycloalkyl group, etc.; and A is single bond, etc. having excellent pest control activity.

Description

DESCRIPTION
PYRIMIDINE COMPOUNDS AND THEIR USE AS PESTICIDES
Technical Field
[0001]
The present invention relates to a pyrimidine compound and use thereof for controlling pests.
Background Art
[0002]
Some compounds exhibiting a pest control activity have been discovered and developed as an active ingredient of a pesticidal agent. For example, some types of pyrimidine compounds are known as an active ingredient thereof (see, for example, Patent References 1 to 3) .
Prior Art Document
Patent Reference
[0003]
[Patent. Reference 1] WO 2009/005690
[Patent Reference 2] WO 2008/098143
[Patent Reference 3] WO 2007/076473
Summary of Invention (Technical Problem)
[0004]
The purpose of the present invention is to provide a novel compound having a pest control activity.
(Solution to Problem)
[0005]
The present inventors have extensively studied to find a compound exhibiting a pest control activity, and then have found that a pyrimidine compound of the following Formula (1) exhibits an excellent activity in controlling pests. Based upon the new findings, the present invention has been completed.
In particular, the present inventions are as follows.
[1] A pyrimidine compound of Formula (1) :
Figure imgf000003_0001
wherein
R1 is C1-C3 chain hydrocarbon group optionally substituted with one or more halogens, hydrogen, halogen or amino group,
R2 is C1-C3 chain hydrocarbon group optionally substituted with one or more halogens, hydrogen, halogen, hydroxy group, mercapto group or amino group,
G1 is nitrogen or -CR5= wherein R5 is C1-C3 chain hydrocarbon group optionally substituted with one or more halogens, hydrogen, halogen or amino group,
R3 is C1-C3 chain hydrocarbon group optionally substituted with one or more halogens, hydrogen, halogen, amino group, nitro group or cyano group,
R4 is C1-C6 chain . hydrocarbon group optionally substituted with one or more halogens, C3-C8 cycloalkyl group optionally substituted with one or more halogens, Cl- C6 alkoxy group . optionally substituted with one or more halogens, C1-C6 alkylthio group optionally substituted with one or more halogens, C1-C6 alkylsulfinyl group optionally substituted with one or more halogens, C1-C6 alkylsulfonyl group optionally substituted with one or more halogens, Cl- C6 alkylamino group optionally substituted with one or more halogens, C2-C8 dialkylamino group optionally substituted with one or more halogens, C2-C6 alkylcarbonylamino group optionally substituted with one or more halogens, C2-C6 alkoxycarbonylamino group optionally substituted with one or more halogens, C2-C6 alkylcarbonyl group optionally substituted with one or more halogens, C2-C6 alkoxycarbonyl group optionally substituted with one or more halogens, C2- C6 alkylcarbamoyl group optionally substituted with one or more halogens, C2-C8 dialkylcarbamoyl group optionally substituted with one or more halogens, phenyl group optionally substituted with one or more atoms or groups selected from the following Group a, 5- to 6-membered aromatic heterocyclic group optionally substituted with one or more atoms or groups selected from the following Group a, hydrogen, halogen, hydroxy group, mercapto group, amino group, nitro group, cyano group or formyl group,
Q is oxygen or -S(0)r- wherein r is 0, 1 or 2,
Cyc is 3- to 8-membered saturated heterocyclic group containing one atom or group selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a ring component wherein n is 0, 1 or 2, and R is Cl—C6 chain hydrocarbon group optionally substituted with one or more halogens, C2-C6 alkylcarbonyl group optionally substituted with one or more halogens, C2-C6 alkoxycarbonyl group optionally substituted with one or more halogens, or hydrogen; 5- to 8-membered saturated heterocyclic group containing two atoms or groups selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a ring component wherein n and R6 are as defined above, provided that the two atoms or groups are not adjacent to each other; C3-C8 cycloalkyl group; or C5-C8 cycloalkenyl group, any of the groups defined as Cyc may be optionally substituted with one or more atoms or groups independently selected from the following Groups βΐ to β3, provided that when one or more groups are selected from Group β2, each group selected from Group β2 is attached to the same one carbon atom of the ring defined as Cyc, and when one or more groups are selected from Group β3, each group selected from Group β3 is attached to two adjacent carbon atoms of the ring defined as Cyc,
A is a single bond, methylene group optionally substituted with one or more atoms or groups selected from the group consisting of C1-C3 alkyl group and halogen, or ethylene group optionally substituted with one or more atoms or groups selected from the group consisting of C1-C3 alkyl group and halogen, and A is attached to the carbon atom of the ring defined as Cyc,
Group a consists of C1-C6 chain hydrocarbon group optionally substituted with one or more halogens, C1-C6 alkoxy group optionally substituted with one or more halogens, C1-C6 alkylthio group optionally substituted with one or more halogens, C1-C6 alkylsulfinyl group optionally substituted with one or more halogens, C1-C6 alkylsulfonyl group optionally substituted with one or more halogens, Cl- C6 alkylamino group optionally substituted with one or more halogens, C2-C8 dialkylamino group optionally substituted with one or more halogens, halogen, hydroxy group, mercapto group, amino group, cyano group and nitro group,
Group βΐ consists of C1-C6 chain hydrocarbon group optionally substituted with one or more halogens, C1-C6 alkoxy group optionally substituted with one or more halogens, C1-C6 alkylthio group optionally substituted with one or more halogens, C1-C6 alkylsulfinyl group optionally substituted with one or more halogens, C1-C6 alkylsulfonyl group optionally substituted with one or more halogens, Cl- C6 alkylamino group optionally substituted with one or more halogens, C2-C8 dialkylamino group optionally substituted with one or more halogens, C2-C6 alkylcarbonylamino group optionally substituted with one or more halogens, C2-C6 alkoxycarbonylamino group optionally substituted with one or more halogens, C2-C6 alkylcarbonyl group optionally substituted with one or more halogens, C2-C6 alkoxycarbonyl group optionally substituted with one or more halogens, C2- C6 alkylcarbamoyl group optionally substituted with one or ■ more halogens, C2-C8 dialkylcarbamoyl group optionally substituted with one or more halogens, halogen, hydroxy group, mercapto group, amino group, nitro group, cyano group and formyl group,
Group β2 consists of bivalent radicals shown by =S,
=0, =N0R7 and -X^T^X2- wherein R7 is C1-C3 alkyl group optionally substituted with one or more halogens or hydrogen, X1 and X2 are independently selected from the group consisting of oxygen and sulfur, and T1 is methylene group optionally substituted with one or more halogens or ethylene group optionally substituted with one or more halogens, and
Group β3 consists of bivalent radicals shown by -T2- and -X3-T3-X4- wherein X3 and X4 are independently selected from the group consisting of oxygen and sulfur, and T2 and T3 are independently selected from the group consisting of methylene group optionally substituted with one or more halogens,
but . excluding the pyrimidine compound of Formula (1) wherein Q is oxygen; G1 is -CH=; R1, R2 and R3 are all hydrogen; R4 is amino group or nitro group; A is a single bond; and Cyc is cyclohexyl group.
[2] The pyrimidine compound of [1] wherein Q is oxygen.
[3] The pyrimidine compound of [1] or [2] wherein R1 is hydrogen, R2 is hydrogen or amino group, G1 is nitrogen or -CR5=, and R5 is hydrogen. [4] The pyrimidine compound of any one of [1] to [3] wherein R3 is hydrogen, and R4 is C1-C6 alkyl group optionally substituted with one or more halogens, C1-C6 alkoxy group optionally substituted with one or more halogens, hydrogen, halogen, amino group, nitro group or cyano group. [5] The pyrimidine compound of any one of [1] to [4] wherein G1 is nitrogen. [6] The pyrimidine compound of any one of [1] to [4] wherein G1 is -CR5=, and R5 is hydrogen.
[7] The pyrimidine compound of any one of [1] to [6] wherein Cyc is 3- to 8-membered saturated heterocyclic group containing one atom or group selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a ring component wherein n and R6 are as defined above, and the 3- to 8-membered saturated heterocyclic group may be optionally substituted with one or more atoms or groups selected from the group consisting of C1-C3 alkyl group optionally substituted with one or more halogens, and halogen; C3-C8 cycloalkyl group optionally substituted with one or more halogens; or C5-C8 cycloalkenyl group optionally substituted with one or more halogens.
[8] The pyrimidine compound of any one of [1] to [7] wherein Ά is a single bond.
[9] The pyrimidine compound of any one of [1] to [8] wherein Cyc is a group of Formula Jl or J2 :
Figure imgf000010_0001
J1
R is halogen,
R9 and R10 are independently selected from the group consisting of C1-C3 alkyl group optionally substituted with one or more halogens, and halogen,
p is an integer, of 0 to 9, provided , that when p is an integer of 2 to 9, each R9 may be different from each other, q is an integer of 0 to 8, provided that when q is an integer of 2 to 8, each R10 may be different from each other, and
Y is oxygen, -S(=0)n-, -NR6- or -CR R12- wherein n is 0, 1 or 2, R6 is C1-C6 chain hydrocarbon group optionally substituted with one or more halogens, C2-C6 alkylcarbonyl group optionally substituted with one or more halogens, C2- C6 alkoxycarbonyl group optionally substituted with one or more halogens, or hydrogen, R11 is halogen, and R12 is hydrogen or halogen.
[10] The pyrimidine compound of any one of [1], [3], [4], [5] or [6] which has a chemical structure of Formula (1- vi) : W
10
Figure imgf000011_0001
wherein R1, R2, R3, R4 and G1 are as defined above, and Z is halogen .
[11] The pyrimidine compound of [10] wherein R1, R2 and R3 are hydrogen; R4 is hydrogen, methyl group or chlorine; G1 is nitrogen; and Z is fluorine.
[12] The pyrimidine compound of [1] wherein
R1 is hydrogen,
R2 is hydrogen or amino group,
G1 is nitrogen or -CR5= wherein R5 is hydrogen,
R3 is hydrogen,
R4 is C1-C6 chain hydrocarbon group optionally substituted with one or more halogens, C1-C6 alkoxy group optionally substituted with one or more halogens, hydrogen, or halogen,
Q is oxygen,
Cyc is 3- to 8-membered saturated heterocyclic group containing one atom or group selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a ring component wherein R6 is C2-C6 alkoxycarbonyl group optionally substituted with one or more halogens; 5- to 8- membered saturated heterocyclic group containing two oxygen atoms as a ring component; C3-C8 cycloalkyl group; or C5-C8 cycloalkenyl group,
any of the groups defined as Cyc may be optionally substituted with one or more atoms or groups selected from the following Groups βΐ to β3,
A is a single bond, methylene group optionally substituted with C1-C3 alkyl group, or ethylene group optionally substituted with C1-C3 alkyl group,
Group βΐ consists of C1-C6 chain hydrocarbon group optionally substituted with one or more halogens, C1-C6 alkoxy group optionally substituted with one or more halogens, C2-C6 alkoxycarbonyl group optionally substituted with one or more halogens, halogen, hydroxy group, and cyano group,
Group β2 consists of bivalent radicals shown by =0, =NOR7 and -X^T^X2- wherein R7 is C1-C3 alkyl group optionally substituted with one or more halogens, X1 and X2 are oxygen, and T1 is ethylene group optionally substituted with one or more halogens, and
Group β3 consists of a bivalent radical shown by -T2- wherein T2 is methylene group optionally substituted with one or more halogens . [13] The pyrimidine compound of [1] wherein
R1 is hydrogen,
R2 is hydrogen,
G1 is nitrogen or -CR5= wherein R5 is hydrogen,
R3 is hydrogen,
R4 is C1-C6 chain hydrocarbon group, hydrogen, or halogen,
Q is oxygen,
Cyc is 3- to 8-membered saturated heterocyclic group containing one atom or group selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a ring component wherein R6 is C2-C6 alkoxycarbonyl group; 5- to 8-membered saturated heterocyclic group containing two oxygen atoms as a ring component; C3-C8 cycloalkyl group; or C5-C8 cycloalkenyl group,
any of the groups defined as Cyc may be optionally substituted with one or more atoms or groups selected from the following Groups βΐ to β3,
A is a single bond, methylene group optionally substituted with C1-C3 alkyl group, or ethylene group optionally substituted with C1-C3 alkyl group,
Group βΐ consists of C1-C6 chain hydrocarbon group optionally substituted with one or more halogens, C1-C6 alkoxy group, C2-C6 alkoxycarbonyl group, halogen, hydroxy group, and cyano group, Group β2 consists of bivalent radicals shown by =0, =N0R7 and -X1-T1-X2- wherein R7 is C1-C3 alkyl group, X1 and X2 are oxygen, and T1 is ethylene group, and
Group β3 consists of a bivalent radical shown by -T2- wherein T2 is methylene group optionally substituted with one or more halogens.
[14] A pesticidal composition comprising the pyrimidine compound of any one of [1] to [13] and an inert carrier.
[15] Use of the pyrimidine compound of any one of [1] to [13] for controlling pests.
[16] A method for controlling pests which comprises a step of applying an effective amount of the pyrimidine compound of any one of [1] to [13] to pests or habitats thereof.
(Effect of Invention)
[0006]
The present compound is useful as an active ingredient of a pesticidal agent because the compound has an excellent activity in controlling pests.
Description of Embodiment
[0007] The "halogen" used herein includes fluorine, chlorine, bromine and iodine.
Throughout the description, for example, "C2-C6" in "C2-C6 alkoxycarbonyl group" means the total number of carbon atoms in the alkoxycarbonyl group.
[0008]
The "C1-C3 chain hydrocarbon group" used herein includes, for example, C1-C3 alkyl group such as methyl group, ethyl group, .propyl group and isopropyl group; C2-C3 alkenyl group such as vinyl group and 2-propenyl group; and C2-C3 alkynyl group such as ethynyl group and 2-propynyl group.
[0009]
The "C1-C3 chain hydrocarbon group optionally substituted with one or more halogens" used herein includes, for example, C1-C3 alkyl group optionally substituted with one or more halogens such as methyl group, ethyl group, propyl group, isopropyl group, difluoromethyl group, trifluoromethyl group, dichloromethyl group, trichloro- methyl group, 2, 2, 2-trifluoroethyl group, 2 , 2 , 2-trichloro- ethyl group, pentafluoroethyl group and perfluoropropyl group; C2-C3 alkenyl group optionally substituted with one or more halogens such as vinyl group, 2-propenyl group, 2 , 2-dichlorovinyl group and 3-chloro-2-propenyl group; and C2-C3 alkynyl group optionally substituted with one or more halogens such as ethynyl group and 2-propynyl group.
[0010]
The "C1-C6 chain hydrocarbon group" used herein includes, for example, C1-C6 alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, 1-methylbutyl group, tert- pentyl group, neopentyl group, hexyl group and isohexyl group; C2-C6 alkenyl group such as vinyl group, 2-propenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-2- propenyl group, 3-methyl-2-butenyl group, 2-pentenyl group and 2-hexenyl group; C2-C6 alkynyl group such as ethynyl group, 2-propynyl group, 2-butynyl group and 3-butynyl group .
[0011]
The "C1-C6 chain hydrocarbon group optionally substituted with one or more halogens" used herein includes, for example, C1-C6 alkyl group optionally substituted with one or more halogens such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, 1-methylbutyl group, tert-pentyl group, neopentyl group, hexyl group, isohexyl group, difluoromethyl group, trifluoromethyl group, dichloromethyl group, trichloro- methyl group, 2 , 2 , 2-trifluoroethyl group, 2 , 2 , 2-trichloro- ethyl group, pentafluoroethyl group, perfluoropropyl group, perfluorobutyl group and perfluorohexyl group; C2-C6 alkenyl group optionally substituted with one or more halogens such as vinyl group, 2-propenyl group, 3-chloro-2- propenyl group, 2-chloro-2-propenyl group, 3 , 3-dichloro-2- propenyl group, 2-butenyl group, 3-butenyl group, 2-methyl- 2-propenyl group, 3-methyl-2-butenyl group, 2-pentenyl group and 2-hexenyl group; C2-C6 alkynyl group optionally substituted with one or more halogens such as ethynyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, 3- chloro-2-propynyl group and 3-bromo-2-propynyl group.
[0012]
The "C3-C8 cycloalkyl group optionally substituted with one or more halogens" used herein includes, for example, cyclopropyl group, 2 , 2-difluorocyclopropyl group, 2 , 2-dichlorocyclopropyl group, 2 , 2-dibromocyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group.
[0013]
The "C1-C6 alkoxy group optionally substituted with one or more halogens" used herein includes, for example, methoxy group, trifluoromethoxy group, ethoxy group, 2,2,2- trifluoroethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutyloxy group, sec-butyloxy group, tert- butyloxy group, pentyloxy group and hexyloxy group. [0014]
The "C1-C6 alkylthio group optionally substituted with one or more halogens" used herein includes, for example, methylthio group, trifluorpmethylthio group, ethylthio group, 2 , 2 , 2-trifluoroethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, pentylthio group and hexylthio group.
[0015]
The "C1-C6 alkylsulfinyl group optionally substituted with one or more halogens" used herein includes, for example, methylsulfinyl group, trifluoromethyl sulfinyl group, ethylsulfinyl group, 2 , 2 , 2-trifluoro ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group, isobutylsulfinyl group, sec- butylsulfinyl group, tert-butylsulfinyl group, pentyl- sulfinyl group and hexylsulfinyl group.
[0016]
The "C1-C6 alkylsulfonyl group optionally substituted with one or more halogens" used herein includes, for example, methylsulfonyl group, trifluoromethyl sulfonyl group and ethylsulfonyl group.
[0017]
The "C1-C6 alkylamino group optionally substituted with one or more halogens" used herein includes, for example, methylamino group, ethylamino group, 2,2,2- trifluoroethylamino group, propylamino group, isopropyl- amino group, butylamino group, pentylamino group and hexylamino group.
[0018]
The "C2-C8 dialkylamino group optionally substituted with one or more halogens" used herein includes, for example, dimethylamino group, diethylamino group, , bis (2, 2, 2-trifluoroethyl ) amino group, and dipropylamino group.
[0019]
The "C2-C6 alkylcarbonylamino group optionally substituted with one or more halogens" used herein includes, for example, acetylamino group, propionylamino group, butanoylamino group, pentanoylamino group, 2,2,2- trifluoroacetylamino group and 2 , 2 , 2-trichloroacetylamino group.
[0020]
The "C2-C6 alkoxycarbonylamino group optionally substituted with one or more halogens" used .herein includes, for example, methoxycarbonylamino group, ethoxycarbonyl- amino group, propoxycarbonylamino group, tert-butoxy- carbonylamino group and 2 , 2 , 2-trichloroethoxycarbonylamino group .
[0021] The "C2-C6 alkylcarbamoyl group optionally substituted with one or more halogens" used herein includes, for example, methylcarbamoyl group, ethylcarbamoyl group and 2 , 2 , 2-trifluoroethylcarbamoyl group.
[0022]
The "C2-C8 . dialkylcarbamoyl group optionally substituted with one or more halogens" used herein includes, for example, dimethylcarbamoyl group, diethylcarbamoyl group and dipropylcarbamoyl group.
[0023]
The "methylene group optionally substituted with one or more atoms or groups selected from the group consisting of C1-C3 alkyl group and halogen" used herein includes, for example, methylene group, (methyl ) methylene group, (ethyl) methylene group, difluoromethylene group and dichloromethylene group.
[0024]
The "ethylene group optionally substituted with one or more atoms or groups selected from the group consisting of C1-C3 alkyl group and halogen" used herein includes, for example, ethylene group, 1-methylethylene group, 2- methylethylene group, 1 , 1-dimethylethylene group and 2,2- difluoroethylene group.
[0025]
The "C2-C6 alkylcarbonyl group optionally substituted with one or more halogens" used herein includes, for example, acetyl group, propionyl group, butanoyl group, pentanoyl group and 2 , 2 , 2-trifluoroacetyl group.
[0026]
The "C2-C6 alkoxycarbonyl group optionally substituted with one or more halogens" used herein includes, for example, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, 2 , 2 , 2-trifluoroethoxycarbonyl group and tert-butoxycarbonyl group.
[0027]
The "phenyl group optionally substituted with one or more atoms or groups selected from Group a" used herein includes, for example, phenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-aminophenyl group, 3-aminophenyl group, 4-aminophenyl group, 2- cyanophenyl group, 3-cyanophenyl group, -cyanophenyl group, 2-nitrophenyl group, 3-nitrophenyl group, 4-nitrophenyl group, 2-methylphenyl group, 3-methylphenyl group, 4- methylphenyl group, 2- ( trifluoromethyl ) phenyl group, 3- (trifluoromethyl) phenyl group, 4- (trifluoromethyl ) phenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4- methoxyphenyl group, 4- (trifluoromethoxy) phenyl group, 4- (methylthio) phenyl group, 4- (methylsulfinyl ) phenyl group and 4- (methylsulfonyl) phenyl group.
[0028] The "5- to 6-membered aromatic heterocyclic group" used herein includes, for example, 2-pyrrolyl group, 2- furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 5-pyraz.olyl group, 4-pyrazolyl group, 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, pyrazinyl group, 1-pyrrolyl group and 1-pyrazolyl group.
[0029]
The "5- to 6-membered aromatic heterocyclic group optionally substituted with one or more atoms or groups selected from Group a" used herein includes, for example, l-methyl-2-pyrrolyl group, 2-furyl group, 3-furyl group, 5- bromo-2-furyl group, 5-nitro-2-furyl group, 2-methyl-3- furyl group, 2 , 5-dimethyl-3-furyl group, 2 , 4 -dimethyl-3- furyl group, 2-thienyl group, 3-thienyl group, 5-methyl-2- thienyl group, 3-methyl-2-thienyl group, l-methyl-3- trifluoromethyl-5-pyrazolyl group, 5-chloro-l , 3-dimethyl-4- pyrazolyl group, 2-pyridinyl group, 3-pyridinyl group, 4- pyridinyl group, 2-methyl-3-pyridinyl group, 6-methyl-3- pyridinyl group, 2-chloro-3-pyridinyl group, 6-chloro-3- pyridinyl group, pyrazinyl group, 1-pyrrolyl group and 1- pyrazolyl group.
[0030]
The "3- to 8-membered saturated heterocyclic group containing one atom or group selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a . ring component" used herein includes, for example, epoxy group, oxetan-2-yl group, oxetan-3-yl group, tetrahydrofuran-2-yl group, tetrahydrofuran-3-yl group,, tetrahydrothiophen-2-yl group, tetrahydrothiophen-3-yl group, tetrahydropyran-2-yl group, tetrahydropyran-3-yl group, tetrahydropyran- -yl group, tetrahydrothiopyran-3-yl group, tetrahydrothiopyran- 4-yl group, l-oxotetrahydrothiophen-4 -yl group, 1,1-dioxo- tetrahydrothiophen-4-yl group, l-oxotetrahydrothiopyran-4- yl group, 1 , l-dioxotetrahydrothiopyran-4-yl group and piperidin-4-yl group.
[0031]
The "5- to 8-membered saturated heterocyclic group containing two atoms or groups selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a ring component" used herein includes, for example, 1 , 3-dioxolan- 2-yl group and 1 , 3-dioxolan-4-yl group.
[0032]
The "C3-C8 cycloalkyl group" used herein includes, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group.
[0033]
The "C5-C8 cycloalkenyl group" used herein is a 5- to 8-membered unsaturated carbocyclic group having one or more double bonds but less than the maximum allowable double bonds, and specific examples thereof include 1- cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, 3- cyclohexenyl group, 1-cycloheptenyl group, 2-cycloheptenyl group, 3-cycloheptenyl group and 4-cycloheptenyl group.
[0034]
As used herein, when the · 3- to 8-membered saturated heterocyclic group containing one atom or group selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a ring component; 5- to 8-membered saturated heterocyclic group containing two atoms or groups selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a ring component; C3-C8 cycloalkyl group; and C5-C8 cycloalkenyl group are substituted with two or more atoms or groups selected from Group βΐ, the selected atoms or groups may be attached to two different carbon atoms in the ring or attached to the same carbon atom in the ring. In addition, the two or more atoms or groups selected from Group βΐ may be different from each other. The following structures are examples of a cyclohexyl group substituted with two atoms or groups selected from Group βΐ .
Figure imgf000024_0001
[0035]
used herein, when the 3- to 8-membered saturated heterocyclic group containing one atom or group selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a ring component; 5- to 8-membered saturated heterocyclic group containing two atoms or groups selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a ring component; C3-C8 cycloalkyl group; and C5-C8 cycloalkenyl group are substituted with a group selected from Group β2, the selected group is attached to the same one carbon atom in the ring. The following structures are examples of a cyclohexyl group substituted with one group selected from Group β2.
Figure imgf000025_0001
[0036]
As used herein, when the' 3- to 8-membered saturated heterocyclic group containing one atom or group selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a ring component; 5- to 8-membered saturated heterocyclic group containing two atoms or groups selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a ring component; C3-C8 cycloalkyl group; and C5-C8 cycloalkenyl group are substituted with a group selected from Group β3, the selected group is attached to two adjacent carbon atoms in the ring.' The following structures are examples of a cyclohexyl group substituted with one group selected from Group β3.
Figure imgf000026_0001
[0037]
The "3- to 8-membered saturated heterocyclic group containing one atom or group selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a ring component wherein the 3- to 8-membered saturated heterocyclic group may be optionally substituted with one or more atoms or groups selected from Groups βΐ to β3" used herein includes, for example, epoxy group, oxetan-2-yl group, oxetan-3-yl group, tetrahydrofuran-2-yl group, tetrahydrofuran-3-yl group, tetrahydrothiophen-2-yl group, tetrahydrothiophen-3-yl group, tetrahydropyran-2-yl group, tetrahydropyran-3-yl group, tetrahydropyran-4-yl group, tetrahydrothiopyran-3-yl group, tetrahydrothiopyran-4-yl group, 2-trifluoromethyltetrahydrothiopyran-4-yl group, 1- oxotetrahydrothiophen-4-yl group, 1 , 1-dioxotetrahydro- thiophen-4-yl group, l-oxotetrahydrothiopyran-4-yl group, 1 , l-dioxotetrahydrothiopyran-4 -yl group, piperidin-4-yl group, N-methylpiperidin-4-yl group and N-tert- butoxycarbonylpiperidin-4-yl group.
[0038]
The "5- to 8-membered saturated heterocyclic group containing two atoms or groups selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a ring component wherein the 5- to 8-membered saturated heterocyclic group may be optionally substituted with one or more atoms or groups selected from Groups βΐ to β3" used herein includes, for example, 1 , 3-dioxolan-4-yl group and 2 , 2-dimethyl-l , 3-dioxolan-4-yl group..
[0039] .
The "C3-C8 cycloalkyl group optionally substituted with one or more atoms or groups selected from Groups βΐ to β3" used herein includes, for example, C3-C8 cycloalkyl group optionally substituted with one or more atoms or groups selected from Group βΐ such as cyclopropyl group, 2 , 2-difluorocyclopropyl group, 2 , 2-dichlorocyclopropyl group, 2 , 2-dibromocyclopropyl group, cyclobutyl group, cyclopentyl group, 3 , 3-difluorocyclopentyl group, 3,3- dichlorocyclopentyl group, cyclohexyl group, 3- fluorocyclohexyl group, 3-chlorocyclohexyl group, 3,3- difluorocyclohexyl group, 3 , 3-dichlorocyclohexyl group, 4- fluorocyclohexyl group, 4-chlorocyclohexyl group, 4,4- difluorocyclohexyl group, , 4-dichlorocyclohexyl group, 4- cyanocyclohexyl group, 4-trifluoromethylcyclohexyl group, 4-hydroxycyclohexyl group, 4-methoxycyclohexyl group, 4,4- dimethoxycyclohexyl group, 4 -methylthiocyclohexyl group, 4- aminocyclohexyl group, 4-methoxycarbonylcyclohexyl group, 4-acetylcyclohexyl, cycloheptyl group, , 4-difluorocyclo- heptyl group and cyclooctyl group;. C3-C8 cycloalkyl group optionally substituted with one or more groups selected from Group β2 such as 4-oxycyclohexyl group, 1,4- dioxaspiro [ 4.5] decan-8-yl group, 1 , 4 -dithiaspiro [ 4.5 ] decan- 8-yl group and 4- (methoxyimino) cyclohexyl group; C3-C8 cycloalkyl group optionally substituted with one or more groups selected from Group β3 such as 7 , 7-difluoro- bicyclo [ 4.1.0] heptan-3-yl group and 7 , 7-difluoro- bicyclo [ 4.1.0] heptan-2-yl group.
[0040]
The "C5-C8 cycloalkenyl . group optionally substituted with one or more atoms or groups selected from Groups βΐ to β3" used herein includes, for example, 2-cyclopentenyl group, 3-fluoro-2-cyclopentenyl group, 3-chloro-2- cyclopentenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group, 3-fluoro-2-cyclohexenyl group, 3-chloro-2- cyclohexenyl group, 4-fluoro-3-cyclohexenyl group and 4- chloro-3-cyclohexenyl group.
[0041]
The present compound includes, for example, the following pyrimidine compounds.
A pyrimidine compound of Formula (1) wherein Q is oxygen .
A pyrimidine compound of Formula (1) wherein Q is - S(0)r-. A pyrimidine compound of Formula (1) wherein Q is - S (0) r-, and r is 0.
A pyrimidine compound of Formula (1) wherein Q is - S (0) r-, and r is 1.
A pyrimidine compound of Formula (1) wherein Q is - S(0)r-, and r is 2.
[0042]
A pyrimidine compound of Formula (1) wherein R1 is Cl- C3 chain hydrocarbon group optionally substituted with one or more halogens, hydrogen or halogen.
A pyrimidine compound of Formula (1) wherein R1 is hydrogen or halogen.
A pyrimidine compound of Formula (1) wherein R1 is hydrogen.
[0043]
A pyrimidine compound of Formula (1) wherein R2 is Cl- C3 chain hydrocarbon group optionally substituted with one or more halogens, hydrogen, amino group or halogen.
A pyrimidine compound of Formula (1) wherein R2 is hydrogen, amino group or halogen.
A pyrimidine compound of Formula (1) wherein R2 is hydrogen or amino group.
A pyrimidine compound of Formula (1) wherein R2 is hydrogen.
[0044] A pyrimidine compound of Formula (1) wherein G1 is nitrogen.
A pyrimidine compound of Formula (1) wherein G1 is -
CR5= .
A pyrimidine compound of Formula (1) wherein G1 is -
CR5=, and R5 is hydrogen.
[0045]
A pyrimidine compound of Formula (1) wherein R1 is hydrogen, R2 is hydrogen or amino group, G1 is nitrogen or -CR5=, and R5 is hydrogen.
A pyrimidine compound of Formula (1) wherein R1 is hydrogen, R2 is hydrogen, G1 is nitrogen or -CR5=, and R5 is hydrogen.
A pyrimidine compound of Formula (1) wherein R1 is hydrogen, R2 is hydrogen or amino, and G1 is nitrogen.
A pyrimidine compound of Formula (1) wherein R1 is hydrogen, R2 is hydrogen, and G1 is nitrogen.
A pyrimidine compound of Formula (1) wherein R1 is hydrogen, R2 is hydrogen, G1 is -CR5=, and R5 is hydrogen.
[0046]
A pyrimidine compound of Formula (1) wherein R3 is Cl- C3 chain hydrocarbon group optionally substituted with one or more halogens or hydrogen.
A pyrimidine compound of Formula (1) wherein R3 is hydrogen. [0047]
A pyrimidine compound of Formula (1) wherein R4 is Cl- C6 chain hydrocarbon group optionally substituted with one or more halogens, C3-C8 cycloalkyl group optionally substituted with one or more halogens, C1-C6 alkoxy group optionally substituted with one or more halogens, C1-C6 alkylthio group optionally substituted with one or more halogens, C1-C6 alkylsulfinyl group optionally substituted with one or more halogens, C1-C6 alkylsulfonyl group optionally substituted with one or more halogens, C1-C6 alkylamino group optionally substituted with one or more halogens, C2-C8 dialkylamino group optionally substituted with one or more halogens, C2-C6 alkylcarbonylamino group optionally substituted with one or more halogens, C2-C6 alkoxycarbonylamino group optionally substituted with one or more halogens, C2-C6 alkylca.rbonyl group optionally substituted with one or more halogens, C2-C6 alkoxycarbonyl group optionally substituted with one or more halogens, C2- C6 alkylcarbamoyl group optionally substituted with one or more halogens, C2-C8 dialkylcarbamoyl group optionally substituted with one or more halogens, hydrogen, halogen, hydroxy group, mercapto group, amino group, nitro group, cyano group or formyl group.
A pyrimidine compound of Formula (1) wherein R4 is phenyl group optionally substituted with one or more atoms or groups selected from Group a, or 5- to 6-membered aromatic heterocyclic group optionally substituted with one or more atoms or groups selected from Group a.
A pyrimidine compound of Formula (1) wherein R4 is Cl- C6 chain hydrocarbon group optionally substituted with one or more halogens, C1-C6 alkoxy group optionally substituted with one or more halogens, hydrogen, halogen, hydroxy group, mercapto group, amino group, nitro group or cyano group.
A pyrimidine compound of Formula (1) wherein R4 is Cl- C6 alkyl group optionally substituted with one or more halogens or C1-C6 alkoxy group optionally substituted with one or more halogens, hydrogen, halogen, hydroxy group, thiol group, amino group, nitro group or cyano group.
A pyrimidine compound of Formula (1) wherein R4 is Cl- C6 alkyl group optionally substituted with one or more halogens, hydrogen, halogen, hydroxy group, mercapto group, amino group, nitro group or cyano group.
A pyrimidine compound of Formula (1) wherein R4 is Cl- C6 alkyl group optionally substituted with one or more halogens, hydrogen or halogen.
A pyrimidine compound of Formula (1) wherein R4 is methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, 1-methylbutyl group, tert-pentyl group, neopentyl group, hexyl group, isohexyl group, difluoromethyl group, trifluoromethyl group, dichloromethyl group, trichloromethyl group, 2,2,2- trifluoroethyl group, 2,2,2-trichloroethyl group, pentafluoroethyl group, perfluoropropyl group, perfluoro- butyl group, perfluorohexyl group, hydrogen, fluorine, chlorine, bromine or iodine.
A pyrimidine compound of Formula (1) wherein R4 is hydrogen, fluorine, chlorine, bromine, iodine, amino group, methyl group, ethyl group or methoxy group.
A pyrimidine compound of Formula (1) wherein R4 is hydrogen, fluorine, chlorine, bromine, iodine or methyl group.
A pyrimidine compound of Formula (1) wherein R4 is hydrogen, chlorine or methyl group.
A pyrimidine compound of Formula (1) wherein R4 is hydrogen.
A pyrimidine compound of Formula (1) wherein R4 is chlorine.
A pyrimidine compound of Formula (1) wherein R4 is methyl group .
[0048]
A pyrimidine compound of Formula (1) wherein R3 is hydrogen, and R4 is C1-C6 chain hydrocarbon group optionally substituted with one or more halogens, C1-C6 alkoxy group optionally substituted with one or more halogens, hydrogen, halogen, amino group, nitro group or cyano group.
A pyrimidine compound of Formula (1) wherein R3 is hydrogen, and R4 is C1-C6 alkyl group optionally substituted with one or more halogens, C1-C6 alkoxy group optionally substituted with one or more halogens, hydrogen, halogen, amino group, nitro group or cyano group.
A pyrimidine compound of Formula (1) wherein R3 is hydrogen, and R4 is C1-C6 alkyl group optionally substituted with one or more halogens, hydrogen or halogen.
A pyrimidine compound of Formula (1) wherein R3 is hydrogen, and R4 is hydrogen, fluorine, chlorine, bromine, iodine, amino group, methyl group, ethyl group or methoxy group.
A pyrimidine compound of Formula (1) wherein R3 is hydrogen, and R4 is hydrogen, fluorine, chlorine, bromine or methyl group.
A pyrimidine compound of Formula (1) wherein R3 is hydrogen, and R4 is hydrogen, chlorine or methyl group.
A pyrimidine compound of Formula (1) wherein R3 is hydrogen, and R4 is hydrogen.
A pyrimidine compound of Formula (1) wherein R3 is hydrogen, and R4 is chlorine.
A pyrimidine compound of Formula (1) wherein R3 is hydrogen, and R4 is. methyl group. [0049]
A pyrirtiidine compound of Formula (1) wherein A is a single bond, or methylene group optionally substituted with one or more atoms or groups selected from the group consisting of C1-C3 alkyl group and halogen.
A pyrimidine compound of Formula (1) wherein A is a single bond or methylene group.
A pyrimidine compound of Formula (1) wherein A is a single bond.
[0050]
A pyrimidine compound of Formula (1) wherein Cyc is 3- to 8-membered saturated heterocyclic group containing one atom or group selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a ring component wherein R6 is as defined above, and the 3- to 8-membered saturated heterocyclic group may be optionally substituted with one or more atoms or groups selected from Groups βΐ to β3; C3- C8 cycloalkyl group optionally substituted with one or more atoms or groups selected from Groups βΐ to β3; or C5-C8 cycloalkenyl group optionally substituted with one or more atoms or groups selected from Groups βΐ to β3.
[0051]
A pyrimidine compound of Formula (1) wherein Cyc is 3- to 8-membered saturated heterocyclic group containing one atom or group selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a ring component wherein R6 is as defined above, and the 3- to 8-membered saturated heterocyclic group may be optionally substituted with one or more atoms or groups selected from Groups βΐ to β3; C3- C8 cycloalkyl group optionally substituted with one or more atoms or groups selected from Groups βΐ to β3; or C5-C8 cycloalkenyl group optionally substituted with one or more atoms or groups selected from Groups βΐ to β3.
A pyrimidine compound of Formula (1) wherein Cyc is 3- to 8-membered saturated heterocyclic group containing one atom or group selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a ring component wherein R6 is as defined above, and the 3- to 8-membered. saturated heterocyclic group may be optionally substituted with one or more atoms or groups selected from the group consisting of C1-C3 alkyl group optionally substituted with one or more halogens, and halogen; C3-C8 cycloalkyl group optionally substituted with one or more halogens; or C5-C8 cycloalkenyl group optionally substituted with one or more halogens.
A pyrimidine compound of Formula (1) wherein Cyc is 3- to 6-membered saturated heterocyclic group containing one atom or group selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a ring component wherein R6 is as defined above, and the 3- to 6-membered saturated heterocyclic group may be optionally substituted with one or more atoms or groups selected from the group consisting of C.1-C3 alkyl group optionally substituted with one or more halogens, and halogen; C3-C6 cycloalkyl group optionally substituted with one or more halogens; or C5-C6 cycloalkenyl group optionally substituted with one or more halogens.
A pyrimidine compound of Formula (1) wherein Cyc is 3-, to 6-membered saturated heterocyclic group containing one group selected from the group consisting of -S(=0)n- and - NR6- as a ring component wherein R6 is as defined above, and the 3- to 6-membered saturated heterocyclic group may be optionally substituted with one or more atoms or groups selected from the group consisting of C1-C3 alkyl group optionally substituted with one or more halogens, and halogen; C3-C6 cycloalkyl group optionally substituted with one or more halogens; or C5-C6 cycloalkenyl group optionally substituted with one or more halogens.
A pyrimidine compound of Formula (1) wherein Cyc is 3- to 6-membered saturated heterocyclic group containing one group selected from the group consisting of -S(=0)n- and - NR6- as a ring component wherein R6 is as defined above, and the 3- to 6-membered saturated heterocyclic group may be optionally substituted with one or more atoms or groups selected from the group consisting of C1-C3 alkyl group optionally substituted with one or more fluorine atoms, fluorine and chlorine; C3-C6 cycloalkyl group optionally substituted with one or more fluorine or chlorine atoms; or C5-C6 cycloalkenyl group optionally substituted with one or more fluorine or chlorine atoms.
A pyrimidine compound of .Formula (1) wherein Cyc is 3- to 6-membered saturated heterocyclic group containing one - S(=0) n~ as a ring component wherein the 3- to 6-membered saturated heterocyclic group may be optionally substituted with one or more atoms or groups selected from the group consisting of C1-C3 alkyl group optionally substituted with one or more fluorine atoms, fluorine and chlorine; C3-C6 cycloalkyl group optionally substituted with one or more fluorine or chlorine atoms; or C5-C6 cycloalkenyl group optionally substituted with one or more fluorine or chlorine atoms .
[0052]
A pyrimidine compound of Formula (1) wherein Cyc is a group of Jl or J2.
A pyrimidine compound of Formula (1) wherein Cyc is a group of Jl .
A pyrimidine compound of Formula (1) wherein Cyc is a group of J2.
A pyrimidine compound of Formula (1) wherein Cyc is a group of Jl, and p is 0. A pyrimidine compound of Formula (1) wherein Cyc is a group of Jl, p is 0, and Y is -S(=0)n-.or CR1:LR12 wherein n is 0, 1 or 2, R11 is fluorine or chlorine, and R12 is hydrogen, fluorine or chlorine.
A pyrimidine compound of Formula (1) wherein Cyc is a group of Jl, p is 0, Y is -S(=0)n-, and n is 0, 1 or .2.
A pyrimidine compound of Formula (1) wherein Cyc is a group of Jl, p is 0, Y is -S(=0)n-, and n is 0.
A pyrimidine compound of Formula (1) wherein Cyc is a group of Jl, p is 0, Y is -S(=0)n-, and n is 1.
A pyrimidine compound of Formula (1) wherein Cyc is a group of Jl, p is 0, Y is -S(=0)n-, and n is 2.
A pyrimidine compound of Formula (1) wherein Cyc is a group of Jl, p is 0, Y is CR1:LR12, R11 is fluorine or chlorine, and R12 is hydrogen, fluorine or chlorine.
A pyrimidine compound of Formula (1) wherein Cyc is a group of Jl, p is 0, Y is CR11R12, R11 is fluorine, and R12 is fluorine.
A pyrimidine compound of Formula (1) wherein Cyc is a group of Jl, p is 0, Y is CR R12, R11 is chlorine, and R12 is chlorine.
A pyrimidine compound of Formula (1) wherein A is a single bond, and Cyc is a group of Jl or J2.
A pyrimidine compound of Formula (1) wherein A is a single bond, and Cyc is a group of Jl . A pyrimidine compound of Formula (1) wherein A is a single bond, and Cyc is a group of J2.
A pyrimidine compound of Formula (1) wherein A is a single bond; Cyc is a group of Jl or J2; R8 is fluorine or chlorine; R9 and R10 are independently selected from the group consisting of C1-C3 alkyl group. optionally substituted with fluorine or chlorine, fluorine and chlorine; and is -S(=0)n- or CR R12 wherein is 0, 1 or 2, R11 is fluorine or chlorine, and R12 is hydrogen, fluorine or chlorine.
A pyrimidine compound of Formula (1) wherein A is a single bond; Cyc is a group of Jl; R9 is C1-C3 alkyl group optionally substituted with fluorine or chlorine, fluorine, or chlorine; p is an integer of 0 to 2; and Y is -S(=0)n _ or -CR1]"R12- wherein n is 0, 1 or 2, R11 is fluorine or chlorine, and R12 is hydrogen, fluorine or chlorine.
A pyrimidine compound of Formula (1) wherein A is a single bond; Cyc is a group of Jl; R9 is C1-C3 alkyl group optionally substituted with fluorine or fluorine; p is an integer of 0 to 2; and Y is -S(=0)n- or -CR1:LR12- wherein n is 0, 1 or 2, R11 is fluorine, and R12 is hydrogen or fluorine .
A pyrimidine compound of Formula (1) wherein A is a single bond; Cyc is a group of Jl; R9 is C1-C3 alkyl group optionally substituted with chlorine or chlorine; p is an integer of 0 to 2; and Y is -S(=0)n- or -CR T - wherein n is 0, 1 or 2, R11 is chlorine, and R12 is hydrogen or chlorine.
A pyrimidine compound of Formula (1) wherein A is a single bond, Cyc is a group of Jl, and p is 0.
A pyrimidine compound of Formula (1) wherein A is a single bond, Cyc is a group of Jl, p is 0, and Y is - S(=0)n- or CR1:LR12 wherein n is 0, 1 or 2, . R11 is fluorine or chlorine, and R12 is hydrogen, fluorine or chlorine.
A pyrimidine compound of Formula (1) wherein A is a single bond, Cyc is a group of Jl, p is 0, Y is -S{=0)n-r and n is 0, 1 or 2.
A pyrimidine compound of Formula (1) wherein A is a single bond, Cyc is a group of Jl, p is 0, Y is CR1:LR12, R11 is fluorine or chlorine, and R12 is hydrogen, fluorine or chlorine.
A pyrimidine compound of Formula (1) wherein A is a single bond, Cyc is a group of Jl, p is 0, Y is CR11R12, R11 is fluorine, and R12 is fluorine.
A pyrimidine compound of Formula (1) wherein A is a single bond, Cyc is a group of Jl, p is 0, Y is CR1:LR12, R11 is chlorine, and R12 is chlorine.
[0053]
A pyrimidine compound of Formula (1) wherein
Q is oxygen; R1 is hydrogen;
R2 is -hydrogen or amino group;
G1 is nitrogen or -CR5= wherein R5 is hydrogen;
R3 is hydrogen;
R4 is C1-C6 alkyl group optionally substituted with one or more halogens, C1-C6 alkoxy group optionally substituted with one or more halogens, hydrogen, halogen, amino group, nitro group or cyano group; and
Cyc is 3- to 8-membered saturated heterocyclic group containing one atom or group selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a ring component wherein R6 is as defined above, and the 3- to 8- membered saturated heterocyclic group may be optionally substituted with one or more atoms or groups selected from the group consisting of C1-C3 alkyl group optionally substituted with one or more halogens, and halogen; C3-C8 cycloalkyl group optionally substituted with one or more halogens; or C5-C8 cycloalkenyl . group optionally substituted with one or more halogens.
A pyrimidine compound of Formula (1) wherein Q is oxygen; R1 is hydrogen; R2 is hydrogen or amino group; G1 is nitrogen or -CR5= wherein R5 is hydrogen; R3 is hydrogen; R4 is C1-C6 alkyl group optionally substituted with one or more halogens, C1-C6 alkoxy group optionally substituted with one or more halogens, hydrogen, halogen, amino group, nitro group or cyano group; and Cyc is a group of Jl or J2. A pyrimidine compound of Formula (1) wherein..
Q is oxygen;
R1 is hydrogen;
R2 is hydrogen or amino group;
G1 is nitrogen or -CR5= wherein R5 is hydrogen;
R3 is hydrogen;
R4 is hydrogen, fluorine, chlorine, bromine, iodine, amino group, methyl group, ethyl group or methoxy group; and
Cyc is 3- to 8-membered saturated heterocyclic group containing one atom or group selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a ring component wherein R6 is as defined above, and the 3- to 8- membered saturated heterocyclic group may be optionally substituted with one or more atoms or groups selected from the group consisting of C1-C3 alkyl group optionally substituted with one or more halogens, and halogen; C3-C8 cycloalkyl group optionally substituted with one or more halogens; or C5-C8 cycloalkenyl group optionally substituted with one or more halogens..
A pyrimidine compound of Formula (1) wherein Q is oxygen; R1 is hydrogen; R2 is hydrogen or amino group; G1 is nitrogen or -CR5= wherein R5 is hydrogen; R3 is hydrogen; R4 is hydrogen, fluorine, chlorine, bromine, iodine, amino group, methyl group, ethyl group or methoxy group; A is a single bond; and Cyc is a group of Jl or J2.
A pyrimidine compound of Formula (1) wherein Q is oxygen; R1 is hydrogen; R2 is hydrogen or amino group; G1 is nitrogen or -CR5= wherein R5 is hydrogen; R3 is hydrogen; R4 is hydrogen, fluorine, chlorine, bromine, iodine, amino group, methyl group, ethyl, group or methoxy group; A is a single bond; Cyc is a group of Jl or J2 ; R8 is fluorine or chlorine; R9 and R10 are independently selected from the group consisting of C1-C3 alkyl group optionally substituted with fluorine or chlorine, fluorine and chlorine; and Y is -S(=0)n- or -CR R12- wherein n is 0, 1 or 2, R11 is fluorine or chlorine, and R12 is hydrogen, fluorine or chlorine.
[0054]
A pyrimidine compound of Formula (1) wherein Q is oxygen; R1 is hydrogen; R2 is hydrogen or amino group; G1 is nitrogen or -CR5=. wherein R5 is hydrogen; R3 is hydrogen; R4 is hydrogen, fluorine, chlorine, bromine, iodine, amino group, methyl group, ethyl group or methoxy group; A is a single bond; Cyc is a group of Jl; R9 is C1-C3 alkyl group optionally substituted with fluorine or chlorine, fluorine or chlorine; p is an integer of 0 to 2; and Y is -S(=0)n- or -CRUR12- wherein n is 0, 1 or 2, R11 is fluorine or chlorine, and R12 is hydrogen, fluorine or chlorine. A pyrimidine compound of Formula (1) wherein Q is oxygen; R1 is hydrogen; R2 is hydrogen; G1 is nitrogen; R3 is hydrogen; R4 is hydrogen, chlorine or methyl group; A is a single bond; Cyc is a group of Jl; R9 is C1-C3 alkyl group optionally substituted with fluorine or chlorine, fluorine, or chlorine; p is 0 or 1; and Y is -S(=0)n- or - CR11R12- wherein n is 0, 1 or 2, R11 is fluorine or chlorine, and R12 is hydrogen, fluorine or chlorine.
A pyrimidine compound of Formula (1-vi) :
Figure imgf000045_0001
wherein R1, R2, R3, R4, G1 and Z are as defined above.
A pyrimidine compound of Formula (1-vi) wherein R1, R2 and R3 are hydrogen, R4 is hydrogen, methyl group or chlorine, and G1 is nitrogen.
A pyrimidine compound of Formula (1-vi) wherein R1, R2 and R3 are hydrogen, R4 is hydrogen, methyl group or chlorine, G1 is nitrogen, and Z is fluorine.
A pyrimidine compound of Formula (1-vi) wherein R1, R2 and R3 are hydrogen, R4 is hydrogen, methyl group or chlorine, G1 is nitrogen, and Z is chlorine.
A pyrimidine compound of Formula (1-vi) wherein R1, R2 and R3 are hydrogen, R4 is hydrogen, G1 is nitrogen, and Z is fluorine.
A pyrimidine compound of Formula (1-vi) wherein R1, R2 and R3 are hydrogen, R4 is methyl group, G1 is. nitrogen, and Z is fluorine.
A pyrimidine compound of Formula (1-vi) wherein R1, R2 and R3 are hydrogen, R4 is chlorine, G1 is nitrogen, and Z is fluorine .
[0055]
Hereinafter, the processes of the present compounds are explained.
[0056]
The present compound can be prepared by, for example, the following Processes A to G.
[0057]
(Process A)
Among the present compounds, a compound of Formula (1-
Figure imgf000046_0001
wherein R1, R2, R3, R4, A, Cyc and G1 are as defined above, and Q' is oxygen or sulfur [hereinafter, referred to as the present compound (1-i)]
can be prepared by reacting a compound of Formula (2) :
Figure imgf000047_0001
wherein R1, R2, R3, R4 and G1 are as defined above
[hereinafter, referred to as Compound (2)]
with a compound of Formula
Figure imgf000047_0002
wherein A, Cyc and Q' are as defined above [hereinafter, referred to as Compound (3)] .
The reaction is carried out in the presence or absence of a solvent. solvent used herein includes, example, water; ether such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and tert-butyl methyl ether; halogenated hydrocarbon such as dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, and chlorobenzene ; hydrocarbon such as toluene, benzene, and xylene; nitrile such as acetonitrile; an aprotic polar solvent such as N,N- dimethylformamide, N-methylpyrrolidone (hereinafter, referred to as NMP) , 1 , 3-dimethyl-2-imidazolidinone, and dimethylsulfoxide ; and a mixture thereof.
The amount of Compound (3) used herein is generally 1 mol to 2 mol per 1 mol of Compound (2) .
The reaction is generally carried out in the presence of a base. The base used herein includes, for example, a nitrogen-containing heterocyclic compound such as pyridine, picoline, 2 , 6-lutidine, 1, 8-diazabicyclo [5.4.0] -undec-7-ene (hereinafter, referred to as DBU) , and 1,5- diazabicyclo [ 4.3.0 ] -non-5-ene ; tertiary amine such as triethylamine and N-ethyldiisopropylamine ; and an inorganic base such as potassium carbonate and sodium hydride.
The amount of the base used herein is generally 1 mol or more per 1 mol of Compound (2) .
The reaction temperature is generally in the range of
-20°C to 100°C. The reaction time is generally in the range of 0.1 hour to 24 hours.
After the reaction is completed, the present compound (1-i) can be isolated by pouring the reaction mixture into water, extracting the organic solvent, and then concentrating the organic layer; or by pouring the reaction mixture into water, and then collecting the resultant solid with a filter; or by collecting the solid generated in the reaction mixture with a filter. The isolated present compound (1-i) can be further purified by, for example, recrystallization and chromatography.
[0058]
(Process B)
The present compound (1-i) can be prepared by reacting a compound of Formula (4) :
Figure imgf000049_0001
wherein R3, R4, A, Cyc and Q' are as defined above [hereinafter, referred to as Compound (4)]
with a com ound of Formula (5) :
Figure imgf000049_0002
wherein R1, R2 and G1 are as defined above [hereinafter, referred to as Compound (5)].
The reaction is carried out in the presence or absence of a solvent. The solvent used herein includes, for example, water; ether such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and tert-butyl methyl ether; halogenated hydrocarbon such as dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, and chlorobenzene ; hydrocarbon such as toluene, benzene, and xylene; nitrile such as acetonitrile; an aprotic polar solvent such as N,N- dimethylformamide , NMP, 1, 3-dimethyl-2-imidazolidinone, and dimethylsulfoxide; and a mixture thereof.
The amount of Compound (5) used herein is generally 1 mol to 2 mol per 1 mol of Compound (4) .
The reaction is generally carried out in the presence of a base. The base used herein includes, for example, a nitrogen-containing heterocyclic compound such as pyridine, picoline, 2, 6-lutidine, DBU, and 1 , 5-diazabicyclo [ 4.3.0] - non-5-ene; tertiary amine such as triethylamine and N- ethyldiisopropylamine; and an inorganic base such as potassium carbonate and sodium hydride.
The amount of the base used herein is generally 1 mol or more per 1 mol. of Compound (4) .
The reaction temperature is generally in the range of -20°C to 100°C. - The reaction time is generally in the range of 0.1 hour to 24 hours.
After the reaction is completed, the present compound (1-i) can be isolated by pouring the reaction mixture into water, extracting the organic solvent, and then concentrating the organic layer; or by pouring the reaction mixture into water, and then collecting the resultant solid with a filter; or by collecting the solid generated in the reaction mixture with a filter. The isolated present compound (1-i) can be further purified by, for example, recrystallization and chromatography.
[0059]
(Process C)
The present compound (1-i) can be prepared by reacting a compound of Formula (6) :
Figure imgf000051_0001
wherein R1, R2, R3, R4 and G1 are as defined above [hereinafter, referred to as Compound (6)]
with Compound (3) .
The reaction is carried out in the presence or absence of a solvent. The solvent used herein includes, for example, water; ether such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and tert-butyl methyl ether; halogenated hydrocarbon such as dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, and chlorobenzene ; hydrocarbon such as toluene, benzene, and xylene; nitrile such as acetonitrile; an aprotic polar solvent such as N,.N- dimethylformamide, NMP, 1, 3-dimethyl-2-imidazolidinone, and dimethylsulfoxide ; and a mixture thereof.
The amount of Compound (3) used herein is generally 1 mol to 2 mol per 1 mol of Compound (6) .
The reaction is generally carried out in the .presence of a base. The base used herein includes, for example, a nitrogen-containing heterocyclic compound such as pyridine, picoline, 2 , 6-lutidine, DBU, and 1 , 5-diazabicyclo [ .3.0 ] - non-5-ene; tertiary amine such as triethylamine and N- ethyldiisopropylamine ; and an inorganic base such as potassium carbonate and sodium hydride.
The amount of the base used herein is generally 1 mol or more per 1 mol of Compound (6) .
The reaction temperature is generally in the range of -20°C to 100°C. The reaction time is generally in the range of 0.1 hour to 24 hours.
After the reaction is completed, the present compound . (1-i) can be isolated by pouring the reaction mixture into water, extracting the organic solvent, and then concentrating the organic layer; or by pouring the reaction mixture into water, and then collecting the resultant solid with a filter; or by collecting the solid generated in the reaction mixture with a filter. The isolated present compound (1-i) can be further purified by, for example, recrystallization and chromatography.
[0060]
(Process D)
The present compound (1-i) can be prepared by reacting a compound of Formula (7) :
Figure imgf000052_0001
wherein R1, R2, R3,. R4, G1 and Q' are as defined above [hereinafter, referred to as Compound (7)] with a compound of Formula (8) :
Figure imgf000053_0001
wherein A and Cyc are as defined above, and L is a leaving group such as chlorine, bromine, iodine, p- toluenesulfonyloxy group and methanesulfonyloxy group [hereinafter, referred to as Compound (8)].
The reaction is carried out in the presence or absence of a solvent. The solvent used herein includes, for example, water; ether such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and tert-butyl methyl ether; halogenated hydrocarbon such as dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, and chlorobenzene ; hydrocarbon such as toluene, benzene, and xylene; nitrile such as acetonitrile ; an aprotic polar solvent such as N,N- dimethylformamide, NMP, 1, 3-dimethyl-2-imidazolidinone, and dimethylsulfoxide ; and a mixture thereof.
The amount of Compound (8) used herein is generally 1 mol to 2 mol per 1 mol of Compound (7) .
The reaction is generally carried out in . the presence of a base. The base used herein includes, for example, a nitrogen-containing heterocyclic compound such as pyridine, picoline, 2 , 6-lutidine, DBU, and 1 , 5-diazabicyclo [ 4.3.0 ] - non-5-ene; tertiary amine such as triethylamine and N- ethyldiisopropylamine ; and an inorganic base such, as potassium carbonate and sodium hydride.
The amount of the base used herein is generally 1 mol or more per 1 mol of Compound (7) .
The reaction temperature is generally in the range of -20°C to 100°C. The reaction time is generally in. the range of 0.1 hour to 24 hours.
After the reaction is completed, the present compound
(1-i) can be isolated by pouring the reaction mixture into water, extracting the organic solvent, and then concentrating the organic layer; or by pouring the reaction mixture into water, and then collecting the resultant solid with a filter; or by collecting the solid generated in the reaction mixture with a filter. The isolated present compound (1-i) can be further purified by, for example, recrystallization and chromatography.
[0061]
(Process E)
Among the present compounds, a compound of Formula (1- ii) :
Figure imgf000054_0001
wherein R1, R2, R3, R4 and G1 are as defined above, and n-1 is 1 or 2 [hereinafter, referred to as the present compound (1-ii)]
can be prepared by oxidizing a compound of Formula (l-iii!
Figure imgf000055_0001
wherein R1, R2, R3, R4 and G1 are as defined above [hereinafter, referred to as Compound (1-iii)].
The reaction is generally carried out in the presence of a solvent.
The solvent used herein includes, for example, aliphatic halogenated hydrocarbon such as dichloromethane and chloroform; alcohol such as methanol and ethanol; acetic acid; water; and a mixture thereof.
The oxidizing agent used herein includes, for example, hydrogen peroxide solution, sodium periodate and m- chloroperbenzoic acid.
When n-1 is 1 in the present compound (1-ii) , the amount of oxidizing agent used herein is generally 1 mol to 1.2 mol per 1 mol of Compound (1-iii) . When n-1 is 2 in the present compound (1-ii), the amount of oxidizing agent used herein is generally 2 mol to 3 mol per 1 mol of Compound (1-iii) .
The reaction temperature is generally in the range of -20°C to 80°C. The reaction time is generally in the range W 201
55 of 0.1 hour to 12 hours.
After the reaction is completed, the present compound (1-ii) can be isolated by post treatments such as extracting the reaction mixture with an organic solvent, optionally washing the organic layer with an aqueous solution of a reducing agent (e.g. sodium sulfite and sodium thiosulfate) or a base (e.g. sodium bicarbonate), and then drying and concentrating the resultant mixture. The isolated present compound (1-ii) can be further purified by, for example, recrystallization and chromatography .
[0062]
(Process F)
Among the present compounds, a compound of Formula (1- iv) :
Figure imgf000056_0001
wherein R1, R2, R3, R4, A, Cyc and G1 are as defined above, and Q ' ' is -S(O)- or -S(0)2- [hereinafter, referred to as the. present compound (l-iv)]
can be prepared by oxidizing a compound of Formula (1-v) :
Figure imgf000057_0001
wherein R1, R2, R3, R4, A, Cyc and G1 are as defined above [hereinafter, referred to as Compound (1-v)].
[0063]
(Process G)
Among the present compounds, a compound of Formula (1- vi ) :
Figure imgf000057_0002
wherein R1, R2, R3, R4, Z and G1 are as defined above [hereinafter, referred to as the present compound (l-vi)] or a compound of Formula (1-vii) :
Figure imgf000057_0003
wherein R1, R2, R3, R4, Z and G1 are as defined above [hereinafter, referred to as the present compound (1-vii)] can be prepared by reacting a compound of Formula (1-viii):
Figure imgf000058_0001
wherein R1, R2, R3, R4 and G1 are as defined above [hereinafter, referred to as the present compound (1-viii)] with a halogenating agent.
(1) When Z is fluorine
The halogenating agent used herein is a fluorinating agent, and the fluorinating agent includes, for example, (diethylamino) sulfur trifluoride (hereinafter, referred to as DAST) , bis ( 2-methoxyethyl ) aminosulfur trifluoride and 2 , 2-difluoro-1 , 3-dimethyl-imidazolidine .
The reaction is generally carried out in the presence of a solvent. The solvent used herein includes, for example, ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and tert-butyl methyl ether; halogenated hydrocarbons such as dichloromethane , chloroform, carbon tetrachloride, 1, 2-dichloroethane, and chlorobenzene ; hydrocarbons such as toluene, benzene, and xylene; nitriles such as acetonitrile ; aprotic . polar solvents such as N,N- dimethylformamide, NMP, 1, 3-dimethyl-2-imidazolidinone, and dimethylsulfoxide; and a mixture thereof.
The amount of the fluorinating agent used herein is generally 1 mol to 4 mol per 1 mol of the present compound (1-viii) .
The reaction temperature is generally in the range of -20°C to 100°C. The reaction time is generally in the range of 0.1 hour to 24 hours.
After the reaction is completed, the present compounds (1-vi) and (1-vii) can. be isolated by pouring the reaction mixture into water and then extracting the organic solvent, or by collecting the resultant precipitate with a filter. The isolated present compounds (1-vi) and (1-vii) can be further purified by, for example, recrystallization and chromatography .
(2) When Z is chlorine
The halogenating agent used herein is a chlorinating agent, and the chlorinating agent includes, for example, tungsten hexachloride .
The reaction is generally carried out in the presence of a solvent. The solvent used herein includes, for example, ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and tert-butyl methyl ether; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, and chlorobenzene ; hydrocarbons such as toluene, benzene, and xylene; nitriles such as acetonitrile; aprotic polar solvents such as N,N- dimethylformamide, NMP, 1, 3-dimethyl-2-imidazolidinone, and dimethylsulfoxide ; and a mixture thereof.
The amount of the chlorinating agent used herein is generally 1 mol to 4 mol per 1 mol of the present compound ( 1-viii ) .
The reaction temperature is generally in the range of -20°C to 100°C. The reaction time is generally in the range of 0.1 hour to 24 hours.
After the reaction is completed, the present compounds (1-vi) and (1-vii) can be isolated by pouring the reaction mixture into water and then extracting the organic solvent, or by collecting the resultant precipitate with a filter. The isolated present compounds (1-vi) and (1-vii) can be further purified by, for example, recrystallization and chromatography.
(3) When Z is bromine
The halogenating agent used herein is a brominating agent, and the brominating agent includes, for example, bromine, boron tribromide, boron pentabromide , and a mixture thereof.
[0064]
Hereinafter, processes of intermediates of the present compounds are explained.
[0065] (Reference Process 1)
Compound (2) can be prepared by reacting a compound of Formula ( 9 ) :
Figure imgf000061_0001
wherein R3 and R4 are as defined above [hereinafter, referred to as Compound (9)]
with Compound (5) .
The reaction is carried out in the presence or absence of a solvent. The solvent used herein includes, for example, water; ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and tert-butyl methyl ether; halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1 , 2-dichloroethane, and chlorobenzene ; hydrocarbons such as toluene, benzene, and xylene; nitriles such as acetonitrile; aprotic polar solvents such as N,N- dimethylformamide, NMP, 1, 3-dimethyl-2-imidazolidinone, and dimethylsulfoxide; and a mixture thereof.
The amount of Compound (5) used herein is generally 1 mol to 2 mol per 1 mol of Compound (9) .
The reaction is generally carried out in the presence of a base. The base used herein includes, for example, a nitrogen-containing heterocyclic compound such as pyridine, picoline, 2, 6-lutidine, DBU, and 1 , 5-diazabicyclo [ 4.3.0 ] - ηοη-5-ene; tertiary amine such as triethylamine and N- ethyldiisopropylamine ; and an inorganic base such as potassium carbonate and sodium hydride.
The amount of the base used herein is generally 1 mol or more per 1 mol of Compound (9) .
The reaction temperature is generally in the range of -20°C to 100°C. The reaction time is generally in the range of 0.1 hour to 24 hours.
After the reaction is completed, Compound (2) can be isolated by pouring the reaction mixture into water, extracting the organic solvent, and then concentrating the organic layer; or by pouring the reaction mixture into water, and then collecting the resultant solid with a filter; or by collecting the solid generated in the reaction mixture with a filter. The isolated Compound (2) can be further purified by, for example, recrystallization and chromatography.
[0066]
(Reference Process 2)
Among Compound (2), a compound of Formula (2-i) :
Figure imgf000062_0001
wherein R1"1 is C1-C3 chain hydrocarbon group optionally substituted with one or more halogens, or hydrogen; and and R4 are as defined above [hereinafter, referred to
Compound (2-i)]
can be prepared by reacting a compound of Formula (10) :
Figure imgf000063_0001
wherein R3 and R4 are as defined above [hereinafter, referred to as Compound (10)]
with a compound of Formula (11) :
Figure imgf000063_0002
wherein R29 is C1-C6 alkyl group optionally substituted with one or more halogens, and R1"1 are as defined above [hereinafter, referred to as Compound (11)].
The reaction is carried out in the presence or absence of a solvent. The solvent used herein includes, for example, water; ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and tert-butyl methyl ether; halogenated hydrocarbons such as dichloromethane , chloroform, carbon tetrachloride, 1, 2-dichloroethane, and chlorobenzene ; hydrocarbons such as toluene, benzene, and xylene; nitriles such as acetonitrile; aprotic polar solvents such as N,N- dimethylformamide, NMP, 1 , 3-dimethyl-2-imidazolidinone , and dimethylsulfoxide; and a mixture thereof. The amount of Compound (11) used herein is generally 1 mol to 2 mol per 1 mol of Compound (10) .
The reaction temperature is generally in the range of -20°C to 100°C. The reaction time is generally in the range of 0.1 hour to 24 hours.
After the reaction is completed, Compound (2-i) can be isolated by pouring the reaction mixture into water, extracting the organic solvent, and then concentrating the organic layer. The isolated Compound (2-i) can be further purified by, for example, chromatography and distillation.
[0067]
(Reference Process 3)
Compound (10) can be prepared by reacting Compound (9) with hydrazine.
The reaction is carried out in the presence or absence of a solvent. The solvent used herein includes, for example, water; ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and tert-butyl methyl ether; halogenated hydrocarbons such as dichloromethane , chloroform, carbon tetrachloride, 1 , 2-dichloroethane, and chlorobenzene ; hydrocarbons such as toluene, benzene, and xylene; nitriles such as acetonitrile; aprotic polar solvents such as N,N- dimethylformamide, NMP, 1 , 3-dimethyl-2-imidazolidinone , and dimethylsulfoxide ; and a mixture thereof.
The hydrazine used herein includes, for example, hydrazine and hydrazine hydrate.
The amount of hydrazine used herein is generally 1 mol to 10 mol per 1 mol of Compound (9) .
The reaction is generally carried out in the presence of a base. The base used herein includes, for example, a nitrogen-containing heterocyclic compound such as pyridine, picoline, 2 , 6-lutidine, DBU, and 1 , 5-diazabicyclo [ .3.0] - non-5-ene; tertiary amine such as triethylamine and N- ethyldiisopropylamine; and an inorganic base such as potassium carbonate and sodium hydride. The amount of the base used herein is generally 1 mol or more per 1 mol of Compound ( 9 ) .
The reaction temperature is generally in the range of 0°C to 100°C. The reaction time is generally in the range of 0.1 hour to 24 hours.
After the reaction is completed, Compound (10) can be isolated by pouring the reaction mixture into water, extracting the organic solvent, and then concentrating the organic layer; or by pouring the reaction mixture into water, and then collecting the resultant solid with a filter; or by collecting the solid generated in the reaction mixture with a filter. The isolated Compound (10) can be further purified by, for example, recrystallization and chromatography.
[0068] (Reference Process 4)
Compound (4) can be prepared by reacting Compound (9) and Compound (3) .
The reaction is carried out in the presence or absence of a solvent. The solvent used herein includes, for example, water; ethers such as 1,4-dioxane, diethyl ether, tetrahydrof.uran, and tert-butyl methyl ether; . halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, and chlorobenzene; hydrocarbons such as toluene, benzene, and xylene; nitriles such as acetonitrile; aprotic polar -solvents such as N,N- dimethylformamide, NMP, 1 , 3-dimethyl-2-imidazolidinone, and dimethylsulfoxide; and a mixture thereof.
The amount of Compound (3) used herein is generally 1 mol to 2 mol per 1 mol of Compound (9) .
The reaction is generally carried out in the presence of a base. The base used herein includes, for example, a nitrogen-containing heterocyclic compound such as pyridine, picoline, 2 , 6-lutidine, DBU, and 1 , 5-diazabicyclo [ 4.3.0 ] - non-5-ene; tertiary amine such as triethylamine and N- ethyldiisopropylamine; and an inorganic base such as potassium carbonate and sodium hydride.
The amount of the base used herein is generally 1 mol or more per 1 mol of Compound (9) .
The reaction temperature is generally in the range of 0°C to 100°C. The reaction time is generally in the range of 0.1 hour to 24 hours *
After the reaction is completed, Compound (4) can be isolated by pouring the reaction mixture into water and then extracting the organic solvent. The isolated Compound (4) can be further purified by, for example, chromatography [0069]
(Reference Process 5)
Compound (6) can be prepared by reacting Compound (9) with Compound (5) .
The reaction is carried out in the presence or absence of a solvent. The solvent used herein includes, for example, water; ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran, and tert-butyl methyl ether; halogenated hydrocarbons . such as dichloromethane , chloroform, carbon tetrachloride, 1, 2-dichloroethane, and chlorobenzene ; hydrocarbons such as toluene, benzene, and xylene; nitriles such as acetonitrile ; aprotic polar solvents such as N,N- dimethylformamide, NMP, 1 , 3-dimethyl-2-imidazolidinone, and dimethylsulfoxide ; and a mixture thereof.
The amount of Compound (5) used herein is generally 2 mol to 3 mol per 1 mol of Compound (9) .
The reaction is generally carried out in the presence of a base. The base used herein includes, for example, a nitrogen-containing heterocyclic compound such as pyridine, picoline, 2, 6-lutidine, DBU, and 1 , 5-diazabicyclo [ 4.3.0 ] - non-5-ene; tertiary amine such as triethylamine and N- ethyldiisopropylamine; and an inorganic base such as potassium carbonate and sodium hydride.
The amount of the base used herein is generally 2 mol or more per 1 mol of Compound (9) .
The reaction temperature is generally in the range of 0°C to 100°C. The reaction time is generally in the range of 0.1 hour to 24 hours.
After the reaction is completed, Compound (6) can be isolated by pouring the reaction mixture into water, extracting the organic solvent, and then concentrating the organic layer; or by pouring the reaction mixture into water, and then collecting the resultant solid with a filter; or by collecting the solid generated in the reaction mixture with a filter. The isolated Compound (.6) can be further purified by, for example, recrystallization and chromatography.
[0070]
(Reference Process 6)
Among Compound (7), a compound of Formula (7-i) :
Figure imgf000068_0001
(7-i) wherein R1, R2, R3, R4 and G1 are as defined above
[hereinafter, referred to as Compound (7-i) ]
can be prepared by, for example, hydrolyzing Compound (6) :
Figure imgf000069_0001
wherein R1, R2, R3, R4 and G1 are as defined above.
The reaction is carried out in the presence of water as well as a base or an acid. A solvent is optionally used herein, and the solvent includes, for example, ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran, tert-butyl methyl ether, and diglyme; hydrocarbons such as toluene, benzene, and xylene; and nitriles such as acetonitrile .
The base used herein includes, for example, an inorganic base such as potassium carbonate , sodium hydroxide, potassium hydroxide, and sodium hydride; a nitrogen-containing heterocyclic compound such as pyridine, picoline, 2 , 6-lutidine, DBU, and 1 , 5-diazabicyclo [ 4.3.0 ] - non-5-ene; and tertiary amine such as triethylamine and N- ethyldiisopropylamine . When the reaction is carried out in the presence of a base, the amount of the base used herein is generally 0.1 mol to 4 mol per 1 mol of Compound (6) .
The acid used herein includes, for example, an inorganic acid such as hydrochloric acid, hydrobromic acid, and sulfuric acid; and an organic acid such as acetic acid and p-toluenesulfonic acid. When the reaction is carried out in the presence of an acid, the amount of the acid used, herein is generally 0.1 mol or more per 1 mol of Compound (6).
The reaction temperature is generally in the range of 20°C to 120°C. The reaction time is generally in the range of 0.1 hour to 24 hours.
After the reaction is completed, Compound (7-i) can be isolated by pouring the reaction mixture into water, extracting the organic solvent, and then concentrating the organic layer; or by pouring the reaction mixture into water, and · then collecting the resultant solid with a filter; or by collecting the solid generated in the reaction mixture with a filter. The isolated Compound (7- i) can be further purified by, for example, recrystallization and chromatography.
[0071]
(Reference Process 7)
Among Compound (7), a compound of Formula (7-ii) :
Figure imgf000070_0001
wherein R1, R2, R3, R4 and G1 are as defined above [hereinafter, referred to as Compound (7-ii)]
can be prepared by reacting Compound (7-i) with a sulfidizing agent.
The reaction is carried out in the presence or absence of a solvent. The solvent used herein includes, for example, ethers such as 1,4-dioxane, diethyl ether, tetrahydrofuran, tert-butyl methyl ether, and diglyme; halogenated hydrocarbons such as dichloromethane , chloroform, carbon tetrachloride, 1 , 2-dichloroethane , and chlorobenzene ; hydrocarbons such as toluene, benzene, and xylene; nitriles such as acetonitrile; pyridine derivatives such as pyridine, picoline, and lutidine; and a mixture thereof.
The sulfidizing agent used herein includes, for example, phosphorus pentasulfide and Lawesson's reagent [i.e. 2 , 4-bis- ( 4 -methoxyphenyl ) -1, 3-dithia-2, 4- diphosphetane 2 , 4-disulfide] .
The amount of the sulfidizing agent used herein is generally 1 mol or more per 1 mol of Compound (7-i) .
The reaction temperature is generally in the range of
0°C to 200°C. The reaction time is generally in the range of 1 hour to 24 hours.
After the reaction is completed, Compound (7-ii) can be. isolated by pouring the reaction mixture into water, extracting the organic solvent, and then concentrating the organic layer; or by pouring the reaction mixture into water, and then collecting the resultant solid with a filter; or by collecting the solid generated in the reaction mixture with a filter. The isolated Compound (7- ii) can be further purified by, for example, recrystallization and chromatography.
[0072]
Hereinafter, specific examples of the present compounds are illustrated.
[0073]
A compound of Formula (A) :
Figure imgf000072_0001
wherein R1 and R3 are hydrogen; Q is oxygen; and Cyc, A, and R2 are any one of the combinations listed in Tables to 6.
[0074] Table 1
Figure imgf000073_0001
W
73
[0075]
Table 2
Figure imgf000074_0001
W
[0076]
Figure imgf000075_0001
[0077] Table 4
Figure imgf000076_0001
[0078] Table 5
Figure imgf000077_0001
[0079] Table 6
Figure imgf000078_0001
[0080]
A compound of Formula (B) :
Figure imgf000079_0001
wherein R1 and R3 are hydrogen; Q is oxygen; and Cyc, A, and R2 are any one of the combinations listed in Tables to 6.
[0081]
A compound of Formula (C) :
Figure imgf000079_0002
wherein R1 and R3 are hydrogen; Q is oxygen; and Cyc, A, G1 and R2 are any one of the combinations listed in Tables 1 to 6.
[0082]
A compound of Formula (D) :
Figure imgf000079_0003
wherein R1 and R3 are hydrogen; Q is oxygen; and Cyc, A, G1 and R2 are any one of the combinations listed in Tables 1 to 6.
[0083]
A compound of Formula (E) :
Figure imgf000080_0001
wherein R1 and R3 are hydrogen; Q is oxygen; and Cyc, A, and R are any one of the combinations listed in Tables to 6.
[0084]
A compound of Formula (F) :
Figure imgf000080_0002
wherein R1 and R3 are hydrogen; Q is oxygen; and Cyc, A, G1 and R are any one of the combinations listed in Tables 1 to 6.
[0085]
A compound of Formula (G) : W 201
80
Figure imgf000081_0001
wherein R1 and R3 are hydrogen; Q is oxygen; and Cyc, A, and R2 are any one of the combinations listed in Tables to 6.
[0086]
A compound of Formula (H) :
Figure imgf000081_0002
wherein R1 and R3 are hydrogen; Q is sulfur; and Cyc, A, G1 and R2 are any one of the combinations listed in Tables 1 to 6.
[0087]
A compound of Formula (I) :
Figure imgf000081_0003
wherein R1 and R3 are hydrogen; Q is sulfur; and Cyc, A,... G1 and R2 are any one of the combinations listed in Tables 1 to 6. [0088] .
A compound of Formula (J) :
Figure imgf000082_0001
wherein R1 and R3 are hydrogen; Q is sulfur;, and Cyc, A, G1 and R2 are any one of the combinations listed in Tables 1 to 6.
[0089]
The present compounds are effective against pests such as harmful arthropods (e.g. harmful insects and mites), nematodes, and mollusks. The specific examples of the pests are as follows.
[0090]
Hemiptera: Planthoppers (Delphacidae) such as small brown planthopper (Laodelphax striatellus) , brown rice planthopper {Nilaparvata lugens) , and white-backed rice planthopper {Sogatella furcifera) ; leafhoppers
{Deltocephalidae) such as green rice leafhopper {Nephotettix cincticeps) , Taiwan green rice leafhopper (Nephotettix virescens) , and tea green leafhopper (Empoasca onukii) ; aphids (Aphididae) such as cotton aphid {Aphis gossypii) , green peach aphid {Myzus persicae) , cabbage aphid {Brevicoryne brassicae) , spirea aphid (Aphis spiraecola) , potato aphid (Macrosiphum euphorbiae) , foxglove aphid (Aulacorthum solani) , oat bird-cherry aphid (Rhopalosiphum padi) , tropical citrus aphid (Toxoptera citricidus) , and mealy plum aphid (Hyalopterus pruni) ; stink bugs [Pentatomidae) such as green stink bug {Nezara antennata) , bean bug (Riptortus clavetus) , rice bug (Leptocorisa chinensis) , white spotted spined bug [Eysarcoris parvus) , and stink bug {Halyomorpha mista) ; whiteflies (Aleyrodidae) such as . greenhouse whitefly {Trialeurodes vaporariorum) , tobacco whitefly (Bemisia tabaci) , citrus whitefly {Dialeurodes citri) , and orange spiny whitefly [Aleurocanthus spiniferus) ; scales {Coccldae) such as Calfornia red scale (Aonidiella aurantii) , San Jose scale (Comstockaspis perniciosa) , citrus north scale (Unaspis citri), red wax scale (Ceroplastes rubens) , cottonycushion scale [Icerya purchasi) , Japanese mealybug (Planococcus kraunhiae) , Cosmstock mealybug ( Pseudococcus longispinis) , and white peach scale {Pseudaulacaspis pentagona) ; lace bugs (Tingidae) ; bed bugs (Cimicidae) such as bed bug (Cimex lectularius) ; psyllids (Psyllidae) ; and the like.
[0091]
Lepidoptera: Pyralid moths (Pyralidae) such as rice stem borer (Chilo suppressalis) , yellow stem borer [Tryporyza incertulas) , rice leafroller [Cnaphalocrocis medinalis) , cotton leafroller (Notarcha derogata) , indian meal moth (Plodia interpunctella) , oriental corn borer {Ostrinia furnacalis). , cabbage webworm [Hellula undalis) , and bluegrass webworm {Pediasia teterrellus) ; owlet moths (Noctuidae) such as common cutworm {Spodoptera litura) , beet armyworm {Spodoptera exigua) , rice armyworm (Pseudaletia separata) , . cabbage armyworm {Mamestra brassicae) , black cutworm (Agrotis ipsilon) , beet semi- looper (Plusia nigrisigna) , Thoricoplusia spp. , Heliothis spp., and Helicoverpa spp.; white butterflies {Pieridae) such as cabbage butterfly {Pieris rapae) ; tortricid moths (Tortricidae) such as Adoxophyes spp., oriental fruit moth {Grapholita molesta) , soybean pod borer {Leguminivora glycinivorella) , azuki . bean podworm {Matsumuraeses azukivora) , summer fruit tortrix {Adoxophyes orana fasciata) , smaller tea tortrix {Adoxophyes honmai.), oriental tea tortrix {Homona magnanima) , apple tortrix {Archips fuscocupreanus) , and codling moth {Cydia pomonella) ; leafblotch miners {Gracillariidae) such as tea leafroller {Caloptilia theivora) and apple leafminer {Phyllonorycter ringoneella) ; fruitworm moths
{Carposinidae) such as peach fruit moth {Carposina niponensis) ; lyonetiid moths {Lyonetiidae) such as Lyonetia spp.; tussock moths {Lymantriidae) such as Lymantria spp. and Euproctis spp.; yponomeutid moths {Yponomeutidae) such as diainondback moths {Plutella xylostella) ; gelechiid moths (Gelechiidae) such as pink bollworm (Pectinophora gossypiella) and potato tubeworm {Phthorimaea operculella) ; tiger moths {Arctiidae) such as fall webworm {Hyphantria cunea) ; tineid moths (Tineidae) such as casemaking clothes moth {Tinea translucens) and webbing clothes moth (Tineola bisselliella) ; and the like.
[0092]
Thripidae: Thrips {Thripidae) such as yellow citrus thrip ( Frankliniella occidentalis) , melon thrip {Thrips parmi) , yellow tea thrip { Scirtothrips dorsalis) , onion thrip {Thrips tabaci) , flower thrip {Frankliniella intonsa) , and the like.
[0093]
• Diptera: House mosquitos (Culex) such as common house mosquito {Culex pipiens pallens) , small house mosquito
{Culex tritaeniorhynchus) , and tropical house mosquito
(Culex quinquefasciatus) ; Aedes spp. such as yellow fever mosquito {Aedes aegypti) and Asian tiger mosquito {Aedes albopictus) ; Anopheles spp. such as Chinese anopheles
{Anopheles sinensis) ; chironomids {Chironomidae) ; house flies {Muscidae) such as common housefly {Musca domestica) and false stable fly {Muscina stabulans) ; blow flies
{Calliphoridae) ; flesh flies { Sarcophagidae) ; little house fly {Fannia canicularis) ; anthomyiid flies {Anthomyiidae) such as seedcorn fly (Delia platura) and onion fly (Delia antiqua) ; leaf miners (Agromyzidae) such as rice leafminer
{Agromyza oryzae) , rice leafminer (Hydrellia griseola) , vegetable leafminer (Liriomyza sativae) , legume leafminer [Liriomyza, trifolii) , and garden pea leafminer
( Chroma tomyia horticola) ; frit flies (Chloropidae) such as rice stem maggot (Chlorops oryzae) ; fruit flies
(Tephritidae) such as melon fly (Dacus cucurbitae) and Mediterranean fruit fly {Ceratitis capitata) ; Drosophilidae; humpbacked flies (Phoridae) such as humpbacked flies {Megaselia spiracularis) ; sand flies
(Phlebotominae) such as mothfly {Clogmia albipunctata) ; black, flies {Simuliidae) ; horse flies (Tabanidae) such as common horse fly (Tabanus trigonus) ; stable flies { Stomoxyinae) ; and the like.
[0094] ,
Coleoptera: Corn root worms (Diabrotica spp.) such as Western corn root worm [Diabrotica virgifera virgifera) and Sourthern corn root worm (Diabrotica undecimpunctata howardi) ; scarabs (Scarabaeidae) such as cupreous chafer (Anomala cuprea) , soybean beetle (Anomala rufocuprea) , and Japanese beetle (Popillia japonica) ; weevils
(Curculionidae) such as maize weevil (Sitophilus zeamais) , rice water weevil (Lissorhoptrus oryzophilus) , azuki bean weevil (Callosohruchus chinensis) , rice plant weevil {Echinocnemus squameus) , boll weevil (Anthonomus grandis) , and hunting billbug ( Sphenophorus venatus) ; darkling beetles {Tenebrionidae) such as yellow mealworm {Tenebrio molitor) and red flour beetle {Tribolium castaneum) ; leaf beetles (Chrysomelidae) such as rice leaf beetle (Oulema oryzae) , cucurbit leaf beetle [Aulacophora femoralis) , striped flea beetle (Phyllotreta striolata) , and Colorado potato beetle (Leptinotarsa decemlineata) ; dermestid beetles {Dermestidae) such as varied carpet beetle {Anthrenus verbasci) and hide beetle (Dermestes maculates) ; deathwatch beetles {Anobiidae) such as cigarette beetle (Lasioderma serricorne) ; Epilachna insects (Epilachna) such as Twenty-eight-spotted ladybird {Epilachna vigintioctopunctata) ; bark beetles (Scolytidae) such as powder post beetle {Lyctus brunneus) and pine shoot beetle (Tomicus piniperda) ; horned powder-post . beetles [Bostrichidae) ; spider beetles {Ptinidae) ; longhorn beetles {Cerambycidae) such as . white-spotted longicorn beetle {Anoplophora malasiaca) ; Agriotes spp.; rove beetles (Paederus fuscipes) ; and the like.
[0095]
Orthoptera: Asiatic locust (Locusta migratoria) , African mole cricket {Gryllotalpa africana) , rice grasshopper {Oxya yezoensis) , rice grasshopper {Oxya japonica) , cricket [Gry11idae) , and the like. [0096]
Shiphonaptera : Cat flea {Ctenocephalides felis) , dog flea {Ctenocephalides canis) , human flea {Pulex irritans) , oriental rat flea {Xenopsylla cheopis) , and the like.
Anoplura: Human body louse {Pediculus humanus corporis), crab louse {Phthirus pubis), short-nosed cattle louse {Haematopinus eurysternus) , sheep louse {Dalmalinia ovis) , hog louse {Haematopinus suis), and the like.
[0097]
Hymenoptera: Ants {Formicidae) such as pharaoh ant
{Monomorium pharaosis) , negro ant {Formica fusca japonica) , black house ant {Ochetellus glaber) , {Pristomyrmex pungens) , {Pheidole noda) , Acromyrmex spp., and Solenopsis spp. ; Vespoid wasps {Vespoidea) ; Bethylid wasps {Bethylidae) ; sawflies {Tenthredinidae) such as cabbage sawfly {Athalia rosae) and Athalia sawfly {Athalia japonica); and the like.
[0098]
Blattaria: German cockroach {Blattella germanica) , smokybrown cockroach {Periplaneta fuliginosa) , american cockroach {Periplaneta americana) , brown cockroach {Periplaneta brunnea) , oriental cockroach {Blatta orientalis) , and the like.
[0099]
Termitidae: Japanese subterranean termite {Reticulitermes speratus) , Formosan subterranean termite {Coptotermes formosanus), western drywood termite ( Incisitermes minor), tropical drywood termite
{Cryptotermes domes ticus) , black-winged subterranean {Odontotermes formosanus) , drywood-feeding termite {Neotermes koshunensis) , Satsuma termite {Glyptotermes satsumensis) , {Glyptotermes nakajimai), {Glyptotermes fuscus) , {Glyptotermes kodamai) , {Glyptotermes kushimensis) , Japanese damp-wood termite {Hodotermopsis japonica) , {Coptotermes guangzhoensis) , {Reticulitermes miyatakei) , {Reticulitermes flaviceps amamianus) , Reticulitermes sp.r {Nasutitermes takasagoensis) , { Pericapritermes nitobei) , {Sinocapritermes mushae) , eastern subterranean termite {Reticulitermes flavipes) , dark southern subterranean termite {Reticulitermes virginicus) , Arid land subterranean termite {Reticulitermes tibialis) , desert subterranean termite {Heterotermes aureus) , Nevada dampwood termite {Zootermopsis nevadensis) , and the like.
[0100]
Acari: Spider mites {Tetranychidae) such as two- spotted spider mite {Tetranychus urticae) , Kanzawa spider mite {Tetranychus kanzawai) , citrus red mite {Panonychus citri) , European red mite {Panonychus ulmi) , and Oligonychus spp. ; eriophyidmites {Eriophyidae) such as pink citrus rust mite {Aculops pelekassi) , pink citrus rust mite {Phyllocoptruta citri), tomato rust mite {Aculops lycopersici) , purple tea mite {Calacarus carinatus) , tea rust mite (Acaphylla theavagrans) , Japanese pear rust mite (Eriophyes chibaensis) , and apple rust . mite (Aculus schlechtendali) ; tarosonemid mites {Tarsonemidae) such as broad mite {Polyphagotarsonemus latus) ; false spider mites {Tenuipalpidae) such as flat mite {Brevipalpus phoenicis) ; peacock mites {Tuckerellidae) ; ticks {Ixodidae) such, as New Zealand cattle tick {Haemaphysalis . longicornis) , Eaemaphysails flava, Taiwan tick {Dermacentor taiwanicus) , Ixodes ovatus, Taiga tick {Ixodes persulcatus) , black legged tick {Ixodes scapularis) , cattle tick {Boophilus microplus) , and brown dog tick {Rhipicephalus sanguineus) ; acarid mites {Acaridae) such as mold mite {Tyrophagus putrescentiae) and acarid mite {Tyrophagus similis) ; house dust mites ( Pyroglyphidae) such as American house dust mite {Dermatophagoides farinae) and European house dust mite {Dermatophagoides ptrenyssnus) ; cheyletide mites
{Cheyletidae) such as cheyletid mite {Cheyletus eruditus) , Cheyletus malaccensis and Cheyletus moorei; parasitoid mites {Dermanyssidae) such as tropical rat mite {Ornithonyssus bacoti) , northern fowl mite {Ornithonyssus sylviarum) , and poultry redmite {Dermanyssus gallinae) ; chiggers {Trombiculidae) such as Le otromj idium akamushi; spiders {Araneae) such as Japanese foliage spider {Chiracanthium japonicum) and redback spider {Latrodectus hasseltii) ; and the like.
[0101]
Chilopoda: House centipede {Thereuonema hilgendorfi) , Vietnam giant centipede (Scolopendra subspinipes) , and the like.
[0102]
Diplopoda: Garden millipede {Oxidus gracilis) , red millipede (Nedyopus tambanus) , and the like.
[0103]
Isopoda: Common pill bug (Armadillidium vulgare) and the like.
[0104]
Gastropoda : . Tree slug (Limax marginatus) , yellow slug (Limax flavus) , and the like.
[0105]
Nematoda: Rice white-tip nematode (Aphelenchoides besseyi) , strawberry bud nematode (Nothotylenchus acris) , cotton root-knot nematode (Meloidogyne incognita) , northern root-knot nematode (Meloidogyne hapla) , tropical root-knot nematodes (Meloidogyne javanica) , soybean cyst nematode (Heterodera glycines) , potato cyst nematode (Globodera rostochiensis) , coffee root-lesion nematode (Pratylenchus coffeae) , roOt^iesion nematode (Pratylenchus neglectus) , and the like.
[0106] The pesticidal agent of the present invention comprises the present compound and an inert carrier. The pesticidal agent of the present invention is generally formulated into, for example, an emulsion, an oil solution, a powder, a granule, a wettable powder, a flowable formulation, a microcapsule agent, an aerosol, a smoking agent, a toxic bait, or a resin formulation by mixing the present compound and an inert carrier (e.g. solid carrier, liquid carrier, and gas carrier) , and, if necessary, adding a surfactant or other formulation additives.
The pesticidal agent of the present invention generally contains the present compound in an amount of 0.01 wt% to 95 wt%.
[0107]
The solid carrier used herein includes, for example, fine powders and granular materials made from, for example, clays (e.g.. kaolin clay, diatomaceous earth, bentonite, Fubasami clay, and acid clay) / synthetic hydrated silicon oxide; talc; ceramic; other inorganic minerals (e.g. sericite, quartz, sulfur, activated charcoal, calcium carbonate, and hydrated silica) ; and chemical fertilizers (e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and ammonium chloride) .
[0108]
The liquid carrier used herein includes, for example, water; alcohols (e.g. methanol, ethanol, isopropyl alcohol, butanol, hexanol, benzyl alcohol, ethylene glycol, propylene glycol, and phenoxy ethanol); ketones (e.g. acetone, methyl ethyl ketone, and cyclohexanone ) ; aromatic hydrocarbons (e.g. toluene, xylene, ethylbenzene, dodecylbenzene , phenylxylylethane , and methylnaphthalene) ; aliphatic hydrocarbons (e.g. hexane, cyclohexane, kerosene, and light oil); esters (e.g.. ethyl acetate, butyl acetate, isopropyl myristate, ethyl oleate, diisopropyl adipate, diisobutyl adipate, and. propylene glycol monomethyl ether acetate); nitriles (e.g. acetonitrile and isobutyronitrile) ; ethers (e.g. diisopropyl ether, 1,4- dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and 3-methoxy-3-methyl-l-butanol ) ; acid amides (e.g. ■·:■ N, N-dimethylformamide and N,N- dimethylacetamide) ; halogenated hydrocarbons (e.g. dichloromethane, trichloroethane, and carbon tetrachloride); sulfoxides (e.g. dimethyl sulfoxide); propylene carbonate; and vegetable oil (e.g. soybean oil and cottonseed oil).
[0109]
The gas carrier used herein includes, for example, fluorocarbon, butane gas, LPG (liquefied petroleum gas), dimethyl ether and carbon dioxide gas.
[0110]
The surfactant used herein includes,- for example, a non-ionic surfactant such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, and polyethylene glycol fatty acid ester; and an anionic surfactant such as alkyl sulfonate, alkylbenzene sulfonate, and alkyl sulfate. - [0111]
The other formulation additives used herein include, fixing agents, dispersing agents, colorants, stabilizers, and the like; and more specifically, casein, gelatin, saccharides (e.g. starch, gum arabic, cellulose derivatives, and alginic acid), lignin derivatives, bentonite, synthetic water-soluble polymers (e.g. polyvinyl alcohols, polyvinyl pyrrolidones, and polyacrylic acids) , PAP (acidic isopropyl phosphate), BHT ( 2 , 6-di-tert-butyl- -methylphenol ) , BHA (a mixture of 2-tert-butyl-4 -methoxyphenol and 3-tert-butyl-4 - methoxyphenol), and the like.
[0112]
The method for controlling pests in the present invention is performed by applying an effective amount of the present compound to pests directly and/or habitats of pests (e.g. plant body, soil, indoor, and animal body). According to the method for controlling pests in the present invention, the present compound is generally used in the form of a pesticidal agent of the present invention.
The habitats of pests include, for example, paddy fields, dry paddy fields, fields, tea fields, orchards, non-crop lands, houses, seedling raising trays, seedling raising boxes, seedling raising soils, seedling raising mats, and water culture solutions in water culture farms.
[0113]
When the pesticidal agent of the present invention is used for controlling pests in the field of agriculture, the application amount thereof is 1 g to 10, 000 g of the present compound per 10, 000 m2. When the pesticidal agent of the present invention is formulated into, for example, emulsions, wettable powders, and flowable formulations, the pesticidal agent is generally diluted with water so that the active ingredient concentration thereof can be 0.01 ppm to 10,000 ppm. When the pesticidal agent is formulated into, for example, granules and powders, the pesticidal agent is generally used without dilution.
[0114] .
These formulations and water dilutions thereof may be directly sprayed to pests or plants (e.g. crops which need to be protected from pests), or may be applied to a soil of a cultivated land in order to control pests which inhabit the soil.
[0115] The pesticidal agent of the present invention can also be used in the form of a resin preparation which may be, for example, processed into a sheet or a string, and then wound around crops, or put around crops, or laid on the soil surface near the root of crops.
[0116]
The pesticidal agent of the present invention can be used for controlling pests which live in a house. When it is used at a plain surface, the application amount thereof is generally 0.01 mg to 1, 000 mg of the present compound per 1 m2 of the treatment area; and when it is used in an open space, the application amount thereof is generally 0.01 mg to 500 mg of the present compound per 1 m3 of the treatment space. When the pesticidal agent of the present invention is formulated into, for example, emulsions, wettable powders, and flowable formulations, the pesticidal agent is generally diluted with water so that the active ingredient concentration thereof can be 0.1 ppm to 1,000 ppm. When the pesticidal agent is formulated into, for example, oil solution, aerosol, smoking agent and toxic bait, the pesticidal agent is generally used without dilution.
[0117]
The pesticidal agent of the present invention can be used in farmlands where the following "crops" are cultivated.
Agricultural crops: Corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean, peanut, sarrazin, sugar beet, rapeseed, sunflower, sugar cane, tobacco, and the like.
Vegetables: Solanaceae vegetables (e.g. eggplant, tomato, green . pepper, hot pepper, and potato) , Cucurbitaceae vegetables (e.g. cucumber, pumpkin, zucchini, watermelon, and melon), Cruciferae vegetables (e.g. Japanese radish, turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, brown mustard, broccoli, and cauliflower) , Compositae vegetables (e.g. burdock, garland chrysanthemum, artichoke, and lettuce), Liliaceae vegetables (e.g. Welsh onion, onion, garlic, and asparagus) , Umbelliferae vegetables (e.g. carrot, parsley, celery, and parsnip), Chenopodiaceae vegetables (e.g. spinach and Swiss chard), Labiatae vegetables (e.g. Japanese basil, mint, and basil), strawberry, sweat potato, yam, aroid, and the like.
Fruit trees: Pomaceous fruits (e.g. apple, common pear, Japanese pear, Chinese quince, and quince) , stone fleshy fruits (e.g. peach, plum, nectarine, Japanese plum, cherry, apricot, and prune), citrus plants (e.g. Satsuma mandarin, orange, lemon, lime, and grapefruit), nuts (e.g. chestnut, walnut, hazel nut, almond, pistachio, cashew nut, and macadamia nut), berry fruits (e.g. blueberry, cranberry, blackberry, and raspberry) , grape, persimmon, olive, loquat, 9.7 banana, coffee, date, coconut, oil palm, and the like.
Trees other than fruit trees: Tea, mulberry, flowering trees and shrubs (e.g. Rhododendron indicum, Camellia japonica, Hydrangea, Camellia sasanqua, Illicium anisatum, Prunus subg. Cerasus, - Liriodendron tulipifera, Lagerstroemia indica, and Osmanthus fragrans var. aurantiacus ) , street trees (e.g. ash tree, birch, dogwood, eucalyptus, ginkgo, lilac, maple tree, oak, poplar, cercis, Chinese sweet gum, plane tree, zelkova, Japanese arborvitae, fir tree, Japanese hemlock, needle juniper, pine, spruce, yew, elm, and horse-chestnut.) , sweet viburnum, Podocarpus macrophyllus , Japanese cedar, Japanese cypress, croton, spindle tree, Chainese howthorn, and the like.
Lawn: Zoysia (e.g. Japanese lawn grass and mascarene grass), Bermuda grass (e.g. Cynodon dactylon) , bent grass (e.g. creeping bent grass, Agrostis stolonifera, and Agrostis tenuis), bluegrass (e.g. Kentucky bluegrass and rough bluegrass), fescue (e.g. tall fescue, chewing fescue, and creeping fescue), ryegrass (e.g. darnel and perennial. ryegrass), cocksfoot, timothy grass, and the like.
Others: Flowers [e.g. rose, carnation, chrysanthemum, Eustoma grandiflorum Shinners (prairie gentian) , gypsophila, gerbera, pot marigold, salvia, petunia, verbena, tulip, aster, gentian, lily, pansy, cyclamen, orchid, lily of the valley, lavender, stock, ornamental kale, primula, poinsttia, gladiolus, cattleya, daisy, cymbidium, and begonia], bio-fuel plants (e.g. Jatropha, curcas, safflower, Camelina alyssum, switchgrass, Miscanthus, reed canary grass, Arundo donax, kenaf, cassava, willow, and algae) , foliage plant, and the like.
[0118]
The "crops" also include recombinant crops.
[0119]
The pesticidal agent of the present invention can be mixed or used together with other insecticides, acaricides, nematicides, fungicides, plant growth regulators, herbicides and/or synergists. Hereinafter, examples of the active ingredients of the above-mentioned insecticides, acaricides, nematicides, fungicides, plant growth regulators, herbicides and synergists are illustrated.
[0120]
Active ingredients of the insecticides:
(1) Carbamate compounds
Alanycarb, Bendiocarb, Benfuracarb, Butocarboxim, Butoxycarboxim, Carbaryl (NAC) , Carbofuran, Carbosulfan, Cloethocarb, Ethiofencarb, Fenobucarb (BPMC) , Fenothiocarb, Formetanate, Furathiocarb, Isoprocarb (MIPC) , Methiocarb, Methomyl, Metolcarb, Oxamyl, Pirimicarb, Propoxur (PHC) , Thiodicarb, Thiofanox, Triazamate,. Trimethacarb, XMC, and Xylylcarb. (2) Organophosphorus compounds
Acephate, Azamethiphos , Azinphos-ethyl , Azinphos- methyl, Cadusafos, Chlorethoxyfos , Chlorfenvinphos , Chlormephos, Chlorpyrifos , Chlorpyrifos-methyl , Coumaphos, Cyanophos (CYAP) , Demeton-S-methyl , Diazinon, Dichlorvos (DDVP) , Dicrotophos, Dimethoate, Dimethyl inphos ,
Disulfoton, Ethion, Ethoprophos, Etrimfos, Famphur, Fenamiphos, Fenitrothion (MEP) , Fenthion (MPP) , Fosthiazate, Heptenophos, Imicyfos, Isofenphos, Isopropyl O- (methoxyaminothio-phosphoryl ) salicylate, Isoxathion, Malathion, Mecarbam, Mesulfenfos, Methamidophos ,
Methidathion ( DMTP ) , Mevinphos, Monocrotophos , Naled (BRP) , Omethoate, Oxydemeton-methyl , Parathion, Parathion-methyl , Phenthoate (PAP), Phorate, Phosalone, Phosmet (PMP), Phosphamidon, Phoxim, Pirimiphos-methyl , Profenofos, Propetamphos, Prothiofos, Pyraclorfos, Pyridafenthion, Quinalphos, Sulfotep, Tebupirimfos , Temephos, Terbufos, Tetrachlorvinphos, Thiometon, Triazophos, Trichlorphon (DEP) , Vamidothion, Aluminium phosphide, Butathiofos, Dichlorodiisopropyl ether, Dichlofenthion (ECP) , Formothion, Hydrogen phosphide, Oxydeprofos (ESP) , Propaphos, Salithion, and Sulprofos .
(3) Pyrethroid compounds
Acrinathrin, Allethrin, Benfluthrin, Beta-Cyfluthrin, Bifenthrin, Cycloprothrin, Cyfluthrin, Cyhalothrin, Cypermethrin, Deltamethrin, Esfenvalerate, Ethofenprox, Fenpropathrin, Fenvalerate, Flucythrinate , Flufenoprox, Flumethrin, Fluvalinate, Halfenprox, Imiprothrin,
Permethrin, Prallethrin, Pyrethrins, Resmethrin, sigma- Cypermethrin, Silafluofen, Tefluthrin, Tralomethrin, Transfluthrin, Tetramethrin, Phenothrin, Cyphenothrin, alpha-Cypermethrin, zeta-Cypermethrin, lambda-Cyhalothrin, gamma-Cyhalothrin, Furamethrin, tau-Fluvalinate,
Metofluthrin, Profluthrin, Dimefluthrin, Protrifenbute, 2, 3, 5, 6-tetrafluoro-4- (methoxymethyl) benzyl [EZ) -
( 1RS,3RS;1RS, 3SR) -2 , 2-dimethyl-3-prop-l-enylcyclopropane- carboxylate, 2 , 3 , 5 , 6-tetrafluoro-4-methyl benzyl . {EZ) - {1RS,3RS;1RS,3SR) -2 , 2-dimethyl-3-prop-l-enylcyclopropane- carboxylate, 2,3,5, 6-tetrafluoro-4 - (methoxymethyl) benzyl (1RS,3RS;1RS,3SR) -2 , 2-dimethyl-3- ( 2-methyl-l-propenyl ) - cyclopropanecarboxylate, and the like.
(4) Nereistoxin compounds
Cartap, Bensultap, Thiocyclam, Thisultap, Monosultap, and Bisultap.
(5) Neonicotinoid compounds
Imidacloprid, Acetamiprid, Thiamethoxam, Thiacloprid, Dinotefuran, and Clothianidin .
(6) Benzoylurea compounds
Bistrifluron, Chlorfluazuron, Diflubenzuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Lufenuron, Novaluron, Noviflumuron, Teflubenzuron, Triflumuron, and Fluazuron.
(7) Phenylpyrazole compounds
Acetoprole, Ethiprole, Fipronil, Vaniliprole, Pyriprole, and Pyrafluprole .
(8) Bt toxin insecticides
Live spores derived from Bacillus thuringiesis , crystal toxins produced from Bacillus thuringiesis, and a mixture thereof.
(9) Hydrazine compounds
Chromafenozide , Halofenozide , Methoxyfenozide , and Tebufenozide .
(10) Organochlorine compounds.
Aldrin, Dieldrin, Dienochlor, Endosulfan, Methoxychlor , Chlordane, and DDT.
(11) Active ingredients of other insecticides
Machine oil, Nicotine-sulfate, Nicotine, Abamectin, Emamectin-benzoate, Milbemectin, Lepimectin, Spinosad, Spinetoram, Indoxacarb, Metaflumizone, Buprofezin, Cyromazine, Hydroprene, Methoprene, Kinoprene, Pyriproxyfen, Fenoxycarb, Chlorphenapyr, DNOC, Diafenthiuron, Pymetrozine, Flonicamid, Pyrifluquinazone, Pyridalyl, Tolfenpyrad, Flurimfen, Flufenerim, Spirotetramat , Spiromesifen, sulfoxaflor, Chlorantraniliprole , Cyantraniliprole , Flubendiamide , a compound of Formula (K) :
Figure imgf000103_0001
wherein R is chlorine atom, bromine atom or trifluoromethyl group; R200 is chlorine atom, bromine atom or methyl group; and R300 is chlorine atom, bromine atom or cyano group,
a compound of Formula (L) :
Figure imgf000103_0002
wherein R is chlorine atom, bromine atom or iodine atom, Metoxadiazone, Sulfluramid, Arsenic acid, Benclothiaz, Calcium cyanamide, Calcium polysulfide, Metarn-ammonium, Metam-sodium, Potassium oleate, Sulfur, and Tralopyril.
[0121]
Active ingredients of the acaricides:
Acequinocyl, Amitraz, Benzoximate, Bifenaate, Bromopropylate, Chinomethionat , Chlorobenzilate,
Chlorfenson, Clofentezine , Cyflumetofen, Dicofol, Etoxazole, Fenazaquin, Fenbutatin oxide, Fenothiocarb, Fenpyroximate , Fluacrypyrim, Hexythiazox, Propargite (BPPS) , Polynactins, Pyridaben, Pyrimidifen, Tebufenpyrad, Tetradifon,
Spirodiclofen, Amidoflumet, and cyenopyrafen .
[0122]
Active ingredients of nematicides:
Methyl bromide, 1 , 3-Dichloropropene , DCIP, Fosthiazate, Levamisol, Methyisothiocyanate, Morantel tartarate, and Im cyafos .
[0123]
Active ingredients of the fungicides:
sterol biosynthesis-inhibiting compounds such as Azaconazole, Bitertanol, Bromuconazole , Cyproconazole , Difenoconazole, Diniconazole-M, Epoxiconazole, Fenarimol, Fenbuconazole, Flusilazole, Fluquinconazole , Flutriafol, Hexaconazole, Imazalil, Imibenconazole , Ipconazole, Metconazole, Myclobutanil , Nuarimol, Oxpoconazole , Pefurazoate, Penconazole, Prochloraz, Propiconazole , Prothioconazole, Pyrifenox, Simeconazole , Tebuconazole , Tetraconazole, Triadimefon, Triadimenol, Triflumizole , Trifolin, Txiticonazole, Aldimorph, Dodemorph,
Fenpropimorph, Tridemorph, Fenpropidin, Piperalin, Spiroxamine, Fenhexamide, Pyributicarb, Naphtifine, Terbinafine;
cytostatic compounds such as Benomyl,. Carbendezim, Fuberidazole, Thiabendazole, Thiphanate, thiophanate-methyl , Diethofencarb, Zoxamide, Pencycuron, and Fluopicolide;
signal inhibiting compounds such as Chlozolinate, Iprodione, Procymidone, Vinclozolin, Quinoxyfen,
Proquinazid, Fenpiclonil, and Fludioxonil ;
amino acid biosynthesis-inhibiting compounds such as cyprodinil, pyrimethanil , and Mepanipyrim;
nucleic acid biosynthesis-inhibiting compounds such as Metalaxyl, Benalaxyl, and Oxolinic acid;
lipid/membrane synthesis-inhibiting compounds such as Isoprothiolane, Iprobenfos, Tolclofos-methyl , Prothiocarb, Dimethomorph, Benthiavalicarb-isopropyl, . Iprovalicarb, and Mandipropamid;
melanin biosynthesis-inhibiting compounds such as Diclocymet, Carpropamid, Fenoxanil, Fthalide, Tricyclazole , and Pyroquilon;
strobilurin compounds such as Azoxystrobin, Dimoxystrobin, Enestrobin, Fluoxastrobin, Kresoxim-methyl , Metominostrobin, Orysastrobin, Picoxystrobin,
Pyraclostrobin, Pyribencarb, and Trifloxystrobin;
anilide compounds such as Carboxin, Oxycarboxin,
Mepronil, Flutoranil, Furametopyr, Thifluzamide, Boscalid, Penthiopyrad, Fluopyram, Bixafen, Isopyrazam, Penflufen, Sedaxan, and Fluxapyrox.ad;
resistance induced compounds such as Acibenzolar-S- methyl, Probenazole, Tiadinil, and Isotianil; glucan synthesis-inhibiting compounds such as Validamycin A and Polyoxin B;
protein biosynthesis-inhibiting compounds such as Blastcidin-S , Kasugamycin, and Streptomycin;
compounds with mutiple active sites such as Thiuram, Mancozeb, Chlorothalonil, Captan, Dichlofluanid, Folpet, Iminoctadine, and Ziram;
Amisulbrom, Cyazofamid, Ferimzone, Fluazinam, Binapacryl, Dinocap, Famoxadone, Fenamidone, Ethaboxam, Metrafenone, Cyflufenamid, and the like.
[0124]
Active ingredients of the herbicides:
(1) Phenoxy fatty acid compounds
2,4-PA, MCP, MCPB, Phenothiol, Mecoprop, Fluroxypyr, Triclopyr, Clomeprop, and Naproanilide .
(2) Benzoic acid compounds
2,3,6-TBA, Dicamba, Clopyralid, Picloram, Aminopyralid, Quinclorac, and Quinmerac.
(3) Urea compounds
Diuron, Linuron, - Chlortoluron, Isoproturon,
Fluometuron, Isouron, Tebuthiuron, Methabenzthiazuron, Cumyluron, Daimuron, and Methyl-daimuron.
(4) Triazine compounds
Atrazine, Ametoryn, Cyanazine, Simazine, Propazine, Simetryn, Dimethametryn, Prometryn, Metribuzin, Triaziflam, W
106 and Indaziflam.
(5) Bipyridinium compounds
Paraquat and Diquat.
(6) Hydroxybenzonitrile compounds
Bromoxynil and Ioxynil.
(7) Dinitroaniline compounds
Pendimethalin, Prodiamine and Trifluralin.
(8) Organophosphorus compounds
Amiprofos-methyl , Butamifos, Bensulide, Piperophos, Anilofos, Glyphosate, Glufosinate, Glufosinate-P, and Bialaphos.
(9) Carbamate compounds
Di-allate, Tri-allate, Butylate, Benthiocarb, Esprocarb, Molinate, Dimepiperate, Swep, Chlorpropham, Phenmedipham, Phenisopham, Pyributicarb, and Asulam.
(10) Acid amide compounds
Propanil, Propyzamide, Bromobutide, and Etobenzanid.
(11) Chloroacetanilide compounds
Acetochlor, Alachlor, Butachlor, Dimethenamid, Propachlor, Metazachlor, Metolachlor, Pretilachlor, Thenylchlor, and Pethoxamid.
(12) Diphenyl ether compounds
Acifluorfen-sodium, Bifenox, Oxyfluorfen, Lactofen, Fomesafen, Chlomethoxynil , and Aclonifen.
(13) Cyclic imide compounds Oxadiazon, Cinidon-ethyl , Carfentrazone-ethyl ,
Surfentrazone , Flumiclorac-pentyl , Flumioxazin, Pyraflufen- ethyl, Oxadiargyl, Pentoxazone, Fluthiacet-methyl , Butafenacil, Benzfendizone , Bencarbazone , and Saflufenacil . (14) Pyrazole compounds
Benzofenap, Pyrazolate, Pyrazoxyfen, Topramezone, and Pyrasulfotole.
(15.) Triketone compounds
Isoxaflutole, Benzobicyclon, Sulcotrione, Mesotrione, Tembotrione , and Tefuryltrione .
(16) Aryloxyphenoxy-propionic acid compounds
Clodinafop-propargyl , Cyhalofop-butyl , Diclofop-methyl , Fenoxaprop-ethyl , Fluazifop-butyl, Haloxyfop-methyl ,
Quizalofop-ethyl , and Metamifop.
(17) Trioneoxime compounds
Alloxydim-sodium, Sethoxydim, Butroxydim, Clethodim, Cloproxydim, Cycloxydim, Tepraloxydim, Tralkoxydim, and Profoxydim.
(18) Sulfonylurea compounds
Chlorsulfuron, Sulfometuron-methyl , Metsulfuron-methyl , Chlorimuron-ethyl, Tribenuron-methyl , Triasulfuron,
Bensulfuron-methyl , Thifensulfuron-methyl , Pyrazosulfuron- ethyl, Primisulfuron-methyl , Nicosulfuron, Amidosulfuron, Cinosulfuron, Imazosulfuron, Rimsulfuron, Halosulfuron- methyl, Prosulfuron, Ethametsulfuron-methyl , Triflusulfuron-methyl , Flazasulfuron, Cyclosulfamuron, Flupyrsulfuron, Sulfosulfuron, Azimsulfuron, Ethoxysulfuron, Oxasulfuron, Iodosulfuron-methyl-sodium, Foramsulfuron, Mesosulfuron-methyl , Trifloxysulfuron, Tritosulfuron, orthosulfamuron, Flucetosulfuron, and Propyrisulfuron .
(19) Imidazolinone compounds
Imazamethabenz-methyl, Imazamethapyr, Imazamox,
Imazapyr, Imazaquin, Imazethapyr, and the like.
(20) Sulfonamide compounds
Flumetsulam, Metosulam, Diclosulam, Florasulam, Cloransulam-methyl, Penoxsulam, and Pyroxsulam.
(21) Pyrimidinyloxybenzoate compounds
Pyrithiobac-sodium, Bispyribac-sodium, Pyriminobac- methyl, Pyribenzoxim, Pyriftalid, and Pyrimisulfan .
(22) Other compounds
Bentazon, Bromacil, Terbacil, Chlorthiamid, Isoxaben, Dinoseb, Amitrole, Cinmethylin, Tridiphane, Dalapon, Diflufenzopyr-sodium, Dithiopyr, Thiazopyr, Flucarbazone- sodium, Propoxycarbazone-sodium, Mefenacet, Flufenacet, Fentrazamide, Cafenstrole, Indanofan, Oxaziclomefone, Benfuresate, Pyridate, Chloridazon, Norflurazon, Flurtamone, Diflufenican, Picolinafen, Beflubutamid, Clomazone, Amicarbazone, Pinoxaden, Pyraclonil, Pyroxasulfone, Thiencarbazone-methyl, Aminocyclopyrachlor, Ipfencarbazone, and Methiozolin. [0125]
Active ingredients of the synergists:
Piperonyl butoxide, Sesamex, Sulfoxide, N- (2- ethylhexyl ) -8 , 9, 10-trinorborn-5-en-2 , 3-dicarboximide (MGK 264), N-Declyimidazole, WARF-antiresistant , TBPT, TPP, IBP, PSCP, CH3I, t-Phenylbutenone, Diethylmaleate, DMC, FDMC, ETP, and ET .
(Example)
[0126]
Hereinafter, the present inventions are illustrated more specifically by the following Manufacturing Examples, Formulation Examples and Test Examples, but the present inventions are not limited thereto.
[0127]
Hereinafter, Manufacturing Examples of the present compounds are illustrated.
[0128]
Manufacturing Example 1
To a mixture of 0.96 g of 2-methylcyclopropylmethanol and 22 mL of tetrahydrofuran was added 0.45 g of 60 % sodium hydride (in oil) at ice temperature, and the mixture was stirred for 15 minutes. The reaction mixture was added to a mixture of 1.5 g of 4 , 6-dichloropyrimidine and 23 mL of tetrahydrofuran, and the mixture was stirred at 60°C for 2 days. After cooling the reaction mixture to room temperature, water was poured into the reaction mixture and the reaction mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure to obtain 1.9 g of 4- chloro-6- (2-methylcyclopropylmethoxy) pyrimidine (oil) :
Figure imgf000111_0001
A mixture of 0.48 g of 4-chloro-6- (2-methylcyclopropylmethoxy) pyrimidine, 4 mL of NMP and 0.25 g of 1,2,4- triazole sodium was stirred at 50°C for 2 days. After cooling the reaction mixture to room temperature, water was poured into the reaction mixture and the reaction mixture was extracted with ethyl acetate. The organic layer was washed sequentially with aqueous saturated ammonium chloride solution and water, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 0.17 g of Compound 2 :
Figure imgf000111_0002
[0129]
Manufacturing Example 2
A mixture of 10.0 g of 4 , 6-dichloropyrimidine , W
111 of tetrahydrofuran and 7.4 g of imidazole sodium was stirred for 2 days while heating at reflux. After cooling the reaction mixture to room temperature, water was poured into the reaction mixture and the reaction mixture was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 5.4 g of 4-chloro-6- imidazolylpyrimidine :
Figure imgf000112_0001
1H-NMR (CDC13). δ : 7.25-7.26 (1H, m) , 7.35-7.37 (1H, m) , 7.63-7.65 (1H, m) , 8.45-8.47 (1H, m) , 8.86-8.88 (1H, m) .
To a mixture of 0.26 g of. 2-methylcyclopropylmethanol and 10 mL of tetrahydrofuran was added 0.12 g of 60 % sodium hydride (in oil), and the mixture was stirred for 1 hour. To the/reaction mixture was added 0.5 g of 4-chloro- 6-imidazolylpyrimidine , and the mixture was stirred for 1 day at room temperature. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 0.34 g of Compound 3:
Figure imgf000113_0001
[0130]
Manufacturing Example 3
To a mixture of 11.1 g of 1, 2, -triazole, 20 mL of acetonitrile and 20.7 g of N-ethyldiisopropylamine was added 7.34 g of 4 , 5 , 6-trichloropyrimidine at room temperature. The mixture was stirred for 2 hours at room temperature. The reaction mixture was filtered to collect the resultant solid. The solid was washed with acetonitrile and dried to obtain 8.24 g of 5-chloro- , 6- bis ( [l,2,4]triazol-l-yl) -pyrimidine :
Figure imgf000113_0002
■"■H-NMR (CDC13) δ: 8.26 (2H, s), 8.98 (1H, s), 9.12 (2H, s).
To a mixture of 0.50 g of 5-chloro- , 6- bis ( [1, 2, ] triazol-l-yl) -pyrimidine, 4 mL of NMP and 0.17 g of 2-methylcyclopropane-methanol was added 0.32 g of DBU at ice temperature, and the mixture was stirred for 1 hour at ice temperature. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with aqueous saturated ammonium chloride solution and then water, dried over sodium sulfate, and concentrated under reduced pressure to obtain 0.49 g of Compound 13:
Figure imgf000114_0001
[0131]
Manufacturing Example
To a mixture of 2.65 g of 1, 2, 4-triazole, 10 mL of acetonitrile and 4.96 g of N-ethyldiisopropylamine was added 2.61 g of 4 , 6-dichloro-5-methylpyrimidine at room temperature. The mixture was heated for 14 hours at reflux The reaction mixture was cooled and filtered to collect the resultant solid. The solid was washed with acetonitrile and dried to obtain 2.12 g of 5-methyl-4 , 6- bis( [l,2,4]triazol-l-yl) -pyrimidine :
Figure imgf000114_0002
""■H-NMR (DMSO-D6) δ: 2.56 (3H, s), 8.45 (2H, s) , 9.11 (1H, s) , 9.40 (2H, s) .
To a mixture of 0.46 g of 5-methyl-4 , 6- bis ( [1, 2, 4] triazol-l-yl) -pyrimidine, 3 mL of NMP and 0.18 g of 2-methylcyclopropanemethanol was added 0.33 g of DBU at room temperature, and the mixture was stirred for 1 day at room temperature. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate-. The organic layer was washed with aqueous saturated ammonium chloride solution and then water, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 0.42 g of Compound 14:
Figure imgf000115_0001
[0132]
Manufacturing Example 5
To a mixture of 0.25 g of 5-chloro-4 , 6- bis ( [1, 2, 4] triazol-l-yl) -pyrimidine, 3 mL of NMP and 0.17 g of 2, 2-dichloro-3, 3-dimethylcyclopropanemethanol was added 0.17 g of DBU at ice temperature, and the mixture was stirred for 15 minutes at ice temperature. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with aqueous saturated ammonium chloride solution and then water, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 0.28 g of Compound 16:
Figure imgf000115_0002
[0133]
Manufacturing Example 6
To a mixture of 27.6 g of 1, 2, 4-triazole, 100 mL of acetonitrile and 51.7 g of N, N-diisopropylethylamine was added 14.9 g of , 6-dichloropyrimidine at room temperature. The mixture was stirred for 3 hours at room temperature, and then heated for 8 hours at reflex. After cooling and filtering the reaction mixture, the filter residue was washed with acetonitrile and dried to obtain 13.8 g of 4,6- bis ( [ 1 , 2 , ] triazol-l-yl ) -pyrimidine :
Figure imgf000116_0001
1H-NMR (DMSO-D6) δ: 8.11 (1H, d) , 8.50 (2H, s), 9.18 (1H, d) , 9.62 (2H, s) .
To a mixture of 0.43 g of 4 , 6-bis ( [ 1 , 2 , 4 ] triazol-1- yl ) -pyrimidine, 3 mL of NMP and 0.32 g of 1, 4-dioxa- spiro [4.5] decan-8-ol was added 0.36 g of DBU at ice temperature. The mixture was stirred for 7 hours at 80°C. After cooling the reaction mixture to room temperature, water was poured into the reaction mixture and the reaction mixture was extracted with ethyl acetate. The organic layer was washed with aqueous saturated ammonium chloride solution and then water, dried over sodium sulfate, and concentrated under reduced pressure to obtain 0.20 g of Compound
Figure imgf000117_0001
[0134]
Manufacturing Example.7
A mixture of 0.2 g of Compound 27, a catalytic amount of pyridinium p-toluenesulfonate , 10 mL of acetone and 10 mL of water was stirred for 1 day while heating at reflux. After cooling the reaction mixture to room temperature, brine was added to the reaction mixture and the reaction mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure to obtain 0.17 g of Compound 28:
Figure imgf000117_0002
[0135]
Manufacturing Example 8
To a mixture of 0.15 g of Compound 28 and 3 mL of chloroform was added 0.14 g of DAST at ice temperature, and the mixture was stirred for 1 day at room temperature.
Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated sodium bicarbonate solution and then water, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 0.04 g of Compound 29:
Figure imgf000118_0001
[0136]
Manufacturing Example 9
To a mixture of 0.81 g of DAST and 5 mL of chloroform was added a mixture of 0.52 g of Compound 28 and 10 mL of chloroform at -78°C. The mixture was stirred for 1 hour at room temperature. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 0.10 g of Compound 3 :
Figure imgf000118_0002
[0137]
Manufacturing Example 10
To a mixture of 4.56 g of 5-methyl-4 , 6- bis ( [1, 2, 4] triazol-l-yl) -pyrimidine, 20 mL of NMP and 3.16 g of 1, -dioxa-spiro [4.5] decan-8-ol was added 4.0 g of DBU 1 074232
118 at room temperature, and the mixture was stirred for 5 hours at 80°C. After cooling the reaction mixture to room temperature, water was poured into the reaction mixture and the reaction mixture was extracted with ethyl acetate. The organic layer was washed with aqueous saturated ammonium chloride solution and then water, dried over sodium sulfate, and concentrated under reduced pressure to obtain Compound 117:
Figure imgf000119_0001
A mixture of the above-prepared Compound 117, a catalytic amount of p-toluenesulfonic acid monohydrate, 50 mL of acetone and 50 mL of water was stirred for 5 hours while heating at reflux. After cooling the reaction mixture to room temperature, brine was added to the reaction mixture and the reaction mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure to obtain 2.59 g of Compound 78:
Figure imgf000119_0002
[0138]
Manufacturing Example To a mixture of 0.40 g of DAST and 5 mL of methylene chloride was added a mixture of 3 mL of methylene chloride and 0.27 g of Compound 78 at ice temperature. The mixture was stirred for 1 hour at room temperature. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 0.12 g of Compound 35:
Figure imgf000120_0001
[0139]
Manufacturing Example 12
To a mixture of 0.75 g of 5-chloro-4 , 6- bis ( [1, 2, 4] triazol-l-yl) -pyrimidine, 4 mL of NMP and 0.52 g of 1, 4-dioxa-spiro [4.5] decan-8-ol was added 0.60 g of DBU at ice temperature. The mixture was stirred for 1 hour at room temperature. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate.
The organic layer was washed with aqueous saturated ammonium chloride solution and then water, dried over sodium sulfate, and concentrated under reduced pressure to obtain Compound 118:
Figure imgf000121_0001
A mixture of the above-prepared Compound 118, a catalytic amount of pyridinium p-toluenesulfonate , 20 mL of acetone and 20 mL of water was stirred for 1 day while heating at reflux. After cooling the reaction mixture to room temperature, brine was added to the reaction mixture and the reaction mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure to obtain 0.72 g of Compound 80:
Figure imgf000121_0002
[0140]
Manufacturing Example 13
To a mixture of 0.40 g of DAST and 5 mL of methylene chloride was added a mixture of 0.29 g of Compound 80 and 3 mL of methylene chloride at ice temperature, and the mixture was stirred for 1 hour at room temperature. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 0.12 g of Compound 36:
Figure imgf000122_0001
and 0.06 g of Compound 37.
Figure imgf000122_0002
[0141]
Manufacturing Example 14
To a mixture of 0.52 g of Compound 28 and 4 mL of methylene chloride was added 1.58 g of tungsten hexachloride at room temperature. The mixture was stirred for 1 hour while heating at reflux. After cooling the reaction mixture, water was poured into the reaction mixture and the reaction mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 0.4 g of Compound 38:
Figure imgf000122_0003
[0142]
Manufacturing Example 15 To a mixture of 0.27 g of Compound 78 and 3 mL of methylene chloride was added 0.8 g of tungsten hexachloride at room temperature, and the mixture was stirred for 2 hours while heating at reflux. After cooling the reaction mixture, water was poured, into the reaction mixture and the reaction mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The residue, was purified by silica gel chromatography to obtain 0.12 g of Compound 40:
Figure imgf000123_0001
[0143]
Manufacturing Example 16
To a mixture of 0.29 g of Compound 80 and 3 mL of methylene chloride was added 0.8 g of tungsten hexachloride at room temperature, and the mixture was stirred for 2 hours while heating at reflux. After cooling the reaction mixture, water was poured into the reaction mixture and the reaction mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 0.05 g of Compound 41:
Figure imgf000124_0001
[0144]
Manufacturing Example 17
To a mixture of 0.46 g of 5-methyl-4 , 6- bis ( [1, 2, 4] triazol-l-yl) -pyrimidine, 0.20. g of tetrahydropyran-4-ol and 3 mL of NMP was added 0.40 g of DBU at ice temperature, and the mixture was stirred for 2 hours at 80°C. After cooling the reaction mixture to room temperature, water was poured into the reaction mixture and the reaction mixture was extracted with ethyl acetate. The organic layer was washed with aqueous saturated ammonium chloride solution and then water, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 0.28 g of Compound 43:
Figure imgf000124_0002
[0145]
Manufacturing Example 18
To a mixture of 0.46 g of 5-methyl-4 , 6- bis ( [1, 2, 4] triazol-l-yl) -pyrimidine, 0.34 g . of 4- ( trifluoromethyl) cyclohexanol and 3 mL of NMP was added 0.35 g of DBU at ice temperature. The mixture was stirred for 2 hours at 80°C and then for 5 hours at 110°C. After cooling the reaction mixture, water was poured into the reaction mixture and the reaction mixture was extracted with ethyl acetate. The organic layer was washed with aqueous saturated ammonium chloride solution and then water, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 0.11 g of Compound 50:
Figure imgf000125_0001
and 0.14 g of Compound 51
Figure imgf000125_0002
[0146]
Manufacturing Example 19
To a mixture of 1.07 g of , 6-bis ( [ 1 , 2 , 4 ] triazol-1- yl) -pyrimidine, 0.59 g of tetrahydrothiopyran-4-ol and 6 mL of NMP was added 0.85 g of DBU at ice temperature. The mixture was stirred for 7 hours at 70°C. After cooling the reaction mixture, water was poured into the reaction mixture and the reaction mixture was extracted with ethyl acetate. The organic layer was washed with aqueous saturated ammonium chloride solution and then water, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 1.04 g of Compound 62:
Figure imgf000126_0001
[0147]
Manufacturing Example 20
To a mixture of 1.14 g of 5-methyl-4 , 6- bis ( [1, 2, ] triazol-l-yl) -pyrimidine, 0.59 g of tetrahydrothiopyran-4-ol and 6 mL of NMP was added 0.85 g of DBU at ice temperature, and the mixture was stirred for 7 hours at 70°C. After cooling the reaction mixture, water was poured into the reaction mixture and the reaction mixture was extracted with ethyl acetate. The organic layer was washed with aqueous saturated ammonium chloride solution and then water, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 1.07 g of Compound 6 :
Figure imgf000126_0002
[0148] Manufacturing Example 21
To a mixture of 0.26 g of Compound 62 and 3 mL of chloroform was added 0.48 g of m-chloroperbenzoic acid at room temperature. The mixture was stirred for 2 hours at room temperature and then for 2 hours at 50°C. After cooling the reaction mixture, water was poured into the reaction mixture and the reaction mixture was extracted with ethyl acetate. The organic layer was washed with saturated sodium bicarbonate solution and then water, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 0.08 g of Compound 67:
Figure imgf000127_0001
and 0.05 g of Compound 69:
Figure imgf000127_0002
[0149]
Manufacturing Example 22
To a mixture of 0.28 g of Compound 64 and 3 mL of chloroform was added 0.48 g of m-chloroperbenzoic acid at room temperature. The mixture was stirred for 2 hours at room temperature and then for 2 hours at 50°C. After cooling the reaction mixture, water was poured into the reaction mixture and the reaction mixture was extracted with ethyl acetate. The organic layer was washed with saturated sodium bicarbonate solution and then water, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 0.10 g of Compound 68:
Figure imgf000128_0001
and 0.10 g of Compound 70:
Figure imgf000128_0002
[0150]
Manufacturing Example 23
To a mixture of 0.23 g. of 5-methyl-4 , 6- bis ( [1, 2, 4] triazol-l-yl) -pyrimidine, 0.14 g of 4- chlorocyclohexanol and 2 mL of NMP was added 0.04 g of 60 % sodium hydride (in oil) at ice temperature. The mixture was stirred for 2 hours at room temperature. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with aqueous saturated ammonium chloride solution and then water, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 0.07 g of Compound 71:
Figure imgf000129_0001
[0151]
Manufacturing Example 24
To a mixture of 0.35 g of 5-methyl-4 , 6- bis ( [1, 2, 4] triazol-l-yl) -pyrimidine, 0.18 g of 4- fluorocyclohexanol and 3 mL of NMP was added 0.06 g of 60 % sodium hydride (in oil) at ice temperature. The mixture was stirred for 1 hour at room temperature and then for 3 hours at 50°C. After cooling the reaction mixture, water was poured into the reaction mixture and the reaction mixture was extracted with ethyl acetate. The organic layer was washed with aqueous saturated ammonium chloride solution and then water, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 0.11 g of Compound 72:
Figure imgf000129_0002
[0152]
Manufacturing Example To a mixture of 0.42 g of , 6-di ( imidazol-l-yl ) - pyrimidine, 0.24 g of tetrahydrothiopyran-4-ol and 3 mL of NMP was added 0.40 g of DBU at ice temperature. The mixture was stirred for 3 hours at 70°C and then for 5 hours at 80°C. After cooling the reaction mixture, water was poured into the reaction mixture and the reaction mixture was extracted with ethyl acetate. The organic layer was washed with aqueous saturated ammonium chloride solution and then water, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 0.08 g of Compound 74:
Figure imgf000130_0001
[0153]
Manufacturing Example 26
To a mixture of 1.49 g of 5-methyl-4 , 6- bis ([ 1 , 2 , 4 ] triazol-l-yl ) -pyrimidine, 1.03 g of 1,4- dioxaspiro [4.5] decan-7-ol and 5 mL of NMP was added 1.12 g of DBU at ice temperature. The mixture was stirred for 2 hours at 70°C. After cooling the reaction mixture, water was poured into the reaction mixture and the reaction mixture was extracted with ethyl acetate. The organic layer was washed with aqueous saturated ammonium chloride solution and then water, dried over sodium sulfate, and concentrated nder reduced pressure. The residue was purified by silica gel chromatography to obtain 0.63 g of Compound 119:
Figure imgf000131_0001
A mixture of 0.63 g of Compound 119, a catalytic amount of p-toluenesulfonic acid monohydrate, 20 mL of acetone and 30 mL of water was stirred for 2 days while heating at reflux. After cooling the reaction mixture to room temperature, brine was added to the reaction mixture and the reaction mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 0.17 g of Compound 120:
Figure imgf000131_0002
To a mixture of 0.40 g of bis (2- methoxyethyl) aminosulfur trifluoride and 3 mL of methylene chloride was added 0.16 g of Compound 120 at 0°C, and the mixture was stirred for 3 hours at room temperature. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The resultant organic layer was dried over sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 0.05 g of Compound 81:
Figure imgf000132_0001
[0154]
Manufacturing Example 27
To a mixture of 12.0 g of methyl 3-mercaptopropionate and 150 mL of water was added 16.81 g of ethyl 4,4,4- trifluorocrotonate . The mixture was stirred for 1 hour at 35°C. To the mixture was added 30 mL of acetonitrile and a catalytic amount of triethyl benzyl ammonium chloride, and the mixture was stirred for 2 hours at 50°C. After cooling the reaction . mixture to room temperature, water was poured into the reaction mixture and the reaction mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure to obtain a crude product, ethyl 4 , 4 , 4-trifluoro-3- ( 2- methoxycarbonyl-ethylsulfanil ) -butanoate :
Figure imgf000132_0002
1H-NMR (CDC13) δ : 1.25-1.35 (3H, m) , 2.47-2.61 (1H, m) , 2.63-2.72 (2H, m) , 2.81-2.91 (1H, m) , 2.94-3.05 (2H, m) , 3.57-3.69 (1H, m) , 3.71 (3H, s) , 4.15-4.27 (2H, m) .
To a mixture of 100 mL of tetrahydrofuran and 2.5 g of metal sodium was added 3.9 g of methanol at room temperature, and the mixture was stirred for 8 hours at room temperature. The reaction mixture was cooled at ice temperature. To the mixture was added the above-prepared ethyl 4 , 4 , 4-trifluoro-3- (2-methoxycarbonyl-ethylsulfanil) - butanoate, and the mixture was stirred for 3 hours at room temperature. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 16.5 g of a crude product .
A mixture of 4 g of concentrated sulfuric acid and water was heated at reflux. To the mixture was added 5 g of the above-prepared crude product, and the mixture was stirred for 2 hours while heating at reflux. The reaction mixture was cooled to room temperature and extracted with chloroform. The organic layer was dried over sodium sulfate and concentrated under reduced pressure to obtain 3.95 g of 2-trifluoromethyl-tetrahydrothiopyran-4 -one :
Figure imgf000133_0001
To a mixture of 3.95 g of 2-trifluoromethyl- tetrahydrothiopyran-4-one and 30 mL of methanol was added 0.90 g of sodium tetrahydroborate at ice temperature. The mixture was stirred for 3 hours at room temperature. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was dried over sodium sulfate and concentrated under reduced pressure The residue was purified by silica gel chromatography to obtain 0.9 g of 2-trifluoromethyltetrahydrothiopyran-4-ol :
Figure imgf000134_0001
To a mixture of 0.46 . g of 5-methyl-4 , 6- bis ( [1, 2, 4] triazoi-l-yl) -pyrimidine, 0.37 g of 2- trifluoromethyl-tetrahydrothiopyran-4-ol and 3 mL of NMP was added 0.40 g of DBU at room temperature. The mixture was stirred for 5 hours at 80°C. After cooling the reaction mixture, water was poured into the reaction mixture and the reaction mixture was extracted with ethyl acetate. The organic layer was washed with aqueous saturated ammonium chloride solution and then water, dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel chromatography to obtain 0.32 g of Compound 101:.
Figure imgf000134_0002
[0155]
The compounds in the following tables were prepared in a similar manner to the a'bove-mentioned processes.
[0156]
A compound of Formula (1) :
Figure imgf000135_0001
wherein Gyc-A-Q group, R1, R2, R3, R4 and G1 are defined in Tables 7 to 15.
[0157] Table 7
Figure imgf000136_0001
[0158]
Table 8
Figure imgf000137_0001
Figure imgf000138_0001
[0160]
Table 10
Figure imgf000139_0001
[0161]
Table 11
Figure imgf000140_0001
[0162]
Table 12
Figure imgf000141_0001
[0163] Table 13
Figure imgf000142_0001
[0164] Table 14
Figure imgf000143_0001
[0165]
Table 15
Figure imgf000144_0001
[0166]
■"■H-NMR data of the. present compounds listed in Tables 7 to 15 are shown below.
[0167]
Compound 1
1H-NMR (CDC13) δ: 0.36-0.42 (2H, m) , 0.61-0.69 (2H, m) , 1.26-1.38 (1H, m) , 4.28 (2H, d) , 7.24 (1H, s), 8.12 (1H, s), 8.63 (1H, s) , 9.18 (1H, s) .
Compound 2
^- MR (CDCI3) δ: 0.36-0.45 (1H, m) , 0.49-0.58 (1H, m) , 0.76-0.85 (1H, m) , 0.99-1.07 (1H, m) , 1.09 (3H, d) , 4.22- 4.32 (2H, m) , 7.23 (1H, s), 8.11 (1H, s), 8.62 (1H, s), 9.17 (1H, s) .
Compound 3
1H-NMR (CDC13) δ: 0.36-0.43 (1H, m) , 0.50-0.56 (1H, m) , 0.75-0.87 (1H, m) , 0.96-1.05 ( 1H, m) , 1.10 (3H, d) , 4.19- 4.34 (2H, m) , 6.67 (1H, brs) , 7.21 (1H, brs) , 7.60 (1H, brs), 8.41 (1H, brs), 8.62 (1H, brs).
Compound 4
XH-NMR (CDCI3) δ: 1.83-2.05 (4H, m) , 2.11-2.18 (2H, m) , 2.75-2.86 (1H, m), 4.41 (2H, . d) , 7.22 (1H, brs), 8.11 (1H, s), 8.64 (1H, brs), 9.18 (1H, s).
Compound 5
1H-NMR (CDCI3) δ: 1.80-2.06 (4H, m) , 2.09-2.22 (2H, m) , 2.72-2.87 (1H, m) , 4.40 (2H, d) , 6.66 (1H, brs), 7.21 (lH, brs), 7.60 (1H, brs), 8.41 (1H, s), 8.6 (1H, brs).
Compound 6
^- MR (CDCI3) δ: 1.28-1.44 (2H, m) , 1.55-1.74 (4H, m) , 1.78-1.89 (2H, m) , 2.34-2.46 (1H, m) , 4.31 (2H, d) , 7.21 (1H, d) , 8.11 (1H, s), 8.63 (1H, d) , 9.18 (1H, s).
Compound 7
XH-NMR (CDCI3) δ: 1.32-1.40 (2H, m) , 1.56-1.71 (4H, m) , 1.80-1.88 (2H, m) , 2.32-2.44 (1H, m) , 4.31 (2H, d) , 6.66 (1H, brs), 7.21 (1H, brs), 7.60 (1H, brs), 8.41 (1H, s), 8.64 (1H, brs) .
Compound 8 1H-NMR (CDC13) δ: 1.00-1.37 (5H, m) , 1.67-1.89 (6H, m) , 4.24 (2H, d) , 7.21 (1H, d) , 8.11 (1H, s) , 8.63 (1H, d) , 9.18 (lH, s) .
Compound 9
1H-NMR (CDCI3) δ: 0.99-1.15 (2H, m) , 1.16-1.39 (3H, m) , 1.67-1.90 (6H, m) , 4.23 (2H, d), 6.65 (1H, brs), 7.21. (1H, brs), 7.60 (1H, brs), 8.41 (1H, s), 8.64 (1H, brs).
Compound 10
""■H-NMR (CDCI3) δ: 5.27 (2H, d) , 6.80 (1H, brs), 7.23 (1H, brs), 7.62 (1H, brs), 8.45 (1H, brs), 8.70 (1H, brs).
[0168]
Compound 11
1H-NMR (CDCI3) δ: 1.58-1.67 (1H, m), 1.87-1.96 (2H, m) , 2.07-2.18 (1H, m) , 2.32-2.44 (lH,. m) , 3.40-3.48 (1H, m) , 3.73-3.82 (1H, m) , 3.85-3.93 (1H, m) , 3.94-4.00 (1H, m) , 4.41-4.54 (2H, m) , 7.21 (1H, d) , 8.12 (1H, s) , 8.64 (1H, d) , 9.18 (1H, s) .
Compound 12
■"■H-NMR (CDCI3) δ: 1.56-1.65 (1H, m) , 1.84- ■1. ,96 (2H, m) ,
2.06-2.15 (1H, m) , 2.30-2.43 (1H, m) , 3.38- -3 .48 (1H, m) ,
3.71-3.82 (1H, m) , 3.84-4.01 (2H, m) , 4.36- -4 .53 (2H, m) ,
6.65 (1H, s), 7.21 (1H, s), 7.60 (1H, s) , 8 .41 (1H, s) ,
8.64 (1H, s) .
Compound 13
■"■H-NMR (CDCI3) δ: 0.38-0.46 (1H, m) , 0.56- ■0. 63 (1H, m) , 0.79-0.91 (1H, m) , 1.04-1.13 (4H, m) , 4.31-4.48 (2H, m) , 8.20 (1H, s), 8.56 (1H, s), 9.02 (1H, s).
Compound 14
XH-NMR (CDCI3) δ: 0.35-0.43 (1H, m) , 0.51-0.59 (1H, m) , 0.75-0.87 (1H, m) , 1.02-1.15 (4H, m) , 2.45-2.50 (3H, m) , 4.21-4.37 (2H, m) , 8.13 (lH, s), 8.50 (1H, s), 9.03 (1H, s). Compound 15
1H-NMR (CDCI3) δ: 1.32 (3H, s), 1.43 (3H, s), 1.77 (1H, t), 4.48-4.67 (2H, m) , 7.28 (1H, s), 8.12 (1H, s),.8.66 (1H, s), 9.18 (1H, s) .
Compound 16
1H-NMR (CDCI3) . δ: 1.35 (3H, s) , 1.45 (3H, s), 1.84 (1H, t) , 4.58 (1H, dd) , 4.80 (1H, dd) , 8.21 (1H, s), 8.60 (1H, s),
9.05 (1H, s) .
Compound 17
1H-NMR (CDCI3) δ: 1.33 (3H, s), 1.44 (3H, s), 1.80 (lH, t) , 2.50 (3H, s), 4.52-4.67 (2H, m) , 8.14 (1H, s), 8.53 (1H, s),
9.06 (1H, s) .
Compound 18
1H-NMR (CDCI3) δ: 0.42-0.48 (2H, m) , 0.55-0.62 (2H, m) , 1.24 (3H, s), 2.50 (3H, s) , 4.24 (2H, s), 8.13 (1H, s), 8.49 (1H, s) , 9.04 (1H, s) .
Compound 19
■"■H-NMR (CDCI3) δ: 0.81-2.43 (10H, m) , 5.43-5.58 (1H, . m) , 7.14-7.18 (1H, m) , 8.11 (1H, s), 8.63 (1H, s), 9.17 (1H, s). Compound 20
1H-NMR (CDC13) δ: 1.24-1.5 (3H, m) , 1.74-1.87 (3H, m) ,
2.23-2.37 (2H, m) , 4.01-4.10 (1H, m) , 5.27-5.37 (1H, m) , 7.25 (1H, s), 8.12 (1H, s), 8.64 (1H, s) , 9.18 (1H, s) .
[0169]
Compound 21
XH-NMR (CDCI3) δ: 0.29-0.50 (2H, m) , 0.51-0.65 (2H, m) ,
1.13-1.20 (1H, m) , 1.41-1.47 (3H, m) , 4.78-4.89 (1H, m) , 7.19 (1H, s), 8.11 (1H, s), 8.59 (1H, s), 9.17 (1H, s).
Compound .22
1H-NMR (CDCI3) δ: 1.62-1.74 (2H, m) , 1.75-1.91 (4H, m) ,
1.95-2.07 (2H, m) , 5.48-5.58 (1H, m) , 7.16 (1H, s), 8.11 (1H, s), 8.64 (1H, s), 9.17 (1H, s).
Compound 23
1H-NMR (CDCI3) δ: 1.20-1.51 (4H, m) , 1.54-1.66 (2H, m) ,
1.75-1.89 (2H, m) , 1.93-2.07 (2H, m) , 5.12-5.24 (1H, m) , 7.17 (1H, s), 8.11 (1H, s), 8.62 (1H, s), 9.17 (1H, s).
Compound 24
1H-NMR (CDCI3) δ: 0.80-0.93 (9H, m) , 1.00-1.53 (5H, . m) , 1.77-1.93 (2H, m) , 2.09-2.26 (2H, m) , 4.99-5.12 (1H, m) ,
7.13-7.18 (1H, m) , 8.08-8.14 (1H, m) , 8.59-8.65 (1H, m) , 9.13-9.20 (lH,m) .
Compound 25
^-NMR (CDCI3) δ: 1.45-1.65 (6H, m) , 1.67-1.89 (4H, m) , 1.98-2.12 (2H, m) , 5.31-5.41 (1H, m) , 7.15 (1H, d) , 8.11 (1H, s), 8.62 (1H, d) , 9.17 (1H, s) .
Compound 26
1H-NMR (CDC13) δ: 0.27-0.38 (1H, m) , 0.43-0.51 (1H, m) , 0.51-0.65 (2H, m) , 1.11-1.24 (1H, m) , 1.45 (3H, d) , 2.45 (3H, s), 4.82-4.92 (1H, m) , 8.13 (1H, s), 8.47 (1H, s), 9.01 (1H, s) .
Compound 27
XH-NMR (CDCI3) δ: 1.63-1.74 (2H, m) , 1.84-2.08 (6H, m) , 3.96-4.00 (4H, m) , 5.27-5.36 (1H, m) , 7.19 (1H, s), 8.11 (1H, s), 8.63 (1H, s) , 9.17 (1H, s).
Compound 28
^- MR (CDCI3) δ: 2.14-2.35 (4H, m) , 2.38-2.49 (2H, m) ,
2.59-2.71 (2H, m) , 5.60-5.67 (1H, m), 7.26 (1H, s), 8.13 (1H, s), 8.66 (1H, s), 9.19 (1H, s) .
Compound 29
1H-NMR (CDCI3) δ: 2.14-2.36 (4H, m) , 2.39-2.49 (2H, m) ,
2.60-2.71 (2H, m) , 5.59-5.67 (1H, m) , 7.26 (1H, s), 8.13 (1H, s), 8.66 (1H, s),:9.19 (1H, s).
Compound 30
1H-NMR (CDCI3) δ: 1.50-1.63 (2H, m) , 1.85-1.98 (1H, m) , 2.11-2.21 (2H, m) , 2.47 (3H, s), 2.62-2.81 (4H, m) , 4.28 (2H, d) , 8.13 (1H, s), 8.52 (1H, s), 9.05 (1H, s).
[0170]
Compound 31 (trans)
1H-NMR (CDCI3) δ: 1.72-1.92 (4H, m) , 2.08-2.24 (4H, m) , 2 . 4 4 (3H, s), 2.71-2.81 (1H, m) , 5.29-5.39 ( 1H, m) , 8.13 (1H, s), 8.51 (1H, s), 9.04 (1H, s). .
Compound 32 (cis)
1H-NMR (CDC13) δ: 1.82-2.14 (8H, m) , 2.48 (3H, s), 2.74- 2.84 (1H, m) , 5.28-5.36 (1H, m) , 8.14 (1H, s), 8.50 (1H, s), 9.04 (1H, s) .
Compound 33 (cis/trans mixture)
XH-NMR (CDCI3) δ: 1.40-2.23 (9H, m) , 3.76-3.90 (lH, m) , 5.16-5.23 (0.5H, m) , 5.26-5.33 (0.5H, m) , 7.17 (0.5H, d) , 7.21 (0.5H, d) , 8.11 (1H, d) , 8.61-8.64 (1H, m) , 9.17 (1H, s) .
Compound 34
1H-NMR (CDCI3) δ: 1.96-2.61 (6H, m) , 5.07-5.20 (1H, m) , 5.37-5.52 (1H, m) , 7.19-7.23 (1H, m) , 8.13 (1H, s.) , 8.64 (1H, s) , 9.19 (1H, s) .
Compound 35
1H-NMR (CDCI3) δ: 1.93-2.22 (8H, m) , 2.47 (3H, s), 5.39- 5.48 (1H, m) , 8.15 (1H, s), 8.52 (1H, s), 9.07 (1H, s).
Compound 36
1H-NMR (CDCI3) δ: 1.95-2.29 (8H, m) , 5.51 (1H, brs), 8.21 (1H, s), 8.58 (lH, s), 9.04 (1H, s).
Compound 37
1H-NMR (CDCI3) δ: 2.05-2.62 (6H, m) , 5.10-5.21 (1H, m) , 5.47-5.59 (1H, m) , 8.21 (1H, s), 8.58 (1H, s), 9.03 (1H, s). Compound 38 1H-N R (CDCI3) δ: 1.99-2.21 (4H, m) , 2.36-2.48 (2H, m) , 2.53-2.65 (2H, m) , 5.38 (1H, brs), 7.22 (1H, s), 8.11 (1H, s) , 8.63 (1H, s) , 9.18 (1H, s) .
Compound 39
^"H-NMR (CDCI3) δ: 1.86-2.17 (4H, m) , 2.25-2.35 (1H, m) , 2.46-2.60 (2H, m) , 2.68-2.79 (1H, m) , 3.85 (3H, s), 5.40- 5.51 (1H, m) , 7.22 (1H, s), 8.12 (1H, s), 8.64 (1H, s), 9.18 (lH, s) .
Compound 40
^-NMR (CDCI3) δ: 2.07-2.18 (4H, m) , 2.42-2.49 (5H, m) ,
2.56-2.63 (2H, m) , 5.40 (1H, brs), 8.14 (1H, s), 8.51 (1H, s) , 9.05 (1H, s) .
[0171]
Compound 41
^- MR (CDCI3) δ: 2.06-2.22 (4H, m) , 2.38-2.51 (2H, m) ,
2.57-2.70 (2H, m) , 5.47 (1H, brs), 8.20 (1H, s) , 8.57 (1H, s) , 9.03 (1H, s) .
Compound 42
"""H-NMR (CDCI3) δ: 1.77-1.92 (2H, m) , 2.02-2.15 (2H, m) , 3.56-3.69 (2H, m) , 3.93-4.05 (2H, m) , 5.34-5.45 (1H, m) , 7.22 (1H, d), 8.12 (1H, s), 8.62 (1H, d) , 9.18 (1H, s).
Compound 43
XH-NMR (CDCI3) δ: 1.80-1.92 (2H, m) , 2.05-2.16 (2H, m) ,
2.47 (3H, s), 3.62-3.70 (2H, m) , 3.96-4.05 (2H, m) , 5.38-
5.48 (1H, m) , 8.14 (1H, s), 8.51 (1H, s), 9.04 (1H, s). Compound 44
1H-NMR (CDC13) δ: 1.86-1.98 (2H,- m) , 2.07-2.19 (2H, m) , 3.64-3.73 (2H, m) , 3.97-4.07 (2H, m) , 5.44-5.54 (1H, m) , 8.20 (1H, s), 8.57 (1H, s), 9.03 (1H, s).
Compound 45
1H-N R (CDCI3) δ: 1.22-1.32 (3H, m) , . 1.45-2.48 (9H, m) , 4.08-4.21 (2H, m) , 5.07-5.23 (1H, m) , 7.16 (1H, s), 8.11 (1H, s), 8.62 (1H, s), 9.17 (1H, s).
Compound 46
■""H-NMR (CDCI3) δ: 1.27 (3H, t) , 1.49-1.77 (4H, m) , 2.04- 2.16 (2H, m) , 2.17-2.28 (2H, m) , 2.32-2.49 (4H, m) , 4.15 (2H, q) , 5.12-5.24 (1H, m) , 8.12 (1H, s), 8.50 (1H, s), 9.02 (1H, s) .
Compound 47
1H-NMR (CDCI3) δ: 1.28 (3H, t) , 1.60-1.75 (4H, m) , 2.07- 2.18 (2H, m) , 2.19-2.30 (2H, m) , 2.34-2.46 (1H, m) , 4.16(2H,q) ,5.18-5.30 (1H, m) , 8.19 (1H, s) , 8.56 (1H, s), 9.01 (1H, s) .
Compound 48 (trans)
1H-N R (CDCI3) δ: 1.45-1.62 (4H, m) , 2.00-2.14 (3H, m) , 2.22-2.36 (2H, m) , 5.06-5.21 (1H, m) , 7.17 (1H, d) , 8.11 (1H, s), 8.62 (1H, d) , 9.17 (1H, s).
Compound 49 (cls)
1H-N R (CDCI3) δ : 1.58-1.88 (6H, m) , 2.02-2.26 (3H, m) , 5.45-5.52 (1H, m) , 7.25 (1H, s), 8.12 (1H, s), 8.63 (1H, s), 9.18 (1H, s) .
Compound 50 (trans)
^-NMR (CDC13) δ: 1.45-1.64 (4H, m) , 1.99-2.16 (3H, m) , 2.23-2.37 (2H, m) , 2.43 (3H, s) , 5.08-5.21 (1H, m) , 8.13 (1H, s), 8.50 (1H, s), 9.03 (1H, s).
[0172]
Compound 51 (cis)
1H-N R (CDCI3) δ: 1.63-1.92 (6H, m) , 1.94-2.27 (3H, m) , 2.49 (3H, s), 5.49-5.55 (1H, m) , 8.14 (1H, s) , 8.51 (1H, s), 9.04 (1H, s) .
Compound 52 (trans)
1H-NMR (CDCI3) δ: 1.48-1.70 (4H, m) , 2.02-2.22 (3H, m) ,
2.28-2.41 (2H, m) , 5.12-5.28 (1H, m) , 8.20 (1H, s), 8.57
(1H, s) , 9.02 (1H, s) .
Compound 53 (cis)
1H-NMR (CDCI3) δ: 1.62-1.74 (2H, m) , 1.77-1.93 (4H, m) ,
2.06-2.33 (3H,.m), 5.53-5.62 (1H, m) , 8.20 (1H, s), 8.57
(1H, s) , 9.03 (1H, s) .
Compound 54 (cis/trans mixture)
1H-NMR (CDCI3) δ: 0.92-0.99 (3H, m) , 1.03-1.47 (4H, m) ,
1.64-1.89 (4H, m) , 1.94-2.20 (1H, m) , 4.80-4.93 (0.8H, m) ,
5.31-5.39 (0.2H, m) , 7.18 (1H, brs), 8.12 (lH, brs), 8.61
(1H, brs) , 9.17 (1H, brs) .
Compound 55 (cis/trans mixture)
1H-NMR (CDCI3) δ: 0.85-0.99 (4H, m) , 1.01-1.47 (3H, m) , 1.59-2.18 (5H, m) , 5.07-5.18 (0.7H, m) , 5.44-5.52 (0.3H, m) , 7.15 (0.7H, brs) , 7.19 (0.3H, brs), 8.11 (1H, brs), 8.62 (1H, brs) , 9.17 (1H, brs) .
Compound 56 (trans)
1H-NMR (CDC13) δ: 0.87-0.97 (3H, m) , 1.04-1.21 (2H, m) , 1.40-1.55 (3H, m) , 1.73-1.88 (2H, m) , 2.04-2.20 (2H, m) , . 4.99-5.17 (1H, m) , 7.15 (1H, s), 8.11 (1H, s), 8.61 (1H, s), 9.17 (1H, s) .
Compound 57 (cis/trans mixture)
1H-NMR (CDCI3) δ: 0.87-1.87 (8H, m) , 2.13-2.25 (1H, m) , 2.43(2,7H, s), 2.47(0.3H, s) , 4.81-4.92 ( 0.9H, m) , 5.35-5.42 (0.1H, m) , 8.11-8.14 (1H, m) , 8.50 (1H, s), 8.98-9.03 ( 1H, m) . Compound 58 (cis/trans mixture)
■""H-NMR (CDCI3) δ: 0.77-2.17 (12H, m) , 2.41 (2.5H, s), 2.46 (0.5H, s), 5.09-5.21 (0.8H, m) , 5.52-5.57 (0.2H, m) , 8.12
(1H, s), 8.50 (1H, s) , 9.01 (1H, s).
Compound 59 (trans)
H-NMR (CDCI3) δ: 0.91-0.98 (3H, m) , 1.06-1.58 (5H, m) ,
1.78-1.88 (2H, m) , 2.06-2.20 (2H, m) , 2.41 (3H, s) , 5.01- 5.20 (1H, m) , 8.12 (1H, s), 8.50 (1H, s), 9.01 (1H, s).
Compound 60
^-NMR (CDCI3) δ: 1.65-2.23 (6H, m) , 5.64-5.76 (1H, m) , 5.83-5.95 (1H, m) , 5.99-6.10 (1H, m) , 7.19 (1H, s), 8.11 (1H, s)., 8.63 (1H, s), 9.17 (1H, s).
[0173] Compound 61
1H-N R ( CDCI 3 ) δ: 1.68-2.21 (6H, m) , 2.44 (3H, s), 5.67- 5.74 (1H, m) , 5.87-5.94 (1H, m) , 5.99-6.07 (1H, m), 8.12 (1H, s), 8.51 (1H, s), 9.02 (1H, s).
Compound 62
1H-NMR (CDCI3) δ: 2.00-2.12 (2H, m) , 2.20-2.32 (2H, m) , 2.59-2.74 (2H, m) , 2.82-2.97 (2H, m) , 5.25-5.36 (1H, m) , 7.21 (1H, d) , 8.12 (1H, s), 8.61 (1H, d) , 9.17 (1H, s) .
Compound 63
1H-NMR ( C DC I 3 ) δ: 1.30-1.69 (6H, m) , 1.74-1.86 (2H, m) , 1.93-2.05 (2H, in ) , 2.44 (3H, s), 5.19-5.29 (1H, m) , 8.12 (1H, s), 8.50 (1H, s), 9.01 (1H, s).
Compound 64
1H-NMR ( C DC I 3 ) δ: 2.03-2.16 (2H, m) , 2.22-2.32 (2H, m) , 2.48 (3H, s), 2.63-2.72 (2H, m) , 2.86-2.97 ( 2H, m) , 5.30- 5.41 (lR, m) , 8.13 (1H, s), 8.50 (1H, s), 9.04 (1H, s) .
Compound 65
"""H-NMR (CDCI3) δ: 1.66-1.76 (2H, m) , 1.79-2.00 (6H, m) , 3.21 (3H, brs), 3.23 (3H, brs), 5.25-5.35 (1H, m) , 7.18 (1H, s), 8.11 (1H, s), 8.62 (1H, s), 9.17 (1H, s) .
Compound 66
^-NMR (CDCI3) δ: 1.69-1.81 (2H, m) , 1.84-1.98 (6H, m) , 2.45 (3H, s), 3.22 (3H, s) , 3.24 (3H, s) , 5.28-5.40 (1H, m) , 8.14 (1H, brs), 8.51 (1H, brs), 9.03 (1H, brs).
Compound 67 (cis/trans mixture) 1H-NMR (CDCI3) δ: ■ 2.02-3.21 (8H, m) , 5.24-5.62 (1H, m) , 7.25-7.28 (1H, m) , 8.11-8.14 (1H, m) , 8.59-8.68 (1H, m) , 9.15-9.21 (1H, m) .
Compound 68 (cis/trans mixture)
1H-NMR (CDCI3) δ: 2.13-2.18 (2H, m) , 2.50 (3H, s), 2.57- 3.18 (6H, m) , 5.33-5.36 (0.4H, m) , 5.56-5.60 (0.6H, m) , 8.14 (1H, s), 8.50 (0.4H, s), 8.54 (0.6H, s), 9.06 (0.4H, s) , 9.08 (0.6H, s) .
Compound 69
XH-NMR (CDCI3) δ: 2.41-2.61 (4H, m) , 2.97-3.10 (2H, m) , 3.29-3.43 (2H, m) , 5.54-5.62 (1H, m) , 7.27 (1H, d) , 3.13 (1H, s), 8.65 (1H, d), 9.18 (1H, s) .
Compound 70
1H-N R (CDCI3) δ: 2.42-2.62 (7H, m) , 2.99-3.14 (2H, m) , 3.28-3.39 (2H, m) , 5.55-5.64 (1H, m) , 8.15 (1H, s), 3.53 (1H, s) , 9.08 (1H, s) .
[0174]
Compound 71
"""H-NMR (CDCI3) δ: 1.14-2.79 (10H, m) , 3.62-4.49. (2H, m) , 5.10-5.77 (1H, m) , 8.13 (1H, s), 8.46-8.55 (1H, m) , 9.04 (1H, s) .
Compound 72
1H-NMR (CDCI3) δ: 1.58-2.16 (7H, m) , 2.46 (3H, s), 3.61- 4.89 (2H, m) , 5.21-5.35 (1H, m) , 8.13 (1H, s), 8.50 (1H, s), 9.03 (1H, s) . Compound 73
■""H-N R (CDC13) δ: 2.11-2.21 (2H, m) , 2.22-2.32 (2H, m) ,
2.60-2.71 (2H, m) , 2.92-3.03 (2H, m) , 5.37-5.49 (1H, m) ,
8.20 (1H, s), 8.56 (1H, s) , 9.03 (1H, s) .
Compound 74
1H-NMR (CDCI3) δ: 1.95-2.10 (2H, m) , 2.22-2.33 (2H, m) , 2.62-2.73 (2H, m) , 2.82-2.93 (2H, m) , 5.23-5.36 ( 1H , m) , 6.65 (1H, brs), 7.21 (1H, brs), 7.60 (1H, brs), 8.41 (1H, s) , 8.61 (1H, s) .
Compound 75
■"■fi-NMR (CDCI3) δ: 1.99-2.14 (2H, m) , 2.22-2.34 (5H, m) ,
2.61-2.74 (2H, m) , 2.84-2.97 (2H, m) , . 5.27-5.40 (1H, m) ,
7.21 (1H, brs) , 7.44 (1H, s) , 8.04 (1H, s) , 8.53 (1H, s) . Compound 76
^H-NMR (CDCI3) δ: 1.37-1.51 (2H, m) , 1.64-1.85 (2H, m) , 1.87-1.99 (3H, m) , 2.08-2.23 (2H, m) , 4.24-4.36 (2H, m) ,
7.22 (1H, s), 8.12 (1H, s) , 8.64 (1H, s), 9.18 (1H, s) .
Compound 77
1H-NMR (CDCI3) δ: 1.41-1.53 (2H, m) , 1.69-1.89 (2H, m) , 1.91-2.02 (3H, m), 2.07-2.26 (2H, m) , 2.47 (3H, s), 4.33 (2H, d) , 8.14 (1H, .s) , .8.52 (1H, s), 9.05 (1H, s) .
Compound 78
^- MR (CDCI3) δ: 2.13-2.36 (4H, m) , 2.37-2.49 (5H, m) , 2.56-2.71 (2H, m) , 5.57-5.68, (1H, m) , 8.12 (1H, s),. 8.52 (1H, s) , 9.04 (1H, s) . Compound 79
1H-NMR (CDC13) δ: 1.52-3.91 (13H, m) , 5.18-5.46 (1H, m) , 8.09-8.19 (1H, m) , 8.47-8.57 (1H, m) , 8.99-9.08 (1H, m) . Compound 80
1H-NMR (CDCI3) δ: 2.15-2.30 (2H, m) , 2.32-2.50 (4H, m) , 2.65-2.79 (2H, m) , 5.65-5.77 (1H, m) , 8.21 (1H, s), 8.61 (1H, brs) , 9.05 (1H, s) .
[0175]
Compound 81
1H-NMR (CDCI3) δ: 1.60-1.78 (2H, m) , 1.79-2.00 (2H, m) , 2.01-2.21 (3H, m) , 2.44 (3H, s), 2.49-2.61 (1H, m) , 5.37- 5.50 (1H, m) , 8.13 (1H, s), 8.52 (1H, s), 9.04 (1H, s).
Compound 82
"""H-NMR (CDCI3) δ: 1.00-1.39 (5H, m) , 1.68-1.93 (6H, m) , 2.46 (3H, s), 4.25 (2H, d) , 8.13 (1H,. s), 8.52 (1H, s), 9.03 (1H, s) .
Compound 83
1H-NMR (CDCI3) δ: 1.01-1.31 (5H, m) , 1.32 (3H, d) , 1.59- 1.91 (6H, m) , 2.43 (3H, s) , 5.16-5.25 (1H, m) , 8.13 (1H, s), 8.50 (1H, s) , 9.01 (1H, s) .
Compound 84
XH-NMR (CDCI3) δ: 1.24-1.31 (3H, m) , 1.50-1.61 (1H, m) , 1.75-1.94 (1H, m) , 2.00-2.23 (2H, m) , 2.49 (3H s), 4.05- 4.55 (4H, m) , 8.13 (1H, s), 8.51 (1H, s), 9.04 (1H, s). . Compound 85 1H-N R (CDCI3) δ: 2.21-2.30 (1H, m) , 2.33-2.44. (1H, m) ,
2.51 (3H, s), 3.95-4.18 (4H, m) , 5.69-5.78 (1H, m) , 8.18 (1H, s), 8.57 (1H, s), 9.10 (1H, s).
Compound 86
'"H-NMR (CDCI3) δ: 1.08 (3H, d) , 1.21-1.36 (1H, m) , 1.69- 1.85 (3H, m) , 1.94-2.07 (1H, m) , 2.12-2.29 (2H, m) , 2.42 (3H, s), 5.06-5.14 (1H, m) , 8.12 (1H, s), 8.51 (1H, s), 9.02 (1H, s) .
Compound 87
1H-NMR (CDCI3) δ: 0.93-1.10 (2H, m) , 1.13-1.34 (3H, m) , 1.42-1.54 (1H, m) , 1.62-1.85 (7H, m) , 2.45 (3H, s), 4.48 (2H, t), 8.13 (1H, s), 8.52 (1H, s), 9.03 (1H, s) .
Compound 88 (cis/trans mixture)
"""H-NMR (CDCI3) δ: 0.8.9 (9H, s) , 1.00-1.93 (7H, m) , 2.09- 2.28 (2H, m) , 2.41 (1.9H, s), 2.47 (1.1H, s) , 5.02-5.14 (0.7H, m) , 5.42-5.50 (0.3H, m) , 8.11-8.14 (1H, m) , 8.48-
8.52 (1H, m) , 8.99-9.03 (1H, m) .
Compound 89
"""H-NMR (CDCI3) δ : 0.80-2.30 (14H,. m) , 2.42-2.51 (3H, m) , 4.91-5.11 (0.6H, m) , 5.66-5.77 (0.4H, m) , 8.08-8.17 (1H, m) , 8.44-8.52 (1H, m) , 9.00-9.05. ( 1H, m) .
Compound 90
^"H-NMR (CDCI3) δ: 2.06-2.21 (1H, m) , 2.37-2.52 (1H, m) , 2.94-3.15 (3H, m) , 3.21-3.32 (1H, m) , 5.86-5.96 (1H,. m) , 7.23 (1H, d) , 8.11 (1H, s) , 8.65 (1H, d) , 9.17 (1H, s). [0176]
Compound 91
1H-NMR (CDC13) δ: 2.06-2.27 (1H, m) , 2.38-2.55 (4H, m) , 2.94-3.19 (3H, m) , 3.23-3.35 (1H, m) , 5.86-6.00 (1H, m) , 8.13 (1H, s), 8.53 (1H, s), 9.05 (1H, s).
Compound 92
^- MR (CDCI3) δ: 1.34-1.63 (3H, m) , 1.77-2.08 (5H, m) , 5.34-5.41 (1H, .m) , .7.24 (1H, s), 8.12 (1H, s), 8.70 (1H, s), 9.19 (1H, s) .
Compound 93
1H-NMR (CDCI3) δ: 1.37-1.65 (3H, m) , 1.78-1.88 (1H, m) , 1.89-1.98 (3H, m) , 1.98-2.10 (1H, m) , 2.49 (3H, s) , 5.35- 5.46 (1H, m), 8.14 (1H, s), 8.58 (1H, s) , 9.06 (1H, s).
Compound 94
''"H-NMR (CDCI3) δ: 2.51 (3H, s) , 2.62-2.73 (2H, m) , 3.18- 3.31 (1H, m) , 3.33-3.46 (2H, m) , 3.52-3.63 (1H, m), 5.88- 5.99 (1H, m) , 8.14 (1H, s)f 8.54 (1H, s), 9.09 (1H, s).
Compound 95 (cis/trans mixture)
1H-NMR (CDCI3) δ: 2.41 (2.2H, s), 2.50 (0.8H, s), 2.60-3.58 (6H, m) , 5.79-5.90 (0.3H, m) , 6.15-6.21 (0.7H, m) , 8.13 (1H, brs), 8.53 (0.3H, s), 8.55 (0.7H, s), 9.06 (0.3H, s), 9.08 (0.7H, s) .
Compound 96
1H-NMR (CDCI3) δ: 1.41 (3H, s) , 1.47 (3H, s) , 2.50 (3H, d) , 3.91-3.94 (1H, m) , 4.16-4.19 (1H, m) , 4.51-4.55 (3H, m) , 8.13 (1H, s), 8.52 (1H, s), 9.06 (1H, s).
Compound 97
1H-NMR (CDC13) δ: 1.72-1.83 (1H, m) , 2.08-2.21 (1H, m) , 2.47 (3H, s), 2.74-2.88 (1H, m) , 3.69-3.76 (1H, m) , 3.78- 3.87 (1H, m) , 3.89-3.97 (2H, m) , 4.37 (1H, dd) , 4.46 (1H, dd) , 8.13 (1H, s), 8.52 (1H, s) , 9.05 (1H, s) .
Compound 98
''"H-NMR (CDCI3) δ: 1.74-1.83 (1H, m) , 1.90-2.05 (2H, m) , 2.07-2.17 (1H, m) , 2.49 (3H, s), 3.81-3.89 (1H, m) , 3.91- 3.98 (1H, m) , 4.30-4.39 (1H, m) , 4.43 (1H, dd) , 4.51 (1H, dd) , 8.13 (1H, s), 8.52 (1H, s), 9.05 (1H, s).
Compound 99
'''H-NMR (CDCI3) δ: 1.38-1.74 (5H, m) , 1.87-1.97 (1H, m) , 2.49 (3H, s), 3.43-3.56 (1H, m) , 3.69-3.80. (1H, m) , 3.99- 4.08 (1H, m) , 4.38-4.50 (2H, m) , 8.13 (1H, s) , 8.52 (1H, s), 9.04 (1H, s) .
Compound 100
1H-NMR (CDCI3) δ: 1.60-1.73 (1H, m) , 1.87-2.02 (1H, m) , 2.11-2.31 (2H, m) , 2.45 (3H, s), 2.50-2.62 (2H, m) , 2.71- 2.80 (1H, m) , 2.94-3.04 (1H, m) , 5.30-5.42 (1H, m) ,' 8.13 (1H, s), 8.51 (1H, s), 9.03 (1H, s).
[0177]
Compound 101 (cis/trans mixture)
1H-NMR (CDCI3) δ: 1.41-3.70 (10H, m) , 5.17-5.28 (0.5H, m) , 5.32-5.41 (0.5H, m) , 8.13 (1H, s), 8.50 (1H, s) , 9.04 (0.5H, s) , 9.05 (0.5H, s) .
Compound 102 (cis/trans mixture)
1H-NMR (CDC13) δ: 1.61-3.82 ( 11H, m) , 5.29-5.44 (0.5H, m) , 5.91-6.04 (0.5H, m) , 8.13 (1H, s), 8.52 (0.5H, s), 8.54 (0.5H, s) , 9.06 (1H, s) .
Compound 103
1H-NMR (CDC13) δ: 1.73-1.90 (1H, m), 2.09-2.25 (1H, m) , 2.27-2.40 (2H, m) , 2.48 (3H, s), 2.94-3.07 (1H, m) , 3.09- 3.27 (2H, m) , 3.62-3.73 (1H, m) , 5.61-5.73 (1H, m) , 8.13 (1H, s), 8.54 (1H, s), 9.08 (1H, s).
Compound 104
^- MR (CDCI3) δ: 2.09-2.21 (2H, m) , 2.47-2.52 (3H, m) , 2.57-3.23 (5H, m) , 5.29-5.64 (1H, m) , 8.12-8.15 (1H, m) , 8.49-8.56 (1H, m) , 9.04-9.09 (1H, m) .
Compound 105
1H-NMR (CDCI3) δ: 2.01-3.58 (10H, m) , 5.28-5.51 (1H, m) , 8.12-8.16 (1H, m) , 8.50-8.55 (1H, m) , 9.05-9.09 (1H, m) . Compound 106
1H-NMR (CDCI3) δ: 1.48 (9H, s), 1.73-1.87 (2H, m) , 1.95- 2.07 (2H, m) , 2.46 (3H, s), 3.32-3.45 (2H, m) , 3.67-3.79 (2H, m) , 5.37-5.46 (1H, m) , 8.13 (1H, s), 8.51 (1H, s), 9.04 (1H, s) .
Compound 107
1H-N R (CDC13) δ: 1.41 (3H, s), 1.41 (3H, s), 2.51 (3H, s), 3.22 (1H, dd) , 4.46 (1H, dd) , 4.72 (1H, dd) , 8.13 (1H, s), 8.53 (1H, s) , 9.06 (1H, s) .
Compound 108
1H-NMR (CDCI3) δ: 1.45-1.50 (3H, m) , 2.46-2.49 (3H, m) , 2.72 (1H, dd) , 2.87-2.92 (1H, m)', 3.27-3.32 (1H, m) , 5.20- 5.30 (1H, m) , 8.13 (1H, s) , 8.51 (1H, s) , 9.04 (1H, s).
Compound 109
^- MR (CDCI3) δ: 1.51 (3H, s), 2.51 (3H, s), 2.76 (1H, d) , 2.90 (1H, d) , 4.36 (1H, d) , 4.64 (1H, d) , 8.14 (1H, s), 8.52 (1H, s) , 9.06 (1H, s) .
[0178]
Compound 111
^-NMR (CDCI3) δ: 1.84-1.99 (2H, m) , 2.03-2.14 (2H, m) , 2.33 (3H, s), 2.35-2.42 (2H, m) , 2.46 (3H, s) , 2.63-2.74 (2H, m) , 5.20-5.33 (1H, m) , 8.13 (1H, s), 8.50 (1H, s), 9.03 (1H, s) .
Compound 112
^H-NMR (CDCI3) δ: 2.51 (3H, s), 2.78 (1H, dd) , 2.94 (1H, dd), 3.40-3.47 (1H, m), 4.33 (1H, dd) , 4.82 (1H, dd) , 8.14 (1H, s), 8.52 (1H, s), 9.06 (1H, s) .
Compound 113
1H-NMR (CDCI3) δ: 2.43-2.53 (1H, m) , 2.54 (3H, s), 2.85- 2.95 (1H, m) , 4.36-4.45 (1H, m) , 4.54-4.63 (1H, m) , 5.90- 5.98 (1H, m) , 8.14.(1H, s) , 8.54 (1H, s), 9.09 (1H, s).
Compound 114
"""H-NMR (CDCI3) δ: 1.00 (3H, t) , 1.86 (2H, q) , 2.50 (3H, s), 3.95-4.16 (4H, m) , 4.43 (2H, s) , 8.13 (1H, s) , 8.52 (1H, s) , 9.05 (1H, s) .
Compound 115
"""H-NMR' (CDC13) δ : 0.41-0.48 (2H, m) , 0.55-0.61 (2H, m) , 1.23 (3H, s), 4.23 (2H, s) , 7.26 (1H, d) , 8.12 (1H, s), 8.61 (1H, d) , 9.18 (1H, s) .
Compound 116
■""H-NMR (CDCI3) δ : 1.41 (3H, s), 1.47 (3H, s), 3.89 (1H, dd) , 4.17 (1H, dd) , 4.43-4.58 (3H, m). , 7.29 (1H, d) , 8.12 (1H, s), 8.65 (1H, d) , 9.18 (1H, s) .
Compound 117
1H-NMR (CDCI3) δ : 1.64-2.08 (8H, m) , 2.44 (3H, s) , 3.97- 4.02 (4H, m) , 5.32-5.42 (1H, m) , 8.13 (1H, s) , 8.51 (1H, s), 9.02 (1H, s) .
Compound 118
1H-NMR (CDCI3) δ : 1.63-1.77. (2H, m) , 1.88-2.01 (2H, m) , 2.02-2.09 (4H, m) , 3.97-4.01 (4H, m) , 5.40-5.48 (1H, m) , 8.20 (1H, s), 8.57 (1H, s) , 9.02 (1H, s) .
Compound 119
"""H-NMR (CDCI3) δ : 1.43-1.94 (6H, m) , 2.09-2.32 (2H, m) , 2.40 (3H, s), 3.88-4.06 (4H, m) , 5.27-5.41 (1H, m) , 8.10 (1H, s), 8.49 (1H, s), 9.00 (1H, s) .
Compound 120
■"■H-NMR (CDCI3) δ : 1.84-2.00 (1H, m) , 2.06-2.22 (3H, m) , 2.42 (3H, s) , 2.44-2.51 (2H, m) , 2.67-2.85 (2H, m) , 5.69- 5.77 (1H, m) , 8.13 (1H, s), 8.51 (1H, s), 9.04 (1H, s).
[0179]
Hereinafter, Formulation Examples are illustrated, in which "parts" denotes "parts by weight".
[0180]
Formulation Example 1
10 Parts of any one of Compounds 1 to 120 is. dissolved in a mixture of 35 parts of xylene and 35 parts of N,N- dimethylformamide . To the mixture is added 14 parts of polyoxyethylenestyryl phenyl ether and 6 parts of calcium dodecylbenzene sulfonate. The mixture is mixed to prepare an emulsion of the corresponding compound..
[0181]
Formulation Example 2
4 Parts of sodium lauryl sulfate, 2 parts of calcium lignin sulfonate, 20 parts of synthetic hydrated silicon oxide (fine powder) and 54 parts of diatomaceous earth are mixed. To the mixture is further added 20 parts of any one of Compounds 1 to 120. The mixture is mixed to prepare wettable powders of the corresponding compound.
[0182]
, Formulation Example 3
To 2 parts of any one of Compounds 1 to 120 is added 1 part of synthetic hydrated silicon oxide ( fine powder ) , 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay, and the mixture is mixed. To the mixture is added an appropriate amount of water. Then, the mixture is stirred, granulated by a granulator, and dried under ventilation to prepare granules of the corresponding compound.
[0183]
Formulation Example 4
1 Part of any one of Compounds 1 to 120 is dissolved in an appropriate amount of acetone. To the mixture is added 5 parts of synthetic hydrated silicon oxide (fine powder), 0.3 part of PAP and 93.7 parts of Fubasami clay.
The mixture is stirred and mixed sufficiently, and the acetone is removed by distillation to prepare powders of the corresponding compound.
[0184]
Formulation Example 5
35 Parts of a mixture of polyoxyethylene alkyl ether sulfate ammonium salt and white carbon (weight ratio = 1:1),
10 parts of any one of Compounds 1 to 120, and 55 parts of water are mixed. The mixture is finely ground by a wet grinding process to prepare a formulation of the corresponding compound.
[0185]
Formulation Example 6
0.1 Part of any one of Compounds 1 to 120 is dissolved in 5 parts of xylene, and 5 parts of trichloroethane, and the mixture is mixed with 89.9 parts of deodorized kerosene to prepare an oil solution of the corresponding compound.
[0186]
Formulation Example 7
10 mg of any one of Compounds 1 to 120 is dissolved in 0.5 ml of acetone. The solution is treated with 5 g of animal solid feedstuff powders (breeding-propagation solid feedstuff powder CE-2, commercially available from . CLEA Japan Inc.) and homogeneously mixed. Then, the acetone is removed by distillation to prepare a toxic bait of the corresponding. compound.
[0187]
Formulation Example 8
0.1 Part - of any one of Compounds 1 to 120 and 49.9 parts of Neothiozole (CHUOU KASEI Co., Ltd.) are put into an aerosol can. After attaching an aerosol valve to the aerosol can,, the aerosol can is charged with 25 parts of dimethyl ether and 25 parts of LPG, and shaken. Then, an actuator is attached to the aerosol can to prepare an oily aerosol of the corresponding compound.
[0188]
Formulation Example 9
An aerosol container is charged with 50 parts of distilled water and a mixed solution of 0.6 part of any one of Compounds 1 to 120, 0.01 part of BHT ( 2 , 6-di-tert-butyl- -methylphenol ) , 5 parts of xylene, 3.39 parts of deodorized kerosene and 1 part of an emulsifying agent (Atmos 300, a registered trade name of ATMOS CHEMICAL LTD) . After attaching a valve to the aerosol container, the aerosol container is charged with 40 parts of a propellant (LPG) through the valve under a pressurized condition to prepare an aqueous aerosol.
[0189]
Hereinafter, the pesticidal activity of the present compound is--demonstrated by Test Examples.
[0190]
Test Example 1
In order to prepare test spray solutions, each of Compounds 1 to 3, 9, 14, 29, 31, 34 to 38, 40, 41, 51, 62, 64, 67 to 72, 74, 75, 77, 81, 87, 94, 95, 101, 104, 105 and 115 was prepared into a formulation by following Formulation Example 5 and diluted with water so that the active ingredient concentration would be 500 ppm.
Cumber seedlings (first true leaf stage) were planted in a plastic cup. About 30 cotton aphids {Aphis gossypii) were inoculated into the cumber seedlings and were left for 1 day. Each of the above-prepared dilutions (20 ml) was sprayed over different seedlings.
6 Days after spraying, the number of the cotton aphids alive on the leaves of the cucumber plants was counted to calculate a control value by the following formula:
Control value (%) = {1 - (Cb * Tai)/(Cai Tb) } χ 100 wherein the variables mean as follows:
Cb: Insect number in non-treated district before treatment Cai : Insect number in non-treated district on observation Tb : Insect number in treated district before treatment Tai : Insect number in treated district on observation
As a result, the control value was 90% or more in the districts treated with the test spray solutions containing any one of Compounds 1 to 3, 9, 14, 29, 31, 34 to 38, 40, 41, 51, 62, 64, 67 to 72, 74, 75, 77, 81, 87, 94, 95, 101, 104, 105 and 115.
[0191]
Test Example 2
In order to prepare test spray solutions, each of Compounds 1 to 4, 11, 13, 14, 16, 17, 21, 25, 29, 31, 34 to 38, 40, 41, 43, 49 to 51, 57 to 59, 62, 63, 64, 67, 68, 70, 71, 72, 73, 74, 81 to 84, 87, 94, 95, 99 to 102, 104, 105 and 115 was prepared into a formulation by following Formulation Example 5 and diluted with water so that the active ingredient concentration would be 500 ppm.
Tomato seedlings (third true leaf stage) were planted in a polyethylene cup. Adult tobacco whiteflies (Bemisia tabaci) were released into the tomato seedlings and allowed to lay eggs for about 24 hours. The tomato seedlings were stored in a greenhouse for 8 days, larvae hatched from the laid eggs, and each of the above-prepared solutions was sprayed to different larvae at a rate of 10 ml per cup. Then, the cup was stored in a greenhouse at 25°C. After 7 days, the number of the larvae alive on the leaves of the tomato plants was counted to calculate a control value by the following formula:
Control value (%) = {1 - <Cb χ Tai)/(Cai χ Tb)) χ 100
wherein the variables mean as follows:
Cb : Insect number in non-treated district before treatment Cai: Insect number in non-treated district on observation Tb : Insect number in treated district before treatment
Tai : Insect number in treated district on observation
As a result, the control value was 90% or more in the districts treated with the test spray solutions containing any one of Compounds 1 to 4, 11, 13, 14, 16, 17, 21, 25, 29, 31, 34 to 38, 40, 41, 43, 49 to 51, 57 to 59, 62, 63, 64, 67, 68, 70, 71, 72, 73, 74, 81 to 84, 87, 94, 95, 99 to 102, 104, 105 and 115.
Industrial Applicability
[0192]
The present compound has an excellent controlling effect on pests, and thus it is useful as an active ingredient for a. pesticidal agent.

Claims

1. A pyrimidine compound of Formula (1):
Figure imgf000172_0001
wherein
R1 is C1-C3 chain hydrocarbon group optionally substituted with one or more halogens, hydrogen, halogen or amino group,
R2 is C1-C3 chain hydrocarbon group optionally substituted with one or more halogens, hydrogen, halogen, hydroxy group, mercapto group or amino group,
G1 is nitrogen or -CR5= wherein R5 is. C1-C3 chain hydrocarbon group optionally substituted with one or more halogens, hydrogen, halogen or amino group,
R3 is C1-C3 chain hydrocarbon group optionally substituted with one or more halogens, hydrogen, halogen, amino group, nitro group or cyano group,
R4 is C1-C6 chain hydrocarbon group optionally substituted with one or more halogens, C3-C8 cycloalkyl group optionally substituted with one or more halogens, Cl- C6 alkoxy group optionally substituted with one or more halogens, C1-C6 alkylthio group optionally substituted with one or more, halogens, . C1-C6 alkylsulfinyl group optionally substituted with one or more halogens, C1-C6 alkylsulfonyl group optionally substituted with one or more halogens, Cl- C6 alkylamino group optionally substituted with one or more halogens, C2-C8 dialkylamino group optionally substituted with one or more halogens, C2-C6 alkylcarbonylamino group optionally substituted with one or. more halogens, C2-C6 alkoxycarbonylamino group optionally substituted with one or more halogens, C2-C6 alkylcarbonyl group optionally substituted with one or more halogens, C2-C6 alkoxycarbonyl group optionally substituted with one or more halogens, C2- C6 alkylcarbamoyl group optionally substituted with one or more halogens, C2-C8 dialkylcarbamoyl group optionally substituted with one or more halogens, phenyl group optionally substituted with one or more atoms or groups selected from the following Group a, .5- to 6-membered aromatic heterocyclic group optionally substituted with one or more atoms or groups selected from the following Group a, hydrogen, halogen, hydroxy group, mercapto group, amino group, nitro group, cyano group or formyl group,
Q is oxygen or -S(0)r- wherein r is 0, 1 or 2,
Cyc is 3- to 8-membered saturated heterocyclic group containing one atom or group selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a ring component wherein n is 0, 1 or 2, and R6 is C1-C6 chain hydrocarbon group optionally substituted with one or more halogens, C2-C6 alkylcarbonyl group optionally substituted with one or more halogens, C2-C6 alkoxycarbonyl group optionally substituted with one or more halogens, or hydrogen; 5- to 8-membered saturated heterocyclic group containing two atoms or groups selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a ring component wherein n and R6 are as defined above, provided that the two atoms or groups are not adjacent to each other; C3-C8 cycloalkyl group; or C5-C8 cycloalkenyl group, any of the groups defined as Cyc may be optionally substituted with one or more atoms or groups independently selected from the following Groups βΐ to β3, provided that when one or more groups are selected from Group β2, each group selected from Group β2 is attached to the same one carbon atom of the ring defined as Cyc, and when one or more groups are selected from Group β3, each group selected from Group β3 is attached to two adjacent carbon atoms of the ring defined as Cyc,
A is a single bond, methylene group optionally substituted with one or more atoms or groups selected from the group consisting of C1-C3 alkyl group and halogen, or ethylene group optionally substituted with one or more atoms or groups selected from the group consisting of C1-C3 alkyl group and halogen, . and A is attached to the carbon atom of the ring defined as Cyc,
Group a consists of C1-C6 chain hydrocarbon group optionally substituted with one or more halogens, C1-C6 alkoxy group optionally substituted with one or more halogens, C1-C6 alkylthio group optionally substituted with one or more halogens, C1-C6 alkylsulfinyl group optionally substituted with one or more halogens, C1-C6 alkylsulfonyl group optionally substituted with one or more halogens, Cl- C6 alkylamino group optionally substituted with one or more halogens, C2-C8. dialkylamino group optionally substituted with one or more halogens, halogen, hydroxy group, mercapto group, amino group, cyano group and nitro group,
Group βΐ consists of C1-C6 chain hydrocarbon group optionally substituted with one or more halogens, C1-C6 alkoxy group optionally substituted with one or more halogens, C1-C6 alkylthio group optionally substituted with one or more halogens, C1-C6 alkylsulfinyl group optionally substituted with one or more halogens, C1-C6 alkylsulfonyl group optionally substituted with one or more halogens, Cl- C6 alkylamino group optionally substituted with one or more halogens, C2-C8 dialkylamino group optionally substituted with one or, more halogens, C2-C6 alkylcarbonylamino group optionally substituted with one or more halogens, C2-C6 alkoxycarbonylamino group optionally substituted with one or more halogens, C2-C6 alkylcarbonyl group optionally substituted with one or more halogens, C2-C6 alkoxycarbonyl group optionally substituted with one or more halogens, C2- C6 alkylcarbamoyl group optionally substituted with one or more halogens, C2-C8 dialkylcarbamoyl group optionally substituted with one or more halogens, halogen, hydroxy group, mercapto group, amino group, nitro group, cyano group and formyl group,
Group β2 consists of bivalent radicals shown by =S, =0, =NOR7 and -X^T^X2- wherein R7 is C1-C3 alkyl group optionally substituted with one or more halogens or hydrogen, X1 and X2 are independently selected from the group consisting of oxygen and sulfur, and T1 is methylene group optionally substituted with one or more halogens or ethylene group optionally substituted with one or more halogens, and
Group β3 consists of bivalent radicals . shown by -T2- and -X3-T3-X4- wherein X3 and X4 'are independently selected from the group consisting of oxygen and sulfur, and T2 and T3 are independently selected from the group consisting of methylene group optionally substituted with one or more halogens,
but excluding the pyrimidine compound of Formula (1) wherein Q is oxygen; G1 is -CH=; R1, R2 and R3 are all hydrogen; R4 is amino group or nitro group; A is a single bond; and Cyc is cyclohexyl group.
2. The pyrimidine compound of claim 1 wherein Q is oxygen.
3. The pyrimidine compound of claim 1 or 2 wherein R1 is hydrogen, R2 is hydrogen or amino group, G1 is nitrogen or -CR5=, and R5 is hydrogen.
4. The pyrimidine compound of any one of claims 1 to 3 wherein R3 is hydrogen, and R4 is C1-C6 alkyl group optionally substituted with one or more halogens, C1-C6 alkoxy group optionally substituted with one or more halogens, hydrogen, halogen, amino group, nitro group or cyano group.
5. The pyrimidine compound of any one of claims 1 to 4 wherein G1 is nitrogen.
6. The pyrimidine compound of any one of claims 1 to 4 wherein G1 is -CR5=, and R5 is hydrogen.
7. The pyrimidine compound of any one of claims 1 to 6 wherein Cyc is 3- to 8-membered saturated heterocyclic group containing one atom or group selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a ring component wherein the 3- to 8-membered saturated heterocyclic group may be optionally substituted with one or more atoms or groups selected from the group consisting of C1-C3 alkyl group optionally substituted with one or more halogens, and halogen; C3-C8 cycloalkyl group optionally substituted with one or more halogens; or C5-C8 cycloalkenyl group optionally substituted with one or more halogens .
8. The pyrimidine compound of any one of claims 1 to 7 wherein A is a single bond.
9. The pyrimidine compound of any one of claims 1 to 8 wherein C c is a roup of Formula Jl or J2 :
Figure imgf000178_0001
J1 J2
wherein
R8 is halogen,
R9 and R10 are independently selected from the group consisting of C1-C3 alkyl group optionally substituted with one or more halogens, and halogen,
p is an integer of 0 to 9, provided that when p is an integer of 2 to 9, each R9 may be different from each other, q is an integer of 0 to 8, provided that when q is an integer of 2 to 8, each R10 may be different from each other, and
Y is oxygen, -S(=0)n-, -NR6- or -CR1^12- wherein n is 0, 1 or 2, R6 is C1-C6 chain hydrocarbon group optionally substituted with one or more halogens, C2-C6 alkylcarbonyl group optionally substituted with one or more halogens, C2- C6 alkoxycarbonyl group optionally substituted with one or more halogens," or hydrogen, R11 is halogen, and R12 is hydrogen or halogen.
10. The pyrimidine compound of any one of claims 1, 3, 4, 5 or 6 which has a chemical structure of Formula (1-vi) :
Figure imgf000179_0001
R2 (l-vi)
wherein R1, R2, R3, R4 and G1 are the same as R1, R2, R3, R4 and G1 of claim 1 respectively, and Z is halogen.
11. The pyrimidine compound of claim 10 wherein R1, R2 and R3 are hydrogen; R4 is hydrogen, methyl group or chlorine; G1 is nitrogen; and Z is fluorine.
12. The pyrimidine compound of claim 1 wherein
R1 is hydrogen,
R2 is hydrogen or amino group, G1 is nitrogen or -CR5= wherein R5 is hydrogen, R3 is hydrogen,
R4 is C1-C6 chain hydrocarbon group optionally substituted with one or more halogens, C1-C6 alkoxy group optionally substituted with one or more halogens, hydrogen, or halogen,
Q is oxygen,
Cyc is 3- to 8-membered saturated heterocyclic group containing one atom or group selected from the group consisting of oxygen, -S(=0)n~ and -NR6- as a ring, component wherein R6 is . C2-C6 alkoxycarbonyl group optionally substituted with one or more halogens; 5- to 8- membered saturated heterocyclic group containing two oxygen atoms as a ring component; C3-C8 cycloalkyl group; or C5-C8 cycloalkenyl group,
any of the groups defined as Cyc may be optionally substituted with one or more atoms or groups, selected from the following Groups βΐ to β3,
A is a single bond, methylene group optionally substituted with C1-C3 alkyl group, or ethylene group optionally substituted with C1-C3 alkyl group,
Group βΐ consists of C1-C6 chain hydrocarbon group optionally substituted with one or more halogens, C1-C6 alkoxy group optionally substituted with one or more halogens, C2-C6 alkoxycarbonyl group optionally substituted 180 with one or more halogens, halogen, hydroxy group, and cyano group,
Group β2 consists of bivalent radicals shown by =0, =N0R7 and -X^T1-*2- wherein R7 is C1-C3 alkyl group optionally substituted with one or more halogens, X1 and X2 are oxygen, and T1 is ethylene group optionally substituted with one or more halogens, and
Group β3 consists of a bivalent radical shown by -T2- wherein T2 is methylene group optionally substituted with one or more halogens.
13. The pyrimidine compound of claim 1 wherein
R1 is hydrogen,
R2 is hydrogen,
. G1 is nitrogen or -CR5= wherein R5 is hydrogen,
R3 is hydrogen,
R4 is C1-C6 chain hydrocarbon group, hydrogen, or halogen,
Q is oxygen,
Cyc is 3- to 8-membered saturated heterocyclic group containing one atom or group selected from the group consisting of oxygen, -S(=0)n- and -NR6- as a ring component wherein R6 is C2-C6 alkoxycarbonyl group; 5- to 8-membered saturated heterocyclic group containing two oxygen atoms as a ring component; C3-C8 cycloalkyl group; 181 or C5-C8 ■ cycloalkenyl group,
any of the groups defined as Cyc may be optionally substituted with one or more atoms or groups selected from the following Groups βΐ to β3,
A is a single bond, methylene group optionally substituted with C1-C3 alkyl group, or ethylene group optionally substituted with C1-C3 alkyl group,
Group βΐ consists of C1-C6 chain hydrocarbon group optionally substituted with one or more halogens, C1-C6 alkoxy group, C2-C6 alkoxycarbonyl group, halogen, hydroxy group, and cyano group,
Group β2 consists of bivalent radicals shown by =0, =N0R7 and -X^T^-X2- wherein R7 is C1-C3 alkyl group, X1 and X2 are oxygen, and T1 is ethylene group, and
Group β3 consists of a bivalent radical shown by -T2- wherein T2 is methylene group optionally substituted with one or more halogens .
14. A pesticidal composition comprising the pyrimidine compound of any one of claims 1 to 13 and an inert carrier.
15. Use of the pyrimidine compound of any one of claims 1 to 13 for controlling pests.
16. A method for controlling pests which comprises a step applying an effective amount of the pyrimidine compoun any one of claims 1 to 13 to pests or habitats thereof.
PCT/JP2011/074232 2010-10-15 2011-10-14 Pyrimidine compounds and their use as pesticides WO2012050237A1 (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8458781B2 (en) 2011-08-15 2013-06-04 Bank Of America Corporation Method and apparatus for token-based attribute aggregation
US8572687B2 (en) 2011-08-15 2013-10-29 Bank Of America Corporation Apparatus and method for performing session validation
US8572724B2 (en) 2011-08-15 2013-10-29 Bank Of America Corporation Method and apparatus for network session validation
US8572686B2 (en) 2011-08-15 2013-10-29 Bank Of America Corporation Method and apparatus for object transaction session validation
US8726340B2 (en) 2011-08-15 2014-05-13 Bank Of America Corporation Apparatus and method for expert decisioning
US8752157B2 (en) 2011-08-15 2014-06-10 Bank Of America Corporation Method and apparatus for third party session validation
US8752123B2 (en) 2011-08-15 2014-06-10 Bank Of America Corporation Apparatus and method for performing data tokenization
US8850515B2 (en) 2011-08-15 2014-09-30 Bank Of America Corporation Method and apparatus for subject recognition session validation
US9159065B2 (en) 2011-08-15 2015-10-13 Bank Of America Corporation Method and apparatus for object security session validation
US9253197B2 (en) 2011-08-15 2016-02-02 Bank Of America Corporation Method and apparatus for token-based real-time risk updating
US9361443B2 (en) 2011-08-15 2016-06-07 Bank Of America Corporation Method and apparatus for token-based combining of authentication methods

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006072426A1 (en) * 2005-01-05 2006-07-13 Bayer Cropscience Aktiengesellschaft Alkinyl-oxypyrimidine used in the form of pesticides
WO2007076473A2 (en) 2005-12-23 2007-07-05 Kalypsys, Inc. Substituted pyrimidinyloxy ureas useful as inhibitors of protein kinases
WO2008098143A2 (en) 2007-02-08 2008-08-14 Trius Therapeutics Antimicrobial compounds and methods of use
WO2009005690A2 (en) 2007-06-29 2009-01-08 Gilead Sciences, Inc. Antiviral compounds
WO2010119879A1 (en) * 2009-04-16 2010-10-21 Sumitomo Chemical Company, Limited Pyrimidine compound and its use for pest control
WO2010119878A1 (en) * 2009-04-16 2010-10-21 Sumitomo Chemical Company, Limited Pyrimidine compound and its use for pest control

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006072426A1 (en) * 2005-01-05 2006-07-13 Bayer Cropscience Aktiengesellschaft Alkinyl-oxypyrimidine used in the form of pesticides
WO2007076473A2 (en) 2005-12-23 2007-07-05 Kalypsys, Inc. Substituted pyrimidinyloxy ureas useful as inhibitors of protein kinases
WO2008098143A2 (en) 2007-02-08 2008-08-14 Trius Therapeutics Antimicrobial compounds and methods of use
WO2009005690A2 (en) 2007-06-29 2009-01-08 Gilead Sciences, Inc. Antiviral compounds
WO2010119879A1 (en) * 2009-04-16 2010-10-21 Sumitomo Chemical Company, Limited Pyrimidine compound and its use for pest control
WO2010119878A1 (en) * 2009-04-16 2010-10-21 Sumitomo Chemical Company, Limited Pyrimidine compound and its use for pest control

Cited By (11)

* Cited by examiner, † Cited by third party
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US8572687B2 (en) 2011-08-15 2013-10-29 Bank Of America Corporation Apparatus and method for performing session validation
US8572724B2 (en) 2011-08-15 2013-10-29 Bank Of America Corporation Method and apparatus for network session validation
US8572686B2 (en) 2011-08-15 2013-10-29 Bank Of America Corporation Method and apparatus for object transaction session validation
US8726340B2 (en) 2011-08-15 2014-05-13 Bank Of America Corporation Apparatus and method for expert decisioning
US8752157B2 (en) 2011-08-15 2014-06-10 Bank Of America Corporation Method and apparatus for third party session validation
US8752123B2 (en) 2011-08-15 2014-06-10 Bank Of America Corporation Apparatus and method for performing data tokenization
US8850515B2 (en) 2011-08-15 2014-09-30 Bank Of America Corporation Method and apparatus for subject recognition session validation
US9159065B2 (en) 2011-08-15 2015-10-13 Bank Of America Corporation Method and apparatus for object security session validation
US9253197B2 (en) 2011-08-15 2016-02-02 Bank Of America Corporation Method and apparatus for token-based real-time risk updating
US9361443B2 (en) 2011-08-15 2016-06-07 Bank Of America Corporation Method and apparatus for token-based combining of authentication methods

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