Azolyloxy heterocyclic compound or salt thereof, agrochemical composition, and herbicide
Patent Information
- Application Number
- AU2025253856
- Authority / Receiving Office
- AU · AU
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2025-02-04
- Filing Date
- 2025-04-04
- Publication Date
- 2026-09-17
Abstract
Description
[0019] (7) The pesticide composition according to (6), further comprising a surfactant.
[0020] (8) A herbicide comprising the azolyloxy heterocyclic compound or the salt thereof according to (1) to (5) as an active ingredient.
[0021] (9) The herbicide according to (8), which has a herbicidal activity on a weed growing in a dry field, a paddy field, an orchard, a lawn, a non-crop land, a greenhouse, a seedling raising facility, or a plant factory where a useful plant having agricultural, horticultural and industrial uses is cultured.
[0022] (10) The herbicide according to (9), wherein the useful plant having agricultural, horticultural and industrial uses is a plant transformed in culturing by a breeding method or a gene recombination technique.
[0023] (11) A method for controlling weeds using an active ingredient amount of the azolyloxy heterocyclic compound or the salt thereof according to (1) to (5).
[0024] (12) A method for controlling weeds, wherein the pesticide composition according to (6) or (7) is simultaneously or dividedly applied to a useful plant having agricultural, horticultural and industrial uses or a place where a useful plant having agricultural, horticultural and industrial uses is to be grown or is growing.
[0025] (13) The method for controlling weeds according to (11) or (12), wherein the place to which the herbicide according to (8) is applied is a paddy field, a dry field, a lawn, an orchard, a non-crop land, a greenhouse, a seedling raising facility, or a plant factory.
[0026] (14) A method of using a herbicide, wherein the herbicide according to any one of (8) to (10) is used for controlling weeds on useful plants having agricultural, horticultural and industrial uses.
[0027] (15) A compound which is a production intermediate of the compound represented by the general formula [I] or the salt thereof according to (1), represented by general formula [VI],
[0028] [Chem. 2] R3
[0029] wherein, A1 represents an oxygen atom or a sulfur atom, A4, A5, A6 and A7 each independently represent a nitrogen atom, C-H, or C-R4, R1 represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C6 cycloalkyl group, or a C3-C6 halocycloalkyl group, R3 represents a hydrogen atom, a halogen atom, an azido group, a cyano group, a nitro group, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 halocycloalkyl group, a phenyl group, a pentahalosulfanyl group, or a C1-C6 alkoxycarbonyl group, R4 each independently represents a halogen atom, an azido group, a cyano group, a nitro group, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 haloalkyl group, a hydroxy group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a pentahalosulfanyl group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylthio group, a C1-C6 haloalkylsulfinyl group, a C1-C6 haloalkylsulfonyl group, a formyl group, a carboxyl group, an aminocarbonyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylcarbonyl group, an amino group, a mono (C1-C6 alkyl) amino group, or a di (C1-C6 alkyl) amino group.
[0030] (16) A compound which is a production intermediate of the compound represented by the general formula [I] or the salt thereof according to (1), represented by general formula [IX],
[0031] [Chem. 3] R3
[0032] wherein, A3 represents an oxygen atom or a sulfur atom, A4, A5, A6 and A7 each independently represent a nitrogen atom, C-H, or C-R4, R1 represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C6 cycloalkyl group, or a C3-C6 halocycloalkyl group, R3 represents a hydrogen atom, a halogen atom, an azido group, a cyano group, a nitro group, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 halocycloalkyl group, a phenyl group, a pentahalosulfanyl group, or a C1-C6 alkoxycarbonyl group, R4 each independently represents a halogen atom, an azido group, a cyano group, a nitro group, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 haloalkyl group, a hydroxy group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a pentahalosulfanyl group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylthio group, a C1-C6 haloalkylsulfinyl group, a C1-C6 haloalkylsulfonyl group, a formyl group, a carboxyl group, an aminocarbonyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylcarbonyl group, an amino group, a mono (C1-C6 alkyl) amino group, or a di (C1-C6 alkyl) amino group.
[0033] (17) A method for producing the compound represented by the general formula [I] or the salt thereof according to (1), characterized in that the compound or the salt thereof according to (15) or (16) is used as a raw material. [Effect of the Invention]
[0034] The azolyloxy heterocyclic compound represented by the general formula [I] or the salt thereof of the present invention can control various weeds occurring in dry fields, paddy fields, orchards, non-crop lands, and the like, and has an excellent action and effect as a pesticide.
[0035] The compound which is a production intermediate of the compound represented by the general formula [I] or the salt thereof of the present invention is a compound that is useful as an intermediate in the production of the azolyloxy heterocyclic compound represented by the general formula [I] or the salt thereof of the present invention described above. DETAILED DESCRIPTION
[0036] Symbols and terms described in the present specification will be described.
[0037] In the present invention, the "halogen atom" refers to a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
[0038] In the present invention, the expression of "C1-C6" or the like indicates that the number following the element symbol represents the number of carbon atoms, and in this example, the number of carbon atoms may be any number ranging from 1 to 6.
[0039] In the present invention, unless otherwise specified, the "C1-C6 alkyl group" refers to a linear or branched alkyl group having 1 to 6 carbon atoms, and examples thereof include groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, neopentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl.
[0040] In the present invention, unless otherwise specified, the "C2-C6 alkenyl group" refers to a linear or branched alkenyl group having 2 to 6 carbon atoms, and examples thereof include groups such as vinyl, 1-propenyl, isopropenyl, 2-propenyl, 1-butenyl, 1-methyl-1-propenyl, 2-butenyl, 1-methyl-2-propenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1,3-butadienyl, 1-pentenyl, 1-ethyl-2-propenyl, 2-pentenyl, 1-methyl-1-butenyl, 3-pentenyl, 1-methyl-2-butenyl, 4-pentenyl, 1-methyl-3-butenyl, 3-methyl-1-butenyl, 1,2-dimethyl-2-propenyl, 1,1-dimethyl-2-propenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1,2-dimethyl-1-propenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,3-pentadienyl, 1-vinyl-2-propenyl, 1-hexenyl, 1-propyl-2-propenyl, 2-hexenyl, 1-methyl-1-pentenyl, 1-ethyl-2-butenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-4-pentenyl, 1-ethyl-3-butenyl, 1-(isobutyl)vinyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-2-propenyl, 1-(isopropyl)-2-propenyl, 2-methyl-2-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1,3-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1,5-hexadienyl, 1-vinyl-3-butenyl and 2,4-hexadienyl.
[0041] In the present invention, unless otherwise specified, the "C2-C6 alkynyl group" refers to a linear or branched alkynyl group having 2 to 6 carbon atoms, and examples thereof include groups such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 1-methyl-2-propynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 1-ethyl-2-propynyl, 2-pentynyl, 3-pentynyl, 1-methyl-2-butynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-hexynyl, 1-(n-propyl)-2-propynyl, 2-hexynyl, 1-ethyl-2-butynyl, 3-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 4-methyl-1-pentynyl, 3-methyl-1-pentynyl, 5-hexynyl, 1-ethyl-3-butynyl, 1-ethyl-1-methyl-2-propynyl, 1-(isopropyl)-2-propynyl, 1,1-dimethyl-2-butynyl and 2,2-dimethyl-3-butynyl.
[0042] In the present invention, unless otherwise specified, the "C1-C6 haloalkyl group" refers to a linear or branched haloalkyl group having 1 to 6 carbon atoms substituted with 1 to 13 halogen atoms which are the same or different, and examples thereof include groups such as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, chlorodifluoromethyl, dichlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, pentafluoroethyl, 1-chloroethyl 2-chloroethyl, 1,1-dichloroethyl, 2,2-dichloroethyl, 2,2,2-trichloroethyl, 1,1,2,2-tetrachloroethyl, pentachloroethyl, 1-bromoethyl, 2-bromoethyl, 2,2,2-tribromoethyl, 1-iodoethyl, 2-iodoethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2-trichloroethyl, 1-fluoropropyl, 2-fluoropropyl, 3-fluoropropyl, 1,1-difluoropropyl, 2,2-difluoropropyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-fluoropropane-2-yl, 2-fluoropropane-2-yl, 1,1-difluoropropane-2-yl, 1,2-difluoropropane-2-yl, 1,3-difluoropropane-2-yl, 1,2,3-trifluoropropane-2-yl, 1,1,3,3-tetrafluoropropane-2-yl, 1,1,1,3,3,3-hexafluoropropane-2-yl, heptafluoropropane-2-yl, 1-chloropropyl, 2-chloropropyl, 3-chloropropyl, 1,1-dichloropropyl, 2,2-dichloropropyl, 3,3-dichloropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentachloropropyl, heptachloropropyl, 1-chloropropane-2-yl, 2-chloropropane-2-yl, 1,1-dichloropropane-2-yl, 1,2-dichloropropane-2-yl, 1,3- dichloropropane-2-yl, 1,2,3-trichloropropane-2-yl, 1,1,3,3-tetrachloropropane-2-yl, 1,1,1,3,3,3-hexachloropropane-2-yl, heptachloropropane-2-yl, 1-bromopropyl, 2-bromopropyl, 3-bromopropyl, 1-bromopropane-2-yl, 2-bromopropane-2-yl, 1-iodopropyl, 2-iodopropyl, 3-iodopropyl, 1-iodopropane-2-yl, 2-iodopropane-2-yl, 1-fluorobutyl, 2-fluorobutyl, 3-fluorobutyl, 4-fluorobutyl, 4,4-difluorobutyl, 4,4,4-trifluorobutyl, 3,3,4,4,4-pentafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, nonafluorobutyl, 1,1,1-trifluorobutane-2-yl, 4,4,4-trifluorobutane-2-yl, 3,3,4,4,4-pentafluorobutane-2-yl, nonafluorobutane-2-yl, 1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propane-2-yl, 1-chlorobutyl, 2-chlorobutyl, 3-chlorobutyl, 4-chlorobutyl, 4,4-dichlorobutyl, 4,4,4-trichlorobutyl, nonachlorobutyl, 1,1,1-trichlorobutane-2-yl, 4,4,4-trichlorobutane-2-yl, nonachlorobutane-2-yl, 1-bromobutyl, 2-bromobutyl, 3-bromobutyl, 4-bromobutyl, 1-iodobutyl, 2-iodobutyl, 3-iodobutyl, 4-iodobutyl, 4-chloro-1,1,2,2,3,3,4,4-octafluorobutyl, 4-bromo-1,1,2,2,3,3,4,4-octafluorobutyl, 1-fluoropentyl, 2-fluoropentyl, 3-fluoropentyl, 4-fluoropentyl, 5-fluoropentyl, 5,5,5-trifluoropentyl, 4,4,5,5,5-pentafluoropentyl, 3,3,4,4,5,5,5-heptafluoropentyl, 2,2,3,3,4,4,5,5,5-nonafluoropentyl, undecafluoropentyl, 1-chloropentyl, 2-chloropentyl, 3-chloropentyl, 4-chloropentyl, 5-chloropentyl, 5,5,5-trichloropentyl, 4,4,5,5,5-pentachloropentyl, 3,3,4,4,5,5,5-heptachloropentyl, 2,2,3,3,4,4,5,5,5-nonachloropentyl, undecachloropentyl, 1-bromopentyl, 2-bromopentyl, 3-bromopentyl, 4-bromopentyl, 5-bromopentyl, 5-iodopentyl, 1-fluorohexyl, 2-fluorohexyl, 3-fluorohexyl, 4-fluorohexyl, 5-fluorohexyl, 6-fluorohexyl, 6,6,6-trifluorohexyl, 5,5,6,6,6-pentafluorohexyl, 4,4,5,5,6,6,6-heptafluorohexyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl, tridecafluorohexyl, 1-chlorohexyl, 2-chlorohexyl, 3-chlorohexyl, 4-chlorohexyl, 5-chlorohexyl, 6-chlorohexyl, 5-bromohexyl, 6-bromohexyl, 5-iodohexyl and 6-iodohexyl.
[0043] In the present invention, unless otherwise specified, the "C3-C6 cycloalkyl group" refers to a cycloalkyl group having 3 to 6 carbon atoms, and examples thereof include groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
[0044] In the present invention, unless otherwise specified, the "C3-C6 halocycloalkyl group" refers to a cycloalkyl group having 3 to 6 carbon atoms substituted with 1 to 11 halogen atoms which are the same or different, and examples thereof include groups such as 1-fluorocyclopropyl, 2-fluorocyclopropyl, 2,2-difluorocyclopropyl, 2,2,3,3-tetrafluorocyclopropyl, 1-chlorocyclopropyl, 2-chlorocyclopropyl, 2,2-dichlorocyclopropyl, 2,2,3,3-tetrachlorocyclopropyl, 2,2-dibromocyclopropyl, 2,2-diiodocyclopropyl, 1-fluorocyclobutyl, 2-fluorocyclobutyl, 3- fluorocyclobutyl, 3,3-difluorocyclobutyl, heptafluorocyclobutyl, 2-chlorocyclobutyl, 3-chlorocyclobutyl, 3,3-dichlorocyclobutyl, 3,3-dibromocyclobutyl, 3,3-diiodocyclobutyl, 1-fluorocyclopentyl, 2- fluorocyclopentyl, 3-fluorocyclopentyl, 2,2-difluorocyclopentyl, 3,3-difluorocyclopentyl, nonafluorocyclopentyl, 2,2-dichlorocyclopentyl, 3,3-dichlorocyclopentyl, 2,2-dibromocyclopentyl, 3,3-dibromocyclopentyl, 2,2-diiodocyclopentyl, 3,3-diiodocyclopentyl, 1-fluorocyclohexyl, 2-fluorocyclohexyl, 3-fluorocyclohexyl, 4-fluorocyclohexyl, 2,2-difluorocyclohexyl, 3,3-difluorocyclohexyl, 4,4-difluorocyclohexyl, 1-chlorocyclohexyl, 2-chlorocyclohexyl, 3-chlorocyclohexyl, 4-chlorocyclohexyl, 2,2-dichlorocyclohexyl, 3,3-dichlorocyclohexyl, 4,4-dichlorocyclohexyl, 3,3-dibromocyclohexyl, 4,4-dibromocyclohexyl, 3,3-diiodocyclohexyl, 4,4-diiodocyclohexyl and perfluorocyclohexyl.
[0045] In the present invention, unless otherwise specified, the "cyano C3-C6 cycloalkyl group" refers to a group in which any position of the C3-C6 cycloalkyl group is substituted with a cyano group, i.e., a (cyano)-(C3-C6 cycloalkyl)-group, where the cycloalkyl moiety is as defined above, and examples thereof include groups such as 1-cyanocyclopropyl, 2-cyanocyclopropyl, 1-cyanocyclobutyl, 2-cyanocyclobutyl, 3-cyanocyclobutyl, 1-cyanocyclopentyl, 3-cyanocyclopentyl, 1-cyanocyclohexyl, and 4-cyanocyclohexyl.
[0046] In the present invention, unless otherwise specified, the "heterocyclyl group" refers to a non-aromatic heterocycle having a monocyclic or fused bicyclic ring structure containing, as ring members, one or more heteroatoms selected from an oxygen atom, a sulfur atom, or a nitrogen atom in addition to a carbon atom and containing 5 to 12 ring membered atoms. Examples of the monocyclic heterocycles include groups such as isoxazolinyl, piperidinyl, piperazinyl, azetidinyl, aziridinyl, morpholinyl, tetrahydropyranyl, tetrahydrofuryl, oxetanyl, oxiranyl, dioxanyl (e.g., 1,3-dioxanyl, 1,4-dioxanyl, etc.), dioxolanyl (e.g., 1,3-dioxolanyl, etc.), thianyl, tetrahydrothienyl, thietanyl, and thiiranyl, and the specific examples of the bicyclic heterocyclic groups include groups such as indolinyl, isoindolinyl, chromanyl, isochromanyl, tetrahydroisoquinolinyl, benzotetrahydrofuryl, benzotetrahydrothienyl, isobenzotetrahydrofuryl, isobenzotetrahydrothienyl, benzodioxolyl, dihydrobenzoisoxazinyl, dihydrobenzoisothiazinyl, 1-oxidetetrahydroquinolinyl, tetrahydroquinolinyl, dihydroquinolinyl, dihydroquinolinonyl, dihydroisoquinolinonyl, dihydrocoumarinyl, dihydroisocoumarinyl, isoindolinonyl, benzodioxanyl, benzoxazolinonyl, quinolizidinyl, indolizidinyl, tropanyl, nortropanyl, quinuclidinyl, 3-azabicyclo[3.1.0]hexanyl, and 6-oxa-3-azabicyclo[3.1.0]hexanyl.
[0047] When the heteroatom of the above "heterocyclyl group" is a nitrogen atom, the nitrogen atom may be an N-oxide.
[0048] Here, the substitution position is not particularly limited. That is, the heterocyclyl group encompasses all position isomers thereof. For example, when the heterocyclyl group is a piperidinyl group, the piperidinyl group includes a 1-piperidinyl group, a 2-piperidinyl group, a 3-piperidinyl group, or a 4-piperidinyl group.
[0049] In the present invention, unless otherwise specified, the "C6-C12 aryl group" refers to an aryl group having 6 to 12 carbon atoms, and examples thereof include groups such as phenyl, 1-naphthyl, and 2-naphthyl.
[0050] In the present invention, unless otherwise limited, the "heteroaryl group" refers to an aromatic heterocycle having a monocyclic or fused bicyclic ring structure containing, as ring members, one or more heteroatoms selected from an oxygen atom, a sulfur atom, and a nitrogen atom in addition to a carbon atom and containing 5 to 12 ring membered atoms. Examples of the monocyclic heterocycles include groups such as pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, triazinyl, thienyl, furanyl, pyrrolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, imidazolyl, triazolyl, thiadiazolyl, oxadiazolyl and tetrazolyl, and examples of the fused bicyclic moiety formed by fusing one of these monocyclic heterocyclic groups with a phenyl ring or with any of the monocyclic heterocyclic groups so as to form a C8-C10 bicyclic group include groups such as indolyl, benzimidazolyl, indazolyl, benzotriazolyl, isoquinolinyl, quinolinyl, benzothiazolyl, benzofuranyl, benzothienyl, benzoisoxazolyl, pyrazolopyridyl, quinazolinyl, quinoxalinyl and cinnolinyl, and groups similar to these.
[0051] Here, the substitution position is not particularly limited. That is, the heteroaryl group encompasses all position isomers thereof. For example, when the heteroaryl group is a pyridyl group, the pyridyl group includes a 2-pyridyl group, a 3-pyridyl group, or a 4-pyridyl group.
[0052] In the present invention, unless otherwise specified, the "C7-C14 aralkyl group" refers to an alkyl group having 7 to 14 carbon atoms and substituted at any position by an aryl group, i.e., a (C6-C12 aryl)-(C1-C2 alkyl)-group, where the aryl moiety is as defined above, and the C1-C2 alkyl moiety refers to a methyl group or an ethyl group, and examples thereof include groups such as benzyl, 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, naphthalen-1-ylmethyl, and naphthalen-2-ylmethyl. An aralkyl group is also referred to as an arylalkyl group.
[0053] In the present invention, unless otherwise specified, the "heteroaralkyl group" refers to an alkyl group having 6 to 14 carbon atoms and substituted at any position by a heteroaryl group, i.e., a (heteroaryl)-(C1-C2 alkyl)-group, where the heteroaryl moiety is as defined above, the C1-C2 alkyl moiety refers to a methyl group or an ethyl group, and examples thereof include a C5-C12 heteroaryl group C1-C2 alkyl group. Specific examples of the C6-C14 heteroaralkyl group include groups such as pyridylmethyl, pyridylethyl, indolylmethyl, furylmethyl, thienylmethyl, and pyrrolylmethyl.
[0054] In the present invention, unless otherwise specified, the "C1-C6 alkoxy group" refers to a (C1-C6 alkyl)-O-group in which the alkyl moiety is as defined above, and examples thereof include groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1-ethylpropoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, and n-hexyloxy.
[0055] In the present invention, unless otherwise specified, the "C2-C6 alkenyloxy group" refers to a (C2-C6 alkenyl)-O-group in which the alkenyl moiety is as defined above, and examples thereof include groups such as vinyloxy, 1-propenyloxy, isopropenyloxy, 2-propenyloxy, 1-butenyloxy, 1-methyl-1-propenyloxy, 2-butenyloxy, 1-methyl-2-propenyloxy, 3-butenyloxy, 2-methyl-1-propenyloxy, 2-methyl-2-propenyloxy, 1,3-butadienyloxy, 1-pentenyloxy, 1-ethyl-2-propenyloxy, 2-pentenyloxy, 1-methyl-1-butenyloxy, 3-pentenyloxy, 1-methyl-2-butenyloxy, 4-pentenyloxy, 1-methyl-3-butenyloxy, 3-methyl-1-butenyloxy, 1,2-dimethyl-2-propenyloxy, 1,1-dimethyl-2-propenyloxy, 2-methyl-2-butenyloxy, 3-methyl-2-butenyloxy, 1,2-dimethyl-1-propenyloxy, 2-methyl-3-butenyloxy, 3-methyl-3-butenyloxy, 1,3-pentadienyloxy, 1-vinyl-2-propenyloxy, 1-hexenyloxy, 1-propyl-2-propenyloxy, 2-hexenyloxy, 1-methyl-1-pentenyloxy, 1-ethyl-2-butenyloxy, 3-hexenyloxy, 4-hexenyloxy, 5-hexenyloxy, 1-methyl-4-pentenyloxy, 1-ethyl-3-butenyloxy, 1-(isobutyl)vinyloxy, 1-ethyl-1-methyl-2-propenyloxy, 1-ethyl-2-methyl-2-propenyloxy, 1-(isopropyl)-2-propenyloxy, 2-methyl-2-pentenyloxy, 3-methyl-3-pentenyloxy, 4-methyl-3-pentenyloxy, 1,3-dimethyl-2-butenyloxy, 1,1-dimethyl-3-butenyloxy, 3-methyl-4-pentenyloxy, 4-methyl-4-pentenyloxy, 1,2-dimethyl-3-butenyloxy, 1,3-dimethyl-3-butenyloxy, 1,1,2-trimethyl-2-propenyloxy, 1,5-hexadienyloxy, 1-vinyl-3-butenyloxy, and 2,4-hexadienyloxy.
[0056] In the present invention, unless otherwise specified, the "C2-C6 alkynyloxy group" refers to a (C2-C6 alkynyl)-O-group in which the alkynyl moiety is as defined above, and examples thereof include groups such as ethynyloxy, 1-propynyloxy, 2-propynyloxy, 1-butynyloxy, 1-methyl-2-propynyloxy, 2-butynyloxy, 3-butynyloxy, 1-pentynyloxy, 1-ethyl-2-propynyloxy, 2-pentynyloxy, 3-pentynyloxy, 1-methyl-2-butynyloxy, 4-pentynyloxy, 1-methyl-3-butynyloxy, 2-methyl-3-butynyloxy, 1-hexynyloxy, 1-(n-propyl)-2-propynyloxy, 2-hexynyloxy, 1-ethyl-2-butynyloxy, 3-hexynyloxy, 1-methyl-2-pentynyloxy, 1-methyl-3-pentynyloxy, 4-methyl-1-pentynyloxy, 3-methyl-1-pentynyloxy, 5-hexynyloxy, 1-ethyl-3-butynyloxy, 1-ethyl-1-methyl-2-propynyloxy, 1-(isopropyl)-2-propynyloxy, 1,1-dimethyl-2-butynyloxy, and 2,2-dimethyl-3-butynyloxy.
[0057] In the present invention, unless otherwise specified, the "C1-C6 haloalkoxy group" refers to a (C1-C6 haloalkyl)-O-group in which the haloalkyl moiety is as defined above, and examples thereof include groups such as difluoromethoxy, dichloromethoxy, trifluoromethoxy, trichloromethoxy, tribromomethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 1-chloroethoxy, 2-chloroethoxy, 1-bromoethoxy, 2-bromoethoxy, 2,2-difluoroethoxy, 1,2-dichloroethoxy, 2,2-dichloroethoxy, 2,2,2-trifluoroethoxy, 2,2,2-trichloroethoxy, 1,1,2,2-tetrafluoroethoxy, pentafluoroethoxy, 2-bromo-2-chloroethoxy, 2-chloro-1,1,2,2-tetrafluoroethoxy, 1-chloro-1,2,2,2-tetrafluoroethoxy, 1-chloropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 2-bromo-1-methylethoxy, 3-iodopropoxy, 2,3-dichloropropoxy, 2,3-dibromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trifluoro-2-propoxy, 3,3,3-trichloropropoxy, 3-bromo-3,3-difluoropropoxy, 2,2-difluoropropoxy, 3,3-dichloro-3-fluoropropoxy, 2,2,3,3-tetrafluoropropoxy, 1-bromo-3,3,3-trifluoropropoxy, 2,2,3,3,3-pentafluoropropoxy, 2,2,2-trifluoro-1-trifluoromethylethoxy, heptafluoropropoxy, heptafluoro-2-propoxy, 1,2,2,2-tetrafluoro-1-trifluoromethylethoxy, 1,1,2,3,3,3-hexafluoropropoxy, 2-chlorobutoxy, 3-chlorobutoxy, 4-chlorobutoxy, 2-chloro-1,1-dimethylethoxy, 4-bromobutoxy, 3-bromo-2-methylpropoxy, 2-bromo-1,1-dimethylethoxy, 2,2-dichloro-1,1-dimethylethoxy, 2-chloro-1-chloromethyl-2-methylethoxy, 4,4,4-trifluorobutoxy, 3,3,3-trifluoro-1-methylpropoxy, 3,3,3-trifluoro-2-methylpropoxy, 2,3,4-trichlorobutoxy, 2,2,2-trichloro-1,1-dimethylethoxy, 4-chloro-4,4-difluorobutoxy, 4,4-dichloro-4-fluorobutoxy, 4-bromo-4,4-difluorobutoxy, 2,4-dibromo-4,4-difluorobutoxy, 3,4-dichloro-3,4,4-trifluorobutoxy, 3,3-dichloro-4,4,4-trifluorobutoxy, 4-bromo-3,3,4,4-tetrafluorobutoxy, 4-bromo-3-chloro-3,4,4-trifluorobutoxy, 2,2,3,3,4,4-hexafluorobutoxy, 2,2,3,4,4,4-hexafluorobutoxy, 2,2,2-trifluoro-1-methyl-1-trifluoromethylethoxy, 3,3,3-trifluoro-2-trifluoromethylpropoxy, 2,2,3,3,4,4,4-heptafluorobutoxy, 3,3,4,4,4-pentafluoro-2-butoxy, 2,3,3,3-tetrafluoro-2-trifluoromethylpropoxy, 1,1,2,2,3,3,4,4-octafluorobutoxy, nonafluorobutoxy, perfluoro-tert-butoxy, 4-chloro-1,1,2,2,3,3,4,4-octafluorobutoxy, 5,5,5-trifluoropentoxy, 4,4,5,5,5-pentafluoropentoxy, 3,3,4,4,5,5,5-heptafluoropentoxy, 3,3,4,4,5,5,5-heptafluoro-2-pentoxy, 2,2,3,3,4,4,5,5,5-nonafluoropentoxy, 2,2,3,3,4,4,5,5-octafluoropentoxy, perfluoropentoxy, 4,4,5,5,5-pentafluoro-2-butoxy, 2,2-bis(trifluoromethyl)propoxy, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyloxy, 3,3,4,4,5,5,6,6,6-nonafluorohexyloxy, 4,4,5,5,6,6,6-heptafluorohexyloxy, 2,2,3,3,4,4,5,5,6,6-decafluorohexyloxy, 4,4,4-trifluoro-3,3-bis(trifluoromethyl)butyloxy, and perfluorohexyloxy.
[0058] In the present invention, unless otherwise specified, the "C3-C6 cycloalkyloxy group" refers to a (C3-C6 cycloalkyl)-O-group in which the cycloalkyl moiety is as defined above, and examples thereof include groups such as cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, and cyclohexyloxy.
[0059] In the present invention, unless otherwise specified, the "C6-C12 aryloxy group" refers to a (C6-C12 aryl)-O-group, and examples thereof include groups such as phenoxy, naphthalen-1-yloxy, and naphthalen-2-yloxy.
[0060] In the present invention, unless otherwise specified, the "heteroaryloxy group" refers to a (heteroaryl)-O-group in which the heteroaryl moiety is as defined above, and examples thereof include groups such as pyridyloxy, pyrimidyloxy, pyrazinyloxy, pyridazinyloxy, thienyloxy, and indolyloxy.
[0061] In the present invention, unless otherwise specified, the "C7-C14 aralkyloxy group" refers to a (C7-C14 aralkyl)-O-group in which the aralkyl moiety is as defined above, and examples thereof include groups such as benzyloxy, 1-phenylethyloxy, 2-phenylethyloxy, 3-phenylpropyloxy, 4-phenylbutyloxy, naphthalen-1-ylmethyloxy, and naphthalen-2-ylmethyloxy.
[0062] In the present invention, unless otherwise specified, the "heteroaralkyloxy group" refers to a (heteroaralkyl)-O-group in which the heteroaralkyl moiety is as defined above, and examples thereof include groups such as pyridylmethyloxy, pyridylethyloxy, indolylmethyloxy, furylmethyloxy, thienylmethyloxy, and pyrrolylmethyloxy.
[0063] In the present invention, unless otherwise specified, the "pentahalosulfanyl group" refers to an X6-sulfanyl group substituted with 5 halogen atoms which are the same or different, and examples thereof include groups such as chlorotetrafluorosulfanyl, bromotetrafluorosulfanyl, and pentafluorosulfanyl.
[0064] In the present invention, unless otherwise specified, the "C1-C6 alkylthio group" refers to a (C1-C6 alkyl)-S-group in which the alkyl moiety is as defined above, and examples thereof includes groups such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, and hexylthio.
[0065] In the present invention, unless otherwise specified, the "C1-C6 alkylsulfinyl group" refers to a (C1-C6 alkyl)-S(=O)-group in which the alkyl moiety is as defined above, and examples thereof include groups such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tertbutylsulfinyl, pentylsulfinyl, and hexylsulfinyl.
[0066] In the present invention, unless otherwise specified, the "C1-C6 alkylsulfonyl group" refers to a (C1-C6 alkyl)-S(=O)2 group in which the alkyl moiety is as defined above, and examples thereof include groups such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, and hexylsulfonyl.
[0067] In the present invention, unless otherwise specified, the "C1-C6 haloalkylthio group" refers to a (C1-C6 haloalkyl)-S-group in which the haloalkyl moiety is as defined above, and examples thereof include groups such as fluoromethylthio, difluoromethylthio, trifluoromethylthio, trichloromethylthio, 2,2,2-trifluoroethylthio, pentafluoroethylthio, 2,2,2-trichloroethylthio, 3,3,3-trifluoropropylthio, 1,1,2,3,3,3-hexafluoropropylthio, heptafluoropropylthio, 1,1,1,3,3,3-hexafluoropropane-2-ylthio, heptafluoropropane-2-ylthio, and 4,4,4-trifluorobutylthio.
[0068] In the present invention, unless otherwise specified, the "C1-C6 haloalkylsulfinyl group" refers to a (C1-C6 haloalkyl)-S(=O)-group in which the haloalkyl moiety is as defined above, and examples thereof include groups such as difluoromethylsulfinyl, trifluoromethylsulfinyl, trichloromethylsulfinyl, 2,2,2-trifluoroethylsulfinyl, 2,2,2-trichloroethylsulfinyl, pentafluoroethylsulfinyl, 3,3,3-trifluoropropylsulfinyl, heptafluoropropylsulfinyl, and heptafluoro-2-propylsulfinyl.
[0069] In the present invention, unless otherwise specified, the "C1-C6 haloalkylsulfonyl group" refers to a (C1-C6 haloalkyl)-S(=O)2 group in which the haloalkyl moiety is as defined above, and examples thereof include groups such as difluoromethylsulfonyl, trifluoromethylsulfonyl, trichloromethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, pentafluoroethylsulfonyl, 3,3,3-trifluoropropylsulfonyl, heptafluoropropylsulfonyl, heptafluoro-2-propylsulfonyl, and nonafluorobutylsulfonyl.
[0070] In the present invention, unless otherwise specified, the "C3-C6 cycloalkylthio group" refers to a (C3-C6 cycloalkyl)-S-group in which the cycloalkyl moiety is as defined above, and examples thereof include groups such as cyclopropylthio, cyclobutylthio, cyclopentylthio, and cyclohexylthio.
[0071] In the present invention, unless otherwise specified, the "C3-C6 cycloalkylsulfinyl group" refers to a (C3-C6 cycloalkyl)-S(=O)-group in which the cycloalkyl moiety is as defined above, and examples thereof include groups such as cyclopropylsulfinyl, cyclobutylsulfinyl, cyclopentylsulfinyl, and cyclohexylsulfinyl.
[0072] In the present invention, unless otherwise specified, the "C3-C6 cycloalkylsulfonyl group" refers to a (C3-C6 cycloalkyl)-S(=O)2-group in which the cycloalkyl moiety is as defined above, and examples thereof include groups such as cyclopropylsulfonyl, cyclobutylsulfonyl, cyclopentylsulfonyl, and cyclohexylsulfonyl.
[0073] In the present invention, unless otherwise specified, the "C3-C6 halocycloalkylthio group" refers to a (C3-C6 halocycloalkyl)-S-group in which the halocycloalkyl moiety is as defined, and examples thereof include groups such as 2,2-difluorocyclopropylthio, 2,2-dichlorocyclopropylthio, 3,3-difluorocyclobutylthio, 3,3- dichlorocyclobutylthio, 3-fluorocyclopentylthio, 3,3-difluorocyclopentylthio, nonafluorocyclopentylthio, 3,3-dichlorocyclopentylthio, 4,4-difluorocyclohexylthio, and 4,4-dichlorocyclohexylthio.
[0074] In the present invention, unless otherwise specified, the "C3-C6 halocycloalkylsulfinyl group" refers to a (C3-C6 halocycloalkyl)-S(=O)-group in which the halocycloalkyl moiety is as defined above, examples thereof include groups such as 2,2-difluorocyclopropylsulfinyl, 2,2-dichlorocyclopropylsulfinyl, 3,3-difluorocyclobutylsulfinyl, 3,3-dichlorocyclobutylsulfinyl, 3-fluorocyclopentylsulfinyl, 3,3-difluorocyclopentylsulfinyl, nonafluorocyclopentylsulfinyl, 3,3-dichlorocyclopentylsulfinyl, 4,4-difluorocyclohexylsulfinyl, and 4,4-dichlorocyclohexylsulfinyl.
[0075] In the present invention, unless otherwise specified, the "C3-C6 halocycloalkylsulfonyl group" refers to a (C3-C6 halocycloalkyl)-S(=O)2-group in which the halocycloalkyl moiety is as defined above, and examples thereof include groups such as 2,2-difluorocyclopropylsulfonyl, 2,2-dichlorocyclopropylsulfonyl, 3,3-difluorocyclobutylsulfonyl, 3-fluorocyclopentylsulfonyl, 3,3-difluorocyclopentylsulfonyl, nonafluorocyclopentylsulfonyl, 3,3-dichlorocyclopentylsulfonyl, 4,4-difluorocyclohexylsulfonyl, and 4,4-dichlorocyclohexylsulfonyl.
[0076] In the present invention, unless otherwise specified, the "C6-C12 arylthio group" refers to a (C6-C12 aryl)-S-group in which the aryl moiety is as defined above, and examples thereof include groups such as phenylthio, 1-naphthylthio, and 2-naphthylthio.
[0077] In the present invention, unless otherwise specified, the "C6-C12 arylsulfinyl group" refers to a (C6-C12 aryl)-S(=O)-group in which the aryl moiety is as defined above, and examples thereof include groups such as phenylsulfinyl, 1-naphthylsulfinyl, and 2-naphthylsulfinyl.
[0078] In the present invention, unless otherwise specified, the "C6-C12 arylsulfonyl group" refers to a (C6-C12 aryl)-S(=O)2-group in which the aryl moiety is as defined above, and examples thereof include groups such as phenylsulfonyl, 1-naphthylsulfonyl, and 2-naphthylsulfonyl.
[0079] In the present invention, unless otherwise specified, the "heteroarylthio group" refers to a (heteroaryl)-S-group in which the heteroaryl moiety is as defined above, and examples thereof include groups such as pyridin-2-ylthio, pyridin-3-ylthio, pyridin-4-ylthio, pyrazin-2-ylthio, pyridazin-3-ylthio, pyridazin-4-ylthio, pyrimidine-2-ylthio, pyrimidine-4-ylthio, pyrimidine-5-ylthio, thiazole-2-ylthio, thiazole-4-ylthio, and thiazole-5-ylthio.
[0080] In the present invention, unless otherwise specified, the "heteroarylsulfinyl group" refers to a (heteroaryl)-S(=O)-group in which the heteroaryl moiety is as defined above, and examples thereof include groups such as pyridin-2-ylsulfinyl, pyridin-3-ylsulfinyl, pyridin-4-ylsulfinyl, pyrazin-2-ylsulfinyl, pyridazin-3-ylsulfinyl, pyridazin-4-ylsulfinyl, pyrimidin-2-ylsulfinyl, pyrimidin-4-ylsulfinyl, pyrimidin-5-ylsulfinyl, thiazol-2-ylsulfinyl, thiazol-4-ylsulfinyl and thiazol-5-ylsulfinyl.
[0081] In the present invention, unless otherwise specified, the "heteroarylsulfonyl group" refers to a (heteroaryl)-S(=O)2-group in which the heteroaryl moiety is as defined above, and examples thereof include groups such as pyridin-2-ylsulfonyl, pyridin-3-ylsulfonyl, pyridin-4-ylsulfonyl, pyrazin-2-ylsulfonyl, pyridazin-3-ylsulfonyl, pyridazin-4-ylsulfonyl, pyrimidin-2-ylsulfonyl, pyrimidin-4-ylsulfonyl, pyrimidin-5-ylsulfonyl, thiazol-2-ylsulfonyl, thiazol-4-ylsulfonyl, and thiazol-5-ylsulfonyl.
[0082] In the present invention, the "formyl group" refers to a H-C (=O)-group.
[0083] In the present invention, the "carboxyl group" refers to a HO-C (=O)- group.
[0084] In the present invention, the "aminocarbonyl group" refers to a H2N-C (=O)-group.
[0085] In the present invention, unless otherwise specified, the "C1-C6 alkoxycarbonyl group" refers to a (C1-C6 alkoxy)-C(=O)-group in which the alkoxy moiety is as defined above, and examples thereof include groups such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, n-pentoxycarbonyl, 1-methylbutoxycarbonyl, 2-methylbutoxycarbonyl, 3-methylbutoxycarbonyl, 1-ethylpropoxycarbonyl, 1,1-dimethylpropoxycarbonyl, 1,2-dimethylpropoxycarbonyl, and n-hexyloxycarbonyl.
[0086] In the present invention, unless otherwise specified, the "C1-C6 alkylcarbonyl group" refers to a (C1-C6 alkyl)-C(=O)-group in which the alkyl moiety is as defined above, and examples thereof include groups such as methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, n-butylcarbonyl, sec-butylcarbonyl, isobutylcarbonyl, tert-butylcarbonyl, n-pentylcarbonyl, 1-methylbutylcarbonyl, 2-methylbutylcarbonyl, 3-methylbutylcarbonyl, 1-ethylpropylcarbonyl, 1,1-dimethylpropylcarbonyl, 1,2-dimethylpropylcarbonyl, and neopentylcarbonyl.
[0087] In the present invention, the "formylthio group" refers to a H-C (=O)-S- group.
[0088] In the present invention, the "aminothiocarbonyl group" refers to a H2N-C (=S)-group.
[0089] In the present invention, unless otherwise specified, the "C1-C6 alkylcarbonylthio group" refers to a (C1-C6 alkyl)-C(=O)-S-group in which the alkyl moiety is as defined above, and examples thereof include groups such as methylcarbonylthio, ethylcarbonylthio, isopropylcarbonylthio, and tert-butylcarbonylthio.
[0090] In the present invention, unless otherwise specified, the "mono(C1-C6 alkyl)amino group" refers to a (C1-C6 alkyl)-NH-group in which the alkyl moiety is as defined above, and examples thereof include groups such as methylamino, ethylamino, isopropylamino, n-propylamino, and tert-butylamino.
[0091] In the present invention, unless otherwise specified, the "di(C1-C6 alkyl)amino group" refers to a (C1-C6 alkyl)2 N-group in which the alkyl moiety is as defined above, and the two alkyl groups may be different from each other, and examples thereof include groups such as dimethylamino, methylethylamino, and methyl-n-propylamino.
[0092] In the present invention, the "(di(C1-C6 alkyl)sulfinylidene)amino group" refers to a (C1-C6 alkyl)2 S (=O)=N-group, and the two alkyl groups may be different from each other, and examples thereof include groups such as (S,S-dimethylsulfinylidene)amino, (S,S-diethylsulfinylidene)amino, and (S-ethyl-S-methylsulfinylidene)amino.
[0093] In the present invention, unless otherwise specified, the "mono(C1-C6 alkyl)aminocarbonyl group" refers to a (C1-C6 alkyl)-NH-C (=O)-group in which the alkyl moiety is as defined above, and examples thereof include groups such as methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, isopropylaminocarbonyl, and tert-butylaminocarbonyl.
[0094] In the present invention, unless otherwise specified, the "di(C1-C6 alkyl)aminocarbonyl group" refers to a (C1-C6 alkyl)2 N-C(=O)-group in which the alkyl moiety is as defined above, and the two alkyl groups may be different from each other, and examples thereof include groups such as dimethylaminocarbonyl, diethylaminocarbonyl, and diisopropylaminocarbonyl.
[0095] In the present invention, the expression "may be substituted with one or more substituents selected from R5 substituents" indicates that a hydrogen atom bonded to a carbon atom or a nitrogen atom in the substituent may be substituted by any R5, and the number of R5 to be substituted is arbitrarily selected within each specified number of the carbon atom or the nitrogen atom. When two or more R5 are present in the substituent, each R5 may be the same or different from each other.
[0096] In the present invention, the expression "the nitrogen atom may be substituted with one or more substituents selected from R6 substituents" indicates that the hydrogen atom bonded to the nitrogen atom is substituted with one or two R6, and when two R6 are present, each R6 may be the same or different from each other.
[0097] In the present invention, the expression "R6 may form a 3 to 7-membered heterocyclic ring together with a nitrogen atom bound thereto" indicates that a heterocyclic ring structure may be formed including a nitrogen atom to be bound, and examples thereof include the formation of piperidinyl, piperazinyl, azetidinyl, aziridinyl, and morpholinyl.
[0098] In the present invention, the expression "may be substituted with one or more substituents selected from R7 substituents" indicates that a hydrogen atom bonded to a carbon atom in the substituent may be substituted by any R7, and the number of R7 to be substituted is arbitrarily selected within each specified number of the carbon atom. When two or more R5 are present in the substituent, each R5 may be the same as or different from each other.
[0099] In the present invention, the expression "when A1 is a nitrogen atom, A3 represents an oxygen atom or a sulfur atom" indicates either a combination in which A1 is a nitrogen atom and A3 is an oxygen atom or a combination in which A1 is a nitrogen atom and A3 is a sulfur atom.
[0100] In the present invention, the expression "when A3 is a nitrogen atom, A1 represents an oxygen atom or a sulfur atom" indicates either a combination in which A3 is a nitrogen atom and A1 is an oxygen atom or a combination in which A3 is a nitrogen atom and A1 is a sulfur atom.
[0101] In the present invention, the salt is more specifically an agriculturally acceptable salt, and the salt is a salt of, a hydroxy group, a carboxyl group, amino group or a nitrogen atom or the like in a pyridine ring or the like, when such a group exist in the structure in the present compound represented by the general formula [I], with a metal or an organic base, or with a mineral acid or an organic acid. Examples of the metal may include alkali metals such as sodium or potassium, or alkaline earth metals such as magnesium or calcium, examples of the organic base may include triethylamine or diisopropylamine, examples of the mineral acid may include phosphoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, boric acid, and sulfuric acid, and examples of the organic acid may include formic acid, acetic acid, lactic acid, ascorbic acid, succinic acid, fumaric acid, maleic acid, oxalic acid, citric acid, benzoic acid, salicylic acid, tartaric acid, methanesulfonic acid, 4-toluenesulfonic acid and trifluoromethanesulfonic acid.
[0102] Next, representative examples of the compounds included in the azolyloxy heterocyclic compounds of the present invention represented by the general formula [I] are shown in Tables 1 to 70. However, the compound included in the azolyloxy heterocyclic compound of the present invention is not limited thereto. In addition, the compound numbers in the table are referenced in the description below.
[0103] The compound included in the azolyloxy heterocyclic compound of the present invention can have geometric isomers of E-form and Z-form depending on the kind of the substituent, and the present invention encompasses such E-isomers, Z-isomers or a mixture containing E-isomers and Z-isomers in any ratio. The compounds encompassed in the present invention can have optical isomers caused by the existence of one or more asymmetric carbon atoms and asymmetric sulfur atoms, and the present invention encompasses any optically active substances, racemates or diastereomers.
[0104] Examples of the compound which is a production intermediate of the azolyloxy heterocyclic compound of the present invention represented by general formulae [VI] and [IX] are shown in Tables 71 to 73. Note that the compound included in the compound which is a production intermediate of the azolyloxy heterocyclic compound of the present invention (the compound represented by the general formula [I] or the salt thereof) is not limited thereto. In addition, the compound numbers in the table are referenced in the description below.
[0105] The following signs in the table in the present specification respectively represent, for example, the corresponding groups as shown below. Me : methyl, Et : ethyl, Pr : n-propyl, Bu : n-butyl, Pen : n-pentyl, Hex : n-hexyl, Nonyl : n-nonyl, iPr : isopropyl, iBu : isobutyl, sBu : sec-butyl, tBu : tert-butyl, cPr : cyclopropyl, cBu : cyclobutyl, cPen : cyclopentyl, cHex : cyclohexyl, Bn : benzyl, Ph : phenyl, Py : pyridyl, (1-CN)cPr : 1-cyanocyclopropan-1-yl, (2,2-F2)cPr : 2,2-difluorocyclopropan-1-yl, (4-CF3)Ph : 4-(trifluoromethyl)phenyl, (3-Cl)2-Py : 3-chloropyridin-2-yl
[0106] [Table 1] f3c \ A6 A5 ^A7 < 1 1 J N= / (A) R2 COMPOUND No. A5 A5 A7 R2 A-0001 CH CH CH H A-0002 CH CH CH Me A-0003 CH CH CH Et A-0004 CH CH CH Pr A-0005 CH CH CH CH2CH2Ph A-0006 CH CH CH chf2 A-0007 CH CH CH cf3 A-0008 CH CH CH ch2cf3 A-0009 CH CH CH ch2ch2cf3 A-0010 CH CH CH ch2ch2ch2cf3 A-0011 CH CH CH cPr A-0012 CH CH CH (1-CN)cPr A-0013 CH CH CH (2,2-F2)cPr A-0014 CH CH CH Ph A-0015 CH CH CH (2-F)Ph A-0016 CH CH CH (3-F)Ph A-0017 CH CH CH (4-F)Ph A-0018 CH CH CH (2-CI)Ph A-0019 CH CH CH (3-CI)Ph A-0020 CH CH CH (4-CI)Ph A-0021 CH CH CH (2-Me)Ph A-0022 CH CH CH (3-Me)Ph A-0023 CH CH CH (4-Me)Ph A-0024 CH CH CH (2-Ph)Ph A-0025 CH CH CH (2-SMe)Ph A-0026 CH CH CH (2-SOMe)Ph A-0027 CH CH CH (2-SO2Me)Ph A-0028 CH CH CH (3-SMe)Ph A-0029 CH CH CH (3-SOMe)Ph A-0030 CH CH CH (3-SO2Me)Ph A-0031 CH CH CH (4-SMe)Ph A-0032 CH CH CH (4-SOMe)Ph A-0033 CH CH CH (4-SO2Me)Ph A-0034 CH CH CH (2-CN)Ph A-0035 CH CH CH (3-CN)Ph A-0036 CH CH CH (4-CN)Ph 5
[0107] [Table 2] COMPOUND No. A5 A6 A7 R2 A-0037 CH CH CH (2-CO2H)Ph A-0038 CH CH CH (2-CO2Me)Ph A-0039 CH CH CH (2-CONH(iPr))Ph A-0040 CH CH CH (2,6-F2)Ph A-0041 CH CH CH (3,5-F2)Ph A-0042 CH CH CH (2,4,6-F3)Ph A-0043 CH CH CH (2,4,6-CI3)Ph A-0044 CH CH CH 2-Py A-0045 CH CH CH 3-Py A-0046 CH CH CH 4-Py A-0047 CH CH CH (3-CI)2-Py A-0048 CH CH CH (3-Me)2-Py A-0049 CH CH CH (3-CF3)2-Py A-0050 CH CH CH Pyridazin-3-yl A-0051 CH CH CH Pyrimidin-2-yl A-0052 CH CH CH (4-CF3)Pyrimidin-2-yl A-0053 CH CH CH Pyrimidin-5-yl A-0054 CH CH CH Pyrazin-2-yl A-0055 CH CH CH Furan-2-yl A-0056 CH CH CH lsoxazol-5-yl A-0057 CH CH CH Thiophen-2-yl A-0058 CH CH CH Thiazol-2-yl A-0059 CH CH CH OH A-0060 CH CH CH OMe A-0061 CH CH CH OEt A-0062 CH CH CH OPr A-0063 CH CH CH OCHF2 A-0064 CH CH CH ocf3 A-0065 CH CH CH och2chf2 A-0066 CH CH CH och2cf3 A-0067 CH CH CH och2sf5 A-0068 CH CH CH och2ch2sf5 A-0069 CH CH CH sf5 A-0070 CH CH CH ch2sf5 A-0071 CH CH CH ch2ch2sf5 A-0072 CH CH CH ch2ch2ch2sf5 A-0073 CH CH CH sh A-0074 CH CH CH SMe A-0075 CH CH CH SEt A-0076 CH CH CH SPr A-0077 CH CH CH S(iPr) A-0078 CH CH CH SOMe
[0108] COMPOUND No. A5 A6 A7 R2 A-0079 CH CH CH SOEt A-0080 CH CH CH SO2Me A-0081 CH CH CH SO2Et A-0082 CH CH CH NHEt A-0083 CH CH CH NMe2 A-0084 CH CH CH NEt2 A-0085 CH CH CH Pyrrolidin-1-yl A-0086 CH CH CH Piperidin-1-yl A-0087 CH CH CH Morpholin-4-yl A-0088 CH CH CH CN A-0089 CH CH CH CO2Et A-0090 CH CH CH CONH(iPr) A-0091 CH CH CH CONH(cPr) A-0092 CH CH CH CONHPh A-0093 CH CH CH Pyrrolidine-1-carbonyl A-0094 CH CH CH Piperidine-1 -carbonyl A-0095 CH CH CH Morpholine-4-carbonyl A-0096 CH CH CH F A-0097 CH CH CH Cl A-0098 CH CH CH Br A-0099 CH CH CH I A-0100 CH CH CH n3 A-0101 CH CH CH no2 A-0102 CF CH CH H A-0103 CF CH CH Me A-0104 CF CH CH Et A-0105 CF CH CH Pr A-0106 CF CH CH chf2 A-0107 CF CH CH cf3 A-0108 CF CH CH ch2cf3 A-0109 CF CH CH ch2ch2cf3 A-0110 CF CH CH cPr A-0111 CF CH CH (2,2-F2)cPr A-0112 CF CH CH Ph A-0113 CF CH CH (2-Me)Ph A-0114 CF CH CH (3-Me)Ph A-0115 CF CH CH (4-Me)Ph A-0116 CF CH CH OMe A-0117 CF CH CH OEt A-0118 CF CH CH OPr A-0119 CF CH CH ochf2 A-0120 CF CH CH OCF3
[0109] COMPOUND No. A5 A6 A7 R2 A-0121 CF CH CH OCH2CHF2 A-0122 CF CH CH och2cf3 A-0123 CF CH CH SMe A-0124 CF CH CH SEt A-0125 CF CH CH S(iPr) A-0126 CF CH CH NHEt A-0127 CF CH CH NMe2 A-0128 CF CH CH CONH(iPr) A-0129 CF CH CH F A-0130 CF CH CH Cl A-0131 CF CH CH Br A-0132 CF CH CH I A-0133 CMe CH CH H A-0134 CMe CH CH Me A-0135 CMe CH CH Et A-0136 CMe CH CH Pr A-0137 CMe CH CH chf2 A-0138 CMe CH CH cf3 A-0139 CMe CH CH ch2cf3 A-0140 CMe CH CH ch2ch2cf3 A-0141 CMe CH CH cPr A-0142 CMe CH CH (2,2-F2)cPr A-0143 CMe CH CH Ph A-0144 CMe CH CH (2-Me)Ph A-0145 CMe CH CH (3-Me)Ph A-0146 CMe CH CH (4-Me)Ph A-0147 CMe CH CH OMe A-0148 CMe CH CH OEt A-0149 CMe CH CH OPr A-0150 CMe CH CH ochf2 A-0151 CMe CH CH ocf3 A-0152 CMe CH CH och2chf2 A-0153 CMe CH CH och2cf3 A-0154 CMe CH CH SMe A-0155 CMe CH CH SEt A-0156 CMe CH CH S(iPr) A-0157 CMe CH CH NHEt A-0158 CMe CH CH NMe2 A-0159 CMe CH CH CONH(iPr) A-0160 CMe CH CH F A-0161 CMe CH CH Cl A-0162 CMe CH CH Br
[0110] COMPOUND No. A5 A6 A7 R2 A-0163 CMe CH CH I A-0164 CH CF CH H A-0165 CH CF CH Me A-0166 CH CF CH Et A-0167 CH CF CH Pr A-0168 CH CF CH chf2 A-0169 CH CF CH cf3 A-0170 CH CF CH ch2cf3 A-0171 CH CF CH ch2ch2cf3 A-0172 CH CF CH cPr A-0173 CH CF CH (2,2-F2)cPr A-0174 CH CF CH Ph A-0175 CH CF CH (2-CI)Ph A-0176 CH CF CH (2-Me)Ph A-0177 CH CF CH (3-Me)Ph A-0178 CH CF CH (4-Me)Ph A-0179 CH CF CH (3,5-F2)Ph A-0180 CH CF CH (4-F)(2-Me)Ph A-0181 CH CF CH OMe A-0182 CH CF CH OEt A-0183 CH CF CH OPr A-0184 CH CF CH OC D2O D3 A-0185 CH CF CH ochf2 A-0186 CH CF CH ocf3 A-0187 CH CF CH och2chf2 A-0188 CH CF CH och2cf3 A-0189 CH CF CH SMe A-0190 CH CF CH SEt A-0191 CH CF CH S(iPr) A-0192 CH CF CH NHEt A-0193 CH CF CH NMe2 A-0194 CH CF CH Morpholin-4-yl A-0195 CH CF CH CONH(iPr) A-0196 CH CF CH F A-0197 CH CF CH Cl A-0198 CH CF CH Br A-0199 CH CF CH I A-0200 CF CF CH H A-0201 CF CF CH Me A-0202 CF CF CH Et A-0203 CF CF CH Pr A-0204 CF CF CH chf2
[0111] COMPOUND No. A5 A6 A7 R2 A-0205 CF CF CH cf3 A-0206 CF CF CH ch2cf3 A-0207 CF CF CH ch2ch2cf3 A-0208 CF CF CH cPr A-0209 CF CF CH (2,2-F2)cPr A-0210 CF CF CH Ph A-0211 CF CF CH (2-Me)Ph A-0212 CF CF CH (3-Me)Ph A-0213 CF CF CH (4-Me)Ph A-0214 CF CF CH OMe A-0215 CF CF CH OEt A-0216 CF CF CH OPr A-0217 CF CF CH ochf2 A-0218 CF CF CH ocf3 A-0219 CF CF CH och2chf2 A-0220 CF CF CH och2cf3 A-0221 CF CF CH SMe A-0222 CF CF CH SEt A-0223 CF CF CH S(IPr) A-0224 CF CF CH NHEt A-0225 CF CF CH NMe2 A-0226 CF CF CH CONH(IPr) A-0227 CF CF CH F A-0228 CF CF CH Cl A-0229 CF CF CH Br A-0230 CF CF CH I A-0231 CH CCI CH H A-0232 CH CCI CH Me A-0233 CH CCI CH Et A-0234 CH CCI CH Pr A-0235 CH CCI CH chf2 A-0236 CH CCI CH cf3 A-0237 CH CCI CH ch2cf3 A-0238 CH CCI CH ch2ch2cf3 A-0239 CH CCI CH cPr A-0240 CH CCI CH (2,2-F2)cPr A-0241 CH CCI CH Ph A-0242 CH CCI CH (2-Me)Ph A-0243 CH CCI CH (3-Me)Ph A-0244 CH CCI CH (4-Me)Ph A-0245 CH CCI CH OMe A-0246 CH CCI CH OEt
[0112] COMPOUND No. A5 A6 A7 R2 A-0247 CH CCI CH OPr A-0248 CH CCI CH OCHF2 A-0249 CH CCI CH OCF3 A-0250 CH CCI CH OCH2CHF2 A-0251 CH CCI CH och2cf3 A-0252 CH CCI CH SMe A-0253 CH CCI CH SEt A-0254 CH CCI CH S(iPr) A-0255 CH CCI CH NHEt A-0256 CH CCI CH NMe2 A-0257 CH CCI CH CONH(IPr) A-0258 CH CCI CH F A-0259 CH CCI CH Cl A-0260 CH CCI CH Br A-0261 CH CCI CH I A-0262 CH CBr CH H A-0263 CH CBr CH Me A-0264 CH CBr CH Et A-0265 CH CBr CH Pr A-0266 CH CBr CH chf2 A-0267 CH CBr CH cf3 A-0268 CH CBr CH ch2cf3 A-0269 CH CBr CH ch2ch2cf3 A-0270 CH CBr CH cPr A-0271 CH CBr CH (2,2-F2)cPr A-0272 CH CBr CH Ph A-0273 CH CBr CH (2-Me)Ph A-0274 CH CBr CH (3-Me)Ph A-0275 CH CBr CH (4-Me)Ph A-0276 CH CBr CH OMe A-0277 CH CBr CH OEt A-0278 CH CBr CH OPr A-0279 CH CBr CH ochf2 A-0280 CH CBr CH ocf3 A-0281 CH CBr CH och2chf2 A-0282 CH CBr CH och2cf3 A-0283 CH CBr CH SMe A-0284 CH CBr CH SEt A-0285 CH CBr CH S(iPr) A-0286 CH CBr CH NHEt A-0287 CH CBr CH NMe2 A-0288 CH CBr CH CONH(IPr)
[0113] COMPOUND No. A5 A6 A7 R2 A-0289 CH CBr CH F A-0290 CH CBr CH Cl A-0291 CH CBr CH Br A-0292 CH CBr CH I A-0293 CMe CBr CH Ph A-0294 CH CBr CMe Ph A-0295 CH Cl CH Ph A-0296 CH CMe CH H A-0297 CH CMe CH Me A-0298 CH CMe CH Et A-0299 CH CMe CH Pr A-0300 CH CMe CH Bu A-0301 CH CMe CH Pen A-0302 CH CMe CH Hex A-0303 CH CMe CH Nonyl A-0304 CH CMe CH CH2(cPr) A-0305 CH CMe CH CH2((1-F)cPr) A-0306 CH CMe CH CH2((2,2-F2)cPr) A-0307 CH CMe CH CH2((1-CF3)cPr) A-0308 CH CMe CH IPr A-0309 CH CMe CH IBu A-0310 CH CMe CH tBu A-0311 CH CMe CH C(Me)=CH2 A-0312 CH CMe CH CH=CHMe A-0313 CH CMe CH ch2ch2ch=ch2 A-0314 CH CMe CH CsCMe A-0315 CH CMe CH CECPh A-0316 CH CMe CH CH2OH A-0317 CH CMe CH CH(OH)Me A-0318 CH CMe CH CH2CH(OH)Me A-0319 CH CMe CH CH2OMe A-0320 CH CMe CH CH2OEt A-0321 CH CMe CH CH2OPr A-0322 CH CMe CH CH2O(iPr) A-0323 CH CMe CH CH2OCH2CF3 A-0324 CH CMe CH CH2OCH2CH2OMe A-0325 CH CMe CH CH2CH2OMe A-0326 CH CMe CH CH2SMe A-0327 CH CMe CH CH2NHCO2Me A-0328 CH CMe CH CH2Phthalyl A-0329 CH CMe CH CH2C(=NOH)Me A-0330 CH CMe CH CH2CI
[0114] COMPOUND No. A5 A6 A7 R2 A-0331 CH CMe CH chf2 A-0332 CH CMe CH cf3 A-0333 CH CMe CH cf2ci A-0334 CH CMe CH ch2cf3 A-0335 CH CMe CH ch2ch2chf2 A-0336 CH CMe CH ch2ch2cf3 A-0337 CH CMe CH cPr A-0338 CH CMe CH (1-Me)cPr A-0339 CH CMe CH (1-CF3)cPr A-0340 CH CMe CH (1-CN)cPr A-0341 CH CMe CH (1-F)cPr A-0342 CH CMe CH (2,2-F2)cPr A-0343 CH CMe CH cBu A-0344 CH CMe CH ePen A-0345 CH CMe CH cHex A-0346 CH CMe CH Bn A-0347 CH CMe CH (3-Me)Oxetan-2-yl A-0348 CH CMe CH Tetrahydrofuran-2-yl A-0349 CH CMe CH Tetrahydrofuran-3-yl A-0350 CH CMe CH Ph A-0351 CH CMe CH (2-F)Ph A-0352 CH CMe CH (3-F)Ph A-0353 CH CMe CH (4-F)Ph A-0354 CH CMe CH (2-CI)Ph A-0355 CH CMe CH (2-Me)Ph A-0356 CH CMe CH (3-Me)Ph A-0357 CH CMe CH (4-Me)Ph A-0358 CH CMe CH (2-CF3)Ph A-0359 CH CMe CH (3-CF3)Ph A-0360 CH CMe CH (4-CF3)Ph A-0361 CH CMe CH (2-OMe)Ph A-0362 CH CMe CH (3-OMe)Ph A-0363 CH CMe CH (4-OMe)Ph A-0364 CH CMe CH (2-NH2)Ph A-0365 CH CMe CH (2-NO2)Ph A-0366 CH CMe CH (2,4-F2)Ph A-0367 CH CMe CH (2-F)(6-Me)Ph A-0368 CH CMe CH (3,4,5-(OMe)3)Ph A-0369 CH CMe CH 2-Py A-0370 CH CMe CH Pyrrol-1-yl A-0371 CH CMe CH Pyrazol-1-yl A-0372 CH CMe CH lmidazol-1-yl
[0115] COMPOUND No. A5 A6 A7 R2 A-0373 CH CMe CH (3-Me)Pyrazol-1-yl A-0374 CH CMe CH (4-Me)Pyrazol-1-yl A-0375 CH CMe CH (3-CF3)Pyrazol-1-yl A-0376 CH CMe CH (1-Me)Pyrazol-3-yl A-0377 CH CMe CH (1-Me)Pyrazol-4-yl A-0378 CH CMe CH (1-Me)Pyrazol-5-yl A-0379 CH CMe CH (3,5-Me2)Pyrazol-1 -yl A-0380 CH CMe CH (1,3-Me2)Pyrazol-5-yl A-0381 CH CMe CH (1-Et)(3-tBu)Pyrazol-5-yl A-0382 CH CMe CH (1 -Me)(3-CF3)(5-CI)Pyrazol-4-yl A-0383 CH CMe CH (1-Me)(5-oxo)Pyrazolidin-3-yl A-0384 CH CMe CH (2-Me)lmidazol-1-yl A-0385 CH CMe CH (2-CF3)lmidazol-1-yl A-0386 CH CMe CH 1,2,4-Triazol-1-yl A-0387 CH CMe CH 1,2,3-Triazol-2-yl A-0388 CH CMe CH (3,5-Me2)-1,2,4-Triazol-1-yl A-0389 CH CMe CH Oxazol-2-yl A-0390 CH CMe CH (3-Me)Oxazol-5-yl A-0391 CH CMe CH (4,4-Me2)-2-Oxazolin-2-yl A-0392 CH CMe CH (5-tBu)lsoxazol-3-yl A-0393 CH CMe CH (3,5-Me2)lsoxazol-5-yl A-0394 CH CMe CH (5-iPr)-1,2,4-Oxadiazol-3-yl A-0395 CH CMe CH (3-iPr)-1,2,4-Oxadiazol-5-yl A-0396 CH CMe CH (2-iPr)-1,3,4-Oxadiazol-5-yl A-0397 CH CMe CH (4,4-Me2)-2-Thiazolin-2-yl A-0398 CH CMe CH (2-iPr)-1,3,4-Thiadiazol-5-yl A-0399 CH CMe CH (2-CF3)-1,3,4-Thiadiazol-5-yl A-0400 CH CMe CH (4;4-Me2)(3-oxo)lsoxazolin-2-ylmethyl A-0401 CH CMe CH (5,5-Me2)(2,4-dioxo)Oxazolidin-3-ylmethyl A-0402 CH CMe CH (5;5-Me2)(2-oxo)(4-OH)Oxazolidin-3-ylmethyl A-0403 CH CMe CH (5:5-Me2)(2-oxo)Oxazolidin-3-yl A-0404 CH CMe CH (5;5-Me2)(2-oxo)Oxazolidin-3-ylmethyl A-0405 CH CMe CH OH A-0406 CH CMe CH OMe A-0407 CH CMe CH OEt A-0408 CH CMe CH OC2D5 A-0409 CH CMe CH OPr A-0410 CH CMe CH OBu A-0411 CH CMe CH OPen A-0412 CH CMe CH OHex A-0413 CH CMe CH OCH2(cPr) A-0414 CH CMe CH OCH2((1-F)cPr)
[0116] COMPOUND No. A5 A6 A7 R2 A-0415 CH CMe CH OCH2((2,2-F2)cPr) A-0416 CH CMe CH OCH2((1-CF3)cPr) A-0417 CH CMe CH OCH2((2-CF3)-1,3-Dioxolan-2-yl) A-0418 CH CMe CH OCH2CH2((3-CF3)Pyrazol-1-yl) A-0419 CH CMe CH OBn A-0420 CH CMe CH O(iPr) A-0421 CH CMe CH O(iBu) A-0422 CH CMe CH O(sBu) A-0423 CH CMe CH O(tBu) A-0424 CH CMe CH OCH2CH=CH2 A-0425 CH CMe CH och2c=ch A-0426 CH CMe CH OCH2C(Me)=CH2 A-0427 CH CMe CH OCH2CH=CMe2 A-0428 CH CMe CH O(cPr) A-0429 CH CMe CH O((1-Me)cPr) A-0430 CH CMe CH O((1-CN)cPr) A-0431 CH CMe CH O((1-F)cPr) A-0432 CH CMe CH O(cBu) A-0433 CH CMe CH O(cPen) A-0434 CH CMe CH O(cHex) A-0435 CH CMe CH OCH2CH2OMe A-0436 CH CMe CH O(CH2CH2O)2Me A-0437 CH CMe CH OCH2CH2SMe A-0438 CH CMe CH OCH2CH2SOMe A-0439 CH CMe CH OCH2COMe A-0440 CH CMe CH OCH2CO2Me A-0441 CH CMe CH OCH2C(=NOH)Me A-0442 CH CMe CH OCH2C(=NOMe)Me A-0443 CH CMe CH OCH2(Tetrahydrofuran-2-yl) A-0444 CH CMe CH ochf2 A-0445 CH CMe CH ocf3 A-0446 CH CMe CH och2chf2 A-0447 CH CMe CH och2cf3 A-0448 CH CMe CH OCH(CF3)2 A-0449 CH CMe CH och2ch2cf3 A-0450 CH CMe CH och2cf2chf2 A-0451 CH CMe CH och2cf2cf3 A-0452 CH CMe CH och2ch2ch2cf3 A-0453 CH CMe CH O(Oxetan-3-yl) A-0454 CH CMe CH O(T etra hyd rofura n-3-y I) A-0455 CH CMe CH OPh A-0456 CH CMe CH O((1-Me)Pyrazol-5-yl)
[0117] COMPOUND No. A5 A6 A7 R2 A-0457 CH CMe CH O((1-Me)(3-CF3)Pyrazol-5-yl) A-0458 CH CMe CH OCH2SF5 A-0459 CH CMe CH och2ch2sf5 A-0460 CH CMe CH sf5 A-0461 CH CMe CH ch2sf5 A-0462 CH CMe CH ch2ch2sf5 A-0463 CH CMe CH CH2CH2CH2SFs A-0464 CH CMe CH SH A-0465 CH CMe CH SMe A-0466 CH CMe CH SEt A-0467 CH CMe CH SPr A-0468 CH CMe CH SOPr A-0469 CH CMe CH SO2Pr A-0470 CH CMe CH S(iPr) A-0471 CH CMe CH SO(iPr) A-0472 CH CMe CH S(iBu) A-0473 CH CMe CH sch2ch=ch2 A-0474 CH CMe CH sch2c=ch A-0475 CH CMe CH SCH(Me)C=CH A-0476 CH CMe CH S(sBu) A-0477 CH CMe CH S(sPen) A-0478 CH CMe CH S(tBu) A-0479 CH CMe CH S(cPr) A-0480 CH CMe CH S(cBu) A-0481 CH CMe CH S(cPen) A-0482 CH CMe CH SBn A-0483 CH CMe CH SCH2CN A-0484 CH CMe CH SCH2COMe A-0485 CH CMe CH SCH2OMe A-0486 CH CMe CH SCH2CH2OMe A-0487 CH CMe CH SCH(Me)CH2OMe A-0488 CH CMe CH SCH2SMe A-0489 CH CMe CH schf2 A-0490 CH CMe CH sch2chf2 A-0491 CH CMe CH sch2cf3 A-0492 CH CMe CH SAc A-0493 CH CMe CH SCN A-0494 CH CMe CH SCO2Me A-0495 CH CMe CH SCONMe2 A-0496 CH CMe CH S(Oxetan-3-yl) A-0497 CH CMe CH S(Tetrahydrofuran-3-yl) A-0498 CH CMe CH -s)2-
[0118] COMPOUND No. A5 A6 A7 R2 A-0499 CH CMe CH NHEt A-0500 CH CMe CH NHPr A-0501 CH CMe CH NHCH2C(Me)2OH A-0502 CH CMe CH NMe2 A-0503 CH CMe CH NEt2 A-0504 CH CMe CH N(iPr)2 A-0505 CH CMe CH (4,4-F2)Piperidin-1 -yl A-0506 CH CMe CH Morpholino-yl A-0507 CH CMe CH NHCOPr A-0508 CH CMe CH NHCO(IPr) A-0509 CH CMe CH NHCO(cPr) A-0510 CH CMe CH NHCO(cBu) A-0511 CH CMe CH NHCO(cPen) A-0512 CH CMe CH NHSO2Me A-0513 CH CMe CH NHSO2CF3 A-0514 CH CMe CH N=CH-NMe2 A-0515 CH CMe CH nhnh2 A-0516 CH CMe CH CN A-0517 CH CMe CH CH2CN A-0518 CH CMe CH ch2ch2cn A-0519 CH CMe CH CHO A-0520 CH CMe CH COMe A-0521 CH CMe CH COEt A-0522 CH CMe CH C(=NOH)Me A-0523 CH CMe CH CO2Et A-0524 CH CMe CH conh2 A-0525 CH CMe CH CONHMe A-0526 CH CMe CH CONHEt A-0527 CH CMe CH CONHPr A-0528 CH CMe CH CONHBu A-0529 CH CMe CH CONHPen A-0530 CH CMe CH CONHHex A-0531 CH CMe CH CONH(IPr) A-0532 CH CMe CH CONH(IBu) A-0533 CH CMe CH CONH(sBu) A-0534 CH CMe CH CONH(CH2C=CH) A-0535 CH CMe CH CONHC(Me)2CH2CI A-0536 CH CMe CH CONHCH2CH2OH A-0537 CH CMe CH CONHCH(Me)CH2OH A-0538 CH CMe CH CONHC(Me)2CH2OH A-0539 CH CMe CH CONHCH2CH2OMe A-0540 CH CMe CH CONHCH2CF3
[0119] COMPOUND No. A5 A6 A7 R2 A-0541 CH CMe CH CONHCH2CHO A-0542 CH CMe CH CONH(cPr) A-0543 CH CMe CH CONH(cPen) A-0544 CH CMe CH CONH(cHex) A-0545 CH CMe CH CONMe2 A-0546 CH CMe CH CON(Me)iPr A-0547 CH CMe CH CON(Me)OMe A-0548 CH CMe CH Pyrrolidine-1-carbonyl A-0549 CH CMe CH Piperidine-1 -carbonyl A-0550 CH CMe CH Morpholine-1 -carbonyl A-0551 CH CMe CH CONHPh A-0552 CH CMe CH C(=S)NHMe A-0553 CH CMe CH C(=S)NHEt A-0554 CH CMe CH C(=S)NHiPr A-0555 CH CMe CH F A-0556 CH CMe CH Cl A-0557 CH CMe CH Br A-0558 CH CMe CH I A-0559 CH CMe CH n3 A-0560 CH CMe CH no2 A-0561 CF CMe CH H A-0562 CF CMe CH Me A-0563 CF CMe CH Et A-0564 CF CMe CH Pr A-0565 CF CMe CH chf2 A-0566 CF CMe CH cf3 A-0567 CF CMe CH ch2cf3 A-0568 CF CMe CH ch2ch2cf3 A-0569 CF CMe CH cPr A-0570 CF CMe CH (2,2-F2)cPr A-0571 CF CMe CH Ph A-0572 CF CMe CH (2-Me)Ph A-0573 CF CMe CH (3-Me)Ph A-0574 CF CMe CH (4-Me)Ph A-0575 CF CMe CH OMe A-0576 CF CMe CH OEt A-0577 CF CMe CH OPr A-0578 CF CMe CH ochf2 A-0579 CF CMe CH ocf3 A-0580 CF CMe CH och2chf2 A-0581 CF CMe CH och2cf3 A-0582 CF CMe CH SMe
[0120] COMPOUND No. A5 A6 A7 R2 A-0583 CF CMe CH SEt A-0584 CF CMe CH S(iPr) A-0585 CF CMe CH SCH2CF3 A-0586 CF CMe CH NHEt A-0587 CF CMe CH NMe2 A-0588 CF CMe CH Morpholin-4-yl A-0589 CF CMe CH (3,3-F2)Pyrrolidin-1-yl A-0590 CF CMe CH CONH(iPr) A-0591 CF CMe CH F A-0592 CF CMe CH Cl A-0593 CF CMe CH Br A-0594 CF CMe CH 1 A-0595 CH CEt CH H A-0596 CH CEt CH Me A-0597 CH CEt CH Et A-0598 CH CEt CH Pr A-0599 CH CEt CH chf2 A-0600 CH CEt CH cf3 A-0601 CH CEt CH ch2cf3 A-0602 CH CEt CH ch2ch2cf3 A-0603 CH CEt CH cPr A-0604 CH CEt CH (2,2-F2)cPr A-0605 CH CEt CH Ph A-0606 CH CEt CH (2-Me)Ph A-0607 CH CEt CH (3-Me)Ph A-0608 CH CEt CH (4-Me)Ph A-0609 CH CEt CH OMe A-0610 CH CEt CH OEt A-0611 CH CEt CH OPr A-0612 CH CEt CH ochf2 A-0613 CH CEt CH ocf3 A-0614 CH CEt CH och2chf2 A-0615 CH CEt CH och2cf3 A-0616 CH CEt CH SMe A-0617 CH CEt CH SEt A-0618 CH CEt CH S(iPr) A-0619 CH CEt CH NHEt A-0620 CH CEt CH NMe2 A-0621 CH CEt CH CONH(iPr) A-0622 CH CEt CH F A-0623 CH CEt CH Cl A-0624 CH CEt CH Br
[0121] COMPOUND No. A5 A6 A7 R2 A-0625 CH CEt CH I A-0626 CH cch=ch2 CH OEt A-0627 CH CC=CH CH Ph A-0628 CH CCH2OMe CH Ph A-0629 CH CCH2OPr CH OPr A-0630 CH cchf2 CH H A-0631 CH cchf2 CH Me A-0632 CH cchf2 CH Et A-0633 CH cchf2 CH Pr A-0634 CH cchf2 CH chf2 A-0635 CH cchf2 CH cf3 A-0636 CH cchf2 CH ch2cf3 A-0637 CH cchf2 CH ch2ch2cf3 A-0638 CH cchf2 CH cPr A-0639 CH cchf2 CH (2,2-F2)cPr A-0640 CH cchf2 CH Ph A-0641 CH cchf2 CH (2-Me)Ph A-0642 CH cchf2 CH (3-Me)Ph A-0643 CH cchf2 CH (4-Me)Ph A-0644 CH cchf2 CH OMe A-0645 CH cchf2 CH OEt A-0646 CH cchf2 CH OPr A-0647 CH cchf2 CH ochf2 A-0648 CH cchf2 CH ocf3 A-0649 CH cchf2 CH och2chf2 A-0650 CH cchf2 CH och2cf3 A-0651 CH cchf2 CH SMe A-0652 CH cchf2 CH SEt A-0653 CH cchf2 CH S(iPr) A-0654 CH cchf2 CH NHEt A-0655 CH cchf2 CH NMe2 A-0656 CH cchf2 CH CONH(iPr) A-0657 CH cchf2 CH F A-0658 CH cchf2 CH Cl A-0659 CH cchf2 CH Br A-0660 CH cchf2 CH I A-0661 CH ccf3 CH H A-0662 CH ccf3 CH Me A-0663 CH ccf3 CH Et A-0664 CH ccf3 CH Pr A-0665 CH ccf3 CH tBu A-0666 CH ccf3 CH chf2
[0122] COMPOUND No. A5 A6 A7 R2 A-0667 CH ccf3 CH cf3 A-0668 CH ccf3 CH ch2cf3 A-0669 CH ccf3 CH ch2ch2cf3 A-0670 CH ccf3 CH cPr A-0671 CH ccf3 CH (2,2-F2)cPr A-0672 CH ccf3 CH Ph A-0673 CH ccf3 CH (2-Me)Ph A-0674 CH ccf3 CH (3-Me)Ph A-0675 CH ccf3 CH (4-Me)Ph A-0676 CH ccf3 CH OMe A-0677 CH ccf3 CH OEt A-0678 CH ccf3 CH OPr A-0679 CH ccf3 CH ochf2 A-0680 CH ccf3 CH ocf3 A-0681 CH ccf3 CH och2chf2 A-0682 CH ccf3 CH och2cf3 A-0683 CH ccf3 CH SMe A-0684 CH ccf3 CH SEt A-0685 CH ccf3 CH S(iPr) A-0686 CH ccf3 CH NHEt A-0687 CH ccf3 CH NMe2 A-0688 CH ccf3 CH CONH(iPr) A-0689 CH ccf3 CH C(=S)NH(iPr) A-0690 CH ccf3 CH F A-0691 CH ccf3 CH Cl A-0692 CH ccf3 CH Br A-0693 CH ccf3 CH I A-0694 CH C(cPr) CH H A-0695 CH C(cPr) CH Me A-0696 CH C(cPr) CH Et A-0697 CH C(cPr) CH Pr A-0698 CH C(cPr) CH chf2 A-0699 CH C(cPr) CH cf3 A-0700 CH C(cPr) CH ch2cf3 A-0701 CH C(cPr) CH ch2ch2cf3 A-0702 CH C(cPr) CH cPr A-0703 CH C(cPr) CH (2,2-F2)cPr A-0704 CH C(cPr) CH Ph A-0705 CH C(cPr) CH (2-Me)Ph A-0706 CH C(cPr) CH (3-Me)Ph A-0707 CH C(cPr) CH (4-Me)Ph A-0708 CH C(cPr) CH OMe
[0123] COMPOUND No. A5 A6 A7 R2 A-0709 CH C(cPr) CH OEt A-0710 CH C(cPr) CH OPr A-0711 CH C(cPr) CH ochf2 A-0712 CH C(cPr) CH ocf3 A-0713 CH C(cPr) CH och2chf2 A-0714 CH C(cPr) CH och2cf3 A-0715 CH C(cPr) CH SMe A-0716 CH C(cPr) CH SEt A-0717 CH C(cPr) CH S(iPr) A-0718 CH C(cPr) CH NHEt A-0719 CH C(cPr) CH NMe2 A-0720 CH C(cPr) CH CONH(iPr) A-0721 CH C(cPr) CH F A-0722 CH C(cPr) CH Cl A-0723 CH C(cPr) CH Br A-0724 CH C(cPr) CH I A-0725 CH CCHO CH Ph A-0726 CH CCHO CH OPr A-0727 CH CCHO CH SMe A-0728 CH CCO2H CH Ph A-0729 CH cconh2 CH Ph A-0730 CH CCN CH H A-0731 CH CCN CH Me A-0732 CH CCN CH Et A-0733 CH CCN CH Pr A-0734 CH CCN CH chf2 A-0735 CH CCN CH cf3 A-0736 CH CCN CH ch2cf3 A-0737 CH CCN CH ch2ch2cf3 A-0738 CH CCN CH cPr A-0739 CH CCN CH (2,2-F2)cPr A-0740 CH CCN CH Ph A-0741 CH CCN CH (2-Me)Ph A-0742 CH CCN CH (3-Me)Ph A-0743 CH CCN CH (4-Me)Ph A-0744 CH CCN CH OMe A-0745 CH CCN CH OEt A-0746 CH CCN CH OPr A-0747 CH CCN CH ochf2 A-0748 CH CCN CH ocf3 A-0749 CH CCN CH och2chf2 A-0750 CH CCN CH och2cf3
[0124] COMPOUND No. A5 A6 A7 R2 A-0751 CH CCN CH SMe A-0752 CH CCN CH SEt A-0753 CH CCN CH S(iPr) A-0754 CH CCN CH NHEt A-0755 CH CCN CH NMe2 A-0756 CH CCN CH CONH(iPr) A-0757 CH CCN CH F A-0758 CH CCN CH Cl A-0759 CH CCN CH Br A-0760 CH CCN CH I A-0761 CH COH CH Ph A-0762 CH COH CH OEt A-0763 CH COMe CH H A-0764 CH COMe CH Me A-0765 CH COMe CH Et A-0766 CH COMe CH Pr A-0767 CH COMe CH chf2 A-0768 CH COMe CH cf3 A-0769 CH COMe CH ch2cf3 A-0770 CH COMe CH ch2ch2cf3 A-0771 CH COMe CH cPr A-0772 CH COMe CH (2,2-F2)cPr A-0773 CH COMe CH Ph A-0774 CH COMe CH (2-Me)Ph A-0775 CH COMe CH (3-Me)Ph A-0776 CH COMe CH (4-Me)Ph A-0777 CH COMe CH OMe A-0778 CH COMe CH OEt A-0779 CH COMe CH OPr A-0780 CH COMe CH ochf2 A-0781 CH COMe CH ocf3 A-0782 CH COMe CH och2chf2 A-0783 CH COMe CH och2cf3 A-0784 CH COMe CH SMe A-0785 CH COMe CH SEt A-0786 CH COMe CH S(iPr) A-0787 CH COMe CH NHEt A-0788 CH COMe CH NMe2 A-0789 CH COMe CH Morpholin-4-yl A-0790 CH COMe CH CONH(iPr) A-0791 CH COMe CH F A-0792 CH COMe CH Cl
[0125] COMPOUND No. A5 A6 A7 R2 A-0793 CH COMe CH Br A-0794 CH COMe CH I A-0795 CH COEt CH H A-0796 CH COEt CH Me A-0797 CH COEt CH Et A-0798 CH COEt CH Pr A-0799 CH COEt CH chf2 A-0800 CH COEt CH cf3 A-0801 CH COEt CH ch2cf3 A-0802 CH COEt CH ch2ch2cf3 A-0803 CH COEt CH cPr A-0804 CH COEt CH (2,2-F2)cPr A-0805 CH COEt CH Ph A-0806 CH COEt CH (2-Me)Ph A-0807 CH COEt CH (3-Me)Ph A-0808 CH COEt CH (4-Me)Ph A-0809 CH COEt CH OMe A-0810 CH COEt CH OEt A-0811 CH COEt CH OPr A-0812 CH COEt CH ochf2 A-0813 CH COEt CH ocf3 A-0814 CH COEt CH och2chf2 A-0815 CH COEt CH och2cf3 A-0816 CH COEt CH SMe A-0817 CH COEt CH SEt A-0818 CH COEt CH S(iPr) A-0819 CH COEt CH NHEt A-0820 CH COEt CH NMe2 A-0821 CH COEt CH CONH(iPr) A-0822 CH COEt CH F A-0823 CH COEt CH Cl A-0824 CH COEt CH Br A-0825 CH COEt CH I A-0826 CH COCH2OMe CH OEt A-0827 CH cochf2 CH H A-0828 CH cochf2 CH Me A-0829 CH cochf2 CH Et A-0830 CH cochf2 CH Pr A-0831 CH cochf2 CH chf2 A-0832 CH cochf2 CH cf3 A-0833 CH cochf2 CH ch2cf3 A-0834 CH cochf2 CH ch2ch2cf3
[0126] COMPOUND No. A5 A6 A7 R2 A-0835 CH cochf2 CH cPr A-0836 CH cochf2 CH (2,2-F2)cPr A-0837 CH cochf2 CH Ph A-0838 CH cochf2 CH (2-Me)Ph A-0839 CH cochf2 CH (3-Me)Ph A-0840 CH cochf2 CH (4-Me)Ph A-0841 CH cochf2 CH OMe A-0842 CH cochf2 CH OEt A-0843 CH cochf2 CH OPr A-0844 CH cochf2 CH ochf2 A-0845 CH cochf2 CH ocf3 A-0846 CH cochf2 CH och2chf2 A-0847 CH cochf2 CH och2cf3 A-0848 CH cochf2 CH SMe A-0849 CH cochf2 CH SEt A-0850 CH cochf2 CH S(iPr) A-0851 CH cochf2 CH NHEt A-0852 CH cochf2 CH NMe2 A-0853 CH cochf2 CH CONH(iPr) A-0854 CH cochf2 CH F A-0855 CH cochf2 CH Cl A-0856 CH cochf2 CH Br A-0857 CH cochf2 CH I A-0858 CH coch2cf3 CH H A-0859 CH coch2cf3 CH Me A-0860 CH coch2cf3 CH Et A-0861 CH coch2cf3 CH Pr A-0862 CH coch2cf3 CH chf2 A-0863 CH coch2cf3 CH cf3 A-0864 CH coch2cf3 CH ch2cf3 A-0865 CH coch2cf3 CH ch2ch2cf3 A-0866 CH coch2cf3 CH cPr A-0867 CH coch2cf3 CH (2,2-F2)cPr A-0868 CH coch2cf3 CH Ph A-0869 CH coch2cf3 CH (2-Me)Ph A-0870 CH coch2cf3 CH (3-Me)Ph A-0871 CH coch2cf3 CH (4-Me)Ph A-0872 CH coch2cf3 CH OMe A-0873 CH coch2cf3 CH OEt A-0874 CH coch2cf3 CH OPr A-0875 CH coch2cf3 CH ochf2 A-0876 CH coch2cf3 CH ocf3
[0127] COMPOUND No. A5 A6 A7 R2 A-0877 CH COCH2CF3 CH OCH2CHF2 A-0878 CH coch2cf3 CH och2cf3 A-0879 CH coch2cf3 CH SMe A-0880 CH coch2cf3 CH SEt A-0881 CH coch2cf3 CH S(iPr) A-0882 CH coch2cf3 CH NHEt A-0883 CH coch2cf3 CH NMe2 A-0884 CH coch2cf3 CH CONH(iPr) A-0885 CH coch2cf3 CH F A-0886 CH coch2cf3 CH Cl A-0887 CH coch2cf3 CH Br A-0888 CH coch2cf3 CH I A-0889 CH coch2chf2 CH OEt A-0890 CH CSMe CH H A-0891 CH CSMe CH Me A-0892 CH CSMe CH Et A-0893 CH CSMe CH Pr A-0894 CH CSMe CH chf2 A-0895 CH CSMe CH cf3 A-0896 CH CSMe CH ch2cf3 A-0897 CH CSMe CH ch2ch2cf3 A-0898 CH CSMe CH cPr A-0899 CH CSMe CH (2,2-F2)cPr A-0900 CH CSMe CH Ph A-0901 CH CSMe CH (2-Me)Ph A-0902 CH CSMe CH (3-Me)Ph A-0903 CH CSMe CH (4-Me)Ph A-0904 CH CSMe CH OMe A-0905 CH CSMe CH OEt A-0906 CH CSMe CH OPr A-0907 CH CSMe CH ochf2 A-0908 CH CSMe CH ocf3 A-0909 CH CSMe CH och2chf2 A-0910 CH CSMe CH och2cf3 A-0911 CH CSMe CH SMe A-0912 CH CSMe CH SEt A-0913 CH CSMe CH S(iPr) A-0914 CH CSMe CH NHEt A-0915 CH CSMe CH NMe2 A-0916 CH CSMe CH CONH(iPr) A-0917 CH CSMe CH F A-0918 CH CSMe CH Cl
[0128] COMPOUND No. A5 A6 A7 R2 A-0919 CH CSMe CH Br A-0920 CH CSMe CH I A-0921 CH CSOMe CH Ph A-0922 CH CSO2Me CH Ph A-0923 CH cscf3 CH Ph A-0924 CH csocf3 CH Ph A-0925 CH cso2cf3 CH Ph A-0926 CH csf5 CH Ph A-0927 CH cnh2 CH Ph A-0928 CH CNHMe CH Ph A-0929 CH CNMe2 CH Me A-0930 CH CNMe2 CH Ph A-0931 CH cno2 CH Ph A-0932 CH cn3 CH Ph A-0933 CH CH CF H A-0934 CH CH CF Me A-0935 CH CH CF Et A-0936 CH CH CF Pr A-0937 CH CH CF chf2 A-0938 CH CH CF cf3 A-0939 CH CH CF ch2cf3 A-0940 CH CH CF ch2ch2cf3 A-0941 CH CH CF cPr A-0942 CH CH CF (2,2-F2)cPr A-0943 CH CH CF Ph A-0944 CH CH CF (2-Me)Ph A-0945 CH CH CF (3-Me)Ph A-0946 CH CH CF (4-Me)Ph A-0947 CH CH CF OMe A-0948 CH CH CF OEt A-0949 CH CH CF OPr A-0950 CH CH CF ochf2 A-0951 CH CH CF ocf3 A-0952 CH CH CF och2chf2 A-0953 CH CH CF och2cf3 A-0954 CH CH CF SMe A-0955 CH CH CF SEt A-0956 CH CH CF S(iPr) A-0957 CH CH CF NHEt A-0958 CH CH CF NMe2 A-0959 CH CH CF CONH(iPr) A-0960 CH CH CF F
[0129] COMPOUND No. A5 A6 A7 R2 A-0961 CH CH CF Cl A-0962 CH CH CF Br A-0963 CH CH CF I A-0964 CH CH CMe H A-0965 CH CH CMe Me A-0966 CH CH CMe Et A-0967 CH CH CMe Pr A-0968 CH CH CMe chf2 A-0969 CH CH CMe cf3 A-0970 CH CH CMe ch2cf3 A-0971 CH CH CMe ch2ch2cf3 A-0972 CH CH CMe cPr A-0973 CH CH CMe (2,2-F2)cPr A-0974 CH CH CMe Ph A-0975 CH CH CMe (2-Me)Ph A-0976 CH CH CMe (3-Me)Ph A-0977 CH CH CMe (4-Me)Ph A-0978 CH CH CMe OMe A-0979 CH CH CMe OEt A-0980 CH CH CMe OPr A-0981 CH CH CMe ochf2 A-0982 CH CH CMe ocf3 A-0983 CH CH CMe och2chf2 A-0984 CH CH CMe och2cf3 A-0985 CH CH CMe SMe A-0986 CH CH CMe SEt A-0987 CH CH CMe S(iPr) A-0988 CH CH CMe NHEt A-0989 CH CH CMe NMe2 A-0990 CH CH CMe CONH(IPr) A-0991 CH CH CMe F A-0992 CH CH CMe Cl A-0993 CH CH CMe Br A-0994 CH CH CMe I A-0995 CH CMe CH chci2 A-0996 CH CMe CH CCI3 A-0997 CH CMe CH CH2CH2NO2
[0130] [Table 25] O CQ to COMPOUND No. A4 R1 R3 A6 R2 B-0001 CH Me Me CH H B-0002 CH Me Me CH Me B-0003 CH Me Me CH Et B-0004 CH Me Me CH Pr B-0005 CH Me Me CH chf2 B-0006 CH Me Me CH cf3 B-0007 CH Me Me CH ch2cf3 B-0008 CH Me Me CH ch2ch2cf3 B-0009 CH Me Me CH cPr B-0010 CH Me Me CH (2,2-F2)cPr B-0011 CH Me Me CH Ph B-0012 CH Me Me CH (2-Me)Ph B-0013 CH Me Me CH (3-Me)Ph B-0014 CH Me Me CH (4-Me)Ph B-0015 CH Me Me CH OMe B-0016 CH Me Me CH OEt B-0017 CH Me Me CH OPr B-0018 CH Me Me CH ochf2 B-0019 CH Me Me CH ocf3 B-0020 CH Me Me CH och2chf2 B-0021 CH Me Me CH och2cf3 B-0022 CH Me Me CH SMe B-0023 CH Me Me CH SEt B-0024 CH Me Me CH S(iPr) B-0025 CH Me Me CH NHEt B-0026 CH Me Me CH NMe? B-0027 CH Me Me CH CONH(iPr) B-0028 CH Me Me CH F B-0029 CH Me Me CH Cl B-0030 CH Me Me CH Br B-0031 CH Me Me CH 1 B-0032 CH Me tBu CH H B-0033 CH Me tBu CH Me B-0034 CH Me tBu CH Et B-0035 CH Me tBu CH Pr B-0036 CH Me tBu CH chf2
[0131] COMPOUND No. A4 R1 R3 A6 R2 B-0037 CH Me tBu CH cf3 B-0038 CH Me tBu CH ch2cf3 B-0039 CH Me tBu CH ch2ch2cf3 B-0040 CH Me tBu CH cPr B-0041 CH Me tBu CH (2,2-F2)cPr B-0042 CH Me tBu CH Ph B-0043 CH Me tBu CH (2-Me)Ph B-0044 CH Me tBu CH (3-Me)Ph B-0045 CH Me tBu CH (4-Me)Ph B-0046 CH Me tBu CH OMe B-0047 CH Me tBu CH OEt B-0048 CH Me tBu CH OPr B-0049 CH Me tBu CH ochf2 B-0050 CH Me tBu CH OCF3 B-0051 CH Me tBu CH OCH2CHF2 B-0052 CH Me tBu CH och2cf3 B-0053 CH Me tBu CH SMe B-0054 CH Me tBu CH SEt B-0055 CH Me tBu CH S(iPr) B-0056 CH Me tBu CH NHEt B-0057 CH Me tBu CH NMe2 B-0058 CH Me tBu CH CONH(iPr) B-0059 CH Me tBu CH F B-0060 CH Me tBu CH Cl B-0061 CH Me tBu CH Br B-0062 CH Me tBu CH I B-0063 CH Me chf2 CH H B-0064 CH Me chf2 CH Me B-0065 CH Me chf2 CH Et B-0066 CH Me chf2 CH Pr B-0067 CH Me chf2 CH CHF2 B-0068 CH Me chf2 CH cf3 B-0069 CH Me chf2 CH ch2cf3 B-0070 CH Me chf2 CH ch2ch2cf3 B-0071 CH Me chf2 CH cPr B-0072 CH Me chf2 CH (2,2-F2)cPr B-0073 CH Me chf2 CH Ph B-0074 CH Me chf2 CH (2-Me)Ph B-0075 CH Me chf2 CH (3-Me)Ph B-0076 CH Me chf2 CH (4-Me)Ph B-0077 CH Me chf2 CH OMe B-0078 CH Me chf2 CH OEt
[0132] COMPOUND No. A4 R1 R3 A® R2 B-0079 CH Me chf2 CH OPr B-0080 CH Me chf2 CH ochf2 B-0081 CH Me chf2 CH ocf3 B-0082 CH Me chf2 CH och2chf2 B-0083 CH Me chf2 CH och2cf3 B-0084 CH Me chf2 CH och2sf5 B-0085 CH Me chf2 CH och2ch2sf5 B-0086 CH Me chf2 CH SF5 B-0087 CH Me chf2 CH ch2sf5 B-0088 CH Me chf2 CH ch2ch2sf5 B-0089 CH Me chf2 CH ch2ch2ch2sf5 B-0090 CH Me chf2 CH SMe B-0091 CH Me chf2 CH SEt B-0092 CH Me chf2 CH S(iPr) B-0093 CH Me chf2 CH NHEt B-0094 CH Me chf2 CH NMe2 B-0095 CH Me chf2 CH CONH(iPr) B-0096 CH Me chf2 CH F B-0097 CH Me chf2 CH Cl B-0098 CH Me chf2 CH Br B-0099 CH Me chf2 CH I B-0100 CCI Me cf3 CH OH B-0101 CH Me chf2 CMe H B-0102 CH Me chf2 CMe Me B-0103 CH Me chf2 CMe Et B-0104 CH Me chf2 CMe Pr B-0105 CH Me chf2 CMe cf3 B-0106 CH Me chf2 CMe ch2cf3 B-0107 CH Me chf2 CMe ch2ch2chf2 B-0108 CH Me chf2 CMe ch2ch2cf3 B-0109 CH Me chf2 CMe cPr B-0110 CH Me chf2 CMe (2,2-F2)cPr B-0111 CH Me chf2 CMe Ph B-0112 CH Me chf2 CMe (2-Me)Ph B-0113 CH Me chf2 CMe (3-Me)Ph B-0114 CH Me chf2 CMe (4-Me)Ph B-0115 CH Me chf2 CMe OMe B-0116 CH Me chf2 CMe OEt B-0117 CH Me chf2 CMe OPr B-0118 CH Me chf2 CMe ochf2 B-0119 CH Me chf2 CMe ocf3 B-0120 CH Me chf2 CMe OCH2CHF2
[0133] COMPOUND No. A4 R1 R3 A6 R2 B-0121 CH Me chf2 CMe OCH2CF3 B-0122 CH Me chf2 CMe och2sf5 B-0123 CH Me chf2 CMe och2ch2sf5 B-0124 CH Me chf2 CMe sf5 B-0125 CH Me chf2 CMe ch2sf6 B-0126 CH Me chf2 CMe ch2ch2sf5 B-0127 CH Me chf2 CMe ch2ch2ch2sf5 B-0128 CH Me chf2 CMe SMe B-0129 CH Me chf2 CMe SEt B-0130 CH Me chf2 CMe S(iPr) B-0131 CH Me chf2 CMe SCH2CF3 B-0132 CH Me chf2 CMe SO2Me B-0133 CH Me chf2 CMe NHEt B-0134 CH Me chf2 CMe NMe2 B-0135 CH Me chf2 CMe CONH(iPr) B-0136 CH Me chf2 CMe F B-0137 CH Me chf2 CMe Cl B-0138 CH Me chf2 CMe Br B-0139 CH Me chf2 CMe I B-0140 CH Et chf2 CMe H B-0141 CH Et chf2 CMe Me B-0142 CH Et chf2 CMe Et B-0143 CH Et chf2 CMe Pr B-0144 CH Et chf2 CMe chf2 B-0145 CH Et chf2 CMe cf3 B-0146 CH Et chf2 CMe ch2cf3 B-0147 CH Et chf2 CMe ch2ch2cf3 B-0148 CH Et chf2 CMe cPr B-0149 CH Et chf2 CMe (2,2-F2)cPr B-0150 CH Et chf2 CMe Ph B-0151 CH Et chf2 CMe (2-Me)Ph B-0152 CH Et chf2 CMe (3-Me)Ph B-0153 CH Et chf2 CMe (4-Me)Ph B-0154 CH Et chf2 CMe OMe B-0155 CH Et chf2 CMe OEt B-0156 CH Et chf2 CMe OPr B-0157 CH Et chf2 CMe ochf2 B-0158 CH Et chf2 CMe ocf3 B-0159 CH Et chf2 CMe OCH2CHF2 B-0160 CH Et chf2 CMe och2cf3 B-0161 CH Et chf2 CMe och2sf5 B-0162 CH Et chf2 CMe och2ch2sf5
[0134] COMPOUND No. A4 R1 R3 A6 R2 B-0163 CH Et chf2 CMe SFs B-0164 CH Et chf2 CMe ch2sf5 B-0165 CH Et chf2 CMe CH2CH2SFs B-0166 CH Et chf2 CMe ch2ch2ch2sf5 B-0167 CH Et chf2 CMe SMe B-0168 CH Et chf2 CMe SEt B-0169 CH Et chf2 CMe S(iPr) B-0170 CH Et chf2 CMe NHEt B-0171 CH Et chf2 CMe NMe2 B-0172 CH Et chf2 CMe CONH(iPr) B-0173 CH Et chf2 CMe F B-0174 CH Et chf2 CMe Cl B-0175 CH Et chf2 CMe Br B-0176 CH Et chf2 CMe I B-0177 CH iPr chf2 CMe H B-0178 CH iPr chf2 CMe Me B-0179 CH iPr chf2 CMe Et B-0180 CH iPr chf2 CMe Pr B-0181 CH iPr chf2 CMe chf2 B-0182 CH iPr chf2 CMe cf3 B-0183 CH iPr chf2 CMe ch2cf3 B-0184 CH iPr chf2 CMe ch2ch2cf3 B-0185 CH iPr chf2 CMe cPr B-0186 CH iPr chf2 CMe (2,2-F2)cPr B-0187 CH iPr chf2 CMe Ph B-0188 CH iPr chf2 CMe (2-Me)Ph B-0189 CH iPr chf2 CMe (3-Me)Ph B-0190 CH iPr chf2 CMe (4-Me)Ph B-0191 CH iPr chf2 CMe OMe B-0192 CH iPr chf2 CMe OEt B-0193 CH iPr chf2 CMe OPr B-0194 CH iPr chf2 CMe ochf2 B-0195 CH iPr chf2 CMe ocf3 B-0196 CH iPr chf2 CMe OCH2CHF2 B-0197 CH iPr chf2 CMe och2cf3 B-0198 CH iPr chf2 CMe och2sf5 B-0199 CH iPr chf2 CMe och2ch2sf5 B-0200 CH iPr chf2 CMe sf5 B-0201 CH iPr chf2 CMe ch2sf5 B-0202 CH iPr chf2 CMe ch2ch2sf5 B-0203 CH iPr chf2 CMe ch2ch2ch2sf5 B-0204 CH iPr chf2 CMe SMe
[0135] COMPOUND No. A4 R1 R3 A6 R2 B43205 CH iPr chf2 CMe SEt B43206 CH iPr chf2 CMe S(iPr) B43207 CH iPr chf2 CMe NHEt B43208 CH iPr chf2 CMe NMe2 B43209 CH iPr chf2 CMe CONH(iPr) B-0210 CH iPr chf2 CMe F B-0211 CH iPr chf2 CMe Cl B-0212 CH iPr chf2 CMe Br B43213 CH iPr chf2 CMe I B-0214 CH tBu chf2 CMe H B43215 CH tBu chf2 CMe Me B43216 CH tBu chf2 CMe Et B-0217 CH tBu chf2 CMe Pr B43218 CH tBu chf2 CMe CHF2 B43219 CH tBu chf2 CMe cf3 B43220 CH tBu chf2 CMe ch2cf3 B43221 CH tBu chf2 CMe ch2ch2cf3 B43222 CH tBu chf2 CMe cPr B43223 CH tBu chf2 CMe (2,2-F2)cPr B43224 CH tBu chf2 CMe Ph B43225 CH tBu chf2 CMe (2-Me)Ph B43226 CH tBu chf2 CMe (3-Me)Ph B-0227 CH tBu chf2 CMe (4-Me)Ph B43228 CH tBu chf2 CMe OMe B43229 CH tBu chf2 CMe OEt B43230 CH tBu chf2 CMe OPr B43231 CH tBu chf2 CMe ochf2 B43232 CH tBu chf2 CMe ocf3 B43233 CH tBu chf2 CMe och2chf2 B 43234 CH tBu chf2 CMe och2cf3 B43235 CH tBu chf2 CMe och2sf5 B43236 CH tBu chf2 CMe och2ch2sf5 B43237 CH tBu chf2 CMe sf5 B43238 CH tBu chf2 CMe ch2sf5 B43239 CH tBu chf2 CMe ch2ch2sf5 B43240 CH tBu chf2 CMe ch2ch2ch2sf5 B43241 CH tBu chf2 CMe SMe B43242 CH tBu chf2 CMe SEt B43243 CH tBu chf2 CMe S(iPr) B43244 CH tBu chf2 CMe NHEt B43245 CH tBu chf2 CMe NMe2 B43246 CH tBu chf2 CMe CONH(iPr)
[0136] COMPOUND No. A4 R1 R3 A6 R2 B-0247 CH tBu chf2 CMe F B-0248 CH tBu chf2 CMe Cl B-0249 CH tBu chf2 CMe Br B-0250 CH tBu chf2 CMe I B-0251 CH Et cf3 CMe H B-0252 CH Et cf3 CMe Me B-0253 CH Et cf3 CMe Et B-0254 CH Et cf3 CMe Pr B-0255 CH Et cf3 CMe CHF2 B-0256 CH Et cf3 CMe cf3 B-0257 CH Et cf3 CMe ch2cf3 B-0258 CH Et cf3 CMe ch2ch2cf3 B-0259 CH Et cf3 CMe cPr B-0260 CH Et cf3 CMe (2,2-F2)cPr B-0261 CH Et cf3 CMe Ph B-0262 CH Et cf3 CMe (2-Me)Ph B-0263 CH Et cf3 CMe (3-Me)Ph B-0264 CH Et cf3 CMe (4-Me)Ph B-0265 CH Et cf3 CMe OMe B-0266 CH Et cf3 CMe OEt B-0267 CH Et cf3 CMe OPr B-0268 CH Et cf3 CMe ochf2 B-0269 CH Et cf3 CMe ocf3 B-0270 CH Et cf3 CMe och2chf2 B-0271 CH Et cf3 CMe och2cf3 B-0272 CH Et cf3 CMe SMe B-0273 CH Et cf3 CMe SEt B-0274 CH Et cf3 CMe S(iPr) B-0275 CH Et cf3 CMe NHEt B-0276 CH Et cf3 CMe NMe2 B-0277 CH Et cf3 CMe CONH(iPr) B-0278 CH Et cf3 CMe F B-0279 CH Et cf3 CMe Cl B-0280 CH Et cf3 CMe Br B-0281 CH Et cf3 CMe I B-0282 CH Me cf2ci CMe H B-0283 CH Me cf2ci CMe Me B-0284 CH Me cf2ci CMe Et B-0285 CH Me cf2ci CMe Pr B-0286 CH Me cf2ci CMe chf2 B-0287 CH Me cf2ci CMe cf3 B-0288 CH Me cf2ci CMe ch2cf3
[0137] COMPOUND No. A4 R1 R3 A® R2 B-0289 CH Me CF2CI CMe CH2CH2CF3 B-0290 CH Me cf2ci CMe cPr B-0291 CH Me cf2ci CMe (2,2-F2)cPr B-0292 CH Me cf2ci CMe Ph B-0293 CH Me cf2ci CMe (2-Me)Ph B-0294 CH Me cf2ci CMe (3-Me)Ph B-0295 CH Me cf2ci CMe (4-Me)Ph B-0296 CH Me cf2ci CMe OMe B-0297 CH Me cf2ci CMe OEt B-0298 CH Me cf2ci CMe OPr B-0299 CH Me cf2ci CMe ochf2 B-0300 CH Me cf2ci CMe ocf3 B-0301 CH Me cf2ci CMe och2chf2 B-0302 CH Me cf2ci CMe och2cf3 B-0303 CH Me cf2ci CMe SMe B-0304 CH Me cf2ci CMe SEt B-0305 CH Me cf2ci CMe S(iPr) B-0306 CH Me cf2ci CMe NHEt B-0307 CH Me cf2ci CMe NMe2 B-0308 CH Me cf2ci CMe CONH(iPr) B-0309 CH Me cf2ci CMe F B-0310 CH Me cf2ci CMe Cl B-0311 CH Me cf2ci CMe Br B-0312 CH Me cf2ci CMe I B-0313 CH Me c2 F5 CH H B-0314 CH Me c2f5 CH Me B-0315 CH Me c2f5 CH Et B-0316 CH Me c2f5 CH Pr B-0317 CH Me c2f5 CH chf2 B-0318 CH Me c2f5 CH cf3 B-0319 CH Me c2fs CH ch2cf3 B-0320 CH Me c2f5 CH ch2ch2cf3 B-0321 CH Me c2f5 CH cPr B-0322 CH Me C2F 5 CH (2,2-F2)cPr B-0323 CH Me C2F5 CH Ph B-0324 CH Me C2F5 CH (2-Me)Ph B-0325 CH Me c2f5 CH (3-Me)Ph B-0326 CH Me c2f5 CH (4-Me)Ph B-0327 CH Me c2fs CH OMe B-0328 CH Me c2f5 CH OEt B-0329 CH Me c2f5 CH OPr B-0330 CH Me c2f5 CH ochf2
[0138] COMPOUND No. A4 R1 R3 A® R2 B-0331 CH Me c2f5 CH OCF3 B-0332 CH Me C2F5 CH OCH2CHF2 B-0333 CH Me c2f5 CH och2cf3 B-0334 CH Me 02f5 CH SMe B-0335 CH Me c2f5 CH SEt B-0336 CH Me c2f5 CH S(iPr) B-0337 CH Me c2f5 CH NHEt B-0338 CH Me c2f5 CH NMe2 B-0339 CH Me c2f5 CH CONH(iPr) B-0340 CH Me c2f5 CH F B-0341 CH Me c2f5 CH Cl B-0342 CH Me c2f5 CH Br B-0343 CH Me c2f5 CH I B-0344 CH Me c2f5 CMe H B-0345 CH Me c2f5 CMe Me B-0346 CH Me 02f5 CMe Et B-0347 CH Me c2f5 CMe Pr B-0348 CH Me c2f5 CMe chf2 B-0349 CH Me c2f5 CMe cf3 B-0350 CH Me c2f5 CMe ch2cf3 B-0351 CH Me C2F5 CMe ch2ch2cf3 B-0352 CH Me c2f5 CMe cPr B-0353 CH Me 02f5 CMe (2,2-F2)cPr B-0354 CH Me c2f5 CMe Ph B-0355 CH Me C2Fg CMe (2-Me)Ph B-0356 CH Me C2F5 CMe (3-Me)Ph B-0357 CH Me c2f5 CMe (4-Me)Ph B-0358 CH Me c2f5 CMe OMe B-0359 CH Me c2f5 CMe OEt B-0360 CH Me c2f5 CMe OPr B-0361 CH Me c2fs CMe ochf2 B-0362 CH Me c2f5 CMe ocf3 B-0363 CH Me c2f5 CMe och2chf2 B-0364 CH Me C2F 5 CMe och2cf3 B-0365 CH Me C2F5 CMe SMe B-0366 CH Me C2F5 CMe SEt B-0367 CH Me c2f5 CMe S(iPr) B-0368 CH Me c2f5 CMe NHEt B-0369 CH Me c2fs CMe NMe2 B-0370 CH Me c2f5 CMe CONH(iPr) B-0371 CH Me c2f5 CMe F B-0372 CH Me c2f5 CMe Cl
[0139] COMPOUND No. A4 R1 R3 A® R2 B-0373 CH Me c2f5 CMe Br B-0374 CH Me C2F5 CMe I B-0375 N Me Me CMe H B-0376 N Me Me CMe Me B-0377 N Me Me CMe Et B-0378 N Me Me CMe Pr B-0379 N Me Me CMe chf2 B-0380 N Me Me CMe cf3 B-0381 N Me Me CMe ch2cf3 B-0382 N Me Me CMe ch2ch2cf3 B-0383 N Me Me CMe cPr B-0384 N Me Me CMe (2,2-F2)cPr B-0385 N Me Me CMe Ph B-0386 N Me Me CMe (2-Me)Ph B-0387 N Me Me CMe (3-Me)Ph B-0388 N Me Me CMe (4-Me)Ph B-0389 N Me Me CMe OMe B-0390 N Me Me CMe OEt B-0391 N Me Me CMe OPr B-0392 N Me Me CMe ochf2 B-0393 N Me Me CMe ocf3 B-0394 N Me Me CMe OCH2CHF2 B-0395 N Me Me CMe och2cf3 B-0396 N Me Me CMe SMe B-0397 N Me Me CMe SEt B-0398 N Me Me CMe S(iPr) B-0399 N Me Me CMe NHEt B-0400 N Me Me CMe NMe2 B-0401 N Me Me CMe CONH(iPr) B-0402 N Me Me CMe F B-0403 N Me Me CMe Cl B-0404 N Me Me CMe Br B-0405 N Me Me CMe I B-0406 N Me iPr CMe H B-0407 N Me iPr CMe Me B-0408 N Me iPr CMe Et B-0409 N Me iPr CMe Pr B-0410 N Me iPr CMe chf2 B-0411 N Me iPr CMe cf3 B-0412 N Me iPr CMe ch2cf3 B-0413 N Me iPr CMe ch2ch2cf3 B-0414 N Me iPr CMe cPr
[0140] COMPOUND No. A4 R1 R3 A® R2 B-0415 N Me iPr CMe (2,2-F2)cPr B-0416 N Me iPr CMe Ph B-0417 N Me iPr CMe (2-Me)Ph B-0418 N Me iPr CMe (3-Me)Ph B-0419 N Me iPr CMe (4-Me)Ph B-0420 N Me iPr CMe OMe B-0421 N Me iPr CMe OEt B-0422 N Me iPr CMe OPr B-0423 N Me iPr CMe OCH2CH2OMe B-0424 N Me iPr CMe ochf2 B-0425 N Me iPr CMe OCF3 B-0426 N Me iPr CMe OCH2CHF2 B-0427 N Me iPr CMe och2cf3 B-0428 N Me iPr CMe SMe B-0429 N Me iPr CMe SEt B-0430 N Me iPr CMe S(iPr) B-0431 N Me iPr CMe NHEt B-0432 N Me iPr CMe NMe2 B-0433 N Me iPr CMe CONH(iPr) B-0434 N Me iPr CMe F B-0435 N Me iPr CMe Cl B-0436 N Me iPr CMe Br B-0437 N Me iPr CMe I B-0438 N Me tBu CMe H B-0439 N Me tBu CMe Me B-0440 N Me tBu CMe Et B-0441 N Me tBu CMe Pr B-0442 N Me tBu CMe chf2 B-0443 N Me tBu CMe cf3 B-0444 N Me tBu CMe ch2cf3 B-0445 N Me tBu CMe ch2ch2cf3 B-0446 N Me tBu CMe cPr B-0447 N Me tBu CMe (2,2-F2)cPr B-0448 N Me tBu CMe Ph B-0449 N Me tBu CMe (2-Me)Ph B-0450 N Me tBu CMe (3-Me)Ph B-0451 N Me tBu CMe (4-Me)Ph B-0452 N Me tBu CMe OMe B-0453 N Me tBu CMe OEt B-0454 N Me tBu CMe OPr B-0455 N Me tBu CMe ochf2 B-0456 N Me tBu CMe ocf3
[0141] COMPOUND No. A4 R1 R3 A6 R2 B-0457 N Me tBu CMe OCH2CHF2 B-0458 N Me tBu CMe och2cf3 B-0459 N Me tBu CMe SMe B-0460 N Me tBu CMe SEt B-0461 N Me tBu CMe S(iPr) B-0462 N Me tBu CMe NHEt B-0463 N Me tBu CMe NMe2 B-0464 N Me tBu CMe CONH(iPr) B-0465 N Me tBu CMe F B-0466 N Me tBu CMe Cl B-0467 N Me tBu CMe Br B-0468 N Me tBu CMe I B-0469 N Me chf2 CMe H B-0470 N Me chf2 CMe Me B-0471 N Me chf2 CMe Et B-0472 N Me chf2 CMe Pr B-0473 N Me chf2 CMe chf2 B-0474 N Me chf2 CMe cf3 B-0475 N Me chf2 CMe ch2cf3 B-0476 N Me chf2 CMe ch2ch2chf2 B-0477 N Me chf2 CMe ch2ch2cf3 B-0478 N Me chf2 CMe cPr B-0479 N Me chf2 CMe (2,2-Fz)cPr B-0480 N Me chf2 CMe Ph B-0481 N Me chf2 CMe (2-Me)Ph B-0482 N Me chf2 CMe (3-Me)Ph B-0483 N Me chf2 CMe (4-Me)Ph B-0484 N Me chf2 CMe OMe B-0485 N Me chf2 CMe OEt B-0486 N Me chf2 CMe OPr B-0487 N Me chf2 CMe ochf2 B-0488 N Me chf2 CMe ocf3 B-0489 N Me chf2 CMe och2chf2 B-0490 N Me chf2 CMe och2cf3 B-0491 N Me chf2 CMe och2cf2ci B-0492 N Me chf2 CMe och2cci3 B-0493 N Me chf2 CMe och2sf5 B-0494 N Me chf2 CMe och2ch2sf5 B-0495 N Me chf2 CMe SF5 B-0496 N Me chf2 CMe ch2sf5 B-0497 N Me chf2 CMe ch2ch2sf5 B-0498 N Me chf2 CMe ch2ch2ch2sf5
[0142] COMPOUND No. A4 R1 R3 A6 R2 B-0499 N Me chf2 CMe SMe B-0500 N Me chf2 CMe SEt B-0501 N Me chf2 CMe S(iPr) B-0502 N Me chf2 CMe NHEt B-0503 N Me chf2 CMe NMe2 B-0504 N Me chf2 CMe CONH(iPr) B-0505 N Me chf2 CMe F B-0506 N Me chf2 CMe Cl B-0507 N Me chf2 CMe Br B-0508 N Me chf2 CMe I B-0509 N Et chf2 CMe H B-0510 N Et chf2 CMe Me B-0511 N Et chf2 CMe Et B-0512 N Et chf2 CMe Pr B-0513 N Et chf2 CMe chf2 B-0514 N Et chf2 CMe cf3 B-0515 N Et chf2 CMe ch2cf3 B-0516 N iPr chf2 CMe ch2ch2chf2 B-0517 N Et chf2 CMe ch2ch2cf3 B-0518 N Et chf2 CMe cPr B-0519 N Et chf2 CMe (2,2-F2)cPr B-0520 N Et chf2 CMe Ph B-0521 N Et chf2 CMe (2-Me)Ph B-0522 N Et chf2 CMe (3-Me)Ph B-0523 N Et chf2 CMe (4-Me)Ph B-0524 N Et chf2 CMe OMe B-0525 N Et chf2 CMe OEt B-0526 N Et chf2 CMe OPr B-0527 N Et chf2 CMe ochf2 B-0528 N Et chf2 CMe ocf3 B-0529 N Et chf2 CMe och2chf2 B-0530 N Et chf2 CMe och2cf3 B-0531 N Et chf2 CMe och2sf5 B-0532 N Et chf2 CMe och2ch2sf5 B-0533 N Et chf2 CMe sf5 B-0534 N Et chf2 CMe ch2sf5 B-0535 N Et chf2 CMe CH2CH2SFs B-0536 N Et chf2 CMe ch2ch2ch2sf5 B-0537 N Et chf2 CMe SMe B-0538 N Et chf2 CMe SEt B-0539 N Et chf2 CMe S(iPr) B-0540 N Et chf2 CMe NHEt
[0143] COMPOUND No. A4 R1 R3 A® R2 B-0541 N Et chf2 CMe NMe2 B-0542 N Et chf2 CMe CONH(iPr) B-0543 N Et chf2 CMe F B-0544 N Et chf2 CMe Cl B-0545 N Et chf2 CMe Br B-0546 N Et chf2 CMe I B-0547 N iPr chf2 CMe H B-0548 N iPr chf2 CMe Me B-0549 N iPr chf2 CMe Et B-0550 N iPr chf2 CMe Pr B-0551 N iPr chf2 CMe chf2 B-0552 N iPr chf2 CMe cf3 B-0553 N iPr chf2 CMe ch2cf3 B-0554 N iPr chf2 CMe ch2ch2chf2 B-0555 N iPr chf2 CMe ch2ch2cf3 B-0556 N iPr chf2 CMe cPr B-0557 N iPr chf2 CMe (2,2-F2)cPr B-0558 N iPr chf2 CMe Ph B-0559 N iPr chf2 CMe (2-Me)Ph B-0560 N iPr chf2 CMe (3-Me)Ph B-0561 N iPr chf2 CMe (4-Me)Ph B-0562 N iPr chf2 CMe OMe B-0563 N iPr chf2 CMe OEt B-0564 N iPr chf2 CMe OPr B-0565 N iPr chf2 CMe ochf2 B-0566 N iPr chf2 CMe ocf3 B-0567 N iPr chf2 CMe och2chf2 B-0568 N iPr chf2 CMe och2cf3 B-0569 N iPr chf2 CMe och2sf5 B-0570 N iPr chf2 CMe och2ch2sf5 B-0571 N iPr chf2 CMe sf5 B-0572 N iPr chf2 CMe ch2sf5 B-0573 N iPr chf2 CMe ch2ch2sf5 B-0574 N iPr chf2 CMe ch2ch2ch2sf5 B-0575 N iPr chf2 CMe SMe B-0576 N iPr chf2 CMe SEt B-0577 N iPr chf2 CMe S(iPr) B-0578 N iPr chf2 CMe NHEt B-0579 N iPr chf2 CMe NMe2 B-0580 N iPr chf2 CMe CONH(iPr) B-0581 N iPr chf2 CMe F B-0582 N iPr chf2 CMe Cl
[0144] COMPOUND No. A4 R1 R3 A® R2 B-0583 N iPr chf2 CMe Br B-0584 N iPr chf2 CMe I B-0585 N tBu chf2 CMe H B-0586 N tBu chf2 CMe Me B-0587 N tBu chf2 CMe Et B-0588 N tBu chf2 CMe Pr B-0589 N tBu chf2 CMe chf2 B-0590 N tBu chf2 CMe cf3 B-0591 N tBu chf2 CMe ch2cf3 B-0592 N tBu chf2 CMe ch2ch2chf2 B-0593 N tBu chf2 CMe ch2ch2cf3 B-0594 N tBu chf2 CMe cPr B-0595 N tBu chf2 CMe (2,2-F2)cPr B-0596 N tBu chf2 CMe Ph B-0597 N tBu chf2 CMe (2-Me)Ph B-0598 N tBu chf2 CMe (3-Me)Ph B-0599 N tBu chf2 CMe (4-Me)Ph B-0600 N tBu chf2 CMe OMe B-0601 N tBu chf2 CMe OEt B-0602 N tBu chf2 CMe OPr B-0603 N tBu chf2 CMe ochf2 B-0604 N tBu chf2 CMe ocf3 B-0605 N tBu chf2 CMe och2chf2 B-0606 N tBu chf2 CMe och2cf3 B-0607 N tBu chf2 CMe och2sf5 B-0608 N tBu chf2 CMe och2ch2sf5 B-0609 N tBu chf2 CMe sf5 B-0610 N tBu chf2 CMe ch2sf5 B-0611 N tBu chf2 CMe ch2ch2sf5 B-0612 N tBu chf2 CMe ch2ch2ch2sf5 B-0613 N tBu chf2 CMe SMe B-0614 N tBu chf2 CMe SEt B-0615 N tBu chf2 CMe S(iPr) B-0616 N tBu chf2 CMe NHEt B-0617 N tBu chf2 CMe NMe2 B-0618 N tBu chf2 CMe CONH(iPr) B-0619 N tBu chf2 CMe F B-0620 N tBu chf2 CMe Cl B-0621 N tBu chf2 CMe Br B-0622 N tBu chf2 CMe I B-0623 N Me cf3 CH H B-0624 N Me cf3 CH Me
[0145] COMPOUND No. A4 R1 R3 A6 R2 B-0625 N Me cf3 CH Et B-0626 N Me cf3 CH Pr B-0627 N Me cf3 CH chf2 B-0628 N Me cf3 CH cf3 B-0629 N Me cf3 CH ch2cf3 B-0630 N Me cf3 CH ch2ch2cf3 B-0631 N Me cf3 CH cPr B-0632 N Me cf3 CH (2,2-F2)cPr B-0633 N Me cf3 CH Ph B-0634 N Me cf3 CH (2-Me)Ph B-0635 N Me cf3 CH (3-Me)Ph B-0636 N Me cf3 CH (4-Me)Ph B-0637 N Me cf3 CH OMe B-0638 N Me cf3 CH OEt B-0639 N Me cf3 CH OPr B-0640 N Me cf3 CH ochf2 B-0641 N Me cf3 CH ocf3 B-0642 N Me cf3 CH och2chf2 B-0643 N Me cf3 CH och2cf3 B-0644 N Me cf3 CH SMe B-0645 N Me cf3 CH SEt B-0646 N Me cf3 CH S(iPr) B-0647 N Me cf3 CH NHEt B-0648 N Me cf3 CH NMe2 B-0649 N Me cf3 CH CONH(iPr) B-0650 N Me cf3 CH F B-0651 N Me cf3 CH Cl B-0652 N Me cf3 CH Br B-0653 N Me cf3 CH I B-0654 N Me cf3 CF H B-0655 N Me cf3 CF Me B-0656 N Me cf3 CF Et B-0657 N Me cf3 CF Pr B-0658 N Me cf3 CF chf2 B-0659 N Me cf3 CF cf3 B-0660 N Me cf3 CF ch2cf3 B-0661 N Me cf3 CF ch2ch2cf3 B-0662 N Me cf3 CF cPr B-0663 N Me cf3 CF (2,2-F2)cPr B-0664 N Me cf3 CF Ph B-0665 N Me cf3 CF (2-Me)Ph B-0666 N Me cf3 CF (3-Me)Ph
[0146] COMPOUND No. A4 R1 R3 A® R2 B-0667 N Me cf3 CF (4-Me)Ph B-0668 N Me cf3 CF OMe B-0669 N Me cf3 CF OEt B-0670 N Me cf3 CF OPr B-0671 N Me cf3 CF ochf2 B-0672 N Me cf3 CF ocf3 B-0673 N Me cf3 CF och2chf2 B-0674 N Me cf3 CF och2cf3 B-0675 N Me cf3 CF SMe B-0676 N Me cf3 CF SEt B-0677 N Me cf3 CF S(iPr) B-0678 N Me cf3 CF NHEt B-0679 N Me cf3 CF NMe2 B-0680 N Me cf3 CF CONH(iPr) B-0681 N Me cf3 CF F B-0682 N Me cf3 CF Cl B-0683 N Me cf3 CF Br B-0684 N Me cf3 CF I B-0685 N Me cf3 CCI Ph B-0686 N Me cf3 CBr Ph B-0687 N Me cf3 CMe H B-0688 N Me cf3 CMe Me B-0689 N Me cf3 CMe Et B-0690 N Me cf3 CMe Pr B-0691 N Me cf3 CMe CCI3 B-0692 N Me cf3 CMe cf3 B-0693 N Me cf3 CMe ch2cf3 B-0694 N Me cf3 CMe ch2ch2chf2 B-0695 N Me cf3 CMe ch2ch2cf3 B-0696 N Me cf3 CMe cPr B-0697 N Me cf3 CMe (1-Me)cPr B-0698 N Me cf3 CMe (1-CF3)cPr B-0699 N Me cf3 CMe (1-CN)cPr B-0700 N Me cf3 CMe (1-F)cPr B-0701 N Me cf3 CMe (2,2-F2)cPr B-0702 N Me cf3 CMe Ph B-0703 N Me cf3 CMe (2-Me)Ph B-0704 N Me cf3 CMe (3-Me)Ph B-0705 N Me cf3 CMe (4-Me)Ph B-0706 N Me cf3 CMe OMe B-0707 N Me cf3 CMe OEt B-0708 N Me cf3 CMe OPr
[0147] COMPOUND No. A4 R1 R3 A6 R2 B-0709 N Me cf3 CMe OCH2CH2OMe B-0710 N Me cf3 CMe ochf2 B-0711 N Me cf3 CMe ocf3 B-0712 N Me cf3 CMe och2chf2 B-0713 N Me cf3 CMe och2cf3 B-0714 N Me cf3 CMe och2ch2ch2f B-0715 N Me cf3 CMe OCH2(cPr) B-0716 N Me cf3 CMe OCH2((1-F)cPr) B-0717 N Me cf3 CMe OCH2((2,2-F2)cPr) B-0718 N Me cf3 CMe OCH2((1-CF3)cPr) B-0719 N Me cf3 CMe OCH2((2-CF3)-1,3-Dioxolan-2-yl) B-0720 N Me cf3 CMe OCH2(Oxetan-3-yl) B-0721 N Me cf3 CMe OCH2CH2((3-CF3)Pyrazol-1-yl) B-0722 N Me cf3 CMe O(Tetrahydrofuran-3-yl) B-0723 N Me cf3 CMe O(Tetrahydropyran-4-yl) B-0724 N Me cf3 CMe OCH2SF5 B-0725 N Me cf3 CMe och2ch2sf5 B-0726 N Me cf3 CMe sf5 B-0727 N Me cf3 CMe ch2sf5 B-0728 N Me cf3 CMe ch2ch2sf5 B-0729 N Me cf3 CMe ch2ch2ch2sf5 B-0730 N Me cf3 CMe SMe B-0731 N Me cf3 CMe SEt B-0732 N Me cf3 CMe S(iPr) B-0733 N Me cf3 CMe NHEt B-0734 N Me cf3 CMe NMe2 B-0735 N Me cf3 CMe CONH(iPr) B-0736 N Me cf3 CMe F B-0737 N Me cf3 CMe Cl B-0738 N Me cf3 CMe Br B-0739 N Me cf3 CMe I B-0740 N Me cf2ci CMe H B-0741 N Me cf2ci CMe Me B-0742 N Me cf2ci CMe Et B-0743 N Me cf2ci CMe Pr B-0744 N Me cf2ci CMe chf2 B-0745 N Me cf2ci CMe cf3 B-0746 N Me cf2ci CMe ch2cf3 B-0747 N Me cf2ci CMe ch2ch2cf3 B-0748 N Me cf2ci CMe cPr B-0749 N Me cf2ci CMe (2,2-F2)cPr B-0750 N Me cf2ci CMe Ph
[0148] COMPOUND No. A4 R1 R3 A® R2 B-0751 N Me CF2CI CMe (2-Me)Ph B-0752 N Me cf2ci CMe (3-Me)Ph B-0753 N Me cf2ci CMe (4-Me)Ph B-0754 N Me cf2ci CMe OMe B-0755 N Me cf2ci CMe OEt B-0756 N Me cf2ci CMe OPr B-0757 N Me cf2ci CMe ochf2 B-0758 N Me cf2ci CMe ocf3 B-0759 N Me cf2ci CMe och2chf2 B-0760 N Me cf2ci CMe och2cf3 B-0761 N Me cf2ci CMe SMe B-0762 N Me cf2ci CMe SEt B-0763 N Me cf2ci CMe S(iPr) B-0764 N Me cf2ci CMe NHEt B-0765 N Me cf2ci CMe NMe2 B-0766 N Me cf2ci CMe CONH(iPr) B-0767 N Me cf2ci CMe F B-0768 N Me cf2ci CMe Cl B-0769 N Me cf2ci CMe Br B-0770 N Me cf2ci CMe I B-0771 N Me OMe CMe H B-0772 N Me OMe CMe Me B-0773 N Me OMe CMe Et B-0774 N Me OMe CMe Pr B-0775 N Me OMe CMe chf2 B-0776 N Me OMe CMe cf3 B-0777 N Me OMe CMe ch2cf3 B-0778 N Me OMe CMe ch2ch2cf3 B-0779 N Me OMe CMe cPr B-0780 N Me OMe CMe (2,2-F2)cPr B-0781 N Me OMe CMe Ph B-0782 N Me OMe CMe (2-Me)Ph B-0783 N Me OMe CMe (3-Me)Ph B-0784 N Me OMe CMe (4-Me)Ph B-0785 N Me OMe CMe OMe B-0786 N Me OMe CMe OEt B-0787 N Me OMe CMe OPr B-0788 N Me OMe CMe OCH2CH2OMe B-0789 N Me OMe CMe ochf2 B-0790 N Me OMe CMe OCF3 B-0791 N Me OMe CMe OCH2CHF2 B-0792 N Me OMe CMe och2cf3
[0149] COMPOUND No. A4 R1 R3 A® R2 B-0793 N Me OMe CMe SMe B-0794 N Me OMe CMe SEt B-0795 N Me OMe CMe S(iPr) B-0796 N Me OMe CMe NHEt B-0797 N Me OMe CMe NMe2 B-0798 N Me OMe CMe CONH(iPr) B-0799 N Me OMe CMe F B-0800 N Me OMe CMe Cl B-0801 N Me OMe CMe Br B-0802 N Me OMe CMe I B-0803 N Me OEt CMe H B-0804 N Me OEt CMe Me B-0805 N Me OEt CMe Et B-0806 N Me OEt CMe Pr B-0807 N Me OEt CMe chf2 B-0808 N Me OEt CMe cf3 B-0809 N Me OEt CMe ch2cf3 B-0810 N Me OEt CMe ch2ch2cf3 B-0811 N Me OEt CMe cPr B-0812 N Me OEt CMe (2,2-F2)cPr B-0813 N Me OEt CMe Ph B-0814 N Me OEt CMe (2-Me)Ph B-0815 N Me OEt CMe (3-Me)Ph B-0816 N Me OEt CMe (4-Me)Ph B-0817 N Me OEt CMe OMe B-0818 N Me OEt CMe OEt B-0819 N Me OEt CMe OPr B-0820 N Me OEt CMe OCH2CH2OMe B-0821 N Me OEt CMe ochf2 B-0822 N Me OEt CMe ocf3 B-0823 N Me OEt CMe och2chf2 B-0824 N Me OEt CMe och2cf3 B-0825 N Me OEt CMe SMe B-0826 N Me OEt CMe SEt B-0827 N Me OEt CMe S(iPr) B-0828 N Me OEt CMe NHEt B-0829 N Me OEt CMe NMe2 B-0830 N Me OEt CMe CONH(iPr) B-0831 N Me OEt CMe F B-0832 N Me OEt CMe Cl B-0833 N Me OEt CMe Br B-0834 N Me OEt CMe I
[0150] COMPOUND No. A4 R1 R3 A® R2 B-0835 N Me CO2Et CMe H B-0836 N Me CO2Et CMe Me B-0837 N Me CO2Et CMe Et B-0838 N Me CO2Et CMe Pr B-0839 N Me CO2Et CMe chf2 B-0840 N Me CO2Et CMe cf3 B-0841 N Me CO2Et CMe ch2cf3 B-0842 N Me CO2Et CMe ch2ch2cf3 B-0843 N Me CO2Et CMe cPr B-0844 N Me CO2Et CMe (2,2-F2)cPr B-0845 N Me CO2Et CMe Ph B-0846 N Me CO2Et CMe (2-Me)Ph B-0847 N Me CO2Et CMe (3-Me)Ph B-0848 N Me CO2Et CMe (4-Me)Ph B-0849 N Me CO2Et CMe OMe B-0850 N Me CO2Et CMe OEt B-0851 N Me CO2Et CMe OPr B-0852 N Me CO2Et CMe OCH2CH2OMe B-0853 N Me CO2Et CMe ochf2 B-0854 N Me CO2Et CMe OCF3 B-0855 N Me CO2Et CMe OCH2CHF2 B-0856 N Me CO2Et CMe och2cf3 B-0857 N Me CO2Et CMe SMe B-0858 N Me CO2Et CMe SEt B-0859 N Me CO2Et CMe S(iPr) B-0860 N Me CO2Et CMe NHEt B-0861 N Me CO2Et CMe NMe2 B-0862 N Me CO2Et CMe CONH(iPr) B-0863 N Me CO2Et CMe F B-0864 N Me CO2Et CMe Cl B-0865 N Me CO2Et CMe Br B-0866 N Me CO2Et CMe I B-0867 N Me ON CMe H B-0868 N Me CN CMe Me B-0869 N Me CN CMe Et B-0870 N Me CN CMe Pr B-0871 N Me CN CMe chf2 B-0872 N Me CN CMe cf3 B-0873 N Me CN CMe ch2cf3 B-0874 N Me CN CMe ch2ch2cf3 B-0875 N Me CN CMe cPr B-0876 N Me CN CMe (2,2-F2)cPr
[0151] COMPOUND No. A4 R1 R3 A6 R2 B-0877 N Me CN CMe Ph B-0878 N Me CN CMe (2-Me)Ph B-0879 N Me CN CMe (3-Me)Ph B-0880 N Me CN CMe (4-Me)Ph B-0881 N Me CN CMe OMe B-0882 N Me CN CMe OEt B-0883 N Me CN CMe OPr B-0884 N Me CN CMe OCH2CH2OMe B-0885 N Me CN CMe ochf2 B-0886 N Me CN CMe ocf3 B-0887 N Me CN CMe och2chf2 B-0888 N Me CN CMe och2cf3 B-0889 N Me CN CMe SMe B-0890 N Me CN CMe SEt B-0891 N Me CN CMe S(iPr) B-0892 N Me CN CMe NHEt B-0893 N Me CN CMe NMe2 B-0894 N Me CN CMe CONH(iPr) B-0895 N Me CN CMe F B-0896 N Me CN CMe Cl B-0897 N Me CN CMe Br B-0898 N Me CN CMe I B-0899 N Me cPr CMe H B-0900 N Me cPr CMe Me B-0901 N Me cPr CMe Et B-0902 N Me cPr CMe Pr B-0903 N Me cPr CMe chf2 B-0904 N Me cPr CMe cf3 B-0905 N Me cPr CMe ch2cf3 B-0906 N Me cPr CMe ch2ch2cf3 B-0907 N Me cPr CMe cPr B-0908 N Me cPr CMe (2,2-F2)cPr B-0909 N Me cPr CMe Ph B-0910 N Me cPr CMe (2-Me)Ph B-0911 N Me cPr CMe (3-Me)Ph B-0912 N Me cPr CMe (4-Me)Ph B-0913 N Me cPr CMe OMe B-0914 N Me cPr CMe OEt B-0915 N Me cPr CMe OPr B-0916 N Me cPr CMe ochf2 B-0917 N Me cPr CMe ocf3 B-0918 N Me cPr CMe och2chf2
[0152] COMPOUND No. A4 R1 R3 A® R2 B-0919 N Me cPr CMe OCH2CF3 B-0920 N Me cPr CMe SMe B-0921 N Me cPr CMe SEt B-0922 N Me cPr CMe S(iPr) B-0923 N Me cPr CMe NHEt B-0924 N Me cPr CMe NMe2 B-0925 N Me cPr CMe CONH(iPr) B-0926 N Me cPr CMe F B-0927 N Me cPr CMe Cl B-0928 N Me cPr CMe Br B-0929 N Me cPr CMe I B-0930 N Me Ph CMe H B-0931 N Me Ph CMe Me B-0932 N Me Ph CMe Et B-0933 N Me Ph CMe Pr B-0934 N Me Ph CMe chf2 B-0935 N Me Ph CMe cf3 B-0936 N Me Ph CMe ch2cf3 B-0937 N Me Ph CMe ch2ch2cf3 B-0938 N Me Ph CMe cPr B-0939 N Me Ph CMe (2,2-F2)cPr B-0940 N Me Ph CMe Ph B-0941 N Me Ph CMe (2-Me)Ph B-0942 N Me Ph CMe (3-Me)Ph B-0943 N Me Ph CMe (4-Me)Ph B-0944 N Me Ph CMe OMe B-0945 N Me Ph CMe OEt B-0946 N Me Ph CMe OPr B-0947 N Me Ph CMe ochf2 B-0948 N Me Ph CMe ocf3 B-0949 N Me Ph CMe och2chf2 B-0950 N Me Ph CMe och2cf3 B-0951 N Me Ph CMe SMe B-0952 N Me Ph CMe SEt B-0953 N Me Ph CMe S(iPr) B-0954 N Me Ph CMe NHEt B-0955 N Me Ph CMe NMe2 B-0956 N Me Ph CMe CONH(iPr) B-0957 N Me Ph CMe F B-0958 N Me Ph CMe Cl B-0959 N Me Ph CMe Br B-0960 N Me Ph CMe I
[0153] COMPOUND No. A4 R1 R3 A6 R2 B-0961 N Me CF2Br CMe H B-0962 N Me CF2Br CMe Me B-0963 N Me CF2Br CMe Et B-0964 N Me CF2Br CMe Pr B-0965 N Me CF2Br CMe chf2 B-0966 N Me CF2Br CMe cf3 B-0967 N Me CF2Br CMe ch2cf3 B-0968 N Me CF2Br CMe ch2ch2cf3 B-0969 N Me CF2Br CMe cPr B-0970 N Me CF2Br CMe (2,2-F2)cPr B-0971 N Me CF2Br CMe Ph B-0972 N Me CF2Br CMe (2-Me)Ph B-0973 N Me CF2Br CMe (3-Me)Ph B-0974 N Me CF2Br CMe (4-Me)Ph B-0975 N Me CF2Br CMe OMe B-0976 N Me CF2Br CMe OEt B-0977 N Me CF2Br CMe OPr B-0978 N Me CF2Br CMe ochf2 B-0979 N Me CF2Br CMe ocf3 B-0980 N Me CF2Br CMe OCH2CHF2 B-0981 N Me CF2Br CMe och2cf3 B-0982 N Me CF2Br CMe SMe B-0983 N Me CF2Br CMe SEt B-0984 N Me CF2Br CMe S(iPr) B-0985 N Me CF2Br CMe NHEt B-0986 N Me CF2Br CMe NMe2 B-0987 N Me CF2Br CMe CONH(iPr) B-0988 N Me CF2Br CMe F B-0989 N Me CF2Br CMe Cl B-0990 N Me CF2Br CMe Br B-0991 N Me CF2Br CMe I B-0992 N Me Cl CMe H B-0993 N Me Cl CMe Me B-0994 N Me Cl CMe Et B-0995 N Me Cl CMe Pr B-0996 N Me Cl CMe chf2 B-0997 N Me Cl CMe cf3 B-0998 N Me Cl CMe ch2cf3 B-0999 N Me Cl CMe ch2ch2cf3 B-1000 N Me Cl CMe cPr B-1001 N Me Cl CMe (2,2-F2)cPr B-1002 N Me Cl CMe Ph
[0154] COMPOUND No. A4 R1 R3 A6 R2 B-1003 N Me Cl CMe (2-Me)Ph B-1004 N Me Cl CMe (3-Me)Ph B-1005 N Me Cl CMe (4-Me)Ph B-1006 N Me Cl CMe OMe B-1007 N Me Cl CMe OEt B-1008 N Me Cl CMe OPr B-1009 N Me Cl CMe ochf2 B-1010 N Me Cl CMe ocf3 B-1011 N Me Cl CMe och2chf2 B-1012 N Me Cl CMe och2cf3 B-1013 N Me Cl CMe SMe B-1014 N Me Cl CMe SEt B-1015 N Me Cl CMe S(iPr) B-1016 N Me Cl CMe NHEt B-1017 N Me Cl CMe NMe2 B-1018 N Me Cl CMe CONH(iPr) B-1019 N Me Cl CMe F B-1020 N Me Cl CMe Cl B-1021 N Me Cl CMe Br B-1022 N Me Cl CMe I B-1023 N Me Br CMe H B-1024 N Me Br CMe Me B-1025 N Me Br CMe Et B-1026 N Me Br CMe Pr B-1027 N Me Br CMe chf2 B-1028 N Me Br CMe cf3 B-1029 N Me Br CMe ch2cf3 B-1030 N Me Br CMe ch2ch2cf3 B-1031 N Me Br CMe cPr B-1032 N Me Br CMe (2,2-F2)cPr B-1033 N Me Br CMe Ph B-1034 N Me Br CMe (2-Me)Ph B-1035 N Me Br CMe (3-Me)Ph B-1036 N Me Br CMe (4-Me)Ph B-1037 N Me Br CMe OMe B-1038 N Me Br CMe OEt B-1039 N Me Br CMe OPr B-1040 N Me Br CMe ochf2 B-1041 N Me Br CMe ocf3 B-1042 N Me Br CMe och2chf2 B-1043 N Me Br CMe och2cf3 B-1044 N Me Br CMe SMe
[0155] COMPOUND No. A4 R1 R3 A® R2 B-1045 N Me Br CMe SEt B-1046 N Me Br CMe S(iPr) B-1047 N Me Br CMe NHEt B-1048 N Me Br CMe NMe2 B-1049 N Me Br CMe CONH(iPr) B-1050 N Me Br CMe F B-1051 N Me Br CMe Cl B-1052 N Me Br CMe Br B-1053 N Me Br CMe I B-1054 N Me no2 CMe H B-1055 N Me no2 CMe Me B-1056 N Me no2 CMe Et B-1057 N Me no2 CMe Pr B-1058 N Me no2 CMe chf2 B-1059 N Me no2 CMe cf3 B-1060 N Me no2 CMe ch2cf3 B-1061 N Me no2 CMe ch2ch2cf3 B-1062 N Me no2 CMe cPr B-1063 N Me no2 CMe (2,2-F2)cPr B-1064 N Me no2 CMe Ph B-1065 N Me no2 CMe (2-Me)Ph B-1066 N Me no2 CMe (3-Me)Ph B-1067 N Me no2 CMe (4-Me)Ph B-1068 N Me no2 CMe OMe B-1069 N Me no2 CMe OEt B-1070 N Me no2 CMe OPr B-1071 N Me no2 CMe OCHF2 B-1072 N Me no2 CMe ocf3 B-1073 N Me no2 CMe och2chf2 B-1074 N Me no2 CMe och2cf3 B-1075 N Me no2 CMe SMe B-1076 N Me no2 CMe SEt B-1077 N Me no2 CMe S(iPr) B-1078 N Me no2 CMe NHEt B-1079 N Me no2 CMe NMe2 B-1080 N Me no2 CMe CONH(iPr) B-1081 N Me no2 CMe F B-1082 N Me no2 CMe Cl B-1083 N Me no2 CMe Br B-1084 N Me no2 CMe I B-1085 N Me nh2 CMe H B-1086 N Me nh2 CMe Me
[0156] COMPOUND No. A4 R1 R3 A6 R2 B-1087 N Me nh2 CMe Et B-1088 N Me nh2 CMe Pr B-1089 N Me nh2 CMe chf2 B-1090 N Me nh2 CMe cf3 B-1091 N Me nh2 CMe ch2cf3 B-1092 N Me nh2 CMe ch2ch2cf3 B-1093 N Me nh2 CMe cPr B-1094 N Me nh2 CMe (2,2-F2)cPr B-1095 N Me nh2 CMe Ph B-1096 N Me nh2 CMe (2-Me)Ph B-1097 N Me nh2 CMe (3-Me)Ph B-1098 N Me nh2 CMe (4-Me)Ph B-1099 N Me nh2 CMe OMe B-1100 N Me nh2 CMe OEt B-1101 N Me nh2 CMe OPr B-1102 N Me nh2 CMe ochf2 B-1103 N Me nh2 CMe ocf3 B-1104 N Me nh2 CMe och2chf2 B-1105 N Me nh2 CMe och2cf3 B-1106 N Me nh2 CMe SMe B-1107 N Me nh2 CMe SEt B-1108 N Me nh2 CMe S(iPr) B-1109 N Me nh2 CMe NHEt B-1110 N Me nh2 CMe NMe2 B-1111 N Me nh2 CMe CONH(iPr) B-1112 N Me nh2 CMe F B-1113 N Me nh2 CMe Cl B-1114 N Me nh2 CMe Br B-1115 N Me nh2 CMe I
[0157] [Table 52] f3c \ A6 A5' ^A7 \JOU. Md N=^ (C) R2 COMPOUND No. A4 A5 A6 A7 A1 R2 C-0001 CH N CH CH 0 H C-0002 CH N CH CH O Me C-0003 CH N CH CH 0 Et C-0004 CH N CH CH o Pr C-0005 CH N CH CH 0 chf2 C-0006 CH N CH CH 0 cf3 C-0007 CH N CH CH 0 ch2cf3 C-0008 CH N CH CH 0 ch2ch2cf3 C-0009 CH N CH CH 0 cPr C-0010 CH N CH CH 0 (2,2-F2)cPr C-0011 CH N CH CH o Ph C-0012 CH N CH CH 0 (2-Me)Ph C-0013 CH N CH CH 0 (3-Me)Ph C-0014 CH N CH CH o (4-Me)Ph C-0015 CH N CH CH o OMe C-0016 CH N CH CH 0 OEt C-0017 CH N CH CH 0 OPr C-0018 CH N CH CH 0 ochf2 C-0019 CH N CH CH o ocf3 C-0020 CH N CH CH 0 och2chf2 C-0021 CH N CH CH 0 och2cf3 C-0022 CH N CH CH o SMe C-0023 CH N CH CH 0 SEt C-0024 CH N CH CH 0 S(iPr) C-0025 CH N CH CH 0 NHEt C-0026 CH N CH CH 0 NMe2 C-0027 CH N CH CH o CONH(iPr) C-0028 CH N CH CH 0 F C-0029 CH N CH CH 0 Cl C-0030 CH N CH CH 0 Br C-0031 CH N CH CH 0 I C-0032 CH N CMe CH o H C-0033 CH N CMe CH 0 Me C-0034 CH N CMe CH 0 Et C-0035 CH N CMe CH 0 Pr C-0036 CH N CMe CH o tBu
[0158] COMPOUND No. A4 A5 A6 A7 A1 R2 C-0037 CH N CMe CH O chf2 C-0038 CH N CMe CH O cf3 C-0039 CH N CMe CH o ch2cf3 C-0040 CH N CMe CH o ch2ch2cf3 C-0041 CH N CMe CH o cPr C-0042 CH N CMe CH o (2,2-F2)cPr C-0043 CH N CMe CH o Ph C-0044 CH N CMe CH o (2-Me)Ph C-0045 CH N CMe CH o (3-Me)Ph C-0046 CH N CMe CH o (4-Me)Ph C-0047 CH N CMe CH o (2-CF3)Ph C-0048 CH N CMe CH o OMe C-0049 CH N CMe CH o OEt C-0050 CH N CMe CH o OPr C-0051 CH N CMe CH o ochf2 C-0052 CH N CMe CH o ocf3 C-0053 CH N CMe CH o och2chf2 C-0054 CH N CMe CH o och2cf3 C-0055 CH N CMe CH o SMe C-0056 CH N CMe CH o SEt C-0057 CH N CMe CH o S(iPr) C-0058 CH N CMe CH o NHEt C-0059 CH N CMe CH o NMe2 C-0060 CH N CMe CH o CONH(iPr) C-0061 CH N CMe CH o F C-0062 CH N CMe CH o Cl C-0063 CH N CMe CH o Br C-0064 CH N CMe CH o I C-0065 CH CH N CH o H C-0066 CH CH N CH o Me C-0067 CH CH N CH o Et C-0068 CH CH N CH o Pr C-0069 CH CH N CH o chf2 C-0070 CH CH N CH o cf3 C-0071 CH CH N CH o ch2cf3 C-0072 CH CH N CH o ch2ch2cf3 C-0073 CH CH N CH o cPr C-0074 CH CH N CH o (2,2-F2)cPr C-0075 CH CH N CH o Ph C-0076 CH CH N CH o (2-Me)Ph C-0077 CH CH N CH o (3-Me)Ph C-0078 CH CH N CH o (4-Me)Ph
[0159] COMPOUND No. A4 A5 A6 A7 A1 R2 C-0079 CH CH N CH O OMe C-0080 CH CH N CH O OEt C-0081 CH CH N CH o OPr C-0082 CH CH N CH o ochf2 C-0083 CH CH N CH o ocf3 C-0084 CH CH N CH o och2chf2 C-0085 CH CH N CH o och2cf3 C-0086 CH CH N CH o SMe C-0087 CH CH N CH o SEt C-0088 CH CH N CH o S(iPr) C-0089 CH CH N CH o NHEt C-0090 CH CH N CH o NMe2 C-0091 CH CH N CH o CONH(iPr) C-0092 CH CH N CH o F C-0093 CH CH N CH o Cl C-0094 CH CH N CH o Br C-0095 CH CH N CH o I C-0096 CH CH CH N o H C-0097 CH CH CH N o Me C-0098 CH CH CH N o Et C-0099 CH CH CH N o Pr C-0100 CH CH CH N o chf2 C-0101 CH CH CH N o cf3 C-0102 CH CH CH N o ch2cf3 C-0103 CH CH CH N o ch2ch2cf3 C-0104 CH CH CH N o cPr C-0105 CH CH CH N o (2,2-F2)cPr C-0106 CH CH CH N o Ph C-0107 CH CH CH N o (2-Me)Ph C-0108 CH CH CH N o (3-Me)Ph C-0109 CH CH CH N o (4-Me)Ph C-0110 CH CH CH N o OMe C-0111 CH CH CH N o OEt C-0112 CH CH CH N o OPr C-0113 CH CH CH N o ochf2 C-0114 CH CH CH N o ocf3 C-0115 CH CH CH N o och2chf2 C-0116 CH CH CH N o och2cf3 C-0117 CH CH CH N o SMe C-0118 CH CH CH N o SEt C-0119 CH CH CH N o S(iPr) C-0120 CH CH CH N o NHEt
[0160] COMPOUND No. A4 A5 A6 A7 A1 R2 C-0121 CH CH CH N O NMe2 C-0122 CH CH CH N O CONH(iPr) C-0123 CH CH CH N o F C-0124 CH CH CH N o Cl C-0125 CH CH CH N o Br C-0126 CH CH CH N o I C-0127 CH N CH N o H C-0128 CH N CH N o Me C-0129 CH N CH N o Et C-0130 CH N CH N o Pr C-0131 CH N CH N o chf2 C-0132 CH N CH N o cf3 C-0133 CH N CH N o ch2cf3 C-0134 CH N CH N o ch2ch2cf3 C-0135 CH N CH N o cPr C-0136 CH N CH N o (2,2-F2)cPr C-0137 CH N CH N o Ph C-0138 CH N CH N o (2-Me)Ph C-0139 CH N CH N o (3-Me)Ph C-0140 CH N CH N o (4-Me)Ph C-0141 CH N CH N o OMe C-0142 CH N CH N o OEt C-0143 CH N CH N o OPr C-0144 CH N CH N o ochf2 C-0145 CH N CH N o OCF3 C-0146 CH N CH N o OCH2CHF2 C-0147 CH N CH N o och2cf3 C-0148 CH N CH N o SMe C-0149 CH N CH N o SEt C-0150 CH N CH N o S(iPr) C-0151 CH N CH N o NHEt C-0152 CH N CH N o NMe2 C-0153 CH N CH N o CONH(iPr) C-0154 CH N CH N o F C-0155 CH N CH N o Cl C-0156 CH N CH N o Br C-0157 CH N CH N o I C-0158 CH N CMe N o H C-0159 CH N CMe N o Me C-0160 CH N CMe N o Et C-0161 CH N CMe N o Pr C-0162 CH N CMe N o chf2
[0161] COMPOUND No. A4 A5 A6 A7 A1 R2 C-0163 CH N CMe N O cf3 C-0164 CH N CMe N o ch2cf3 C-0165 CH N CMe N o ch2ch2cf3 C-0166 CH N CMe N o cPr C-0167 CH N CMe N o (2,2-F2)cPr C-0168 CH N CMe N o Ph C-0169 CH N CMe N o (2-Me)Ph C-0170 CH N CMe N o (3-Me)Ph C-0171 CH N CMe N o (4-Me)Ph C-0172 CH N CMe N o OMe C-0173 CH N CMe N o OEt C-0174 CH N CMe N o OPr C-0175 CH N CMe N o ochf2 C-0176 CH N CMe N o ocf3 C-0177 CH N CMe N o och2chf2 C-0178 CH N CMe N o och2cf3 C-0179 CH N CMe N o SMe C-0180 CH N CMe N o SEt C-0181 CH N CMe N o S(iPr) C-0182 CH N CMe N o NHEt C-0183 CH N CMe N o NMe2 C-0184 CH N CMe N o CONH(iPr) C-0185 CH N CMe N o F C-0186 CH N CMe N o Cl C-0187 CH N CMe N o Br C-0188 CH N CMe N o I C-0189 CH CH CH CH s H C-0190 CH CH CH CH s Me C-0191 CH CH CH CH s Et C-0192 CH CH CH CH s Pr C-0193 CH CH CH CH s chf2 C-0194 CH CH CH CH s cf3 C-0195 CH CH CH CH s ch2cf3 C-0196 CH CH CH CH s ch2ch2cf3 C-0197 CH CH CH CH s cPr C-0198 CH CH CH CH s (2,2-F2)cPr C-0199 CH CH CH CH s Ph C-0200 CH CH CH CH s (2-Me)Ph C-0201 CH CH CH CH s (3-Me)Ph C-0202 CH CH CH CH s (4-Me)Ph C-0203 CH CH CH CH s OMe C-0204 CH CH CH CH s OEt
[0162] COMPOUND No. A4 A5 A6 A7 A1 R2 C-0205 CH CH CH CH S OPr C-0206 CH CH CH CH s ochf2 C-0207 CH CH CH CH s ocf3 C-0208 CH CH CH CH s och2chf2 C-0209 CH CH CH CH s och2cf3 C-0210 CH CH CH CH s SMe C-0211 CH CH CH CH s SEt C-0212 CH CH CH CH s S(iPr) C-0213 CH CH CH CH s NHEt C-0214 CH CH CH CH s NMe2 C-0215 CH CH CH CH s CONH(iPr) C-0216 CH CH CH CH s F C-0217 CH CH CH CH s Cl C-0218 CH CH CH CH s Br C-0219 CH CH CH CH s I C-0220 CH CH CMe CH s H C-0221 CH CH CMe CH s Me C-0222 CH CH CMe CH s Et C-0223 CH CH CMe CH s Pr C-0224 CH CH CMe CH s chf2 C-0225 CH CH CMe CH s cf3 C-0226 CH CH CMe CH s ch2cf3 C-0227 CH CH CMe CH s ch2ch2cf3 C-0228 CH CH CMe CH s cPr C-0229 CH CH CMe CH s (2,2-F2)cPr C-0230 CH CH CMe CH s Ph C-0231 CH CH CMe CH s (2-Me)Ph C-0232 CH CH CMe CH s (3-Me)Ph C-0233 CH CH CMe CH s (4-Me)Ph C-0234 CH CH CMe CH s OMe C-0235 CH CH CMe CH s OEt C-0236 CH CH CMe CH s OPr C-0237 CH CH CMe CH s ochf2 C-0238 CH CH CMe CH s ocf3 C-0239 CH CH CMe CH s och2chf2 C-0240 CH CH CMe CH s och2cf3 C-0241 CH CH CMe CH s SMe C-0242 CH CH CMe CH s SEt C-0243 CH CH CMe CH s S(iPr) C-0244 CH CH CMe CH s nh2 C-0245 CH CH CMe CH s NMe2 C-0246 CH CH CMe CH s NHCO(iPr)
[0163] COMPOUND No. A4 A5 A6 A7 A1 R2 C-0247 CH CH CMe CH S CONH(iPr) C-0248 CH CH CMe CH S F C-0249 CH CH CMe CH s Cl C-0250 CH CH CMe CH s Br C-0251 CH CH CMe CH s I C-0252 CH N CH CH s H C-0253 CH N CH CH s Me C-0254 CH N CH CH s Et C-0255 CH N CH CH s Pr C-0256 CH N CH CH s chf2 C-0257 CH N CH CH s cf3 C-0258 CH N CH CH s ch2cf3 C-0259 CH N CH CH s ch2ch2cf3 C-0260 CH N CH CH s cPr C-0261 CH N CH CH s (2,2-F2)cPr C-0262 CH N CH CH s Ph C-0263 CH N CH CH s (2-Me)Ph C-0264 CH N CH CH s (3-Me)Ph C-0265 CH N CH CH s (4-Me)Ph C-0266 CH N CH CH s OMe C-0267 CH N CH CH s OEt C-0268 CH N CH CH s OPr C-0269 CH N CH CH s ochf2 C-0270 CH N CH CH s ocf3 C-0271 CH N CH CH s och2chf2 C-0272 CH N CH CH s och2cf3 C-0273 CH N CH CH s SMe C-0274 CH N CH CH s SEt C-0275 CH N CH CH s S(iPr) C-0276 CH N CH CH s NHEt C-0277 CH N CH CH s NMe2 C-0278 CH N CH CH s CONH(iPr) C-0279 CH N CH CH s F C-0280 CH N CH CH s Cl C-0281 CH N CH CH s Br C-0282 CH N CH CH s I C-0283 CH N CMe CH s H C-0284 CH N CMe CH s Me C-0285 CH N CMe CH s Et C-0286 CH N CMe CH s Pr C-0287 CH N CMe CH s chf2 C-0288 CH N CMe CH s cf3
[0164] COMPOUND No. A4 A5 A6 A7 A1 R2 C-0289 CH N CMe CH S ch2cf3 C-0290 CH N CMe CH S ch2ch2cf3 C-0291 CH N CMe CH s cPr C-0292 CH N CMe CH s (2,2-F2)cPr C-0293 CH N CMe CH s Ph C-0294 CH N CMe CH s (2-Me)Ph C-0295 CH N CMe CH s (3-Me)Ph C-0296 CH N CMe CH s (4-Me)Ph C-0297 CH N CMe CH s OMe C-0298 CH N CMe CH s OEt C-0299 CH N CMe CH s OPr C-0300 CH N CMe CH s ochf2 C-0301 CH N CMe CH s ocf3 C-0302 CH N CMe CH s och2chf2 C-0303 CH N CMe CH s och2cf3 C-0304 CH N CMe CH s SMe C-0305 CH N CMe CH s SEt C-0306 CH N CMe CH s S(iPr) C-0307 CH N CMe CH s NHEt C-0308 CH N CMe CH s NMe2 C-0309 CH N CMe CH s CONH(iPr) C-0310 CH N CMe CH s F C-0311 CH N CMe CH s Cl C-0312 CH N CMe CH s Br C-0313 CH N CMe CH s I C-0314 CH CH N CH s H C-0315 CH CH N CH s Me C-0316 CH CH N CH s Et C-0317 CH CH N CH s Pr C-0318 CH CH N CH s chf2 C-0319 CH CH N CH s cf3 C-0320 CH CH N CH s ch2cf3 C-0321 CH CH N CH s ch2ch2cf3 C-0322 CH CH N CH s cPr C-0323 CH CH N CH s (2,2-F2)cPr C-0324 CH CH N CH s Ph C-0325 CH CH N CH s (2-Me)Ph C-0326 CH CH N CH s (3-Me)Ph C-0327 CH CH N CH s (4-Me)Ph C-0328 CH CH N CH s OMe C-0329 CH CH N CH s OEt C-0330 CH CH N CH s OPr
[0165] COMPOUND No. A4 A5 A6 A7 A1 R2 C-0331 CH CH N CH S ochf2 C-0332 CH CH N CH S ocf3 C-0333 CH CH N CH s och2chf2 C-0334 CH CH N CH s och2cf3 C-0335 CH CH N CH s SMe C-0336 CH CH N CH s SEt C-0337 CH CH N CH s S(iPr) C-0338 CH CH N CH s NHEt C-0339 CH CH N CH s NMe2 C-0340 CH CH N CH s CONH(iPr) C-0341 CH CH N CH s F C-0342 CH CH N CH s Cl C-0343 CH CH N CH s Br C-0344 CH CH N CH s I C-0345 CH CH CH N s H C-0346 CH CH CH N s Me C-0347 CH CH CH N s Et C-0348 CH CH CH N s Pr C-0349 CH CH CH N s chf2 C-0350 CH CH CH N s cf3 C-0351 CH CH CH N s ch2cf3 C-0352 CH CH CH N s ch2ch2cf3 C-0353 CH CH CH N s cPr C-0354 CH CH CH N s (2,2-F2)cPr C-0355 CH CH CH N s Ph C-0356 CH CH CH N s (2-Me)Ph C-0357 CH CH CH N s (3-Me)Ph C-0358 CH CH CH N s (4-Me)Ph C-0359 CH CH CH N s OMe C-0360 CH CH CH N s OEt C-0361 CH CH CH N s OPr C-0362 CH CH CH N s ochf2 C-0363 CH CH CH N s ocf3 C-0364 CH CH CH N s och2chf2 C-0365 CH CH CH N s och2cf3 C-0366 CH CH CH N s SMe C-0367 CH CH CH N s SEt C-0368 CH CH CH N s S(iPr) C-0369 CH CH CH N s NHEt C-0370 CH CH CH N s NMe2 C-0371 CH CH CH N s CONH(iPr) C-0372 CH CH CH N s F
[0166] COMPOUND No. A4 A5 A6 A7 A1 R2 C-0373 CH CH CH N S Cl C-0374 CH CH CH N s Br C-0375 CH CH CH N s I C-0376 N CH CMe CH s H C-0377 N CH CMe CH s Me C-0378 N CH CMe CH s Et C-0379 N CH CMe CH s Pr C-0380 N CH CMe CH s chf2 C-0381 N CH CMe CH s cf3 C-0382 N CH CMe CH s ch2cf3 C-0383 N CH CMe CH s ch2ch2cf3 C-0384 N CH CMe CH s cPr C-0385 N CH CMe CH s (2,2-F2)cPr C-0386 N CH CMe CH s Ph C-0387 N CH CMe CH s (2-Me)Ph C-0388 N CH CMe CH s (3-Me)Ph C-0389 N CH CMe CH s (4-Me)Ph C-0390 N CH CMe CH s OMe C-0391 N CH CMe CH s OEt C-0392 N CH CMe CH s OPr C-0393 N CH CMe CH s ochf2 C-0394 N CH CMe CH s ocf3 C-0395 N CH CMe CH s och2chf2 C-0396 N CH CMe CH s och2cf3 C-0397 N CH CMe CH s SMe C-0398 N CH CMe CH s SEt C-0399 N CH CMe CH s S(iPr) C-0400 N CH CMe CH s nh2 C-0401 N CH CMe CH s NMe2 C-0402 N CH CMe CH s NHCO(iPr) C-0403 N CH CMe CH s CONH(iPr) C-0404 N CH CMe CH s F C-0405 N CH CMe CH s Cl C-0406 N CH CMe CH s Br C-0407 N CH CMe CH s I
[0167] [Table 62] f3c \ A6 #~-a4 a5' ^a7 <Va Md A3- / (D) R2 COMPOUND No. A4 A5 A6 A7 A3 R2 D-0001 CH CH CH CH 0 H D-0002 CH CH CH CH 0 Me D-0003 CH CH CH CH 0 Et D-0004 CH CH CH CH 0 Pr D-0005 CH CH CH CH 0 chf2 D-0006 CH CH CH CH 0 cf3 D-0007 CH CH CH CH 0 ch2cf3 D-0008 CH CH CH CH 0 ch2ch2cf3 D-0009 CH CH CH CH 0 cPr D-0010 CH CH CH CH 0 (2,2-F2)cPr D-0011 CH CH CH CH 0 Ph D-0012 CH CH CH CH 0 (2-Me)Ph D-0013 CH CH CH CH 0 (3-Me)Ph D-0014 CH CH CH CH 0 (4-Me)Ph D-0015 CH CH CH CH 0 OMe D-0016 CH CH CH CH 0 OEt D-0017 CH CH CH CH 0 OPr D-0018 CH CH CH CH 0 ochf2 D-0019 CH CH CH CH 0 ocfs D-0020 CH CH CH CH 0 och2chf2 D-0021 CH CH CH CH 0 och2cf3 D-0022 CH CH CH CH 0 och2sf5 D-0023 CH CH CH CH 0 och2ch2sf5 D-0024 CH CH CH CH 0 sf5 D-0025 CH CH CH CH 0 ch2sf5 D-0026 CH CH CH CH 0 ch2ch2sf6 D-0027 CH CH CH CH 0 ch2ch2ch2sf5 D-0028 CH CH CH CH 0 SMe D-0029 CH CH CH CH 0 SEt D-0030 CH CH CH CH 0 S(iPr) D-0031 CH CH CH CH 0 NHEt D-0032 CH CH CH CH 0 NMe2 D-0033 CH CH CH CH 0 CONH(iPr) D-0034 CH CH CH CH 0 F D-0035 CH CH CH CH 0 Cl D-0036 CH CH CH CH 0 Br
[0168] COMPOUND No. A4 A5 A6 A7 A3 R2 D-0037 CH CH CH CH O I D-0038 CH CH CF CH O H D-0039 CH CH CF CH O Me D-0040 CH CH CF CH O Et D-0041 CH CH CF CH O Pr D-0042 CH CH CF CH O chf2 D-0043 CH CH CF CH O cf3 D-0044 CH CH CF CH O ch2cf3 D-0045 CH CH CF CH O ch2ch2cf3 D-0046 CH CH CF CH O cPr D-0047 CH CH CF CH o (2,2-F2)cPr D-0048 CH CH CF CH o Ph D-0049 CH CH CF CH o (2-Me)Ph D-0050 CH CH CF CH o (3-Me)Ph D-0051 CH CH CF CH o (4-Me)Ph D-0052 CH CH CF CH o OMe D-0053 CH CH CF CH o OEt D-0054 CH CH CF CH o OPr D-0055 CH CH CF CH o ochf2 D-0056 CH CH CF CH o ocf3 D-0057 CH CH CF CH o och2chf2 D-0058 CH CH CF CH o och2cf3 D-0059 CH CH CF CH o SMe D-0060 CH CH CF CH o SEt D-0061 CH CH CF CH o S(iPr) D-0062 CH CH CF CH o NHEt D-0063 CH CH CF CH o NMe2 D-0064 CH CH CF CH o CONH(iPr) D-0065 CH CH CF CH o F D-0066 CH CH CF CH o Cl D-0067 CH CH CF CH o Br D-0068 CH CH CF CH o I D-0069 CH CH CMe CH o H D-0070 CH CH CMe CH o Me D-0071 CH CH CMe CH o Et D-0072 CH CH CMe CH o Pr D-0073 CH CH CMe CH o CHF2 D-0074 CH CH CMe CH o cf3 D-0075 CH CH CMe CH o ch2cf3 D-0076 CH CH CMe CH o ch2ch2cf3 D-0077 CH CH CMe CH o cPr D-0078 CH CH CMe CH o (2,2-F2)cPr
[0169] COMPOUND No. A4 A5 A6 A7 A3 R2 D-0079 CH CH CMe CH O Ph D-0080 CH CH CMe CH O (2-Me)Ph D-0081 CH CH CMe CH O (3-Me)Ph D-0082 CH CH CMe CH O (4-Me)Ph D-0083 CH CH CMe CH O OMe D-0084 CH CH CMe CH O OEt D-0085 CH CH CMe CH O OPr D-0086 CH CH CMe CH O ochf2 D-0087 CH CH CMe CH O ocf3 D-0088 CH CH CMe CH O och2chf2 D-0089 CH CH CMe CH O och2cf3 D-0090 CH CH CMe CH O OCH2SF5 D-0091 CH CH CMe CH O och2ch2sf5 D-0092 CH CH CMe CH O SFs D-0093 CH CH CMe CH O ch2sf5 D-0094 CH CH CMe CH O ch2ch2sf5 D-0095 CH CH CMe CH O ch2ch2ch2sf5 D-0096 CH CH CMe CH O SMe D-0097 CH CH CMe CH o SEt D-0098 CH CH CMe CH o S(iPr) D-0099 CH CH CMe CH o NHEt D-0100 CH CH CMe CH o NMe2 D-0101 CH CH CMe CH o CONH(iPr) D-0102 CH CH CMe CH o F D-0103 CH CH CMe CH o Cl D-0104 CH CH CMe CH o Br D-0105 CH CH CMe CH o I D-0106 CH N CH CH o H D-0107 CH N CH CH o Me D-0108 CH N CH CH o Et D-0109 CH N CH CH o Pr D-0110 CH N CH CH o chf2 D-0111 CH N CH CH o cf3 D-0112 CH N CH CH o ch2cf3 D-0113 CH N CH CH o ch2ch2cf3 D-0114 CH N CH CH o cPr D-0115 CH N CH CH o (2,2-F2)cPr D-0116 CH N CH CH o Ph D-0117 CH N CH CH o (2-Me)Ph D-0118 CH N CH CH o (3-Me)Ph D-0119 CH N CH CH o (4-Me)Ph D-0120 CH N CH CH o OMe
[0170] COMPOUND No. A4 A5 A6 A7 A3 R2 D-0121 CH N CH CH O OEt D-0122 CH N CH CH O OPr D-0123 CH N CH CH O ochf2 D-0124 CH N CH CH O ocf3 D-0125 CH N CH CH O och2chf2 D-0126 CH N CH CH O och2cf3 D-0127 CH N CH CH O SMe D-0128 CH N CH CH O SEt D-0129 CH N CH CH O S(iPr) D-0130 CH N CH CH O NHEt D-0131 CH N CH CH O NMe2 D-0132 CH N CH CH O CONH(iPr) D-0133 CH N CH CH O F D-0134 CH N CH CH O Cl D-0135 CH N CH CH O Br D-0136 CH N CH CH O I D-0137 CH CH N CH O H D-0138 CH CH N CH O Me D-0139 CH CH N CH o Et D-0140 CH CH N CH o Pr D-0141 CH CH N CH o chf2 D-0142 CH CH N CH o cf3 D-0143 CH CH N CH o ch2cf3 D-0144 CH CH N CH o ch2ch2cf3 D-0145 CH CH N CH o cPr D-0146 CH CH N CH o (2,2-F2)cPr D-0147 CH CH N CH o Ph D-0148 CH CH N CH o (2-Me)Ph D-0149 CH CH N CH o (3-Me)Ph D-0150 CH CH N CH o (4-Me)Ph D-0151 CH CH N CH o OMe D-0152 CH CH N CH o OEt D-0153 CH CH N CH o OPr D-0154 CH CH N CH o ochf2 D-0155 CH CH N CH o ocf3 D-0156 CH CH N CH o och2chf2 D-0157 CH CH N CH o och2cf3 D-0158 CH CH N CH o SMe D-0159 CH CH N CH o SEt D-0160 CH CH N CH o S(iPr) D-0161 CH CH N CH o NHEt D-0162 CH CH N CH o NMe2
[0171] COMPOUND No. A4 A5 A6 A7 A3 R2 D-0163 CH CH N CH O CONH(iPr) D-0164 CH CH N CH O F D-0165 CH CH N CH o Cl D-0166 CH CH N CH o Br D-0167 CH CH N CH o I D-0168 CH CH CH N o H D-0169 CH CH CH N o Me D-0170 CH CH CH N o Et D-0171 CH CH CH N o Pr D-0172 CH CH CH N o chf2 D-0173 CH CH CH N o cf3 D-0174 CH CH CH N o ch2cf3 D-0175 CH CH CH N o ch2ch2cf3 D-0176 CH CH CH N o cPr D-0177 CH CH CH N o (2,2-F2)cPr D-0178 CH CH CH N o Ph D-0179 CH CH CH N o (2-Me)Ph D-0180 CH CH CH N o (3-Me)Ph D-0181 CH CH CH N o (4-Me)Ph D-0182 CH CH CH N o OMe D-0183 CH CH CH N o OEt D-0184 CH CH CH N o OPr D-0185 CH CH CH N o OCHF2 D-0186 CH CH CH N o ocf3 D-0187 CH CH CH N o och2chf2 D-0188 CH CH CH N o och2cf3 D-0189 CH CH CH N o SMe D-0190 CH CH CH N o SEt D-0191 CH CH CH N o S(iPr) D-0192 CH CH CH N o NHEt D-0193 CH CH CH N o NMe2 D-0194 CH CH CH N o CONH(iPr) D-0195 CH CH CH N o F D-0196 CH CH CH N o Cl D-0197 CH CH CH N o Br D-0198 CH CH CH N o I D-0199 N CH CH CH o H D-0200 N CH CH CH o Me D-0201 N CH CH CH o Et D-0202 N CH CH CH o Pr D-0203 N CH CH CH o chf2 D-0204 N CH CH CH o cf3
[0172] COMPOUND No. A4 A5 A6 A7 A3 R2 D-0205 N CH CH CH O ch2cf3 D-0206 N CH CH CH O ch2ch2cf3 D-0207 N CH CH CH O cPr D-0208 N CH CH CH O (2,2-F2)cPr D-0209 N CH CH CH O Ph D-0210 N CH CH CH O (2-Me)Ph D-0211 N CH CH CH O (3-Me)Ph D-0212 N CH CH CH O (4-Me)Ph D-0213 N CH CH CH O OMe D-0214 N CH CH CH O OEt D-0215 N CH CH CH O OPr D-0216 N CH CH CH o ochf2 D-0217 N CH CH CH o ocf3 D-0218 N CH CH CH o och2chf2 D-0219 N CH CH CH o och2cf3 D-0220 N CH CH CH o och2sf5 D-0221 N CH CH CH o och2ch2sf5 D-0222 N CH CH CH o sf5 D-0223 N CH CH CH o ch2sf5 D-0224 N CH CH CH o ch2ch2sf5 D-0225 N CH CH CH o ch2ch2ch2sf5 D-0226 N CH CH CH o SMe D-0227 N CH CH CH o SEt D-0228 N CH CH CH o S(iPr) D-0229 N CH CH CH o NHEt D-0230 N CH CH CH o NMe2 D-0231 N CH CH CH o CONH(iPr) D-0232 N CH CH CH o F D-0233 N CH CH CH o Cl D-0234 N CH CH CH o Br D-0235 N CH CH CH o I D-0236 N CH CF CH o H D-0237 N CH CF CH o Me D-0238 N CH CF CH o Et D-0239 N CH CF CH o Pr D-0240 N CH CF CH o chf2 D-0241 N CH CF CH o cf3 D-0242 N CH CF CH o ch2cf3 D-0243 N CH CF CH o ch2ch2cf3 D-0244 N CH CF CH o cPr D-0245 N CH CF CH o (2,2-F2)cPr D-0246 N CH CF CH o Ph
[0173] COMPOUND No. A4 A5 A6 A7 A3 R2 D-0247 N CH CF CH O (2-Me)Ph D-0248 N CH CF CH O (3-Me)Ph D-0249 N CH CF CH O (4-Me)Ph D-0250 N CH CF CH O OMe D-0251 N CH CF CH O OEt D-0252 N CH CF CH O OPr D-0253 N CH CF CH O ochf2 D-0254 N CH CF CH O ocf3 D-0255 N CH CF CH O OCH2CHF2 D-0256 N CH CF CH O och2cf3 D-0257 N CH CF CH O SMe D-0258 N CH CF CH O SEt D-0259 N CH CF CH o S(iPr) D-0260 N CH CF CH o NHEt D-0261 N CH CF CH o NMe2 D-0262 N CH CF CH o CONH(iPr) D-0263 N CH CF CH o F D-0264 N CH CF CH o Cl D-0265 N CH CF CH o Br D-0266 N CH CF CH o I D-0267 N CH CMe CH o H D-0268 N CH CMe CH o Me D-0269 N CH CMe CH o Et D-0270 N CH CMe CH o Pr D-0271 N CH CMe CH o chf2 D-0272 N CH CMe CH o cf3 D-0273 N CH CMe CH o ch2cf3 D-0274 N CH CMe CH o ch2ch2cf3 D-0275 N CH CMe CH o cPr D-0276 N CH CMe CH o (2,2-F2)cPr D-0277 N CH CMe CH o Ph D-0278 N CH CMe CH o (2-Me)Ph D-0279 N CH CMe CH o (3-Me)Ph D-0280 N CH CMe CH o (4-Me)Ph D-0281 N CH CMe CH o OMe D-0282 N CH CMe CH o OEt D-0283 N CH CMe CH o OPr D-0284 N CH CMe CH o ochf2 D-0285 N CH CMe CH o OCF3 D-0286 N CH CMe CH o OCH2CHF2 D-0287 N CH CMe CH o och2cf3 D-0288 N CH CMe CH o OCH2SFs
[0174] COMPOUND No. A4 A5 A6 A7 A3 R2 D-0289 N CH CMe CH O OCH2CH2SF5 D-0290 N CH CMe CH O sf5 D-0291 N CH CMe CH o ch2sf5 D-0292 N CH CMe CH o ch2ch2sf5 D-0293 N CH CMe CH o ch2ch2ch2sf5 D-0294 N CH CMe CH o SMe D-0295 N CH CMe CH o SEt D-0296 N CH CMe CH o S(iPr) D-0297 N CH CMe CH o NHEt D-0298 N CH CMe CH o NMe2 D-0299 N CH CMe CH o CONH(iPr) D-0300 N CH CMe CH o F D-0301 N CH CMe CH o Cl D-0302 N CH CMe CH o Br D-0303 N CH CMe CH o I D-0304 CH CH CH CH s H D-0305 CH CH CH CH s Me D-0306 CH CH CH CH s Et D-0307 CH CH CH CH s Pr D-0308 CH CH CH CH s chf2 D-0309 CH CH CH CH s cf3 D-0310 CH CH CH CH s ch2cf3 D-0311 CH CH CH CH s ch2ch2cf3 D-0312 CH CH CH CH s cPr D-0313 CH CH CH CH s (2,2-F2)cPr D-0314 CH CH CH CH s Ph D-0315 CH CH CH CH s (2-Me)Ph D-0316 CH CH CH CH s (3-Me)Ph D-0317 CH CH CH CH s (4-Me)Ph D-0318 CH CH CH CH s OMe D-0319 CH CH CH CH s OEt D-0320 CH CH CH CH s OPr D-0321 CH CH CH CH s ochf2 D-0322 CH CH CH CH s ocf3 D-0323 CH CH CH CH s och2chf2 D-0324 CH CH CH CH s och2cf3 D-0325 CH CH CH CH s SMe D-0326 CH CH CH CH s SEt D-0327 CH CH CH CH s S(iPr) D-0328 CH CH CH CH s NHEt D-0329 CH CH CH CH s NMe2 D-0330 CH CH CH CH s CONH(iPr)
[0175] COMPOUND No. A4 A5 A6 A7 A3 R2 D-0331 CH CH CH CH S F D-0332 CH CH CH CH S Cl D-0333 CH CH CH CH s Br D-0334 CH CH CH CH s I
[0176] [Table 71] R3 R \ A6 >~A4 A5' ^A7 N JI JI J N Me [VI] NH2 M 3 \ A6 y^A4 A5' ^A7 xXAA N y NH2 e [ IX ] A3H COMPOUND No. R3 A4 A5 A6 A7 A1 A3 E-0001 chf2 CH CH CH CH 0 - [VI] E-0002 chf2 CH CH CF CH 0 - [VI] E-0003 chf2 CH CH CCI CH 0 - [VI] E-0004 chf2 CH CH CBr CH 0 — [VI] E-0005 chf2 CH CH Cl CH 0 - [VI] E-0006 chf2 CH CH CMe CH 0 — [VI] E-0007 chf2 CH CH CEt CH 0 - [VI] E-0008 chf2 CH CH cchf2 CH 0 — [VI] E-0009 chf2 CH CH ccf3 CH 0 - [VI] E-0010 cf3 CH CF CH CH 0 - [VI] E-0011 cf3 CH CF CMe CH 0 - [VI] E-0012 cf3 CH CCI CH CH 0 - [VI] E-0013 cf3 CH CBr CH CH 0 - [VI] E-0014 cf3 CH Cl CH CH 0 — [VI] E-0015 cf3 CH CMe CH CH 0 - [VI] E-0016 cf3 CH CEt CH CH 0 — [VI] E-0017 cf3 CH cchf2 CH CH 0 — [VI] E-0018 cf3 CH ccf3 CH CH 0 - [VI] E-0019 cf3 CH CH CH CH 0 - [VI] E-0020 cf3 CH CH CF CH 0 - [VI] E-0021 cf3 CH CH CCI CH 0 - [VI] E-0022 cf3 CH CH CBr CH 0 - [VI] E-0023 cf3 CH CH Cl CH 0 - [VI] E-0024 cf3 CH CH CMe CH 0 — [VI] E-0025 cf3 CH CH CEt CH 0 - [VI] E-0026 cf3 CH CH cchf2 CH 0 - [VI] E-0027 cf3 CH CH ccf3 CH 0 - [VI] E-0028 cf3 CH CH cch2oh CH 0 - [VI] E-0029 cf3 CH CH CCH2OMe CH 0 - [VI] E-0030 cf3 CH CH CCH2OPr CH 0 - [VI] E-0031 cf3 CH CH CCHO CH 0 - [VI] E-0032 cf3 CH CH CCO2H CH 0 - [VI] E-0033 cf3 CH CH CCO2M6 CH 0 — [VI] E-0034 cf3 CH CH CCO2Et CH 0 - [VI] E-0035 cf3 CH CH COH CH 0 - [VI] E-0036 cf3 CH CH COMe CH 0 - [VI]
[0177] COMPOUND No. R3 A4 A5 A6 A7 A1 A3 E-0037 cf3 CH CH CSH CH O — [VI] E-0038 cf3 CH CH CSMe CH o - [VI] E-0039 cf3 CH CH cnh2 CH o - [VI] E-0040 cf3 CH CH CNMe2 CH o - [VI] E-0041 cf3 CH CH CH CF o - [VI] E-0042 cf3 CH CH CH CCI o — [VI] E-0043 cf3 CH CH CH CBr o - [VI] E-0044 cf3 CH CH CH Cl o - [VI] E-0045 cf3 CH CH CH CMe o — [VI] E-0046 cf3 CH CH CH CEt o - [VI] E-0047 cf3 CH CH CH cchf2 o - [VI] E-0048 cf3 CH CH CH ccf3 o - [VI] E-0049 cf3 N CH CH CH o - [VI] E-0050 cf3 N CH CF CH o - [VI] E-0051 cf3 N CH CCI CH o - [VI] E-0052 cf3 N CH CBr CH o - [VI] E-0053 cf3 N CH Cl CH o - [VI] E-0054 cf3 N CH CMe CH o - [VI] E-0055 cf3 N CH CEt CH o - [VI] E-0056 cf3 N CH cchf2 CH o — [VI] E-0057 cf3 N CH ccf3 CH o - [VI] E-0058 cf3 CH N CH CH o — [VI] E-0059 cf3 CH N CF CH o - [VI] E-0060 cf3 CH N CCI CH o - [VI] E-0061 cf3 CH N CBr CH o - [VI] E-0062 cf3 CH N Cl CH o — [VI] E-0063 cf3 CH N CMe CH o - [VI] E-0064 cf3 CH N CEt CH o - [VI] E-0065 cf3 CH N cchf2 CH o - [VI] E-0066 cf3 CH N ccf3 CH o — [VI] E-0067 cf3 CH N CH N o — [VI] E-0068 cf3 CH N CF N o - [VI] E-0069 cf3 CH N CCI N o - [VI] E-0070 cf3 CH N CBr N o - [VI] E-0071 cf3 CH N Cl N o - [VI] E-0072 cf3 CH N CMe N o - [VI] E-0073 cf3 CH N CEt N o — [VI] E-0074 cf3 CH N cchf2 N o - [VI] E-0075 cf3 CH N ccf3 N o - [VI] E-0076 cf3 CH CH CH CH - o [IX] E-0077 cf3 CH CH CF CH - o [IX] E-0078 cf3 CH CH CCI CH - o [IX]
[0178] COMPOUND No. R3 A4 A5 A6 A7 A1 A3 E-0079 cf3 CH CH CBr CH — O [IX] E-0080 cf3 CH CH Cl CH - O [IX] E-0081 cf3 CH CH CMe CH - O [IX] E-0082 cf3 CH CH CEt CH - O [IX] E-0083 cf3 CH CH cchf2 CH - O [IX] E-0084 cf3 CH CH ccf3 CH - O [IX] E-0085 cf3 N CH CH CH - O [IX] E-0086 cf3 N CH CF CH - O [IX] E-0087 cf3 N CH CCI CH — o [IX] E-0088 cf3 N CH CBr CH - o [IX] E-0089 cf3 N CH Cl CH - o [IX] E-0090 cf3 N CH CMe CH - o [IX] E-0091 cf3 N CH CEt CH — o [IX] E-0092 cf3 N CH cchf2 CH - o [IX] E-0093 cf3 N CH ccf3 CH - o [IX] E-0094 cf3 CH N CH CH — o [IX] E-0095 cf3 CH N CF CH - o [IX] E-0096 cf3 CH N CCI CH — o [IX] E-0097 cf3 CH N CBr CH - o [IX] E-0098 cf3 CH N Cl CH — o [IX] E-0099 cf3 CH N CMe CH — o [IX] E-0100 cf3 CH N CEt CH - o [IX] E-0101 cf3 CH N cchf2 CH - o [IX] E-0102 cf3 CH N ccf3 CH — o [IX] E-0103 cf3 CH N CH N - o [IX] E-0104 cf3 CH N CF N - o [IX] E-0105 cf3 CH N CCI N - o [IX] E-0106 cf3 CH N CBr N — o [IX] E-0107 cf3 CH N Cl N - o [IX] E-0108 cf3 CH N CMe N — o [IX] E-0109 cf3 CH N CEt N — o [IX] E-0110 cf3 CH N cchf2 N — o [IX] E-0111 cf3 CH N ccf3 N - o [IX] 10
[0179] <Production Method> The present compound represented by general formula [I] can be produced in accordance with, but not limited to, the production methods shown below. Hereinafter, for example, the "compound represented by general formula [I]", the "compound represented by the formula [I]", and the "compound [I]" refer to the same compound.
[0180] <Production Method 1> A compound represented by general formula [I] among the present compounds can be produced in accordance with the following method, for example.
[0181] [Chem. 4]
[0182] (wherein X, R1, R2, R3, A1, A3, A4, A5, A6 and A7 are as defined above.)
[0183] That is, the compound represented by general formula [I] can be produced by reacting the compound represented by general formula [II] (compound [II]) with a compound represented by general formula [III] (compound [III]) in an appropriate solvent in the presence or absence of an appropriate base.
[0184] The use amount of the compound [III] to be used in the present reaction may be appropriately selected usually from the range of 1 to 100 mol per 1 mol of the compound [II], and is preferably 1 to 20 mol.
[0185] When a base is used in the present reaction, examples of the base that can be used include inorganic bases including: hydroxides of alkali metal such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; hydroxides of alkaline earth metal such as calcium hydroxide and magnesium hydroxide; carbonates of alkali metal such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate; bicarbonates of alkali metal such as sodium bicarbonate and potassium bicarbonate, fluorides of alkali metal such as sodium fluoride and potassium fluoride, or tripotassium phosphate; metal hydrides including: lithium hydride, sodium hydride and potassium hydride; metal salts of alcohol including: sodium methoxide, sodium ethoxide and potassium tert-butoxide; and alkyl lithiums such as methyllithium, butyllithium and phenyllithium; and organic bases including: triethylamine, tributylamine, diisopropylethylamine, N,N-dimethylaniline, pyridine, 2,6-lutidine, 4-N,N-dimethylaminopyridine and 1,8-diazabicyclo[5.4.0]-7-undecene. The use amount of the base may be appropriately selected from the range of 0 to 100 mol per 1 mol of the compound [II], and is preferably 0.1 to 20 mol.
[0186] Examples of the solvent that can be used in the present reaction include ethers such as diethyl ether, methyl tert-butyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1,4-dioxane, monoglyme, and diglyme; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, and chlorobenzene; halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, and 1,3-dimethyl-2-imidazolidinone; alcohols such as methanol, ethanol, 2-propanol, tert-butyl alcohol and methyl cellosolve; esters such as ethyl acetate, isopropyl acetate, butyl acetate and ethyl propionate; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile and propionitrile; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and heptane; pyridines such as pyridine, picoline, and lutidine; tertiary amines such as triethylamine and tributylamine; water; and a mixed solvent thereof. The use amount of the solvent is 0.1 to 1000 liters, preferably 0.2 to 100 liters, per 1 mol of the compound [II].
[0187] The reaction can be carried out in the presence of a catalyst, if necessary. The catalyst contains a metal or a metal salt and a compound as a ligand. Such a catalyst may be prepared in a reaction system (in situ) from a compound as a ligand with a metal or a metal salt described later, or may be prepared in advance outside the reaction system and then introduced into the reaction system. The catalyst may contain components other than the metal, the metal salt and the compound as a ligand. Examples of the metal or the metal salt include copper compounds such as metal copper, copper(I) acetate, copper(II) acetate, copper(I) oxide, copper(II) oxide, copper(I) chloride, copper(II) chloride, copper(I) bromide, copper(II) bromide, copper(I) iodide, bis(acetylacetonato)copper(II); and palladium compounds such as palladium-carbon, palladium chloride, palladium nitrate, palladium acetate, bis(triphenylphosphine)palladium dichloride, and tetrakis(triphenylphosphine)palladium. Examples of the ligand include ethylenediamine, N,N-dimethylethylenediamine, N,N‘-dimethylethylenediamine, tetramethylethylenediamine, 2,2'-bipyridine, 1,10-phenanthroline, neocuproine, 3,4,7,8-tetramethyl-1,10-phenanthroline, 2,9-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, triphenylphosphine, tri-tert-buthylphosphine, 1,1'- bis(diphenylphosphino)ferrocene, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, and 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, and salts thereof. In the combination of the metal or the metal salt and the ligand, the compound as the ligand may be appropriately selected from the range of 0.1 to 10 mol per 1 mol of the metal or the metal salt, and is preferably 1 to 4 mol. The use amount of the catalyst may be appropriately selected from the range of 0.001 to 10 mol as a metal or a metal salt per 1 mol of the compound [II], and is preferably 0.01 to 5 mol.
[0188] The reaction temperature of the present reaction may be selected from the range of any temperature from -78°C to a reflux temperature in the reaction system, and is preferably in the range of 0°C to 180°C.
[0189] The reaction time of the present reaction varies depending on the reaction temperature, the reaction substrate, the reaction amount, and the like, but it is usually 10 minutes to 72 hours.
[0190] After completion of the reaction, the compound [I] can be isolated by performing operations such as pouring the reaction mixture into water or concentrating, and then collecting the precipitated solids by filtration or extracting them with an organic solvent followed by concentration or the like. The isolated compound [I] can be further purified by column chromatography, recrystallization, distillation, or the like, if necessary.
[0191] <Production Method 2> A compound represented by general formula [I] among the present compounds can be produced in accordance with the following method, for example.
[0192] [Chem. 5]
[0193] (wherein X, R1, R2, R3, A1, A3, A4, A5, A6 and A7 are as defined above.)
[0194] That is, the compound represented by general formula [I] can be produced by reacting the compound represented by general formula [IV] (compound [IV]) with a compound represented by general formula [V] (compound [V]) in an appropriate solvent in the presence or absence of an appropriate base.
[0195] The use amount of the compound [V] to be used in the present reaction may be appropriately selected usually from the range of 1 to 100 mol per 1 mol of the compound [IV], and is preferably 1 to 20 mol.
[0196] When a base is used in the present reaction, examples of the base that can be used include inorganic bases including: hydroxides of alkali metal such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; hydroxides of alkaline earth metal such as calcium hydroxide and magnesium hydroxide; carbonates of alkali metal such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate; bicarbonates of alkali metal such as sodium bicarbonate and potassium bicarbonate, fluorides of alkali metal such as sodium fluoride and potassium fluoride, or tripotassium phosphate; metal hydrides including: lithium hydride, sodium hydride and potassium hydride; metal salts of alcohol including: sodium methoxide, sodium ethoxide and potassium tert-butoxide; and alkyl lithiums such as methyllithium, butyllithium and phenyllithium; and organic bases including: triethylamine, tributylamine, diisopropylethylamine, N,N-dimethylaniline, pyridine, 2,6-lutidine, 4-N,N-dimethylaminopyridine and 1,8-diazabicyclo[5.4.0]-7-undecene. The use amount of the base may be appropriately selected from the range of 0 to 100 mol per 1 mol of the compound [IV], and is preferably 0.1 to 20 mol.
[0197] Examples of the solvent that can be used in the present reaction include ethers such as diethyl ether, methyl tert-butyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1,4-dioxane, monoglyme, and diglyme; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, and chlorobenzene; halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, and 1,3-dimethyl-2-imidazolidinone; alcohols such as methanol, ethanol, 2-propanol, tert-butyl alcohol and methyl cellosolve; esters such as ethyl acetate, isopropyl acetate, butyl acetate and ethyl propionate; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile and propionitrile; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and heptane; pyridines such as pyridine, picoline, and lutidine; tertiary amines such as triethylamine and tributylamine; water; and a mixed solvent thereof. The use amount of the solvent is 0.1 to 1000 liters, preferably 0.2 to 100 liters, per 1 mol of the compound [IV].
[0198] The reaction can be carried out in the presence of a catalyst, if necessary. The catalyst contains a metal or a metal salt and a compound as a ligand. Such a catalyst may be prepared in a reaction system (in situ) from a compound as a ligand with a metal or a metal salt described later, or may be prepared in advance outside the reaction system and then introduced into the reaction system. The catalyst may contain components other than the metal, the metal salt and the compound as a ligand. Examples of the metal or the metal salt include copper compounds such as metal copper, copper(I) acetate, copper(II) acetate, copper(I) oxide, copper(II) oxide, copper(I) chloride, copper(II) chloride, copper(I) bromide, copper(II) bromide, copper(I) iodide, bis(acetylacetonato)copper(II); and palladium compounds such as palladium-carbon, palladium chloride, palladium nitrate, palladium acetate, bis(triphenylphosphine)palladium dichloride, and tetrakis(triphenylphosphine)palladium. Examples of the ligand include ethylenediamine, N,N-dimethylethylenediamine, N,N‘-dimethylethylenediamine, tetramethylethylenediamine, 2,2'-bipyridine, 1,10-phenanthroline, neocuproine, 3,4,7,8-tetramethyl-1,10-phenanthroline, 2,9-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, triphenylphosphine, tri-tert-buthylphosphine, 1,1'- bis(diphenylphosphino)ferrocene, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, and 2,2‘-bis(diphenylphosphino)-1,1‘-binaphthyl, and salts thereof. In the combination of the metal or the metal salt and the ligand, the compound as the ligand may be appropriately selected from the range of 0.1 to 10 mol per 1 mol of the metal or the metal salt, and is preferably 1 to 4 mol. The use amount of the catalyst may be appropriately selected from the range of 0.001 to 10 mol as a metal or a metal salt per 1 mol of the compound [IV], and is preferably 0.01 to 5 mol.
[0199] The reaction temperature of the present reaction may be selected from the range of any temperature from -78°C to a reflux temperature in the reaction system, and is preferably in the range of 0°C to 180°C.
[0200] The reaction time of the present reaction varies depending on the reaction temperature, the reaction substrate, the reaction amount, and the like, but it is usually 10 minutes to 72 hours.
[0201] After completion of the reaction, the compound [I] can be isolated by performing operations such as pouring the reaction mixture into water and then collecting the precipitated solids by filtration or extracting them with an organic solvent followed by concentration or the like. The isolated compound [I] can be further purified by column chromatography, recrystallization, distillation, or the like, if necessary.
[0202] <Production Method 3> A compound represented by general formula [I-1] among the present compounds can be produced in accordance with the following method, for example.
[0203] [Chem. 6]
[0204] (wherein R represents a C1-C6 alkyl group, a C1-C6 haloalkyl group, Y' represents O and S, and X, R1, R2, R3, A1, A4, A5, A6 and A7 are as defined above.)
[0205] That is, the compound represented by general formula [I-1] can be produced by reacting the compound represented by general formula [VI] (compound [VI]) with a compound [VII] or a compound [VIII] in an appropriate solvent in the presence or absence of an appropriate base or an appropriate acid.
[0206] The use amount of the compound [VII] or the compound [VIII] to be used in the present reaction may be appropriately selected usually from the range of 1 to 100 mol per 1 mol of the compound [VI], and is preferably 1 to 20 mol.
[0207] When a base is used in the present reaction, examples of the base that can be used include inorganic bases including: hydroxides of alkali metal such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; hydroxides of alkaline earth metal such as calcium hydroxide and magnesium hydroxide; carbonates of alkali metal such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate; bicarbonates of alkali metal such as sodium bicarbonate and potassium bicarbonate, fluorides of alkali metal such as sodium fluoride and potassium fluoride, or tripotassium phosphate; metal hydrides including: lithium hydride, sodium hydride and potassium hydride; metal salts of alcohol including: sodium methoxide, sodium ethoxide and potassium tert-butoxide; and alkyl lithiums such as methyllithium, butyllithium and phenyllithium; and organic bases including: triethylamine, tributylamine, diisopropylethylamine, N,N-dimethylaniline, pyridine, 2,6-lutidine, 4-N,N-dimethylaminopyridine and 1,8-diazabicyclo[5.4.0]-7-undecene. The use amount of the base may be appropriately selected from the range of 0 to 100 mol per 1 mol of the compound [VI], and is preferably 0.1 to 20 mol.
[0208] When an acid is used in the present reaction, examples of the acid that can be used include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, and phosphoric acid, carboxylic acids such as acetic acid and trifluoroacetic acid, and sulfonic acids such as methanesulfonic acid and trifluoromethanesulfonic acid. The use amount of the acid may be appropriately selected from 0 to 100 mol per 1 mol of the compound [VI], and is preferably 0.1 to 20 mol.
[0209] Examples of the solvent that can be used in the present reaction include ethers such as diethyl ether, methyl tert-butyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1,4-dioxane, monoglyme, and diglyme; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, and chlorobenzene; halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, and 1,3-dimethyl-2-imidazolidinone; alcohols such as methanol, ethanol, 2-propanol, tert-butyl alcohol and methyl cellosolve; esters such as ethyl acetate, isopropyl acetate, butyl acetate and ethyl propionate; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile and propionitrile; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and heptane; pyridines such as pyridine, picoline, and lutidine; tertiary amines such as triethylamine and tributylamine; water; and a mixed solvent thereof. The use amount of the solvent is 0.1 to 1000 liters, preferably 0.2 to 100 liters, per 1 mol of the compound [VI].
[0210] The reaction temperature of the present reaction may be selected from the range of any temperature from -78°C to a reflux temperature in the reaction system, and is preferably in the range of 0°C to 180°C.
[0211] The reaction time of the present reaction varies depending on the reaction temperature, the reaction substrate, the reaction amount, and the like, but it is usually 10 minutes to 72 hours.
[0212] After completion of the reaction, the compound [I-1] can be isolated by performing operations such as pouring the reaction mixture into water or concentrating, and then collecting the precipitated solids by filtration or extracting them with an organic solvent followed by concentration or the like. The isolated compound [I-1] can be further purified by column chromatography, recrystallization, distillation, or the like, if necessary.
[0213] <Production Method 4> A compound represented by general formula [I-2] among the present compounds can be produced in accordance with the following method, for example.
[0214] [Chem. 7]
[0215] (wherein R, X, Y', R1, R2, R3, A3, A4, A5, A6 and A7 are as defined above.)
[0216] That is, the compound represented by general formula [I-2] can be produced by reacting the compound represented by general formula [IX] (compound [IX]) with a compound [VII] or a compound [VIII] in an appropriate solvent in the presence or absence of an appropriate base or an appropriate acid.
[0217] The use amount of the compound [VII] or the compound [VIII] to be used in the present reaction may be appropriately selected usually from the range of 1 to 100 mol per 1 mol of the compound [IX], and is preferably 1 to 20 mol.
[0218] When a base is used in the present reaction, examples of the base that can be used include inorganic bases including: hydroxides of alkali metal such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; hydroxides of alkaline earth metal such as calcium hydroxide and magnesium hydroxide; carbonates of alkali metal such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate; bicarbonates of alkali metal such as sodium bicarbonate and potassium bicarbonate, fluorides of alkali metal such as sodium fluoride and potassium fluoride, or tripotassium phosphate; metal hydrides including: lithium hydride, sodium hydride and potassium hydride; metal salts of alcohol including: sodium methoxide, sodium ethoxide and potassium tert-butoxide; and alkyl lithiums such as methyllithium, butyllithium and phenyllithium; and organic bases including: triethylamine, tributylamine, diisopropylethylamine, N,N-dimethylaniline, pyridine, 2,6-lutidine, 4-N,N-dimethylaminopyridine and 1,8-diazabicyclo[5.4.0]-7-undecene. The use amount of the base may be appropriately selected from the range of 0 to 100 mol per 1 mol of the compound [IX], and is preferably 0.1 to 20 mol.
[0219] When an acid is used in the present reaction, examples of the acid that can be used include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, and phosphoric acid, carboxylic acids such as acetic acid and trifluoroacetic acid, and sulfonic acids such as methanesulfonic acid and trifluoromethanesulfonic acid. The use amount of the acid may be appropriately selected from 0 to 100 mol per 1 mol of the compound [IX], and is preferably 0.1 to 20 mol.
[0220] Examples of the solvent that can be used in the present reaction include ethers such as diethyl ether, methyl tert-butyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1,4-dioxane, monoglyme, and diglyme; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, and chlorobenzene; halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, and 1,3-dimethyl-2-imidazolidinone; alcohols such as methanol, ethanol, 2-propanol, tert-butyl alcohol and methyl cellosolve; esters such as ethyl acetate, isopropyl acetate, butyl acetate and ethyl propionate; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile and propionitrile; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and heptane; pyridines such as pyridine, picoline, and lutidine; tertiary amines such as triethylamine and tributylamine; water; and a mixed solvent thereof. The use amount of the solvent is 0.1 to 1000 liters, preferably 0.2 to 100 liters, per 1 mol of the compound [IX].
[0221] The reaction temperature of the present reaction may be selected from the range of any temperature from -78°C to a reflux temperature in the reaction system, and is preferably in the range of 0°C to 180°C.
[0222] The reaction time of the present reaction varies depending on the reaction temperature, the reaction substrate, the reaction amount, and the like, but it is usually 10 minutes to 72 hours.
[0223] After completion of the reaction, the compound [I-2] can be isolated by performing operations such as pouring the reaction mixture into water or concentrating, and then collecting the precipitated solids by filtration or extracting them with an organic solvent followed by concentration or the like. The isolated compound [I-2] can be further purified by column chromatography, recrystallization, distillation, or the like, if necessary.
[0224] <Production Method 5> A compound represented by general formula [I-1] among the present compounds can be produced in accordance with the following method, for example.
[0225] [Chem. 8]
[0226] (wherein X, R1, R2, R3, A1, A4, A5, A6 and A7 are as defined above.)
[0227] That is, the compound represented by the general formula [I-1] (compound [I-1]) can be produced by reacting the compound represented by general formula [X] (compound [X]) with a compound represented by general formula [XI] (compound [XI]) in an appropriate solvent in the presence or absence of an appropriate base to obtain a compound represented by the general formula [XII], and then subjecting the compound to cyclization reaction in an appropriate solvent in the presence or absence of an appropriate base.
[0228] The use amount of the compound [XI] to be used in the present reaction may be appropriately selected usually from the range of 1 to 100 mol per 1 mol of the compound [X], and is preferably 1 to 20 mol.
[0229] When a base is used in the present reaction, examples of the base that can be used include inorganic bases including: hydroxides of alkali metal such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; hydroxides of alkaline earth metal such as calcium hydroxide and magnesium hydroxide; carbonates of alkali metal such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate; bicarbonates of alkali metal such as sodium bicarbonate and potassium bicarbonate, fluorides of alkali metal such as sodium fluoride and potassium fluoride, or tripotassium phosphate; metal hydrides including: lithium hydride, sodium hydride and potassium hydride; metal salts of alcohol including: sodium methoxide, sodium ethoxide and potassium tert-butoxide; and alkyl lithiums such as methyllithium, butyllithium and phenyllithium; and organic bases including: triethylamine, tributylamine, diisopropylethylamine, N,N-dimethylaniline, pyridine, 2,6-lutidine, 4-N,N-dimethylaminopyridine and 1,8-diazabicyclo[5.4.0]-7-undecene. The use amount of the base may be appropriately selected from the range of 0 to 100 mol per 1 mol of the compound [X] or the compound [XII], and is preferably 0.1 to 20 mol.
[0230] The reaction can be carried out in the presence of a catalyst, if necessary. The catalyst contains a metal or a metal salt and a compound as a ligand. Such a catalyst may be prepared in a reaction system (in situ) from a compound as a ligand with a metal or a metal salt described later, or may be prepared in advance outside the reaction system and then introduced into the reaction system. The catalyst may contain components other than the metal, the metal salt and the compound as a ligand. Examples of the metal or the metal salt include copper compounds such as metal copper, copper(I) acetate, copper(II) acetate, copper(I) oxide, copper(II) oxide, copper(I) chloride, copper(II) chloride, copper(I) bromide, copper(II) bromide, copper(I) iodide, bis(acetylacetonato)copper(II); and palladium compounds such as palladium-carbon, palladium chloride, palladium nitrate, palladium acetate, bis(triphenylphosphine)palladium dichloride, and tetrakis(triphenylphosphine)palladium. Examples of the ligand include ethylenediamine, N,N-dimethylethylenediamine, N,N‘-dimethylethylenediamine, tetramethylethylenediamine, 2,2'-bipyridine, 1,10-phenanthroline, neocuproine, 3,4,7,8-tetramethyl-1,10-phenanthroline, 2,9-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, triphenylphosphine, tri-tert-buthylphosphine, 1,1'- bis(diphenylphosphino)ferrocene, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, and 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, and salts thereof. In the combination of the metal or the metal salt and the ligand, the compound as the ligand may be appropriately selected from the range of 0.1 to 10 mol per 1 mol of the metal or the metal salt, and is preferably 1 to 4 mol. The use amount of the catalyst may be appropriately selected from the range of 0.001 to 10 mol as a metal or a metal salt per 1 mol of the compound [X] or the compound [XII], and is preferably 0.01 to 5 mol.
[0231] Examples of the solvent that can be used in the present reaction include ethers such as diethyl ether, methyl tert-butyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1,4-dioxane, monoglyme, and diglyme; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, and chlorobenzene; halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, and 1,3-dimethyl-2-imidazolidinone; alcohols such as methanol, ethanol, 2-propanol, tert-butyl alcohol and methyl cellosolve; esters such as ethyl acetate, isopropyl acetate, butyl acetate and ethyl propionate; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile and propionitrile; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and heptane; pyridines such as pyridine, picoline, and lutidine; tertiary amines such as triethylamine and tributylamine; water; and a mixed solvent thereof. The use amount of the solvent is 0.1 to 1000 liters, preferably 0.2 to 100 liters, per 1 mol of the compound [X] or the compound [XII].
[0232] The reaction temperature of the present reaction may be selected from the range of any temperature from -78°C to a reflux temperature in the reaction system, and is preferably in the range of 0°C to 180°C.
[0233] The reaction time of the present reaction varies depending on the reaction temperature, the reaction substrate, the reaction amount, and the like, but it is usually 10 minutes to 72 hours.
[0234] After completion of the reaction, the compound [I-1] can be isolated by performing operations such as pouring the reaction mixture into water and then collecting the precipitated solids by filtration or extracting them with an organic solvent followed by concentration or the like. The isolated compound [I-1] can be further purified by column chromatography, recrystallization, distillation, or the like, if necessary.
[0235] <Production Method 6> A compound represented by general formula [I-2] among the present compounds can be produced in accordance with the following method, for example.
[0236] [Chem. 9]
[0237] (wherein X, R1, R2, R3, A3, A4, A5, A6 and A7 are as defined above.)
[0238] That is, the compound represented by the general formula [I-2] (compound [I-2]) can be produced by reacting the compound represented by general formula [XIII] (compound [XIII]) with a compound represented by general formula [XIV] (compound [XIV]) in an appropriate solvent in the presence or absence of an appropriate base to obtain a compound represented by the general formula [XV], and then subjecting the compound to cyclization reaction in an appropriate solvent in the presence or absence of an appropriate base.
[0239] The use amount of the compound [XIV] to be used in the present reaction may be appropriately selected usually from the range of 1 to 100 mol per 1 mol of the compound [XIII], and is preferably 1 to 20 mol.
[0240] When a base is used in the present reaction, examples of the base that can be used include inorganic bases including: hydroxides of alkali metal such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; hydroxides of alkaline earth metal such as calcium hydroxide and magnesium hydroxide; carbonates of alkali metal such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate; bicarbonates of alkali metal such as sodium bicarbonate and potassium bicarbonate, fluorides of alkali metal such as sodium fluoride and potassium fluoride, or tripotassium phosphate; metal hydrides including: lithium hydride, sodium hydride and potassium hydride; metal salts of alcohol including: sodium methoxide, sodium ethoxide and potassium tert-butoxide; and alkyl lithiums such as methyllithium, butyllithium and phenyllithium; and organic bases including: triethylamine, tributylamine, diisopropylethylamine, N,N-dimethylaniline, pyridine, 2,6-lutidine, 4-N,N-dimethylaminopyridine and 1,8-diazabicyclo[5.4.0]-7-undecene. The use amount of the base may be appropriately selected from the range of 0 to 100 mol per 1 mol of the compound [XIII] or compound [XV], and is preferably 0.1 to 20 mol.
[0241] The reaction can be carried out in the presence of a catalyst, if necessary. The catalyst contains a metal or a metal salt and a compound as a ligand. Such a catalyst may be prepared in a reaction system (in situ) from a compound as a ligand with a metal or a metal salt described later, or may be prepared in advance outside the reaction system and then introduced into the reaction system. The catalyst may contain components other than the metal, the metal salt and the compound as a ligand. Examples of the metal or the metal salt include copper compounds such as metal copper, copper(I) acetate, copper(II) acetate, copper(I) oxide, copper(II) oxide, copper(I) chloride, copper(II) chloride, copper(I) bromide, copper(II) bromide, copper(I) iodide, bis(acetylacetonato)copper(II); and palladium compounds such as palladium-carbon, palladium chloride, palladium nitrate, palladium acetate, bis(triphenylphosphine)palladium dichloride, and tetrakis(triphenylphosphine)palladium. Examples of the ligand include ethylenediamine, N,N-dimethylethylenediamine, N,N‘-dimethylethylenediamine, tetramethylethylenediamine, 2,2'-bipyridine, 1,10-phenanthroline, neocuproine, 3,4,7,8-tetramethyl-1,10-phenanthroline, 2,9-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, triphenylphosphine, tri-tert-buthylphosphine, 1,1'-bis(diphenylphosphino)ferrocene, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, and 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, and salts thereof. In the combination of the metal or the metal salt and the ligand, the compound as the ligand may be appropriately selected from the range of 0.1 to 10 mol per 1 mol of the metal or the metal salt, and is preferably 1 to 4 mol. The use amount of the catalyst may be appropriately selected from the range of 0.001 to 10 mol as a metal or a metal salt per 1 mol of the compound [XIII] or the compound [XV], and is preferably 0.01 to 5 mol.
[0242] Examples of the solvent that can be used in the present reaction include ethers such as diethyl ether, methyl tert-butyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1,4-dioxane, monoglyme, and diglyme; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, and chlorobenzene; halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, and 1,3-dimethyl-2-imidazolidinone; alcohols such as methanol, ethanol, 2-propanol, tert-butyl alcohol and methyl cellosolve; esters such as ethyl acetate, isopropyl acetate, butyl acetate and ethyl propionate; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile and propionitrile; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and heptane; pyridines such as pyridine, picoline, and lutidine; tertiary amines such as triethylamine and tributylamine; water; and a mixed solvent thereof. The use amount of the solvent is 0.1 to 1000 liters, preferably 0.2 to 100 liters, per 1 mol of the compound [XIII] or the compound [XV].
[0243] The reaction temperature of the present reaction may be selected from the range of any temperature from -78°C to a reflux temperature in the reaction system, and is preferably in the range of 0°C to 180°C.
[0244] The reaction time of the present reaction varies depending on the reaction temperature, the reaction substrate, the reaction amount, and the like, but it is usually 10 minutes to 72 hours.
[0245] After completion of the reaction, the compound [I-2] can be isolated by performing operations such as pouring the reaction mixture into water and then collecting the precipitated solids by filtration or extracting them with an organic solvent followed by concentration or the like. The isolated compound [I-2] can be further purified by column chromatography, recrystallization, distillation, or the like, if necessary.
[0246] <Production Method 7> A compound represented by general formula [I-3] among the present compounds can be produced in accordance with the following method, for example.
[0247] [Chem. 10]
[0248] (wherein R2a represents a C1-C6 alkyl group (the C1-C6 alkyl group may be substituted with one or more substituents selected from R7 substituents), a C2-C6 alkenyl group (the C2-C6 alkenyl group may be substituted with one or more substituents selected from R7 substituents), a C2-C6 alkynyl group (the C2-C6 alkynyl group may be substituted with one or more substituents selected from R7 substituents), a C3-C6 cycloalkyl group (the C3-C6 cycloalkyl group may be substituted with one or more substituents selected from R7 substituents), a heterocyclyl group (the heterocyclyl group may be substituted with one or more substituents selected from R5 substituents), a C6-C12 aryl group (the C6-C12 aryl group may be substituted with one or more substituents selected from R5 substituents), a heteroaryl group (the heteroaryl group may be substituted with one or more substituents selected from R5 substituents and a C7-C14 aralkyl group (the C7-C14 aralkyl group may be substituted with one or more substituents selected from R5 substituents) of R2, Y represents NH, O and S, and Y', R1, R3, A1, A3, A4, A5, A6 and A7 are as defined above.)
[0249] That is, the compound represented by general formula [I-3] (compound [I-3]) can be produced by reacting the compound represented by general formula [XVI] with a compound [XVII] or a compound [XVIII] in an appropriate solvent in the presence or absence of an appropriate base.
[0250] The use amount of the compound [XVII] or the compound [XVIII] to be used in the present reaction may be appropriately selected usually from the range of 1 to 100 mol per 1 mol of the compound [XVI], and is preferably 1 to 20 mol.
[0251] When a base is used in the present reaction, examples of the base that can be used include inorganic bases including: hydroxides of alkali metal such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; hydroxides of alkaline earth metal such as calcium hydroxide and magnesium hydroxide; carbonates of alkali metal such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate; bicarbonates of alkali metal such as sodium bicarbonate and potassium bicarbonate, fluorides of alkali metal such as sodium fluoride and potassium fluoride, or tripotassium phosphate; metal hydrides including: lithium hydride, sodium hydride and potassium hydride; metal salts of alcohol including: sodium methoxide, sodium ethoxide and potassium tert-butoxide; and alkyl lithiums such as methyllithium, butyllithium and phenyllithium; and organic bases including: triethylamine, tributylamine, diisopropylethylamine, N,N-dimethylaniline, pyridine, 2,6-lutidine, 4-N,N-dimethylaminopyridine and 1,8-diazabicyclo[5.4.0]-7-undecene. The use amount of the base may be appropriately selected from the range of 0 to 100 mol per 1 mol of the compound [XVI], and is preferably 0.1 to 20 mol.
[0252] The reaction can be carried out in the presence of a catalyst, if necessary. The catalyst contains a metal or a metal salt and a compound as a ligand. Such a catalyst may be prepared in a reaction system (in situ) from a compound as a ligand with a metal or a metal salt described later, or may be prepared in advance outside the reaction system and then introduced into the reaction system. The catalyst may contain components other than the metal, the metal salt and the compound as a ligand. Examples of the metal or the metal salt include copper compounds such as metal copper, copper(I) acetate, copper(II) acetate, copper(I) oxide, copper(II) oxide, copper(I) chloride, copper(II) chloride, copper(I) bromide, copper(II) bromide, copper(I) iodide, bis(acetylacetonato)copper(II); and palladium compounds such as palladium-carbon, palladium chloride, palladium nitrate, palladium acetate, bis(triphenylphosphine)palladium dichloride, and tetrakis(triphenylphosphine)palladium. Examples of the ligand include ethylenediamine, N,N-dimethylethylenediamine, N,N‘-dimethylethylenediamine, tetramethylethylenediamine, 2,2'-bipyridine, 1,10-phenanthroline, neocuproine, 3,4,7,8-tetramethyl-1,10-phenanthroline, 2,9-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, triphenylphosphine, tri-tert-buthylphosphine, 1,1'- bis(diphenylphosphino)ferrocene, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, and 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, and salts thereof. In the combination of the metal or the metal salt and the ligand, the compound as the ligand may be appropriately selected from the range of 0.1 to 10 mol per 1 mol of the metal or the metal salt, and is preferably 1 to 4 mol. The use amount of the catalyst may be appropriately selected from the range of 0.001 to 10 mol as a metal or a metal salt per 1 mol of the compound [XVI], and is preferably 0.01 to 5 mol.
[0253] Examples of the solvent that can be used in the present reaction include ethers such as diethyl ether, methyl tert-butyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1,4-dioxane, monoglyme, and diglyme; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, and chlorobenzene; halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, and 1,3-dimethyl-2-imidazolidinone; alcohols such as methanol, ethanol, 2-propanol, tert-butyl alcohol and methyl cellosolve; esters such as ethyl acetate, isopropyl acetate, butyl acetate and ethyl propionate; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile and propionitrile; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and heptane; pyridines such as pyridine, picoline, and lutidine; tertiary amines such as triethylamine and tributylamine; water; and a mixed solvent thereof. The use amount of the solvent is 0.1 to 1000 liters, preferably 0.2 to 100 liters, per 1 mol of the compound [XVI].
[0254] The reaction temperature of the present reaction may be selected from the range of any temperature from -78°C to a reflux temperature in the reaction system, and is preferably in the range of 0°C to 180°C.
[0255] The reaction time of the present reaction varies depending on the reaction temperature, the reaction substrate, the reaction amount, and the like, but it is usually 10 minutes to 72 hours.
[0256] After completion of the reaction, the compound [I-3] can be isolated by performing operations such as pouring the reaction mixture into water and then collecting the precipitated solids by filtration or extracting them with an organic solvent followed by concentration or the like. The isolated compound [I-3] can be further purified by column chromatography, recrystallization, distillation, or the like, if necessary.
[0257] <Production Method 8> A compound represented by general formula [I-4] among the present compounds can be produced in accordance with the following method, for example.
[0258] [Chem. 11]
[0259] (wherein R2a, X, Y, R1, R3, A1, A3, A4, A5, A6 and A7 are as defined above.)
[0260] That is, the compound represented by general formula [I-4] (compound [I-4]) can be produced by reacting the compound represented by general formula [XIX] with a compound [XX] in an appropriate solvent in the presence or absence of an appropriate base.
[0261] The use amount of the compound [XX] to be used in the present reaction may be appropriately selected usually from the range of 1 to 100 mol per 1 mol of the compound [XIX], and is preferably 1 to 20 mol.
[0262] When a base is used in the present reaction, examples of the base that can be used include inorganic bases including: hydroxides of alkali metal such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; hydroxides of alkaline earth metal such as calcium hydroxide and magnesium hydroxide; carbonates of alkali metal such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate; bicarbonates of alkali metal such as sodium bicarbonate and potassium bicarbonate, fluorides of alkali metal such as sodium fluoride and potassium fluoride, or tripotassium phosphate; metal hydrides including: lithium hydride, sodium hydride and potassium hydride; metal salts of alcohol including: sodium methoxide, sodium ethoxide and potassium tert-butoxide; and alkyl lithiums such as methyllithium, butyllithium and phenyllithium; and organic bases including: triethylamine, tributylamine, diisopropylethylamine, N,N-dimethylaniline, pyridine, 2,6-lutidine, 4-N,N-dimethylaminopyridine and 1,8-diazabicyclo[5.4.0]-7-undecene. The use amount of the base may be appropriately selected from the range of 0 to 100 mol per 1 mol of the compound [XIX], and is preferably 0.1 to 20 mol.
[0263] The reaction can be carried out in the presence of a catalyst, if necessary. The catalyst contains a metal or a metal salt and a compound as a ligand. Such a catalyst may be prepared in a reaction system (in situ) from a compound as a ligand with a metal or a metal salt described later, or may be prepared in advance outside the reaction system and then introduced into the reaction system. The catalyst may contain components other than the metal, the metal salt and the compound as a ligand. Examples of the metal or the metal salt include copper compounds such as metal copper, copper(I) acetate, copper(II) acetate, copper(I) oxide, copper(II) oxide, copper(I) chloride, copper(II) chloride, copper(I) bromide, copper(II) bromide, copper(I) iodide, bis(acetylacetonato)copper(II); and palladium compounds such as palladium-carbon, palladium chloride, palladium nitrate, palladium acetate, bis(triphenylphosphine)palladium dichloride, and tetrakis(triphenylphosphine)palladium. Examples of the ligand include ethylenediamine, N,N-dimethylethylenediamine, N,N‘-dimethylethylenediamine, tetramethylethylenediamine, 2,2'-bipyridine, 1,10-phenanthroline, neocuproine, 3,4,7,8-tetramethyl-1,10-phenanthroline, 2,9-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, triphenylphosphine, tri-tert-buthylphosphine, 1,1'-bis(diphenylphosphino)ferrocene, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, and 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, and salts thereof. In the combination of the metal or the metal salt and the ligand, the compound as the ligand may be appropriately selected from the range of 0.1 to 10 mol per 1 mol of the metal or the metal salt, and is preferably 1 to 4 mol. The use amount of the catalyst may be appropriately selected from the range of 0.001 to 10 mol as a metal or a metal salt per 1 mol of the compound [XIX], and is preferably 0.01 to 5 mol.
[0264] Examples of the solvent that can be used in the present reaction include ethers such as diethyl ether, methyl tert-butyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1,4-dioxane, monoglyme, and diglyme; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, and chlorobenzene; halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, and 1,3-dimethyl-2-imidazolidinone; alcohols such as methanol, ethanol, 2-propanol, tert-butyl alcohol and methyl cellosolve; esters such as ethyl acetate, isopropyl acetate, butyl acetate and ethyl propionate; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile and propionitrile; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and heptane; pyridines such as pyridine, picoline, and lutidine; tertiary amines such as triethylamine and tributylamine; water; and a mixed solvent thereof. The use amount of the solvent is 0.1 to 1000 liters, preferably 0.2 to 100 liters, per 1 mol of the compound [XIX].
[0265] The reaction temperature of the present reaction may be selected from the range of any temperature from -78°C to a reflux temperature in the reaction system, and is preferably in the range of 0°C to 180°C.
[0266] The reaction time of the present reaction varies depending on the reaction temperature, the reaction substrate, the reaction amount, and the like, but it is usually 10 minutes to 72 hours.
[0267] After completion of the reaction, the compound [I-4] can be isolated by performing operations such as pouring the reaction mixture into water and then collecting the precipitated solids by filtration or extracting them with an organic solvent followed by concentration or the like. The isolated compound [I-4] can be further purified by column chromatography, recrystallization, distillation, or the like, if necessary.
[0268] <Production Method 9> A compound represented by general formula [I-5] among the present compounds can be produced in accordance with the following method, for example.
[0269] [Chem. 12]
[0270] (wherein R2a, X, Y, R1, R3, A1, A3, A4, A5, A6 and A7 are as defined above.)
[0271] That is, the compound represented by general formula [I-5] (compound [I-5]) can be produced by reacting the compound represented by general formula [XXI] (compound [XXI]) with a compound [XXII] in an appropriate solvent in the presence or absence of an appropriate base.
[0272] The use amount of the compound [XXII] to be used in the present reaction may be appropriately selected usually from the range of 1 to 100 mol per 1 mol of the compound [XXI], and is preferably 1 to 20 mol.
[0273] When a base is used in the present reaction, examples of the base that can be used include inorganic bases including: hydroxides of alkali metal such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; hydroxides of alkaline earth metal such as calcium hydroxide and magnesium hydroxide; carbonates of alkali metal such as lithium carbonate, sodium carbonate, potassium carbonate and cesium carbonate; bicarbonates of alkali metal such as sodium bicarbonate and potassium bicarbonate, fluorides of alkali metal such as sodium fluoride and potassium fluoride, or tripotassium phosphate; metal hydrides including: lithium hydride, sodium hydride and potassium hydride; metal salts of alcohol including: sodium methoxide, sodium ethoxide and potassium tert-butoxide; and alkyl lithiums such as methyllithium, butyllithium and phenyllithium; and organic bases including: triethylamine, tributylamine, diisopropylethylamine, N,N-dimethylaniline, pyridine, 2,6-lutidine, 4-N,N-dimethylaminopyridine and 1,8-diazabicyclo[5.4.0]-7-undecene. The use amount of the base may be appropriately selected from the range of 0 to 100 mol per 1 mol of the compound [XXI], and is preferably 0.1 to 20 mol.
[0274] The reaction can be carried out in the presence of a catalyst, if necessary. The catalyst contains a metal or a metal salt and a compound as a ligand. Such a catalyst may be prepared in a reaction system (in situ) from a compound as a ligand with a metal or a metal salt described later, or may be prepared in advance outside the reaction system and then introduced into the reaction system. The catalyst may contain components other than the metal, the metal salt and the compound as a ligand. Examples of the metal or the metal salt include copper compounds such as metal copper, copper(I) acetate, copper(II) acetate, copper(I) oxide, copper(II) oxide, copper(I) chloride, copper(II) chloride, copper(I) bromide, copper(II) bromide, copper(I) iodide, bis(acetylacetonato)copper(II); and palladium compounds such as palladium-carbon, palladium chloride, palladium nitrate, palladium acetate, bis(triphenylphosphine)palladium dichloride, and tetrakis(triphenylphosphine)palladium. Examples of the ligand include ethylenediamine, N,N-dimethylethylenediamine, N,N‘-dimethylethylenediamine, tetramethylethylenediamine, 2,2'-bipyridine, 1,10-phenanthroline, neocuproine, 3,4,7,8-tetramethyl-1,10-phenanthroline, 2,9-diphenyl-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, triphenylphosphine, tri-tert-buthylphosphine, 1,1'-bis(diphenylphosphino)ferrocene, 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, and 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, and salts thereof. In the combination of the metal or the metal salt and the ligand, the compound as the ligand may be appropriately selected from the range of 0.1 to 10 mol per 1 mol of the metal or the metal salt, and is preferably 1 to 4 mol. The use amount of the catalyst may be appropriately selected from the range of 0.001 to 10 mol as a metal or a metal salt per 1 mol of the compound [XXI], and is preferably 0.01 to 5 mol.
[0275] Examples of the solvent that can be used in the present reaction include ethers such as diethyl ether, methyl tert-butyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1,4-dioxane, monoglyme, and diglyme; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, and chlorobenzene; halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane; aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, and 1,3-dimethyl-2-imidazolidinone; alcohols such as methanol, ethanol, 2-propanol, tert-butyl alcohol and methyl cellosolve; esters such as ethyl acetate, isopropyl acetate, butyl acetate and ethyl propionate; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile and propionitrile; aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and heptane; pyridines such as pyridine, picoline, and lutidine; tertiary amines such as triethylamine and tributylamine; water; and a mixed solvent thereof. The use amount of the solvent is 0.1 to 1000 liters, preferably 0.2 to 100 liters, per 1 mol of the compound [XXI].
[0276] The reaction temperature of the present reaction may be selected from the range of any temperature from -78°C to a reflux temperature in the reaction system, and is preferably in the range of 0°C to 180°C.
[0277] The reaction time of the present reaction varies depending on the reaction temperature, the reaction substrate, the reaction amount, and the like, but it is usually 10 minutes to 72 hours.
[0278] After completion of the reaction, the compound [I-5] can be isolated by performing operations such as pouring the reaction mixture into water and then collecting the precipitated solids by filtration or extracting them with an organic solvent followed by concentration or the like. The isolated compound [I-5] can be further purified by column chromatography, recrystallization, distillation, or the like, if necessary.
[0279] (Production Intermediate) The compound [II], the compound [IV], the compound [VI], the compound [IX], the compound [X], the compound [XII], the compound [XIII], the compound [XV], the compound [XVI], the compound [XIX], and the compound [XXI] of the present production methods are compounds that are useful as intermediates in the production of an azolyloxy heterocyclic compound represented by the general formula [I] or a salt thereof of the present invention.
[0280] In particular, the compound which is a production intermediate of the compound (the azolyloxy heterocyclic compound) represented by the general formula [I] or the salt thereof is represented by the general formula [VI],
[0281] [Chem. 13]
[0282] wherein, A1 represents an oxygen atom or a sulfur atom, A4, A5, A6 and A7 each independently represent a nitrogen atom, C-H, or C-R4, R1 represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C6 cycloalkyl group, or a C3-C6 halocycloalkyl group, R3 represents a hydrogen atom, a halogen atom, an azido group, a cyano group, a nitro group, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 halocycloalkyl group, a phenyl group, a pentahalosulfanyl group, or a C1-C6 alkoxycarbonyl group, R4 each independently represents a halogen atom, an azido group, a cyano group, a nitro group, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 haloalkyl group, a hydroxy group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a pentahalosulfanyl group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylthio group, a C1-C6 haloalkylsulfinyl group, a C1-C6 haloalkylsulfonyl group, a formyl group, a carboxyl group, an aminocarbonyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylcarbonyl group, an amino group, a mono (C1-C6 alkyl) amino group, or a di (C1-C6 alkyl) amino group.
[0283] In addition, the compound which is a production intermediate of the compound (the azolyloxy heterocyclic compound) represented by the general formula [I] or the salt thereof is represented by the general formula [IX],
[0284] [Chem. 14] R3
[0285] wherein, A3 represents an oxygen atom or a sulfur atom, A4, A5, A6 and A7 each independently represent a nitrogen atom, C-H, or C-R4, R1 represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C6 cycloalkyl group, or a C3-C6 halocycloalkyl group, R3 represents a hydrogen atom, a halogen atom, an azido group, a cyano group, a nitro group, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 halocycloalkyl group, a phenyl group, a pentahalosulfanyl group, or a C1-C6 alkoxycarbonyl group, R4 each independently represents a halogen atom, an azido group, a cyano group, a nitro group, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 haloalkyl group, a hydroxy group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a pentahalosulfanyl group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylthio 30 group, a C1-C6 haloalkylsulfinyl group, a C1-C6 haloalkylsulfonyl group, a formyl group, a carboxyl group, an aminocarbonyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylcarbonyl group, an amino group, a mono (C1-C6 alkyl) amino group, or a di (C1-C6 alkyl) amino group.
[0286] The compound which is a production intermediate of the compound represented by the general formula [I] or the salt thereof of the present invention is a compound that is useful as an intermediate in the production of the azolyloxy heterocyclic compound represented by the general formula [I] or the salt thereof of the present invention described above.
[0287] (Herbicide) The herbicide of the present invention contains an azolyloxy heterocyclic compound represented by the general formula [I] or a salt thereof of the present invention as an active ingredient. The herbicide of the present invention has excellent herbicidal effects, and some exhibit excellent selectivity between useful plants and weeds, and are useful as a pesticide composition on agricultural land, particularly as a herbicide. That is, the herbicide of the present invention has herbicidal effects on various weeds in a foliage treatment, a soil treatment, a seed dressing treatment, a soil incorporation treatment, a soil treatment before sowing, a soil treatment at the time of sowing, a soil treatment after sowing, a soil cover incorporation treatment at the time of sowing, and the like in a dry field where useful plants are cultured or a non-crop field.
[0288] The herbicide of the present invention can contain an additive component (such as a carrier) that is typically used in a pesticide formulation, as necessary.
[0289] (Additive Component) Examples of the additive component include a carrier such as a solid carrier or a liquid carrier, a surfactant, a binder, a tackifier, a thickener, a coloring agent, a spreader, a sticker, an antifreezing agent, an anticaking agent, a disintegrating agent, and a stabilizing agent, and besides the above, an antiseptic, a plant piece, or the like may be used as the additive component as needed. These additive components may be used alone, or two or more of them may be used in combination.
[0290] Hereinafter, the additive components described above will be described in detail.
[0291] Examples of the solid carrier include mineral carriers such as pyrophyllite clay, kaolin clay, silica clay, talc, diatomite, zeolite, bentonite, acid clay, activated clay, attapulgus clay, vermiculite, pearlite, pumice, white carbon (synthetic silicic acid, synthetic silicate, or the like), and titanium dioxide; vegetable carriers such as woody powder, corn haulm, walnut shell, fruit stone, chaff, sawdust, bran, soybean meal, powdered cellulose, starch, dextrin, and saccgarudes; inorganic salt carriers such as calcium carbonate, ammonium sulfate, sodium sulfate, and potassium chloride; and polymeric carriers such as polyethylene, polypropylene, polyvinyl chloride, polyvinyl acetate, ethylene-vinyl acetate copolymer, and urea-aldehyde resin.
[0292] Examples of the liquid carrier include monohydric alcohols such as methanol, ethanol, propanol, 2-propanol, butanol, and cyclohexanol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, and glycerin; polyhydric alcohol derivatives such as propylene glycol ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, and isophorone; ethers such as ethyl ether, 1,4-dioxane, cellosolve, dipropyl ether, and tetrahydrofuran; aliphatic hydrocarbons such as normal paraffin, naphthene, isoparaffin, kerosene, and mineral oil; aromatic hydrocarbons such as toluene, C9-C10 alkylbenzene, xylene, solvent naphtha, alkyl naphthalene, and high boiling point aromatic hydrocarbons; halogenated hydrocarbons such as 1,2-dichloroethane, chloroform, and carbon tetrachloride; esters such as ethyl acetate, diisopropyl phthalate, dibutyl phthalate, dioctyl phthalate, and dimethyl adipate; lactones such as -butyrolactone; amides such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; nitriles such as acetonitrile; sulfur compounds such as dimethyl sulfoxide; vegetable oils such as soybean oil, rapeseed oil, cottonseed oil, coconut oil, and castor oil; lower alkyl ester of fatty acid derived from the vegetable oils; and water.
[0293] Examples of the surfactants include non-ionic surfactants such as sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene resin acid ester, polyoxyethylene fatty acid diester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene dialkylphenyl ether, polyoxyethylene alkylphenyl ether formalin condensate, polyoxyethylene polyoxypropylene block polymer, alkylpolyoxyethylene polypropylene block polymer ether, polyoxyethylene alkyl amine, polyoxyethylene fatty acid amide, polyoxyethylene fatty acid bisphenyl ether, polyalkylene benzyl phenyl ether, polyoxyalkylene styryl phenyl ether, acetylene diol, polyoxyalkylene-added acetylene diol, polyoxyethylene ether silicone, ester silicone, fluorine surfactant, polyoxyethylene castor oil, and polyoxyethylene hardened castor oil; anionic surfactants such as alkyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene styryl phenyl ether sulfate, alkyl benzenesulfonate, lignin sulfonate, alkyl sulfosuccinate, naphthalene sulfonate, alkylnaphthalene sulfonate, salt of formalin condensate of naphthalene sulfonate, salt of formalin condensate of alkylnaphthalene sulfonate, fatty acid salt, polycarboxylate, N-methyl-fatty acid sarcosinate, resinate, polyoxyethylene alkyl ether phosphate, and polyoxyethylene alkyl phenyl ether phosphate; cationic surfactants such as alkyl amine salts such as lauryl amine hydrochloride, stearyl amine hydrochloride, oleyl amine hydrochloride, stearyl amine acetate, stearyl aminopropylamine acetate, alkyl trimethyl ammonium chloride, and alkyl dimethylbenzarconium chloride; and amphoteric surfactants including a betaine type such as dialkyl diaminoethyl betaine and alkyl dimethylbenzyl betaine, and an amino acid type such as dialkylaminoethyl glycine and alkyl dimethylbenzyl glycine.
[0294] Examples of the binder and the tackifier include carboxymethylcellulose or a salt thereof, dextrin, soluble starch, xanthan gum, guar gum, sucrose, polyvinylpyrrolidone, gum arabic, polyvinyl alcohol, polyvinyl acetate, sodium polyacrylate, polyethylene glycol, polyethylene oxide, and naturally-occurring phospholipid (for example, cephalin acid, lecithin, or the like).
[0295] Examples of the thickener include water-soluble polymers such as xanthan gum, guar gum, carboxymethylcellulose, polyvinylpyrrolidone, carboxyvinyl polymer, acrylic polymer, starch derivative, and polysaccharide; inorganic fine powders such as high purity bentonite and white carbon; and organic fine powders such as organic bentonite.
[0296] Examples of the coloring agent include inorganic pigments such as iron oxide, titanium oxide, and Prussian blue; and organic dyes such as alizarin dye, azo dye, and metal phthalocyanine dye.
[0297] Examples of the spreader include a silicone-based surfactant, cellulose powder, dextrin, processed starch, a polyaminocarboxylic acid chelate compound, crosslinked polyvinylpyrrolidone, a maleic acid / styrene copolymer, a methacrylic acid copolymer, a half ester of a polyhydric alcohol polymer and a dicarboxylic acid anhydride, a water-soluble salt of polystyrenesulfonic acid, polyoxyethylene alkanediols, polyoxyethylene alkynediols, and alkynediols.
[0298] Examples of the sticker include various surfactants such as sodium dialkyl sulfosuccinate, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, and polyoxyethylene fatty acid ester; paraffin, terpene, polyamide resin, polyacrylate, polyoxyethylene, wax, polyvinylalkyl ether, an alkylphenol formalin condensate, and a synthetic resin emulsion
[0299] Examples of the antifreezing agent include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin.
[0300] Examples of the anticaking agent include polysaccharides such as starch, alginic acid, mannose, and galactose; polyvinylpyrrolidone, white carbon, ester gum, and a petroleum resin.
[0301] Examples of the disintegrating agent include sodium tripolyphosphate, sodium hexametaphosphate, a metal stearate, cellulose powder, dextrin, a copolymer of methacrylic acid ester, polyvinylpyrrolidone, a polyaminocarboxylic chelate compound, a styrene sulfonate-isobutylene-maleic anhydride copolymer, and a starch-polyacrylonitrile graft copolymer.
[0302] Examples of the stabilizing agent include desiccants such as zeolite, calcined lime, or magnesium oxide; antioxidants based on phenol, amine, sulfur, phosphoric acid, or the like; and ultraviolet absorbers based on salicylic acid or benzophenone.
[0303] Examples of the antiseptic include potassium sorbate and 1,2- benzthiazolin-3-one.
[0304] Examples of the plant piece include sawdust, coconut shellflower, corncob, and tobacco stem.
[0305] On the other hand, in the herbicide of the present invention, when the above-described additive component is contained, the content thereof is typically selected from the range of 5 to 95 , preferably the range of 20 to 90 in the case of a carrier such as a solid carrier or a liquid carrier, typically selected from the range of 0.1 to 30 , preferably the range of 0.5 to 10 in the case of a surfactant, and selected from the range of 0.1 to 30 , preferably the range of 0.5 to 10 in the case of other additive, on the mass basis.
[0306] The herbicide of the present invention is used while it is prepared into any formulation including dust, powders and granules, granules, wettable powders, watersoluble powders, water-dispersible granules, tablets, Jumbo formulations, emulsifiable concentrates, oils, solutions, suspension concentrates, oily suspensions, emulsions, microemulsions, suspoemulsions, ultra-low volume spraying agents, microcapsules, Mametsubu (registered trademark) formulations, smoking agents, aerosols, baiting agents, pastes, foaming agents, carbon dioxide gas formulations, paints, wood protective paints, and sealing agents.
[0307] In actual use of the formulation, the formulation can be used as it is or after dilution with a diluent such as water to a predetermined concentration. Application of various formulations containing the present compound or dilution products thereof can be conducted by a method ordinarily used, such as dispersion (for example, spraying, misting, atomizing, powder dispersion, granule dispersion, on-water-surface dispersion, or inbox dispersion), in-soil application (for example, mixing or drenching), on-surface application (for example, coating, powder coating, or covering), seed treatment (for example, smearing or dressing treatment), immersion, poison bait, or smoking.
[0308] The herbicide of the present invention can act on useful plants, on a place where useful plants are to be grown or where they are growing, or on a non-crop land, simultaneously or dividedly, thereby controlling the growth of plants that are not desirable for useful plants or plants that are not desirable in terms of land management.
[0309] Since the herbicide of the present invention contains an azolyloxy heterocyclic compound represented by the general formula [I] or the salt thereof of the present invention as an active ingredient, it has herbicidal activity against weeds growing in a dry field, a paddy field, an orchard, a lawn, a non-crop land, a greenhouse, a seedling raising facility, or a plant factory where a useful plant having agricultural, horticultural, and industrial uses is cultured.
[0310] The useful plant may be a plant transformed in culturing by a breeding method or a gene recombination technique. The transformed plant is a plant to which a desired property is imparted by the breeding method or the gene recombination technique described later.
[0311] (Method of Using Herbicide) In the using method of herbicide according to the present invention, the herbicide of the present invention is used for controlling weeds against a useful plant having agricultural, horticultural and industrial uses. That is, the herbicide of the present invention is used for controlling weeds growing in a place where the useful plant is cultured, and is applied to agricultural lands such as a dry field and a paddy field by methods such as foliar spraying. The "useful plant" and the "weeds" are the same as those described below.
[0312] (Pesticide Composition) The pesticide composition of the present invention contains an azolyloxy heterocyclic compound of the present invention or a salt thereof as an active ingredient. The pesticide composition can be used by foliar spraying, in-soil application, on-watersurface dispersion, or the like. The pesticide composition (in particular, the herbicide) of the present invention is used in soils, in particular, the agricultural land (cultivation land) such as a dry field or a paddy field for cultivating useful plants.
[0313] The blending ratio of the active ingredient in the pesticide composition of the present invention is appropriately selected as necessary. In the case of the dust, the granules, or the like, the blending ratio of the active ingredient may be appropriately selected from the range of 0.01 to 10 (by weight), preferably 0.05 to 5 (by weight). In the case of the emulsifiable concentrates, the wettable powders, or the like, the blending ratio of the active ingredient may be appropriately selected from the range of 1 to 50 (by weight), preferably 5 to 30 (by weight). In the case of the suspension concentrates or the like, the blending ratio of the active ingredient may be appropriately selected from the range of 1 to 40 (by weight), preferably 5 to 30 (by weight).
[0314] The application amount of the pesticide composition of the present invention varies depending on the type of compound to be used, target weeds, weeds-emergence tendency, environmental conditions, formulations to be used, and the like. For example, in a case where the pesticide composition of the present invention is used as it is as a herbicide such as dust or granules, the amount of active ingredient may be appropriately selected from the range of 1g to 50kg, preferably 10g to 10kg per hectare. In addition, in the case of use in a liquid state, such as emulsifiable concentrates, wettable powders, suspension concentrates, and the like, the amount of active ingredient may be appropriately selected from the range of 0.1 to 50,000ppm, preferably the range of 10 to 10,000ppm
[0315] In addition, the pesticide composition of the present invention may be, formulated, mixed or used in combination with at least one other pesticide active ingredient such as another disease controller component, an insecticide component, a miticide component, a nematicide component, a synergist component, an attractant component, a repellent component, a herbicide component, a chemical safener component, a microbial pesticide component, a plant growth regulator component, a fertilizer, and a soil conditioner, in addition to the present compound, depending on the intended use.
[0316] In a case where the pesticide composition of the present invention is mixed or used in combination with other pesticide active ingredient or a fertilizer, a formulation of each single component can also be used in combination at the time of application. Furthermore, each of the formulations of each single component may be sequentially used or may be applied at intervals of days. When the formulation is used at intervals of days, the formulations may be used at an interval of, for example, about 1 day to 40 days, although the intervals of days may vary depending on another component to be used.
[0317] When the pesticide composition of the present invention in which at least one compound selected from an azolyloxy heterocyclic compound represented by the general formula [I] and a salt thereof and at least one or more selected from other agrochemical active ingredients are mixed is applied, usually the mixing ratio (mass ratio) thereof may be 100:1 to 1:100, preferably 20:1 to 1:20, and particularly 10:1 to 1:10.
[0318] The blending ratio ( by mass) of the active ingredient in the pesticide composition of the present invention is appropriately selected as necessary. For example, in the case of dust, powders and granules, fine granules, and the like, the blending ratio may be appropriately selected from the range of 0.01 to 20 , preferably 0.05 to 10 . In the case of granules or the like, the blending ratio may be appropriately selected from the range of 0.1 to 30 , preferably 0.5 to 20 . In the case of wettable powders, water-dispersible granules, or the like, the blending ratio may be appropriately selected from the range of 1 to 70 , preferably 5 to 50 . In the case of water-soluble powders, solutions, or the like, the blending ratio may be appropriately selected from the range of 1 to 95 , preferably 10 to 80 . In the case of emulsifiable concentrates or the like, the blending ratio may be appropriately selected from the range of 5 to 90 , preferably 10 to 80 . In the case of oils or the like, the blending ratio may be appropriately selected from the range of 1 to 50 , preferably 5 to 30 . In the case of suspension concentrates or the like, the blending ratio may be appropriately selected from the range of 5 to 60 , preferably 10 to 50 . In the case of emulsions, microemulsions, suspoemulsions, or the like, the blending ratio may be appropriately selected from the range of 5 to 70 , preferably 10 to 60 . In the case of tablets, baiting agents, pastes, or the like, the blending ratio may be appropriately selected from the range of 1 to 80 , preferably 5 to 50 . In the case of smoking agents, the blending ratio may be appropriately selected from the range of 0.1 to 50 , preferably 1 to 30 . In the case of aerosols or the like, the blending ratio may be appropriately selected from the range of 0.05 to 20 , preferably 0.1 to 10 .
[0319] These formulations are sprayed after dilution in an appropriate concentration, or applied directly.
[0320] When the pesticide composition of the present invention is used after dilution with a diluent, the concentrations of the active ingredient is generally 0.1 to 5000ppm. When the formulation is used as it is, the application amount thereof per unit area is 0.1 to 5000g per hectare in terms of the active ingredient compound; however, the application amount is not limited thereto.
[0321] It is needless to say that the pesticide composition of the present invention is sufficiently effective when the present compound is used alone as an active ingredient. However, the pesticide composition may be mixed and used in combination, as necessary, with other pesticides such as an insecticide, a miticide, a nematicide, a synergist, a bactericide, an antiviral agent, an attractant, a herbicide, and a plant growth regulator. In addition, the pesticide composition can be mixed and used in combination with a sticker, another agricultural material, a fertilizer, or the like. In this case, a more excellent effect can be exhibited.
[0322] Next, examples of known herbicide compounds, herbicide active ingredients, and plant growth regulator compounds that may be mixed or used in combination are shown below, but the present invention is not limited thereto.
[0323] Herbicide compounds or herbicide active ingredients: Ioxynil (including a salt with lithium, sodium or the like, or esters of octanoic acid or the like), aclonifen, acrolein, azafenidin, acifluorphen (including a salt with sodium or the like), azimsulfuron, asulam, acetochlor, atrazine, anilofos, amicarbazone, amidosulfuron, amitrole, aminocyclopyrachlor, aminopyralid, amiprophos-methyl, ametryn, Araujia Mosaic Virus, alachlor, Alternaria destruens, alloxydim (including a salt with sodium or the like), ancymidol, icafolin-methyl, isouron, isoxachlortole, isoxafenacil, isoxaflutole, isoxaben, Isodecylalkoholethoxylate, isoproturon, iptriazopyrid, ipfencarbazone, imazaquin, imazapic (including a salt with amine or the like), imazapyr (including a salt of isopropylamine or the like), imazamethabenz, imazamethabenz-methyl, imazamox, imazethapyr, imazosulfuron, indaziflam, indanofan, indolauxipyr-cyanomethyl, eglinazine-ethyl, esprocarb, ethametsulfuron-methyl, ethalfluralin, ethidimuron, ethoxysulfuron, ethoxyfen, ethoxyfen-ethyl, ethofumesate, etobenzanid, epyrifenacil, endothal-disodium, oxadiazon, oxadiargyl, oxaziclomefone, oxasulfuron, oxyfluorfen, oryzalin, Obuda Pepper Virus, orthosulfamuron, orbencarb, oleic acid, cafenstrole, caprylic acid, capric acid, carfentrazone-ethyl, karbutilate, carbetamide, quizalofop, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, Xanthomonas campestris, quinoclamine, quinclorac, quinmerac, citric acid, cumyluron, clacyfos, glyphosate (including a salt of sodium, potassium, amine, propylamine, isopropylamine, ammonium, isopropylammonium, guanidine, monoethanolamine, choline, BAPMA(N,N-bis-(3-aminopropyl)methylamine), dimethylamine or trimesium, or the like), glufosinate (including a salt of amine or sodium, or the like), glufosinate-P, glufosinate-P-sodium, clethodim, clodinafop, clodinafop-propargyl), clopyralid (including monoethanolamine salts), clomazone, chlomethoxyfen, clomeprop, cloransulam-methyl, chloramben, chloridazon, chlorimuron, chlorimuron-ethyl, chlorsulfuron, chlorthal-dimethyl, chlorthiamid, chlorphthalim, chlorflurenol-methyl, chlorpropham, chlorbromuron, chloroxuron, chlorotoluron, ketospiradox (including a salt of sodium, calcium or ammonia), Colletotrichum orbiculare, Colletotrichum gloeosporioides, Colletotrichum truncatum, Chondrostercum purpureum, saflufenacil, sarmentine, cyanazine, cyanamide, diuron, diethatyl-ethyl, dioxopyritrione, dicamba (including a salt of amine, diethylamine, isopropylamine, diglycolamine, dimethylammonium, dioleamine, isopropylammonium, olamine, potassium, trolamine, BAPMA(N,N-bis-(3-aminopropyl)methylamine), choline, sodium or lithium, or esters of methyl ester, or the like), cycloate, cycloxydim, dichlobenil, diclofop, diclofop-P-methyl, diclofop-methyl, dichlorprop, dichlorprop-P (including a salt of dimethylammonium, potassium, sodium, choline, or the like, or eaters of butotyl ester, 2-ethylhexyl ester, isocthyl ester, methyl ester, or the like), diquat, diquat dibromide, dithiopyr, siduron, dinitramine, cinidon-ethyl, cinosulfuron, dinoseb (including a salt of acetic acid, ammonium, diolamine, sodium, trolamine, or the like), dinoterb, cyhalofop, cyhalofop-butyl, cypyrafluone, diphenamid, difenzoquat, diflufenican, diflufenzopyr, simazine, dimesulfazet, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, simetryn, dimepiperate, dimepyrolimet, dimefuron, Pseudomonas fluorescens, cinflubrolin, cinmethylin, swep, Sclerothinia minor, sulcotrione, sulfentrazone, sulfosate, sulfosulfuron, sulfometuron-methyl, sethoxydim, terbacil, daimuron, thaxtomin A, Tobacco Mild Green Mosaic Tobamovirus, Tobacco Rattle Virus, dalapon, thiazopyr, tiafenacil, thiencarbazone (including sodium salts, methyl esters, or the like), thiocarbazyl, thiobencarb, thidiazimin, thidiazuron, thifensulfuron, thifensulfuron-methyl, desmedipham, desmetryne, tetflupyrolimet, thenylchlor, tebutam, tebuthiuron, tepraloxydim, tefuryltrione, terbuthylazine, terbutryn, terbumeton, tembotrione, topramezone, tralkoxydim, triaziflam, triasulfuron, triafamone, tri-allate, trietazine, triclopyr, triclopyr-butotyl, triclopyr-triethylammonium, tritosulfuron, tripyrasulfone, trifludimoxazin, triflusulfuron-methyl, trifluralin, trifloxysulfuron (including a salt of sodium or the like), tribenuron-methyl, tolpyralate, naptalam (including a salt with sodium or the like), naproanilide, napropamide, napropamide-M, nicosulfuron, lactic acid, neburon, norflurazon, Burkholderia rinojensis, vernolate, paraquat, paraquat dichloride, halauxifen, halauxifen-benzyl, halauxifen-methyl, haloxyfop, haloxyfop-P, haloxyfop-etothyl, haloxyfop-P-methyl, halosafen, halosulfuron-methyl, bixlozone, picloram (including a salt with dichloroammonium, trolamine, or the like), picolinafen, bicyclopyrone, bispyribac-sodium, pinoxaden, bipyrazone, bifenox, piperophos, pyraclonil, pyrasulfotole, pyrazoxyfen, pyrazosulfuron-ethyl, pyrazolynate, bilanafos, pyraflufen, pyraflufen-ethyl, pyraquinate, pyridafol, pyrithiobac-sodium), pyridate, pyriftalid, pyributicarb, pyriflubenzoxim, pyribenzoxim, pyrimisulfan, pyriminobac-methyl, pyroxasulfone, pyroxsulam, Phytophthora palmivora, phenisopham, fenuron, fenoxasulfone, fenoxaprop (including methyl, ethyl, and isopropyl ester), fenoxaprop-P (including methyl, ethyl, and isopropyl ester), feproxydim, fenquinotrione, fenthiaprop-ethyl, fentrazamide, fenpyrazone, phenmedipham, Phoma chenopodicola, Phoma herbarum, Phoma macrostoma, butachlor, butafenacil, butamifos, butylate, Puccinia canaliculata, Puccinia thlaspeos, butenachlor, butralin, butroxydim, flazasulfuron, flamprop (including methyl, ethyl, and isopropyl ester), flamprop-M (including methyl, ethyl, and isopropyl ester), primisulfuron, primisulfuron-methyl, fluazifop-butyl, fluazifop-P, fluazifop-P-butyl, fluazolate, fluometuron, fluoroglycofen-ethyl, flucarbazone-sodium, fluchloraminopyr (including tetrahydrofurfuryl ester), fluchloralin, flucetosulfuron, flusulfinam, flucetosulfuron, fluthiacet-methyl, flupyrsulfuron-methyl (including a salt of sodium, calcium or ammonia), flufenauxirim, flufenacet, flufenazopyr, flufenoximacil, flufenpyr-ethyl, flupropanate (including sodium salts), flupoxame, flumioxazin, flumiclorac-pentyl, flumetsulam, fluridone, flurtamone, fluroxypyr (including esters of butomethyl, meptyl or the like, or a salt of sodium, calcium, ammonia, or the like), flurochloridone, pretilachlor, procarbazone (including salts with sodium and the like), prodiamine, prochlorosulfone, prosulfuron, prosulfocarb, propaquizafop, propachlor, propazine, propanil, propyzamide, propisochlor, propyrisulfuron, propham, profluazol, prohexadione-calcium, propoxycarbazone, propoxycarbazone-sodium, propoxydim, bromacil, brompyrazon, prometryn, prometon, bromoxynil (including esters of butyric acid, octanoic acid, heptanoic acid, or the like), bromofenoxim, bromobutide, florasulam, florpyrauxifen, florpyrauxifen-benzyl, hexazinone, pethoxamid, benazolin (including a salt of dimethylammonium, potassium or the like), benazolin-ethyl, penoxsulam, Pepino Mosaic Virus, heptamaloxyloglucan, beflubutamid, beflubutamid-M, pebulate, pelargonic acid, bencarbazone, benquitrione, benzfendizone, bensulide, bensulfuron, bensulfuron-methyl, benzobicyclon, benzofenap, bentazone, pentanochlor, pendimethalin, pentoxazone, benfluralin, benfuresate, fosamine, fomesafen, foramsulfuron, forchlorfenuron, mecoprop (including a salt of sodium, potassium, isopropylamine, triethanolamine, dimethylamine, diolamine, tololamine, choline, or the like, or esters of ethazyl ester, 2-ethylhexyl ester, isoctyl ester, methyl ester, or the like), mecoprop-P-potassium, mesosulfuron (including esters of methyl), mesotrione, metazachlor, metazosulfuron, methabenzthiazuron, metamitron, metamifop, metam (including a salt of sodium), disodium methanalsonate (DSMA), methiozolin, methyldymuron, metoxuron, metosulam, metsulfuron-methyl, metobromuron, metproxybicyclone, metobenzuron, metolachlor, metribuzin, mepiquat chloride, mefenacet, monosulfuron (including methyl, ethyl, and isopropyl ester), monolinuron, molinate, iodosulfuron, iodosulfulon-methyl-sodium, iofensulfuron, iofensulfuron-sodium, lactofen, lancotrione, linuron, rimisoxafen, rimsulfuron, lenacil, 2,2,2-trichloroacetic acid (TCA) (including a salt of sodium, calcium or ammonia), 2,3,6-trichlorobenzoic acid (2,3,6-TBA), 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), 2,4-dichlorophenoxyacetic acid (2,4-D) (including a salt of amine, diethylamine, triethanolamine, isopropylamine, dimethylammonium, diolamine, dodecylammonium, heptylammonium, tetradecylammonium, triethylammonium, tris(2-hydroxypropyl)ammonium, trolamine, choline, sodium, lithium, or the like, or esters of butotyl ester, 2-butoxypropyl ester, 2-ethylhexyl ester, methyl ester, ethyl ester, butyl ester, isobutyl ester, octyl ester, pentyl ester, propyl ester, isoctyl ester, isopropyl ester, meptyl ester, terfuryl ester, or the like), 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB) (including a salt of amine, diethylamine, triethanolamine, isopropylamine, dimethylammonium, choline, sodium, lithium, or the like, or esters of isoctyl ester or the like), 2-amino-3-chloro-1,4-naphthoquinone (ACN), 2-methyl-4-chlorophenoxyacetic acid (MCPA) (including a salt of sodium, dimethylammonium, choline, or the like, or esters of 2-ethylhexyl ester, isoctyl ester, ethyl ester, or the like), 2-methyl-4-chlorophenoxybutyric acid (MCPB) (including sodium salt, ethyl ester, or the like), 4,6-dinitro-O-cresol (DNOC) (including a salt of amine, sodium, or the like), N4-(2,6-difluorophenyl)-6-(1-fluoro-1-methylethyl)-1,3,5-triazine-2,4-diamine (Chemical name, CAS Registry Number: 160699943-2) (WO 2014 / 064094 A, WO 2015 / 162164 A), 4-hydroxy-1-methyl-3-[4-(trifluoromethyl)-2-pyridyl]imidazolidin-2-one (Chemical name, CAS Registry Number: 1708087-22-2) (WO 2015 / 059262 A, WO 2018 / 015476 A), 6-(1-fluorocyclopentyl)-N4-(2,3,5,6-tetrafluorophenyl)-1,3,5-triazine-2,4-diamine (Chemical name, CAS Registry Number: 1820807-75-7) (WO 2015 / 162164 A), 6-(1-fluoro-1-methylethyl)-N4-(2,3,5,6-tetrafluorophenyl)-1,3,5-triazine-2,4-diamine (Chemical name, CAS Registry Number: 1606999-21-6) (WO 2014 / 064094 A, WO 2015 / 162164 A), 6-(1-methylcyclobutyl)-N4-(2,3,5,6-tetrafluorophenyl)-1,3,5-triazine-2,4-diamine (Chemical name, CAS Registry Number: 1607001-97-7) (WO 2014 / 064094 A, WO 2015 / 162164 A), AE-F-150944 (code number), IR-6396 (code number), MCPA-thioethyl, SYP-298 (code number), SYP-300 (code number), S-ethyl dipropyl thiocarbamate (EPTC), S-metolachlor, S-9750 (code number), MSMA, and HW-02 (code number).
[0324] Plant growth regulators: 1-naphthylacetamide, 1-methylcyclopropene, 1,3-diphenylurea, 2,3,5-triiodobenzoic acid), 2-methyl-4-chlorophenoxybutyric acid (MCPB) (including sodium salt, ethyl ester, or the like), 2-(naphthalene-1-yl)acetamide, 2,6-diisopropylnaphthalene, 3-[(6-chloro-4-phenylquinazoline-2-yl)amino]propane-1-ol, 4-oxo-4-(2-phenylethyl)aminobutyric acid (Chemical name, CAS Registry Number: 1083-55-2), 4-chlorophenoxyacetic acid (4-CPA), methyl 5-(trifluoromethyl)benzo[b]thiofen-2-carboxylate, AVG (aminoethoxyvinylglycine), n-decanol, anisiflupurin, aviglycine, ancymidol, abscisic acid, isoprothiolane, inabenfide, indole acetic acid, indole butyric acid, uniconazole, uniconazole-P, ecolyst, ethychlozate, ethephon, epocholeone, calcium chloride, choline chloride, oxine-sulfate, kinetin, calcium peroxide, carvone, calcium formate, cloxyfonac, cloxyfonac-potassium, cloprop, chlormequat, chlormequat-chloride, chlorpropham, choline, cytokinins, oxidized glutathione, cyanamide, sodium cyanate, cyclanilide, dichlorprop (including a salt of dimethylammonium, potassium, sodium, choline, or the like, or esters of 2-ethylhexyl ester, isoctyl ester, methyl ester, or the like), dichlorprop-P (including a salt of sodium, potassium, dimethyl ammonium, or the like, or 2-ethylhexyl ester), diquat, diquat dibromide, dikegulac, gibberellinic acid, gibberellin A4, gibberellin A7, dimethipin, sintofen, jasmone, cis-jasmone, jasmonic acid, methyl jasmonate, streptomycin, calcium polysulfide, daminozide, calcium carbonate, thidiazuron, decan-1-ol, triacontanol, triapenthenol, trinexapac-ethyl, tribufos, paclobutrazol, paraffin, bispyribac-sodium, hymexazol, butralin, fluthiacet-methyl, pyraflufen-ethyl, flumetralin, flurprimidol, flurenol, pronitridine, prohydrojasmon, prohexadione-calcium, heptamaloxyloglucan, 6-benzylaminopurine, pendimethalin, forchlorfenuron, formononetin, maleic hydrazide, mepiquat chloride, mefluidide, lipochitooligosaccharides, e.g. lipochitooligosaccharides SP104, and calcium sulfate.
[0325] Next, examples of known phytotoxicity alleviating compounds that can be mixed or used in combination are shown below.
[0326] Phytotoxicity alleviating compounds: Isoxadifen, isoxadifen-ethyl, oxabetrinil, octane-1,8-diamine, cloquintocet, cloquintcet-mexyl, dietholate, cyometrinil, dichlormid, dicyclonone, cyprosulfamide, daimuron, 1,8-Naphthalic Anhydride, fenchlorazole, fenchlorazole-O-ethyl, fenclorim, furilazole, fluxofenim, flurazole, benoxacor, metcamifen, mephenate, mefenpyr, mefenpyr-ethyl, mefenpyr-diethyl, lower alkyl-substituted benzoic acid, 2,2-dichloro-N-(1,3-dioxolan-2-ylmethyl)-N-(2-propenyl)acetamide (PPG-1292), 2-dichloromethyl-2-methyl-1,3-dioxane (MG-191), 3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine (R-29148), 4-dichloroacetyl-1-oxa-4-azaspiro[4.5]decane (AD-67), 4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid (CL-304415, code number), MON4660 (code number), N1,N2-diallyl-N2-dichloroacetyl glycineamide (DKA-24, code number), 1-bromo-4-[(chloromethyl)sulfonyl]benzene (CSB), 2-propenyl 1-oxa-4-azaspiro[4,5]decan-4-carbodithioate (MG-838, code number), 3-(dichloroacetyl)-2,2-dimethyl-1,3-oxazolidine (R-28725, code number), R-29148 (code number), and 1-(dichloroacetyl)azepane (TI-35, code number).
[0327] Next, examples of known insecticides (insecticide active ingredients), miticides (miticide active ingredients), nematicides (nematicide active ingredients), and synergists (synergist active ingredients) that may be mixed or used in combination are shown below.
[0328] Insecticide active ingredients, miticide active ingredients, nematicide active ingredients, and synergist active ingredients: Acrinathrin, azadirachtin, azamethiphos, acynonapyr, azinphos-ethyl, azinphos-methyl, acequinocyl, acetamiprid, acetoprole, acephate, azocyclotin, abamectin, afidopyropen, afoxolaner, amidoflumet, amitraz, alanycarb, aldicarb, aldoxycarb, allethrin (including d-cis-trans isomer and d-trans isomer), isazophos, isamidofos, isocarbophos, isoxathion, isocycloseram, isofenphos-methyl, isoflualanam, isoprocarb, epsilon-metofluthrin, epsilon-momfluorothrin, ivermectin, imicyafos, imidacloprid, imiprothrin, indazapyroxamet, indoxacarb, umifoxolaner, esfenvalerate, ethiofencarb, ethion, ethiprole, ethylene dibromide, etoxazole, etofenprox, ethoprophos, etrimfos, emamectin, emamectin benzoate, endosulfan, empenthrin, oxazosulfyl, oxamyl, oxydemeton-methyl, oxydeprofos, omethoate, Nuclear polyhedrosis virus, cadusafos, kappa-tefluthrin, kappa-bifenthrin, karanjin, galquin, cartap, Granulosis virus, carbaryl, carbosulfan, carbofuran, gamma-BHC, xylylcarb, quinalphos, kinoprene, chinomethionat, Entero virus, coumaphos, cryolite, clothianidin, clofentezine, chromafenozide, chlorantraniliprole, chlorethoxyfos, chlordane, chloropicrin, chlorpyrifos, chlorpyrifos-methyl, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloroprallethrin, Entomopoxi virus, Irido virus, cyazypyr, cyanophos, diafenthiuron, diamidafos, cyantraniliprole, cyetpyrafen, dienochlor, cyenopyrafen, dioxabenzofos, diofenolan, Sigma virus, cyclaniliprole, cycloxaprid, dicrotophos, dichlofenthion, cyclobutrifluram, cycloprothrin, dichlorvos, dicloromezotiaz, dicofol, dicyclanil, disulfoton, dinotefuran, dinobuton, cyhalodiamide, cyhalothrin (including gamma-isomer and lambda-isomer), cyphenothrin (including (1R)-trans isomer), cyfluthrin (including beta-isomer), diflubenzuron, cyflumetofen, diflovidazin, cyproflanilide, cyhexatin, cypermethrin (including alpha-isomer, beta-isomer, theta-isomer, and zeta-isomer), cybenzoxasulfyl, dimpropyridaz, dimethyl-2,2,2-trichloro-1-hydroxyethylphosphonate (DEP), dimethylvinphos, dimethoate, dimefluthrin, jasmone, cisjasmone, jasmonic acid, methyl jasmonate, silafluofen, cyromazine, Steinernema carpocapsae, Steinernema kushidai, Steinernema glaseri, spidoxamat, spinetoram, spinosad, spirodiclofen, spirotetramat, spiropidion, spirobudifen, spiromesifen, sulcofuron-sodium, sulfiflumin, sulfluramid, sulfoxaflor, sulfoxamyl, sulfotep, diazinon, thiacloprid, tiapyrachlor, thiamethoxam, tioxazafen, thiodicarb, thiocyclam, thiosultap, thionazin, thiofanox, thiometon, tiorantraniliprole, tyclopyrazoflor, tigolaner, tetrachlorantraniliprole, tetrachlorvinphos, tetradifon, tetraniliprole, tetramethylfluthrin, tetramethrin, tebupirimfos, tebufenozide, tebufenpyrad, tefluthrin, teflubenzuron, demeton-S-methyl, temephos, deltamethrin, terbufos, tralomethrin, transfluthrin, triazamate, triazophos, trioxyflanilide, trichlorfon, Trichoderma asperellum, Trichoderma paecilomyces, Trichoderma harzianum, triflumuron, trifluenfuronate, triflumezopyrim, trimethacarb, tolfenpyrad, naled, nicotine, nicofluprole, nitenpyram, nemadectin, Denso virus, novaluron, noviflumuron, paecilomyces lilacinus, Burkholderia cepacia, Burkholderia rinojensis, Verticillium lecanii, hydroprene, Pasteuria nishizawae, Pasteuria penetrans, Bacillus amyloliquefaciens, Bacillus firmus, Bacillus sphaericus, Bacillus subtillis, Bacillus thuringiensis, insect toxin produced by Bacillus thuringiensis, Bacillus thuringiensis subsp. Aizawai, Bacillus thuringiensis subsp. Israelensis, Bacillus thuringiensis subsp. Kurstaki, Bacillus thuringiensis subsp. Tenebrionis, Bacillus popilliae, Bacillus licheniformis, vadescana, vamidothion, parathion, parathion-methyl, halfenprox, halofenozide, bioallethrin, bioallethrin S-cyclopentenyl, pioxaniliprole, bioresmethrin, bis-(2-chloro-1-methylethyl)ether (DCIP), bistrifluron, bisulflufen, hydramethylnon, vinylfluthrin, bifenazate, bifenthrin, pyflubumide, piperflanilide, piperonyl butoxide, pymetrozine, pyraclofos, pyrafluprole, pyridaphenthion, pyridaben, pyridalyl, pyrifluquinazon, pyriprole, pyriproxyfen, pirimicarb, pyrimidifen, pyriminostrobin, pirimiphos-methyl, pyrethrine, famphur, fipronil, fenazaquin, fenamiphos, fenitrothion, fenoxycarb, fenothiocarb, phenothrin (including (1R)-trans isomer), fenobucarb, fenthion, phenthoate, fenvalerate, fenpyroximate, fenbutatin oxide, fenpropathrin, fenmezoditiaz, fonofos, sulfuryl fluoride, butocarboxim, butoxycarboxim, buprofezin, furathiocarb, prallethrin, fluacrypyrim, fluazaindolizine, fluazuron, fluensulfone, fluopyram, sodium fluoroacetate, fluxametamide, fluchlordiniliprole, flucycloxuron, flucythrinate, fluthrin, fluvalinate (including tau-isomer), flupyradifurone, flupyrazofos, flupyrimin, flupyroxystrobin, flufiprole, flufenerim, flufenoxystrobin, flufenoxuron, fluhexafon, flubendiamide, flupentiofenox, flumetnicam, flumethrin, fluralaner, flurimfen, prothiofos, protrifenbute, flonicamid, propaphos, propargite, prohydrojasmon, profenofos, broflanilide, profluthrin, propetamphos, propoxur, flometoquin, bromopropylate, hexythiazox, hexaflumuron, Paecilimyces tenuipes, Paecilomyces fumosoroceus, Paecilomyces lilacinus, heptafluthrin, heptenophos, permethrin, benclothiaz, benzpyrimoxan, bensultap, benzoximate, bendiocarb, benfuracarb, bentioflumin, Pochonia chlamydosporia, Beauveria tenella, Beauveria bassiana, Beauveria brongniartii, phoxim, phosalone, fosthiazate, fosthietan, phosphamidon, phosmet, polynactins, formetanate, phorate, machine oil, malathion, mivorilaner, milbemectin, mecarbam, mesulfenfos, methomyl, metaldehyde, metaflumizone, methamidophos, metham, methiocarb, methidathion, methyl isothiocyanate, methyl bromide, methoxychlor, methoxyfenozide, methothrin, metofluthrin, methoprene, metolcarb, mevinphos, meperfluthrin, modoflaner, Monacrosporium phymatophagum, monocrotophos, momfluorothrin, Trichoderma harzianum, litlure-A, litlure-B, aluminium phosphide, zinc phosphide, phosphine, lufenuron, rescalure, resmethrin, lepimectin, rotenone, Cytoplasmic polyhedrosis virus, fenbutatin oxide, calcium cyanide, organotins, nicotine-sulfate, (Z)-11-tetradecenyl=acetate, (Z)-11-hexadecenal, (Z)-11-hexadecenyl=acetate, (Z)-9,12-tetradecadienyl=acetate, (Z)-9-tetradecene-1-ol, (Z,E)-9,11-tetradecadienyl=acetate, (Z,E)-9,12-tetradecadienyl=acetate, 1,1,1-trichloro-2,2-bis(4-chlorophenyl)ethane (DDT), 1,3-dichloropropene, 4,6-dinitro-o-cresol (DNOC), Bt proteins (Cry1Ab, Cry1Ac, Cry1Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, and Cry34 / 35Ab1), methyl eugenol, 4-(p-acetoxyphenyl)-2-butanone, (Z)-10-tetradecenyl=acetate, (E,Z)-4,10-tetradecadienyl=acetate, (Z)-8-dodecenyl=acetate, (Z)-13-icosen-10-one, 14-methyl-1-octadecene, AKD-1193 (code number), BCS-AA10147 (code number), CL900167 (code number), O,O-diethyl-O-[4-(dimethylsulfamoyl)phenyl]-phosphorothionate (DSP), O-ethyl-O-4-(nitrophenyl)phenylphosphonothioate (EPN), RU15525 (code number), XMC, Z-13-icosen-10-one, ZXI8901 (code number), and F4260 (code number).
[0329] Next, examples of known bactericides (bactericide active ingredients) or disease controller compounds that can be mixed or used in combination are shown below.
[0330] Bactericide active ingredients or disease controller compounds: Agrobacterium radiobacter, azaconazole, acibenzolar-S-methyl, azoxystrobin, anilazine, amisulbrom, aminotipyr, aminopyrifen, ametoctradin, aldimorph, isotianil, isopyrazam, isofetamid, isoflucypram, isoprothiolane, ipconazole, ipflufenoquin, ipfentrifluconazole, iprodione, iprovalicarb, iprobenfos, imazalil, iminoctadine-albesilate, iminoctadine-triacetate, imibenconazole, inpyrfluxam, imprimatin A, imprimatin B, edifenphos, etaconazole, ethaboxam, ethirimol, ethoxyquin, etridiazole, enestroburin, enoxastrobin, epoxiconazole, organic oils, oxadixyl, oxazinylazole, oxathiapiprolin, oxycarboxin, oxine-copper, oxytetracycline, oxpoconazole-fumarate, oxolinic acid, copper dioctanoate, octhilinone, ofurace, orysastrobin, o-phenylphenol, kasugamycin, captafol, galquin, carpropamid, carbendazim, carboxin, carvone, Candida oleophila, Candida saitoana, quinaminoprole, quinoxyfen, quinofumelin, chinomethionat, captan, quinconazole, quintozene, guazatine, cufraneb, coumethoxystrobin, coumoxystrobin, Gliocradium catenulatum, Cryptococcus albidus, kresoxim-methyl, clozylacon, Clonostachys rosea, chlozolinate, chloroinconazide, chlorothalonil, chloroneb, Chaetomium cupreum, Coniothyrium minitans, cyazofamid, diethofencarb, diclocymet, dichlofluanid, dichlobentiazox, diclomezine, dicloran, dichlorophen, dithianon, diniconazole, diniconazole-M, zineb, dinocap, dipymetitrone, diphenylamine, difenoconazole, cyflufenamid, diflumetorim, cyproconazole, cyprodinil, simeconazole, dimethirimol, dimethyl disulfide, dimethomorph, cymoxanil, dimoxystrobin, Pseudozyma flocculosa, Pseudomonas aureofaciens, Pseudomonas chlororaphis, Pseudomonas syringae, Pseudomonas flurorescens, Pseudomonas rhodesiae, ziram, silthiofam, Zucchini yellow mosaic virus, streptomycin, Streptomyces griseoviridis, Streptomyces lygicus, spiroxamine, sedaxane, seboctylamine, zoxamide, solatenol, dazomet, Talaromyces flavus, tiadinil, thiabendazole, thiram, thiophanate, thiophanate-methyl, thifluzamide, tecnazene, tecloftalam, tetraconazole, debacarb, tebuconazole, tebufloquin, terbinafine, dodine, dodemorph, triadimenol, triadimefon, triazoxide, trichlamide, triclopyricarb, Trichoderma asperellum, Trichoderma atroviride, Trichoderma gamsii, Trichoderma stromaticum, Trichoderma paecilomyces, Trichoderma harzianum, Trichoderma viride, Trichoderma virens, Trichoderma polysporum, Trichoderma harzianum rifai, Trichoderma lignorum, tricyclazole, triticonazole, tridemorph, triflumizole, trifloxystrobin, triforine, tolylfluanid, tolclofos-methyl, tolnifanide, tolprocarb, nabam, natamycin, naftifine, nitrapyrin, nitrothal-isopropyl, nuarimol, copper nonyl phenol sulphonate, Paenibacillus polymyxa, Burkholderia cepacia, Burkholderia rinojensis, Bacillus amyloliquefaciens, Bacillus simplex, Bacillus subtilis, Bacillus pumilus, Bacillus mycoides, Bacillus licheniformis, harpin protein, Variovorax paradoxus, validamycin, valifenalate, Pantoea agglomerans, picarbutrazox, bixafen, picoxystrobin, Pythium oligandrum, pydiflumetofen, bitertanol, binapacryl, hinokitiol, Erwinia carotovora, Rhizobium vitis, biphenyl, bifemetstrobin, piperalin, hymexazol, pyraoxystrobin, pyraclostrobin, pyraziflumid, pyrazophos, pyrapropoyne, pyrametostrobin, pyriofenone, pyrisoxazole, pyridachlometyl, pyrifenox, pyributicarb, pyribencarb, pyrimethanil, pyroquilon, vinclozolin, ferbam, famoxadone, phenazine oxide, fenamidone, fenaminstrobin, fenarimol, feneptamidoquin, fenoxanil, fenopyramid, ferimzone, fenpiclonil, fenpicoxamid, fenpyrazamine, fenbuconazole, fenfuram, fenpropidin, fenpropimorph, fenhexamid, folpet, phthalide, Fusarium oxysporum, bupirimate, fuberidazole, blasticidin-S, furametpyr, furalaxyl, furancarboxylic acid, fluazinam, fluindapyr, fluoxastrobin, fluoxapiprolin, fluoxytioconazole, fluopicolide, fluopimomide, fluopyram, fluoroimide, fluxapyroxad, fluquinometoate, fluquinconazole, furconazole, furconazole-cis, fludioxonil, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, flufenoxadiazam, flufenoxystrobin, flubeneteram, flumetylsulforim, flumetover, flumorph, Phlebiopsis gigantea, proquinazid, prochloraz, procymidone, prothiocarb, prothioconazole, bronopol, propamocarb-hydrochloride, propiconazole, propineb, probenazole, bromuconazole, flometoquin, florylpicoxamid, hexaconazole, benalaxyl, benalaxyl-M, benodanil, benomyl, pefurazoate, penconazole, pencycuron, benzovindiflupyr, benthiazole, benthiavalicarb-isopropyl, penthiopyrad, penflufen, boscalid, fosetyl (including a salt of aluminum, calcium, sodium, or the like), polyoxin, polycarbamate, Bordeaux mixture, mancopper, mancozeb, mandipropamid, mandestrobin, maneb, microbutanil, mineral oils, mildiomycin, methasulfocarb, metam, metalaxyl, metalaxyl-M, metarylpicoxamid, metiram, methyltetraprole, metconazole, metominostrobin, metrafenone, mepanipyrim, mefentrifluconazole, meptyldinocap, mepronil, iodocarb, laminarin, ledprona, phosphorous acid and salts, copper oxychloride, silver, copper(II) acetate, cuprous oxide, cupric hydroxide, potassium bicarbonate, sodium bicarbonate, sulfur, oxyquinoline sulfate, copper sulfate, UK-2A (code number), dodecylbenzenesulfonic acid bisethylenediamine copper (II) salt (DBEDC), triphenyltin acetate (TPTA), triphenyltin chloride (TPTC), and triphenyltin hydroxide (TPTH).
[0331] Next, examples of known biological pesticides that can be mixed or used in combination are shown below.
[0332] Biological pesticides: Haplothrips brevitubus, Franklinothrips vespiformis, Diglyphus isaea, Encarsia formosa, Amblyseius cucumeris, Pseudaphycus malinus, Amblyseius womersleyi, Aphidius colemani, Eretmocerus eremicus, Aphidoletes aphidimyza, Amblyseius swirskii, Orius strigicollis, Phytoseiulus persimilis, Amblyseius degenerans, Phytoseiulus persimilis, Orius sauteri, Dacnusa sibirica, Amblyseius californicus, Chrysoperla nipponesis, and Anicetus beneficus.
[0333] Next, examples of known agricultural materials that can be mixed or used in combination are shown below.
[0334] Agricultural materials: Ethylene, hypochlorous acid water (limited to those obtained by electrolyzing hydrochloric acid or an aqueous potassium chloride solution), sodium bicarbonate, vinegar, humic substances, humic acid, fulvic acid, seaweed extract, polysaccharide, amino acid, microbial materials, animal and plant-derived functional components, microbial metabolite, microbial activator, soil spreading agent, soil permeability regulating material, soil water retention material, and biostimulants.
[0335] Next, examples of agricultural fertilizer components that can be mixed or used in combination are shown below. Examples of the fertilizers include an inorganic fertilizer and an organic fertilizer.
[0336] Agricultural fertilizer ingredients: Ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium dihydrogen phosphate, urea ammonium nitrate, urea, lime nitrogen, potassium nitrate, superphosphate of lime, double superphosphate of lime, potassium dihydrogen phosphate, potassium chloride, potassium sulfate, potassium carbonate, potassium silicate, potassium phosphite, oil cake, fish powder, rice bran, bat guano, and fermented chicken manure.
[0337] The useful plants in the present invention include field crops or paddy crops, garden crops (vegetables and fruit trees), ornamental trees (flowering trees, roadside trees), grasses, flowers, foliage plants, medicinal plants, and lumbers. Examples thereof include, but are not limited to, the following.
[0338] Field crops or paddy crops: Corn, rice, wheat, durum wheat, barley, rye, triticale, spelt wheat, compactum wheat, oats, sorghum, cotton, soybean, alfalfa, peanut, common bean, lima bean, azuki bean, cowpea, mung bean, vigna mungo, runner bean, ricebean, moth bean, tepary bean, broad bean, pea, chickpea, lentil, lupin, pigeon pea, buckwheat, sugar beet, rapeseed, canola, sunflower, sugarcane, cassava, yam, oil palm, physic nut, hemp, flux, quinoa, safflower, tea plant, mulberry, tobacco, camelina sativa, teff, guayule, para rubber tree, and the like.
[0339] Garden crops (vegetables): Solanaceous vegetables (eggplant, tomato, green pepper, hot pepper, potato, and the like), Cucurbitaceae vegetables (cucumber, pumpkin, zucchini, watermelon, melon, squash, and the like), Cruciferae vegetables (Japanese radish, turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, brown mustard, broccoli, cauliflower, and the like), Compositae vegetables (burdock, garland chrysanthemum, artichoke, lettuce, and the like), Liliaceae vegetables (welsh onion, onion, garlic, asparagus, and the like), Umbelliferae vegetables (carrot, parsley, celery, parsnip, and the like), Chenopodiaceae vegetables (spinach, Swiss chard, and the like), Labiatae vegetables (Japanese basil, mint, basil, lavender, and the like), strawberry, sweet potato, yam, aroid, sesame, and the like.
[0340] Garden crops (fruit trees): Pomaceous fruits (apple, common pear, Japanese pear, Chinese white pear, Chinese quince, quince, and the like), kernel fruits (peach, plum, nectarine, Japanese plum, cherry, apricot, prune, and the like), citrus fruits (Satsuma mandarin, orange, lemon, lime, grapefruit, and the like), nuts (chestnut, walnut, Asian Hazel, almond, hazelnut, pistachio, cashew nut, macadamia nut, pecan nut, and the like), berry fruits (blueberry, cranberry, blackberry, raspberry, and the like), grape, persimmon, olive, loquat, banana, coffee, date, coconut palm, oil palm, and the like.
[0341] Ornamental trees (flowering trees and roadside trees): Ash tree, birch, dogwood, eucalyptus, ginkgo, lilac, maple tree, oak, poplar, cercis, liquidamber, plane tree, zelkova, Japanese arborvitae, fir tree, Japanese hemlock, needle juniper, pine, spruce, yew, elm, Japanese horse-chestnut, Sweet viburnum, Largeleaf podocarp, Japanese cedar, Japanese cypress, croton, Japanese spindle, Japanese photinia, and the like.
[0342] Grasses: Grass (Japanese lawn grass, mascarene grass, and the like), Bermuda grass (Cynodon dactylon and the like), bent grass (redtop, creeping bent grass, common bent, and the like), bluegrass (Kentucky bluegrass, rough bluegrass, and the like), fescue (tall fescue, chewing fescue, creeping fescue, and the like), ryegrass (italian ryegrass, perennial ryegrass, and the like), cocksfoot, timothy grass, and the like.
[0343] Flowers and foliage plants: Rose, carnation, chrysanthemum, Eustoma grandiflorum, gypsophila, gerbera, marigold, salvia, petunia, verbena, tulip, aster, gentian, lily, pansy, cyclamen, orchid, lily of the valley, lavender, stock, ornamental kale, primula, poinsettia, gladiolus, cattleya, daisy, verbena, cymbidium, begonia, and the like.
[0344] Medicinal plants: Chamomiles, licorice, turmeric, Chinese ginseng, coptis, peony, poppy, and the like.
[0345] Lumbers: Pines, spruces, Pinus, cypress, Japanese cedar, Japanese cypress, eucalyptus, and the like.
[0346] In addition, the useful plants in the present invention also include plants provided with tolerance to herbicides by a classical breeding method, a gene recombination technique and genome editing, and examples of the herbicides include 4-hydroxyphenylpyruvate dioxygenase (4-HPPD) inhibitors such as isoxaflutole, acetolactate synthase (ALS) inhibitors such as imazethapyr and tifensulfuron-methyl, 5-enolpyruvylshikimate-3-phosphate (EPSP) synthase inhibitors such as glyphosate, glutamine synthase inhibitors such as glufosinate, acetyl-CoA carboxylase (ACCace) inhibitors such as sethoxydim, protoporphyrinogen oxidase (PPO) inhibitors such as flumioxazin and epyrifenacil, photosystem II inhibitors such as bromoxynil, and then dicamba, and 2,4-D.
[0347] Examples of the useful plants provided with tolerance by a classical breeding method include rapeseed, wheat, sunflower, rice, and corn having tolerance to imidazolinone ALS inhibitory herbicides such as imazethapyr, which are already commercially available under the product name of Clearfield <registered trademark>. Similarly, Cultivance has been developed as a soybean tolerant to imidazolinone ALS inhibitory herbicides.
[0348] Similarly, a soybean provided with tolerance to sulfonylurea ALS inhibitory herbicides such as tifensulfuron-methyl, by a classical breeding method, is already commercially available under the product name of STS soybean. Similarly, sorghum provided with tolerance to sulfonylurea acetolactate synthase (ALS) inhibitory herbicides, by a classical breeding method, is already commercially available. Similarly, sugar beet provided with tolerance to acetolactate synthase (ALS) inhibitory herbicides such as thiencarbazone, by a classical breeding method, is already commercially available. Similarly, examples of the useful plants provided with tolerance to acetyl-CoA carboxylase (ACCace) inhibitors such as trione oxime and aryloxyphenoxypropionic acid herbicides by a classical breeding method include SR-corn and wheat tolerant to quizalofop. The useful plants provided with tolerance to an acetyl-CoA carboxylase (ACCace) inhibitor are described in Proceedings of the National Academy of Sciences of the United States of America (Proc. Natl. Acad. Sci USA), Vol. 87, pp. 7175-7179 (1990) and the like. A mutant acetyl-CoA carboxylases (ACCace) tolerant to an acetyl-CoA carboxylase (ACCace) inhibitor is reported in Weed Science, vol. 53, pp. 728-746 (2005) and the like, and a plant tolerant to an acetyl-CoA carboxylase inhibitor can be generated by introducing a gene of such a mutant acetyl-CoA carboxylase into a plant by a gene recombination technique, or by introducing a mutation related to provide tolerance into a plant acetyl-CoA carboxylase (ACCace). In addition, plants tolerant to an acetyl-CoA carboxylase (ACCace) inhibitor or herbicide can be generated by introducing into the plant cell a nucleic acid for introduction of base-substitution mutation represented by Chimeraplasty Technique (Gura T. 1999. Repairing the Genome's Spelling Mistakes. Science 285: 316-318) to induce a site-specific amino acid substitution mutation into a plant (acetyl-CoA carboxylase (ACCace) / herbicide target) gene.
[0349] Examples of useful plants provided with tolerance by a gene recombination technique include corn, soybean, cotton, rapeseed, sugar beet, and alfalfa varieties tolerant to glyphosate, which are already commercially available under the product names of Roundup Ready <registered trademark>, Roundup Ready 2 <registered trademark>, Agrisure GT <registered trademark>, GlyTol <registered trademark> and the like. Similarly, soybeans and corn varieties provided with tolerance to both glyphosate and ALS inhibitors by a gene recombination technique include Optimum <registered trademark> GAT. Similarly, corn, soybean, cotton, and rapeseed varieties provided with tolerance to glufosinate by a gene recombination technique are already commercially available under the product names of LibertyLink <registered trademark> and the like. Similarly, cotton provided with tolerance to bromoxynil by a gene recombination technique is already commercially available under the product name of BXN. Similarly, soybeans provided with tolerance to HPPD inhibitors by a gene recombination technique is already commercially available under the product name of Herbicide-tolerant Soybean line as a variety tolerant to mesotrione and glufosinate, and under the product name of Credenz <registered trademark> as a variety tolerant to HPPD inhibitors, glyphosate and glufosinate. Similarly, corn, soybean and cotton provided woth tolerance to 2,4-D or ACCase inhibitors by a gene recombination technique are already commercially available under the product name of Enlist <registered trademark> and the like. Similarly, a soybean variety provided with tolerance to 2,4-D, glyphosate and glufosinate by a gene recombination technique is already commercially available under the product name of Enlist E3. Similarly, soybean provided with tolerance to dicamba by a gene recombination technique is already commercially available under the product name of Roundup Ready 2 Xtend < registered trademark> as a variety tolerant to dicamba and glyphosate. Similarly, a soybean variety tolerant to HPPD inhibitors such as isoxaflutole and is also tolerant to nematodes due to HPPD inhibitor tolerance by a gene recombination technique is registered as GMB151 in the United States.
[0350] A plant having modified tolerance to herbicides is widely known, and examples thereof include alfalfa, apple, barley, eucalyptus, flax, grape, lentil, rapeseed, pea, potato, rice, sugar beet, sunflower, tobacco, tomato, turf grass, and wheat having tolerance to glyphosate (see, for example, US 5,188,642, US 4,940,835, US 5,633,435, US 5,804,425, and US 5,627,061), bean, cotton, soybean, pea, potato, sunflower, tomato, tobacco, corn, sorghum, and sugarcane having tolerance to dicamba (see, for example, WO 2008 / 051633 A, US 7,105,724 and US 5,670,454), soybean, sugar beet, potato, tomato, and tobacco having tolerance to glufosinate (see, for example, US 6,376,754, US 5,646,024, and US 5,561,236), cotton, peppers, apple, tomato, sunflower, tobacco, potato, corn, cucumber, wheat, soybean, sorghum, and cereal crops having tolerance to 2,4-D (see, for example, US 6,153,401, US 6,100,446, WO 2005 / 107437 A, US 5,608,147 and US 5,670,454), canola, corn, barnyard millet, barley, cotton, Indian mustard, lettuce, lentil, melon, foxtail millet, oat, rapeseed, potato, rice, rye, sorghum, soybean, sugar beet, sunflower, tobacco, tomato, and wheat having tolerance to an ALS inhibitory herbicide (for example, a sulfonylurea herbicide or an imidazolinone herbicide) (see, for example, US 5,013,659, WO 2006 / 060634 A, US 4,761,373, US 5,304,732, US 6,211,438, US 6,211,439 and US 6,222,100), particularly, rice having tolerance to an imidazolinone herbicide is known, which includes rice having tolerance to a specific mutation in acetolactate synthase gene (for example, S653N, S654K, A122T, S653(At)N, S654(At)K, A122(At)T) (see, for example, US 2003 / 0217381 and WO 2005 / 020673 A), barley, sugarcane, rice, corn, tobacco, soybean, cotton, rapeseed, sugar beet, wheat, and potato having tolerance to HPPD inhibitory herbicides (for example, isoxazole herbicides such as isoxaflutole, triketone herbicides such as sulcotrione and mesotrione, and pyrazole herbicides such as pyrazolinate) or diketonitrile which is a degradation product of isoxaflutole (see, for example, WO 2004 / 055191 A, WO 1996 / 38567 A, WO 1997 / 049816 A, and US 6,791,014), and wheat, soybean, cotton, sugar beet, rapeseed, rice, corn, sorghum, sugarcane, and sugar beet having tolerance to PPO inhibitory herbicides (see, for example, US 2002 / 0073443, US 2008 / 0052798, Pest Management Science, 61, 2005, 277285).
[0351] Examples of plants provided with herbicide tolerance by conventional varietal improvement techniques or genome breeding techniques include rice "Clearfield <registered trademark> Rice", wheat "Clearfield <registered trademark> Wheat", sunflower "Clearfield <registered trademark> Sunflower", lentil "Clearfield <registered trademark> Lentils", and canola "Clearfield <registered trademark> Canola" having tolerance to imidazolinone ALS inhibitory herbicides such as imazethapyr and imazamox, soybean "STS soybean" having tolerance to sulfonylurea ALS inhibitory herbicides such as thifensulfuron methyl, corn "SR corn" (also known as "Poast Protected <registered trademark> corn") having tolerance to acetyl-CoA carboxylase inhibitors such as a trione oxime herbicide and an aryloxyphenoxypropionate herbicide, sunflower "ExpressSun <registered trademark>" having tolerance to sulfonylurea herbicides such as tribenuron, rice "Provisia <registered trademark> Rice" having tolerance to acetyl-CoA carboxylase inhibitors such as quizalofop, canola "Triazine Tolerant Canola" having tolerance to a photosystem II inhibitor, and sorghum "Igrowth <registered trademark>" having tolerance to an imidazolinone herbicide.
[0352] An example of a plant provided with herbicide tolerance by a genome editing technique includes canola "SU Canola <registered trademark>" having sulfonylurea herbicide tolerance using Rapid Trait Development System (RTDS) <registered trademark>. The RTDS <registered trademark> corresponds to the introduction of an oligonucleotide-directed mutation in genome editing techniques, and is a technique enabling the introduction of a mutation through Gene Repair Oligonucleotide (GRON), that is, DNA and RNA chimeric oligonucleotide without cutting DNA in the plant. Other examples thereof include corn in which herbicide tolerance and the phytic acid content are reduced by using zinc finger nucleases to delete an endogenous gene IPK1 (see, for example, Nature 459, 437-441, 2009), and rice provided with herbicide tolerance by using CRISPR / Cas9 (see, for example, Rice, 7, 5 2014).
[0353] An example of a plant provided with herbicide tolerance by a new plant breeding technique includes soybean obtained by providing properties of a GM rootstock to a scion using a varietal improvement technique using grafting. A specific example thereof includes soybean obtained by providing glyphosate tolerance to a non-transgenic soybean scion using Roundup Ready <registered trademark> having glyphosate tolerance as a rootstock (see Weed Technology 27, 412, 2013).
[0354] The useful plant also includes a plant capable of synthesizing, for example, selective toxins known as genus Bacillus using a gene recombination technique.
[0355] Examples of insecticidal toxins expressed in such a gene recombinant plant include: insecticidal proteins derived from Bacillus cereus and Bacillus popilliae; -endotoxins derived from Bacillus thuringiensis such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry14Ab-1, Cry2Ab, Cry3A, Cry3Bb1, and Cry9C; insecticidal proteins such as VIP1, VIP2, VIP3, and VIP3A; insecticidal proteins derived from nematodes; toxins generated by animals such as scorpion toxin, spider toxin, bee toxin, and insect-specific neurotoxins; mold fungi toxins; plant lectin; agglutinin; protease inhibitors such as a trypsin inhibitor, a serine protease inhibitor, patatin, cystatin, and a papain inhibitor; ribosome-inactivating proteins (RIP) such as lycine, corn-RIP, abrin, saporin, and briodin; steroid-metabolizing enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glucosyl transferase, and cholesterol oxidase; ecdysone inhibitors; HMG-CoA reductases; ion channel inhibitors such as a sodium channel inhibitor and a calcium channel inhibitor; juvenile hormone esterase; diuretic hormone receptors; stilbene synthase; bibenzyl synthase; chitinase; and glucanase.
[0356] Toxins expressed in such a gene recombinant plant also include: hybrid toxins of -endotoxin proteins such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry14Ab-1, Cry2Ab, Cry3A, Cry3Bb1, Cry9C, Cry34A, Cry34Ab, and Cry35Ab and insecticidal proteins such as VIP1, VIP2, VIP3, and VIP3A; partially deleted toxins; and modified toxins. The hybrid toxins are produced by a new combination of the different domains of these proteins using a recombinant technique. As the partially deleted toxin, Cry1Ab whose amino acid sequence is partially deleted is known. The modified toxin is produced by substitution of one or more of the amino acids of natural toxins.
[0357] Examples of these toxins and recombinant plants capable of synthesizing these toxins are described in EP-A-0374753, WO 93 / 07278 A, WO 95 / 34656 A, EP-A-0427529, EP-A-451878, WO 03 / 052073 A, and the like. The toxins contained in these recombinant plants provide tolerance particularly to insect pests belonging to Coleoptera, Diptera, and Lepidoptera, to the plants.
[0358] A gene recombinant plant which has one or more insecticidal pest tolerance genes and expresses one or more toxins is already known, and some are commercially available. Examples of the gene recombinant plant include YieldGard <registered trademark> (a corn variety expressing Cry1Ab toxin), YieldGard Rootworm <registered trademark> (a corn variety expressing Cry3Bb1 toxin), YieldGard Plus <registered trademark> (a corn variety expressing Cry1Ab and Cry3Bb1 toxins), Herculex I <registered trademark> (a corn variety expressing Cry1Fa2 toxin and phosphinotricine N-acetyl transfelase (PAT) to provide tolerance to glufosinate), NuCOTN33B <registered trademark> (a cotton variety expressing Cry1Ac toxin), Bollgard I <registered trademark> (a cotton variety expressing Cry1Ac toxin), Bollgard II <registered trademark> (a cotton variety expressing Cry1Ac and Cry2Ab toxins), VIPCOT <registered trademark> (a cotton variety expressing VIP toxins), NewLeaf <registered trademark> (a potato variety expressing Cry3A toxin), NatureGuard <registered trademark> Agrisure <registered trademark> GT Advantage (GA21 glyphosate-tolerant trait), Agrisure <registered trademark> CB Advantage (Bt11 corn borer (CB) trait), Protecta <registered trademark>, Intacta <registered trademark>, and SmartStax <registered trademark>.
[0359] The plant provided with pest tolerance using a classical breeding method or a gene recombination technique includes, soybeans having the aphid tolerance gene such as Rag1(Resistance to Aphis glycines 1) gene and Rag2(Resistance to Aphis glycines 2) gene, soybeans tolerant to Heterodera glycines, cotton tolerant to Meloidogyne incognita, Kanto BPH1, which is a rice tolerant to Nilaparvata lugens, and fukuminori, which is a soybean tolerant to Prodenia litura.
[0360] The useful plants also include those that have been provided with tolerance to nematodes using a classical breeding method or a gene recombination technique. Examples of the gene recombination technique that provides nematode tolerance include RNA interferometric technique (RNAi).
[0361] As the plant provided with pest tolerance using RNAi, corn that is tolerant to pests belonging to Lepidoptera (e.g., corn borers, corn ear worms, cutworms such as black cutworms, and fall army worms) and pests belonging to Coleoptera (corn rootworms) is commercially available or developed as SmartStax <registered trademark>, SmartStax <registered trademark> Pro or Genuity <registered trademark> SmartStax Pro.
[0362] The useful plant also includes a plant produced using a gene recombination technique to have ability to generate antipathogenic substances having a selective action.
[0363] Examples of the antipathogenic substances include PR proteins (PRPs, described in EP-A-0392225); ion channel inhibitors such as a sodium channel inhibitor and a calcium channel inhibitor (KP1, KP4, and KP6 toxins and the like produced by viruses are known); stilbene synthase; bibenzyl synthase; chitinase; glucanase; and substances generated by microorganisms, such as a peptide antibiotic substance, an antibiotic substance having a hetero ring, and a protein factor associated with resistance to plant diseases (referred to as a plant disease-resistant gene and described in WO 03 / 000906 A). These antipathogenic substances and gene recombinant plants producing these antipathogenic substances are described in EP-A-0392225, WO 95 / 33818 A, EP-A-0353191, and the like.
[0364] The useful plant also includes a crop to which a useful trait such as oil component modification and enhancement trait in amino acid content is provided using a gene recombination technique. Examples thereof include VISTIVE <registered trademark> (low linolenic soybean with reduced linolenic content) or high-lysine (high oil) corn (corn with increased lysine or oil content).
[0365] The useful plant also includes a crop to which a useful trait such as dry resistance is provided using a gene recombination technique to maintain and increase the yield. Examples thereof include DroughtGard <registered trademark>, AGRISURE ARTESIAN <registered trademark>, OPTIMUM <registered trademark> A UAMAX <registered trademark> (cone to which dry resistance is provided) and the like.
[0366] The herbicide of the present invention also exhibits a control effect on the above-exemplified pests and the like, which have acquired tolerance to existing herbicides. Furthermore, the herbicide of the present invention can be applied to plants that have acquired characteristics such as pest tolerance, disease resistance, and herbicide tolerance by a gene recombination, artificial mating, and the like.
[0367] The "plant transformed in culturing by a breeding method or a gene recombination technique" in the present invention includes plants provided with tolerance by New Plant Breeding Techniques (NBTs) established by combining molecular biological techniques with existing mating techniques, as well as those provided with tolerance by classical mating, or by a gene recombination technique. The NBTs are described in the publication "NBT (new plant breeding techniques)" (International Academic Publishing Co., Ltd., written by Ryo Osawa, and Hiroshi Ezura), the review "Genome Editing Tools in Plants"(Genes 2017,8, 399, written by Tapan Kumar Mohanta, Tufail Bashir, Abeer Hashem, Elsayed Fathi Abd Allah and Hanhong Bae), and the like. Examples of the above new plant breeding techniques include a genome breeding technique and a genome editing technique. The genome breeding technique is a technique for improving breeding using genome information, and includes a DNA marker (also referred to as a genome marker or a gene marker) breeding technique and a genomic selection. For example, the DNA marker breeding is a method in which a progeny having a target useful trait gene is selected from a large number of mating progenies using a DNA marker which is a DNA sequence serving as a mark of an existence position on a specific useful trait gene on the genome. By analyzing the mating progenies using a DNA marker when the progeny is a young plant, the time required for breeding can be effectively shortened.
[0368] In addition, the genomic selection is a technique in which a prediction formula is created from a phenotype and genome information obtained in advance to predict the characteristics from the prediction formula and the genome information without any evaluation of the phenotype, and is a technique contributing to improvement in efficient breeding. The new breeding techniques is generic term of varietal improvement (breeding) technique that combines molecular biological techniques. Examples of the new breeding techniques include cisgenesis / intragenesis, introduction of an oligonucleotide-directed mutation, RNA-dependent DNA methylation, genome editing, grafting onto a GM rootstock or a scion, reverse breeding, agroinfiltration, and Seed Production Technology (SPT). The genome editing technique is a technique for converting genetic information in a sequence-specific manner, making it possible to delete base sequences, substitute an amino acid sequence, and introduce an exogeneous gene. Examples of tools for the technique include Zinc-Finger Nucleases (ZFN, ZFNs), TALEN, CRISPR / Cas9, CRISPER / Cpf1, and Meganuclease, which each enable sequence-specific cleavage. There are also sequencespecific genomic modification techniques, such as CAS9 nickases and Target-AID, which have been made by modifying the above tools.
[0369] Furthermore, stack varieties having a combination of useful traits such as the classical herbicide traits or herbicide tolerant gene, an insecticidal pest tolerance gene, an antipathogenic substance production gene, oil component modification, enhancement trait in amino acid content, and a dry resistance trait, are also included.
[0370] Examples of the non-crop land where the herbicide of the present invention and the pesticide composition of the present invention (the concept is that it contains the herbicide) are used include a levee, a river bed, a roadside and a road slope, a railroad, a green field of a park, a ground, a parking lot, an airport, a land for an industrial facility such as a factory and a storage facility, a fallow land, a non-crop land where breeding of weeds are required to be controlled, such as an unused land in a city, an orchard, a pasture, a land ground, a forest ground, a river, a waterway, a canal, and a reservoir.
[0371] As described above, the herbicide of the present invention and the pesticide composition of the present invention (the concept is that it contains the herbicide) have herbicidal effects on various weeds. Examples of the weeds include, but are not limited to, the following.
[0372] Urticaceae weeds: Urtica urens.
[0373] Polygonaceae weeds: Polygonum convolvulus, Polygonum lapathifolium, Polygonum pensylvanicum, Polygonum persicaria, Polygonum longisetum, Polygonum aviculare, Polygonum arenastrum, Polygonum cuspidatum, Rumex japonicus, Rumex crispus, Rumex obtusifolius, Rumex acetosa, Rumex acetosella, and Persicaria nepalensis.
[0374] Portulacaceae weeds: Portulaca oleracea.
[0375] Caryophyllaceae weeds: Stellaria media, Stellaria aquatica, Cerastium holosteoides, Cerastium glomeratum, Spergula arvensis, Silene gallica, and Stellaria alsine.
[0376] Molluginaceae weeds: Mollugo verticillata.
[0377] Amaranthaceae weeds: Amaranthus retroflexus, Amaranthus viridis, Amaranthus lividus, Amaranthus spinosus, Amaranthus hybridus, Amaranthus palmeri, Amaranthus patulus, Waterhemp (Amaranthus tuberculatus=Amaranthus rudis=Amaranthus tamariscinus), Amaranthus blitoides, Amaranthus deflexus, Amaranthus quitensis, Amaranshus spinosus, Alternanthera philoxeroides, Alternanthera sessilis, Alternanthera tenella, Amaranthus powelii, Amaranthus rudis, Amaranthus albus, Amaranthus patulus, Chenopodium album, Chenopodium ambrosioides, Kochia scoparia, Salsola kali, and Atriplex spp.
[0378] Papaveraceae weeds: Papaver rhoeas, Papaver dubium, and Argemone mexicana.
[0379] Brassicaceae weeds: Raphanus raphanistrum, Raphanus sativus, Sinapis arvensis, Capsella bursa-pastoris, Brassica juncea, Brassica napus, Brassica rapa, Descurainia pinnata, Rorippa islandica, Rorippa sylvestris, Thlaspi arvense, Myagrum rugosum, Lepidium virginicum, Coronopus didymus, Descurarinia sophia, Rorippa indica, Sisymnrium officinale, Cardamine flexuosa, Nasturtium officinale, and Draba nemoresa.
[0380] Capparaceae weeds: Cleome affinis.
[0381] Fabaceae weeds: Aeschynomene indica, Aeschynom enerudis, Aeschynomene denticulata, Aeschynomene rudis, Sesbania exaltata, Cassia obtusifolia, Cassia occidentalis, Desmodium tortuosum, Desmodium adscendens, Desmodium illinoense, Trifolium repens, Pueraria lobata, Vicia angustifolia, Indigofera hirsuta, Indigofera truxillensis, Vigna sinensis, Crotalaria incana, Vicia sativa, Medicago lupulina, Vicia hirsuta, Kummerowia striata, and Medicago polymorpha.
[0382] Oxalidaceae weeds: Oxalis corniculata, Oxalis strica, Oxalis oxyptera, and Oxalis debilis.
[0383] Geraniaceae weeds: Geranium carolinense, Erodium cicutarium, Dove's Foot Crane's-bill (Geranium mole) and Hedgerow Crabe's-bill (Geranium pyrenaicum).
[0384] Euphorbiaceae weeds: Euphorbia helioscopia, Euphorbia maculata, Euphorbia hum istrata, Euphorbia esula, Euphorbia heterophylla, Euphorbia brasiliensis, Acalypha australis, Croton glandulosus, Croton lobatus, Phyllanthus corcovadensis, Ricinus com m unis, Astraea lobata, Chamaesyce hirta, and Chamaesyce hyssopifolia.
[0385] Malvaceae weeds: Abutilon theophrasti, Sida rhombiforia, Sida cordifolia, Sida spinosa, Sida glaziovii, Sida santaremnensis, Sida urens, Hibiscus trionum, Anoda cristata, Malvastrum corom andelianum, and Triumfetta rhomboidea.
[0386] Onagraceae weeds: Ludwigia epilobioides, Ludwigia octovalvis, Ludwigia decurre, Ludwigia leptocarpa, Oenothera biennis, and Oenothera laciniata. 5
[0387] Sterculiaceae weeds: Waltheria indica. Violaceae weeds: Viola arvensis and Viola tricolor.
[0388] Cucurbitaceae weeds: 10 Sicyos angulatus, Echinocystis lobata, and Momordica charantia.
[0389] Lythraceae weeds: Ammannia multiflora, Ammannia auriculata, Ammannia coccinea, Lythrum salicaria, and Rotala indica.
[0390] Elatinaceae weeds: 15 Elatine triandra and Elatine californica.
[0391] Apiaceae weeds: Oenanthe javanica, Daucus carota, Coniumm aculatum, and Cyclospermum leptophyllum.
[0392] Araliaceae weeds: 20 Hydrocotyle sibthorpioides and Hydrocotyle ranunculoides.
[0393] Ceratophyllaceae weeds: Ceratophyllum demersum.
[0394] Cabom baceae weeds: Cabomba caroliniana. 25
[0395] Haloragaceae weeds: Myriophyllum aquaticum, Myriophyllum verticillatum, Myriophyllum matogrossense, Myriophyllum spicatum, Myriophyllum heterophyllum, and the like.
[0396] Sapindaceae weeds: Cardiospermum halicacabum. 30
[0397] Prim ulaceae weeds: Anagallis arvensis.
[0398] Asclepiadaceae weeds: Asclepias syriaca and Ampelamus albidus.
[0399] Rubiaceae weeds: 35 Galium aparine, Galium spurium var. echinospermon, Spermacoce latifolia, Diodella teres, Richardia brasiliensis, and Borreria alata.
[0400] Convolvulaceae weeds: Ipomoea nil, Ipomoea hederacea, Ipomoea purpurea, Ipomoea hederacea var. integriuscula, Ipomoea lacunosa, Ipomoea triloba, Ipooea acuminata, Ipomoea hederifolia, Ipomoea coccinea, Ipomoea quamoclit, Ipomoea grandifolia, Ipomoea aristolochiafolia, Ipomoea cairica, Convolvulus arvensis, Calystegia hederacea, Calystegia japonica, Merremia hedeacea, Merremia aegyptia, Merremia cissoides, and Jacquemontia tamnifolia.
[0401] Boraginaceae weeds: Myosotis arvensis, Myosotis arvensis, Lithospermum officinale, Echium plantagineum, and Heliotropium indicum.
[0402] Lamiaceae weeds: Lamium purpureum, Lamium amplexicaule, Leonotis nepetaefolia, Hyptis suaveolens, Hyptis lophanta, Leonurus sibiricus, Stachys arvensis, Leonurus sibiricus, and Marsypianthes chamaedrys.
[0403] Solanaceae weeds: Datura stramonium, Solanum nigrum, Solanum americanum, Solanum ptycanthum, Solanum sarrachoides, Solanum rostratum, Solanum aculeatissimum, Solanum sisym briifolium, Solanum carolinense, Physalis angulata, Physalis subglabrata, and Nicandra physaloides.
[0404] Linderniaceae weeds: Lindernia procumbens, Lindernia dubia, and Lindernia angustifolia.
[0405] Plantaginaceae weeds: Plantago asiatica, Plantago lanceolata, Plantago major, Callitriche palustris, Limnophila sessiliflora, Dopatrium junceum, Gratiola japonica, Bacopa rotundifolia, Veronica hederaefolia, Veronica persica, Veronica arvensis, Veronica anagallis-aquatica, and Plantago tomentosa.
[0406] Asteraceae weeds: Xanthium pensylvanicum, Xanthium occidentale, Xanthium italicum, Helianthus annuus, Matricaria chamomilla, Matricaria perforata, Chrysanthemum segetum, Matricaria matricarioides, Artemisia princeps, Artemisia vulgaris, Artemisia verlotorum, Solidago altissima, Taraxacum officinale, Galinsoga ciliata, Galinsoga parviflora, Senecio vulgaris, Senecio brasiliensis, Senecio grisebachii, Conyza bonariensis, Conyza sumatrensis, Conyza canadensis, Ambrosia artemisiifolia, Ambrosia trifida, Bidens tripartita, Bidens pilosa, Bidens frondosa, Bidens subalternans, Cirsium arvense, Cirsium vulgare, Silybum marianum, Carduus nutans, Lactuca serriola, Sonchus oleraceus, Sonchus asper, Wedeliaglauca, Melampodium perfoliatum, Emilia sonchifolia, Emilia fosbergii, Tagetes minuta, Blainvillea latifolia, Blainvillea dichotoma, Tridax procumbens, Porophyllum ruderale, Acanthospermum australe, Acanthospermum hispidum, Cardiosperm um halicacabum, Ageratum conyzoides, Eupatorium perfoliatum, Eclipta alba, Erechtites hieracifolia, Gamochaeta spicata, Gnaphalium spicatum, Jaegeria hirta, Parthenium hysterophorus, Siegesbeckia orientalis, Soliva sessilis, Eclipta prostrata, Centipeda minima, Anthemis cotula, Cirsium setosum, Centurea cyanus, Coreopsis lanceolata, Rudbeckia hirta, Rudbeckia laciniata, Rudbeckia laciniata var. hortensis Bailey, Bidens subaltemans, Gymnocoronis spilanthoides, Hypochaeris chillensis, and Pluchea sagittalis.
[0407] Alism ataceae weeds: Sagittaria pygmaea, Sagittaria trifolia, Sagittaria sagittifolia, Sagittaria montevidensis, Sagittaria aginashi, Alisma canaliculatum, and Alisma plantago-aquatica.
[0408] Limnocharitaceae weeds: Limnocharis flava.
[0409] Hydrocharitaceae weeds: Limnobium spongia, Hydrilla verticillata, Najas guadalupensis, and Egeria densa.
[0410] Araceae weeds: Pistia stratiotes.
[0411] Lemnaceae weeds: Lemna aoukikusa, Spirodela polyrhiza, and Wolffia globosa.
[0412] Potamogetonaceae weeds: Potamogeton distinctus, Potamogetoncrispus, Potamogeton illinoensis, Stuckenia pectinata.
[0413] Liliaceae weeds: Allium canadense, Allium vineale, and Allium macrostemon.
[0414] Pontederiaceae weed: Eichhornia crassipes, Heteranthera limosa, Monochoria korsakowii, Monochoria vaginalis, and Heterandera reniformis.
[0415] Commelinaceae weeds: Commelina communis, Commelina bengharensis, Commelina erecta, Murdannia keisak, and Doveweed (Murdannia nudiflora).
[0416] Poaceae weeds: Echinochloa crus-galli, Echinochloa oryzicola, Echinochloa crus-galli var formosensis, Echinochloa oryzoides, Echinochloa colona, Echinochloa crus-pavonis, Setaria viridis, Setaria faberi, Setaria glauca, Setaria geniculata, Digitaria ciliaris, Digitaria sanguinalis, Digitaria horizontalis, Digitaria insularis, Eleusine indica, Poa annua, Poa trivialis, Poa pratensis, Alospecurus aequalis, Alopecurus myosuroides, Avena fatua, Sorghum halepense, Sorghum vulgare, Sorghum arundinaceum, Agropyron repens, Lolium multiflorum, Lolium perenne, Lolium rigidum, Bromus catharticus, Bromus sterilis, Bromus japonicus, Bromus secalinus, Bromus tectorum, Hordeum jubatum, Aegilops cylindrica, Phalaris arundinacea, Phalaris minor, Apera spica-venti, Panicum dichotomiflorum, Panicum texanum, Panicum maximum, Brachiaria platyphylla, Brachiaria ruziziensis, Brachiaria plantaginea, Brachiaria decumbens, Brachiaria brizantha, Brachiaria humidicola, Urochloa mutica, Cenchrus echinatus, Cenchrus pauciflorus, Eriochloa villosa, Chloris gayana, Chlorisvirgata, Eragrostis pilosa, Eragrostis plana, Rhynchelitrum repens, Dactyloctenium aegyptium, Ischaem um rugosum, Isachne globosa, Oryza sativa, Paspalum notatum, Paspalum maritimum, Paspalum distichum, Pennisetum clandestinum, Pennisetum setosum, Rottboellia cochinchinensis, Leptochloa chinensis, Leptochloa fascicularis, Leptochloa panicea, Leptochloa filiformis, Leptochloa panicoides, Leersia japonica, Leersia hexandra, Leersia sayanuka, Leersia oryzoides, Glyceria leptorrhiza, Glyceria acutiflora, Glyceria maxima, Agrostis gigantea, Agrostis stolonifera, Cynodon dactylon, Dactylis glomerata, Eremochloa ophiuroides, Festucaarun dinacea, Festuca rubra, Imperata cylindrica, Miscanthus sinensis, Panicum virgatum, Zoysia japonica, Luziola peruviana, Melinis repens, and Spartina anglica.
[0417] Cyperaceae weeds: Cyperus microiria, Cyperus iria, Cyperus compressus, Cyperus difformis, Cyperus flaccidus, Cyperus globosus, Cyperus nipponics, Cyperus odoratus, Cyperus serotinus, Cyperus rotundus, Cyperus esculentus, Kyllinga gracillima, Kyllinga brevifolia, Fimbristylis miliacea, Fimbristylis dichotoma, Eleocharis acicularis, Eleocharis kuroguwai, Schoenoplectiella hotarui, Schoenoplectiella juncoides, Schoenoplectiella wallichii, Schoenoplectiella mucronatus, Schoenoplectiella triangulatus, Schoenoplectiella nipponicus, Schoenoplectiella triqueter, Bolboschoenus koshevnikovii, Bolboschoenus fluviatilis, and Scirpus tabernaemontani.
[0418] Equisetaceae weeds: Equisetum arvense and Equisetum palustre.
[0419] Salviniaceae weeds: Salvinia natans.
[0420] Azollaceae weeds: Azolla japonica, Azollaim bricata, Salvinia natanas, and Azolla cristata.
[0421] Marsileaceae weeds: Marsilea quadrifolia.
[0422] Ricciaceae weeds: Ricciocarpus natans.
[0423] Rosaceae weeds: Alchemilla monticola.
[0424] Ranunculaceae weeds: Ranunculus muricatus and Ranunculus sardous.
[0425] Fumarioideae weeds: Fumaria officinalis.
[0426] Characeae weeds: Chara braunii.
[0427] Eriocaulaceae weeds: Eriocaulon cinereum.
[0428] Zygnemataceae weeds: Spirogyra arcla.
[0429] Others: Filamentous algaes (Pithophora and Cladophora), mosses, bryophyte, hornworts, cyanobacteria, bracken, and suckers of perennial crops (for example, pomaceous fruits, stone fruits, berry fruits, nuts, citrus fruits, hop, and grape).
[0430] The mutation in the species of the above weeds is not particularly limited. That is, the weeds (herbicide-tolerant weeds) having got less sensitive (also referred to as exhibiting tolerance) to a specific herbicide are also included. The reduction of sensitivity may be caused due to either a mutation at the target site (target-site mutation) or a factor that is not a target-site mutation (non-target-site mutation). The target-site mutation includes a mutation in which an amino acid substitution is caused in a protein that is a target site due to a mutation of a nucleic acid sequence portion (open reading frame) corresponding to an amino acid sequence of a protein, and a mutation in which a protein at the target site expressed in an excessive or reduced amount due to mutations such as a deletion of a suppressor sequence in a promoter region, amplification of an enhancer sequence, or an increase or decrease in the copy number of a gene. The non-target-site mutation includes an increase in metabolism, malabsorption, transition failure, and external excretion, and the like. Examples of the factors of the increase in metabolism include increases in activities of metabolic enzymes such as cytochrome P450 monooxygenase, aryl acylamidase, esterase, and glutathione S-transferase. Examples of the external excretion include transportation into vacuoles by ABC transporters.
[0431] Examples of the herbicide-resistant weed (resistant weed) include weeds resistant to 5-enolpyruvylshikimate-3-phosphate (EPSP) synthase inhibitors such as glyphosate, weeds resistant to hormone disruption herbicides such as 2,4-D and dicamba, weeds resistant to an acetolactate synthase (ALS) inhibitor, weeds resistant to an acetyl-CoA carboxylase (ACCace) inhibitor, weeds resistant to a protoporphyrinogen oxidase (PPO) inhibitor, weeds resistant to an auxinic herbicide, weeds resistant to a 4-hydroxyphenylpyruvate dioxygenase (4-HPPD) inhibitor, weeds resistant to a photosystem II inhibitor, weeds resistant to a photosystem I electron converter, weeds resistant to a carotenoid biosynthesis inhibitor, weeds resistant to a glutamine synthase inhibitor, weeds resistant to a phytoene desaturase (PDS) inhibitor, weeds resistant to a fatty acid biosynthesis inhibitor, weeds resistant to a very-long-chain fatty acid elongase (VLCFAE) inhibitor, weeds resistant to an auxin transport inhibitor, weeds resistant to a dihydropteroate (DHP) synthetase inhibitor, weeds resistant to a cellulose synthetase inhibitor, weeds resistant to a microtubule polymerase inhibitor, and weeds resistant to a mitosis / microtubule formation inhibitor.
[0432] The resistant weeds having a combination of (stacked) resistance to two or more groups (arbitrarily selected two groups, arbitrarily selected three groups, arbitrarily selected four groups, arbitrarily selected five groups, six groups, seven groups, or eight groups) in the above groups can also effectively controlled. As examples of the stacked resistant weeds, Waterhemp (Amaranthus tuberculatus=Amaranthus rudis=Amaranthus tamariscinus) resistant to all of the acetolactate synthase (ALS) inhibitor, the protoporphyrinogen oxidase (PPO) inhibitor, the 4-hydroxyphenylpyruvate dioxygenase (4-HPPD) inhibitor, the photosystem II inhibitor, and 2,4-D is known, but is also effectively controlled. The stack may be a combination of target-site mutations, a combination of non-target-site mutations, or a combination of a target-site mutation and a non-target-site mutation.
[0433] The herbicides of the present invention and pesticide composition of the present invention (the concept is that it contains the herbicide) may be applied simultaneously or dividedly to the above useful plants (the useful plants having agricultural, horticultural and industrial uses), or to a place (cultivation area) where the useful plants are to be grown, a place where the useful plants are growing, or to a non-crop land. "Applied simultaneously or dividedly" means applying the herbicide or pesticide composition in one or more times. In this case, weeds may already be generated in the useful plant or the cultivation area of the useful plant, or weeds may not be generated yet.
[0434] Examples of the method of applying the herbicide of the present invention and the pesticide composition of the present invention (the concept is that it contains the herbicide) simultaneously or dividedly to useful plants, or to a place where the useful plants are to be grown or where the useful plants are growing, or to a non-crop land simultaneously or dividedly include a foliage treatment, a soil treatment, a root part treatment, a shower treatment, a smoking treatment, a water surface treatment, a seed treatment, and a hydroponic liquid treatment.
[0435] Examples of the foliage treatment include methods of treating the herbicide of the present invention and the pesticide composition containing the herbicide of the present invention on a surface of foliage, trunks, fruits, flowers (including before, during, and after flowering), ears, or the entire plant surface.
[0436] Examples of the soil treatment include soil dispersion, soil incorporation, and chemical drenching into the soil. In addition, examples of the place where the soil treatment is performed include a planting hole, a planting furrow, a vicinity of the planting hole, the vicinity of the planting furrow, the entire surface of the cultivation area, the parts between the soil and the plant, an area between roots, an area beneath the trunk, a main furrow, growing soil, a box for raising seedlings, a tray for raising seedlings, and a seedbed. Examples of the timing of the treatment include before sowing, at the time of sowing, after sowing, seedling raising period, before settled planting, at the time of settled planting, and growing time after settled planting. In addition, in the soil treatment, the herbicide of the present invention and the pesticide composition of the present invention(the concept is that it contains the herbicide) may be mixed with an irrigation liquid, and examples thereof include injection into an irrigation facility (an irrigation tube, an irrigation pipe, a sprinkler, or the like), mixing into an interrow flooding liquid, and mixing into a hydroponic liquid. In addition, the irrigation liquid and the active ingredients may be mixed in advance and treated using an appropriate irrigating method, for example, the above-described irrigation method and other irrigation methods such as water sprinkling and flooding.
[0437] Examples of the root part treatment include a method of immersing a root part of the useful plant into a chemical liquid containing the herbicide of the present invention and the pesticide composition of the present invention (the concept is that it contains the herbicide) and a method of adhering a solid formulation containing the herbicide of the present invention and the pesticide composition of the present invention (the concept is that it contains the herbicide) to a root part of the useful plant.
[0438] Examples of the shower treatment include a method of showering a diluted solution of the herbicide of the present invention and the pesticide composition of the present invention (the concept is that it contains the herbicide) onto the foliage or the like of the useful plant.
[0439] Examples of the smoking treatment include a method of scattering a diluted solution of the herbicide of the present invention and the pesticide composition of the present invention (the concept is that it contains the herbicide) in the air into a mist form to adhere it on the foliage or the like of the useful plant.
[0440] Examples of the water surface treatment include a method of spraying a chemical liquid or a solid formulation containing the herbicide of the present invention and the pesticide composition of the present invention (the concept is that it contains the herbicide) on a paddy field in a flooding state.
[0441] Examples of the seed treatment include a treatment of the herbicide of the present invention and the pesticide composition of the present invention (the concept is that it contains the herbicide) on a seed or a vegetative propagation organ. In particular, an example of the vegetative propagation organ includes a seed potato.
[0442] Examples of the hydroponic liquid treatment include a method of mixing or incorporating a chemical liquid or a solid formulation containing the herbicide of the present invention and the pesticide composition of the present invention (the concept is that it contains the herbicide) into a hydroponic liquid (a hydroponic liquid mixing treatment, a hydroponic liquid incorporation treatment, or the like).
[0443] The herbicide of the present invention and the pesticide composition of the present invention (the concept is that it contains the herbicide) can be applied by a spot treatment. The spot treatment is a concept opposite to a uniform treatment of the herbicide of the present invention and the pesticide composition of the present invention (the concept is that it contains the herbicide), and refers to a treatment in which the herbicide of the present invention and the pesticide composition of the present invention (the concept is that it contains the herbicide) are selectively sprayed at a place where weeds are grown or a place where weeds are likely to be grown. The "treatment at a place" refers to a treatment performed on a plant or soil where weeds are grown or are likely to be grown. In addition, only a case where all places where weeds are grown and where weeds are likely to be grown are selectively treated in a continuous cultivation area is not regarded as the spot treatment. That is, in a case where a part of the cultivation area is subjected to an area treatment or even in a case where a part of a place where weeds are grown or a place where weeds are likely to be grown is not subjected to a treatment with the herbicide of the present invention and the pesticide composition of the present invention (the concept is that it contains the herbicide), it is included in the spot treatment when a place subjected to a spot treatment is present in the continuous cultivation area.
[0444] <Weeds Controlling Method> The method for controlling weeds of the present invention is a method in which an active ingredient amount of the azolyloxy heterocyclic compound or the salt thereof of the present invention (the present compound represented by the general formula [I]) is applied to weeds to control.
[0445] In the method for controlling weeds of the present invention, the pesticide composition (specifically, the herbicide) of the present invention is simultaneously or dividedly applied to a useful plant having agricultural, horticultural and industrial uses, or a place where the useful plant having agricultural, horticultural and industrial uses is to be grown, or is growing.
[0446] The places to which the herbicide containing the azolyloxy heterocyclic compound of the present invention or a salt thereof is applied to control weeds may be a paddy field, a dry field, a lawn, an orchard, a non-crop land, a greenhouse, a seedling raising facility, a plant factory, or the like. [Examples]
[0447] Next, the production methods, the formulation methods, and the applications of the present compound will be described in detail in the following Examples, but the present invention is not limited to these Examples in any way.
[0448] The melting point, which is a physical property of the present compound, was determined by MP-500V micro melting point measuring apparatus manufactured by Yanako. The refractive index was determined by using Abbe refractometer manufactured by ATAGO CO., LTD. 1H NMR spectrum was determined by using JNM-ECZL500R (500 MHz), JNM-ECZL400S (400 MHz), JNM-LA400 (400 MHz), JNM-ECS300 (300 MHz), JNM-LA300 (300 MHz) manufactured by JEOL Ltd., or Spinsolve 80ULTRA (80 MHz) manufactured by Magritek, and tetramethylsilane (TMS) as the internal standard.
[0449] Methods of producing production intermediates of the present compound are also described.
[0450] (Example 1) Production of 4- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy -2-phenylbenzoxazole (Present Compound Number: A-0014)
[0451] 1) 1-Methyl-5-(2-nitrophenoxy)-3-(trifluoromethyl)-1H-pyrazole
[0452] 2-Fluoronitrobenzene (25.00 g, 177 mmol) was dissolved in N,N- dimethylformamide (200 mL), 1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-ol (32.3 g, 194 mmol) and potassium carbonate (36.6 g, 265 mmol) were sequentially added, and the mixture was stirred at 100 °C for 6 hours. The reaction solution was poured into ice water, and the precipitated solid was collected by filtration, washed with water, and dried under reduced pressure to give 1-methyl-5-(2-nitrophenoxy)-3-(trifluoromethyl)-1H-pyrazole (47.67 g, yield: 94 ).
[0453] 1H NMR (400 MHz, CDCl3 / TMS) (ppm): 8.07-8.04 (1H, m), 7.69-7.65 (1H, m), 7.42-7.38 (1H, m), 7.32-7.29 (1H, m), 5.85 (1H, s), 3.87 (1H, s)
[0454] 2) 2- [1-Methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy aniline
[0455] 1-Methyl-5-(2-nitrophenoxy)-3-(trifluoromethyl)-1H-pyrazole (47.67 g, 166 mmol) was dissolved in ethanol (400 mL), and hot water (200 mL), iron powder (46.3 g, 829 mmol) and ammonium chloride (4.44 g, 83.0 mmol) were sequentially added, and the mixture was stirred at 80 °C for 1 hour. The reaction solution was filtered, and the filtrate was concentrated under reduced pressure. The residue was extracted with ethyl acetate, the organic layer was washed sequentially with water and saturated brine, dried with anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The residue was washed with hexane and dried under reduced pressure to give 2- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy aniline (38.83 g, yield: 91 ).
[0456] 1H NMR (400 MHz, CDCl3 / TMS) (ppm): 7.06-7.02 (1H, m), 6.94-6.92 (1H, m), 6.85-6.83 (1H, m), 6.75-6.71 (1H, m), 5.78 (1H, s), 3.84 (3H, s), 3.82 (2H, br s)
[0457] 3) 2,4-Dibromo-6- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5- yl]oxy aniline
[0458] 2- [1-Methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy aniline (38.83 g, 151 mmol) was dissolved in chloroform (400 mL), and N-bromosuccinimide (56.4 g, 317 mmol) was added under ice-cooling, and the mixture was warmed to 20 °C and stirred for 16 hours. The reaction solution was poured into a saturated sodium bicarbonate solution, sodium thiosulfate solution was added, and the mixture was extracted with chloroform. The organic layer was dried with anhydrous sodium sulfate and the solvent was distilled under reduced pressure. The residue was purified by silica gel column chromatography to give 2,4-dibromo-6- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy aniline (49.89 g, yield: 80 ).
[0459] 1H NMR (400 MHz, CDCl3 / TMS) (ppm): 7.44 (1H, d), 6.98 (1H, d), 5.91 (1H, s), 4.31 (2H, br s), 3.82 (3H, s)
[0460] 4) N-(2,4-Dibromo-6- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5- yl]oxy phenyl)benzamide
[0461] 2,4-Dibromo-6- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5- yl]oxy aniline (49.89 g, 120mmol) was dissolved in chloroform (400 mL), pyridine (14.5 mL, 180 mmol) and benzoyl chloride (15.3 mL, 132 mmol) were sequentially added under ice-cooling, and the mixture was warmed to 20 °C and stirred for 48 hours. The reaction solution was poured into methanol and the solvent was distilled under reduced pressure. The residue was extracted with ethyl acetate, and the organic layer was washed sequentially with diluted hydrochloric acid, water and saturated brine, dried with anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The residue was purified by silica gel column chromatography to give N-(2,4-dibromo-6- [1- methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy phenyl)benzamide (54.08 g, yield: 87 ).
[0462] 1H NMR (400 MHz, CDCl3 / TMS) (ppm): 7.86-7.83 (2H, m), 7.67 (1H, d), 7.61-7.57 (1H, m), 7.52-7.48 (2H, m), 7.39 (1H, br s), 7.18 (1H, d), 5.99 (1H, s), 3.73(3H, s)
[0463] 5) 6-Bromo-4- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy -2- phenylbenzoxazole (Present Compound Number: A-0272)
[0464] N-(2,4-dibromo-6- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5- yl]oxy phenyl)benzamide (54.08 g, 104 mmol) was dissolved in monoglyme (500 mL), and copper(I) iodide (992 mg, 5.21 mmol), 1,10-phenanthroline (1.87 g, 10.4 mmol) and cesium carbonate (67.8 g, 208 mmol) were added sequentially, and the mixture was stirred at 100 °C for 5 hours. Additional copper(I) iodide (500 mg), 1,10-phenanthroline (1.0 g) and cesium carbonate (20 g) were added sequentially to the reaction solution and further stirred at 90 °C for 16 hours. The solvent was distilled under reduced pressure and the residue was poured into ice water and extracted with ethyl acetate. The organic layer was washed sequentially with diluted hydrochloric acid, water and saturated brine, dried with anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The residue was purified by silica gel column chromatography to give 6-bromo-4- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy -2-phenylbenzoxazole (31.11 g, yield: 68 ).
[0465] 1H NMR (400 MHz, CDCl3 / TMS) (ppm): 8.24-8.21 (2H, m), 7.64 (1H, d), 7.58-7.51 (3H, m), 7.16 (1H, d), 6.02 (1H, s), 3.91 (3H, s)
[0466] Melting point: 132-133 °C
[0467] 6) 4- [1-Methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy -2- phenylbenzoxazole (Present Compound Number: A-0014)
[0468] 6-Bromo-4- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy -2- phenylbenzoxazole (31.11 g, 71.0 mmol) was dissolved in ethyl acetate (300 mL), and ethanol (300 mL), triethylamine (14.8 mL, 105 mmol) and palladium-carbon (load content: 10 , 1.50 g) were added sequentially, and the mixture was stirred at 20 °C for 1 hour in a hydrogen atmosphere. The reaction solution was filtered and the solvent was distilled under reduced pressure. The precipitated solid was filtered off and the solvent was further distilled under reduced pressure. The residue was purified by silica gel column chromatography to give 4- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy -2-phenylbenzoxazole (24.80 g, yield: 97 ).
[0469] 1H NMR (300 MHz, CDCl3 / TMS) (ppm): 8.28-8.25 (2H, m), 7.55-7.26 (5H, m), 7.02 (1H, m), 5.97 (1H, s), 3.92 (3H, s)
[0470] Melting point 84-85 °C
[0471] (Example 2) Production of N-isopropyl-4- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy benzoxazole-2-carboxamide (Present Compound Number: A-0090)
[0472] 1) 5,5‘-[(2-nitro-1,3-phenylene)bis(oxy)]bis[1-methyl-3-(trifluoromethyl)- 1H-pyrazole]
[0473] 2,6-Difluoronitrobenzene (20.0 g, 126 mmol) was dissolved in N,N- dimethylformamide (400 mL), 1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-ol (45.9 g, 276 mmol) and potassium carbonate (43.4 g, 314 mmol) were sequentially added, and the mixture was stirred at 60 °C for 16 hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed sequentially with water and saturated brine, dried with anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The residue was purified by silica gel column chromatography to give 5,5‘-[(2-nitro-1,3-phenylene)bis(oxy)]bis[1-methyl-3-(trifluoromethyl)-1H-pyrazole] (36.0 g, yield: 63 ).
[0474] 1H NMR (300 MHz, CDCl3 / TMS) (ppm): 7.51 (1H, t), 7.03 (2H, d), 6.13 (2H, s), 3.82 (6H, s)
[0475] 2) 5-[3-(Benzyloxy)-2-nitrophenoxy]-1-methyl-3-(trifluoromethyl)-1H- pyrazole
[0476] 5,5‘-[(2-N itro- 1,3-phenylene)bis(oxy)]bis [ 1 -methyl-3-(trifluoromethyl)- 1H-pyrazole] (46.0 g, 102 mmol) was dissolved in N,N-dimethylformamide (400 mL), benzyl alcohol (11.0 g, 102 mmol) and sodium hydride (60 dispersed in mineral oil, 4.89 g, 122 mmol) were sequentially added under ice cooling, and the mixture was stirred at 20 °C for 3 hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed sequentially with water and saturated brine, dried with anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The residue was washed with hexane to give 5-[3-(benzyloxy)-2-nitrophenoxy]-1-methyl-3-(trifluoromethyl)-1H-pyrazole (34.0 g, yield: 85 ).
[0477] 1H NMR (300 MHz, CDCl3 / TMS) (ppm): 7.42-7.30 (6H, m), 6.91 (1H, d), 6.72 (1H, d), 6.06 (1H, s), 5.23 (2H, s), 3.78 (3H, s)
[0478] 3) 2-amino-3- [1-methyl-3-(trifluoromethyl)1H-pyrazol-5-yl]oxy phenol (Present Compound Number: E-0019)
[0479] 5-[3-(Benzyloxy)-2-nitrophenoxy]-1-methyl-3-(trifluoromethyl)-1H- pyrazole (15.0 g, 38.1 mmol) was dissolved in ethanol (200 mL), ethyl acetate (100 mL) and a suspension of palladium-carbon (load content: 5 , 1.5 g) in ethanol (30 mL) were sequentially added, and the mixture was stirred at 20 °C for 10 hours in a hydrogen atmosphere. The reaction solution was filtered and the solvent was distilled under reduced pressure. The residue was extracted with ethyl acetate, the organic layer was washed with water, dried with anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The residue was washed with hexane to give 2-amino-3- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy phenol (10.0 g, yield: 96 ).
[0480] 1H NMR (400 MHz, CDCl3 / TMS) (ppm): 6.65-6.56 (3H, m), 5.81 (1H, s), 3.83 (3H, s), 3.78 (2H, br s)
[0481] 4) Ethyl 4- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5- yl]oxy benzoxazole-2-carboxylate (Present Compound Number: A-0089)
[0482] 2-Amino-3- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy phenol (3.0 g, 11 mmol) was dissolved in pyridine (100 mL), ethyl chloroglyoxylate (7.5 g, 55 mmol) was added under ice-cooling, and the mixture was stirred at 100 °C for 4 hours. The solvent was distilled under reduced pressure, the residue was poured into water and extracted with ethyl acetate. The organic layer was washed sequentially with a copper(II) sulfate aqueous solution, water, and saturated brine, dried with anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The residue was purified by silica gel column chromatography and further washed with hexane to give ethyl 4- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy benzoxazole-2-carboxylate (2.0 g, yield: 51 ).
[0483] 1H NMR (300 MHz, CDCl3 / TMS) (ppm):7.56-7.48 (2H, m), 7.11-7.08 (1H, m), 5.96 (1H, s), 4.58 (2H, q), 3.88 (3H, s), 1.49 (3H, t)
[0484] Melting point: 110-112 °C
[0485] 5) N-Isopropyl-4- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5- yl]oxy benzoxazole-2-carboxamide (Present Compound Number: A-0090)
[0486] Ethyl 4- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5- yl]oxy benzoxazole-2-carboxylate (500 mg, 1.41 mmol) was dissolved in ethanol (20 mL), isopropylamine (166 mg, 2.81 mmol) was added, and the mixture was stirred in a sealed tube at 120 °C for 16 hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed sequentially with water and saturated brine, dried with anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The residue was purified by silica gel column chromatography and further washed with hexane:diisopropyl ether (1:1) to give N-isopropyl-4- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy benzoxazole-2-carboxamide (393 mg, yield: 76 ).
[0487] 1H NMR (300 MHz, CDCl3 / TMS) (ppm): 7.55-7.43 (2H, m), 7.07-7.04 (2H, m), 5.97 (1H, s), 4.32 (2H, q), 3.88 (3H, s), 1.30 (3H, t)
[0468] Melting point: 130-131 °C
[0489] (Example 3) Production of 4- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5- yl]oxy benzoxazole (Present Compound Number: A-0001)
[0490] 2-Amino-3- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy phenol (4.0 g, 15 mmol) was dissolved in ethyl orthoformate (20 mL) and stirred at reflux for 3 hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed sequentially with water and saturated brine, dried with anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The residue was purified by silica gel column chromatography and further washed with hexane to give 4- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl] oxy benzoxazole (3.1 g, yield: 75 ).
[0491] 1H NMR (300 MHz, CDCl3 / TMS) (ppm): 8.11 (1H, s), 7.48-7.40 (2H, m), 7.08 (1H, d), 5.89 (1H, s), 3.90(3H, s)
[0492] Melting point 85-86 °C
[0493] (Example 4) Production of 4- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy -2-morpholinobenzoxazole (Present Compound Number: A-0087)
[0494] 4- [1-Methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy benzoxazole (150 mg, 0.53 mmol) was dissolved in acetonitrile (10 mL), morpholine (55 mg, 0.63 mmol), copper(II) bromide (12 mg, 0.054 mmol) and acetic acid (64 mg, 1.1 mmol) were added sequentially, and the mixture was stirred at 50 °C for 16 hours. The reaction solution was filtered through silica gel and the solvent was distilled under reduced pressure. The residue was purified by silica gel column chromatography to give 4- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy -2-morpholinobenzoxazole (79 mg, yield: 40 ).
[0495] 1H NMR (300 MHz, CDCl3 / TMS) (ppm): 7.14-6.85 (3H, m), 5.85 (1H, s), 3.87 (3H, s), 3.83-3.69 (8H, m)
[0496] Melting point 88-90 °C
[0497] (Example 5) Production of 4- [1-methyl-3-(trifluoromethyl)-1H-1,2,4-triazol-5-yl]oxy -2-propoxybenzoxazole (Present Compound Number: B-0639)
[0498] 1) 4-(Methoxymethoxy)-2-(methylthio)benzoxazole
[0499] 2-Amino-3-(methoxymethoxy)phenol (described in WO 2023 / 112856 pamphlet, 430 mg, 2.54 mmol) was dissolved in ethanol (20 mL), ethyl potassium xanthate (530 mg, 3.31 mmol) was added, and the mixture was stirred at reflux for 4 hours. The reaction solution was poured into water, aqueous citric acid was added thereto, and the mixture was extracted with ethyl acetate. The organic layer was washed sequentially with water and saturated brine, the organic layer was dried with anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure to give crude 4- (methoxymethoxy)benzoxazole-2-thiol (550 mg).
[0500] The obtained crude 4-(methoxymethoxy)benzoxazole-2-thiol was dissolved in tetrahydrofuran (10 mL), iodomethane (0.19 mL, 3.05 mmol) and potassium carbonate (455 mg, 3.29 mmol) were sequentially added, and the mixture was stirred at 20 °C for 2 hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed sequentially with water and saturated brine, the organic layer was dried with anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The residue was purified by silica gel column chromatography to give 4-(methoxymethoxy)-2-(methylthio)benzoxazole (430 mg, yield: 75 ).
[0501] 1H NMR (300 MHz, CDCl3 / TMS) (ppm): 7.18-7.10 (2H, m), 7.05-7.02 (1H, m), 5.44 (2H, s), 3.54 (3H, s), 2.77 (3H, s)
[0502] 2) 2-(methylthio)benzoxazol-4-ol
[0503] 4-(Methoxymethoxy)-2-(methylthio)benzoxazole (430 mg, 1.91 mmol) was dissolved in dichloromethane (20 mL), trifluoroacetic acid (10 mL) was added, and the mixture was stirred at 20 °C for 2 hours. The reaction solution was poured into water and extracted with dichloromethane. The organic layer was washed sequentially with a sodium bicarbonate solution and an aqueous citric acid solution, the organic layer was dried with anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The residue was purified by silica gel column chromatography to obtain 2-(methylthio)benzoxazol-4-ol (340 mg, yield: 98 ).
[0504] 1H NMR (300 MHz, CDCl3 / TMS) (ppm): 7.13 (1H, t), 7.01 (1H, d), 6.82 (1H, d), 6.65 (1H, s), 2.74 (3H, s)
[0505] 3) 4- [1-Methyl-3-(trifluoromethyl)-1H-1,2,4-triazol-5-yl]oxy -2- (methylsulfonyl)benzoxazole
[0506] 2-(Methylthio)benzoxazol-4-ol (340 mg, 1.88 mmol) was dissolved in N,N-dimethylformamide (20 mL), sodium hydride (55 dispersed in mineral oil, 106 mg, 2.43 mmol) and 1-methyl-5-(methylsulfonyl)-3-(trifluoromethyl)-1H-1,2,4-triazole (described in WO 2006 / 099957 pamphlet, 860 mg, 3.75 mmol) were sequentially added and stirred at 90 °C for 2 hours. The reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed sequentially with water and saturated brine, the organic layer was dried with anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The residue was purified by silica gel column chromatography to give crude 4- [1-methyl-3-(trifluoromethyl)-1H-1,2,4-triazol-5-yl]oxy -2-(methylthio)benzoxazole (770 mg).
[0507] The obtained crude 4- [1-methyl-3-(trifluoromethyl)-1H-1,2,4-triazol-5- yl]oxy -2-(methylthio)benzoxazole was dissolved in chloroform (20 mL), 3- chloroperbenzoic acid (wetted with 35 water, 1.19 g, 4.48 mmol) was added, and the mixture was stirred at 20 °C for 4 hours. The reaction solution was poured into a saturated sodium bicarbonate solution, a sodium thiosulfate solution was added, and the mixture was extracted with chloroform. The organic layer was washed sequentially with a saturated sodium bicarbonate solution and saturated brine, the organic layer was dried with anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The residue was purified by silica gel column chromatography to give 4- [1-methyl-3-(trifluoromethyl)-1H-1,2,4-triazol-5-yl]oxy -2-(methylsulfonyl)benzoxazole (570 mg, yield: 84 ).
[0508] 1H NMR (400 MHz, CDCl3 / TMS) (ppm): 7.66-7.59 (3H, m), 3.97 (3H, s), 3.42 (3H, s)
[0509] 4) 4- [1-Methyl-3-(trifluoromethyl)-1H-1,2,4-triazol-5-yl]oxy -2- propoxybenzoxazole (Present Compound Number: B-0639)
[0510] 4- [1-Methyl-3-(trifluoromethyl)-1H-1,2,4-triazol-5-yl]oxy -2- (methylsulfonyl)benzoxazole (270 mg, 0.75 mmol) was dissolved in 1-propanol (10 mL), triethylamine (0.26 mL, 1.85 mmol) was added, and the mixture was stirred at 20 °C for 4 hours. The solvent was distilled under reduced pressure and the residue was purified by silica gel column chromatography to give 4- [1-methyl-3-(trifluoromethyl)-1H-1,2,4-triazol-5-yl]oxy -2-propoxybenzoxazole (200 mg, yield: 78 ).
[0511] 1H NMR (300 MHz, CDCl3 / TMS) (ppm): 7.29-7.16 (3H, m), 4.45 (2H, t), 3.93 (3H, s), 1.85 (2H, sext), 1.03 (3H, t)
[0512] Refractive index n20D 1.4962
[0513] (Example 6) Production of 2,6-dimethyl-4- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy benzoxazole (Present Compound Number: A-0296)
[0514] 1) 2-Bromo-4-methyl-6- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5- yl]oxy aniline
[0515] 4-Methyl-2- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy aniline (described in WO 97 / 18196 pamphlet, 1.00 g, 3.68 mmol) was dissolved in dichloromethane (10 mL), bromine (648 mg, 4.05 mmol) was added and stirred at 20 °C for 16 hours. The reaction solution was poured into water and extracted with dichloromethane. The organic layer was washed sequentially with water and saturated brine, the organic layer was dried with anhydrous magnesium sulfate, and the solvent was distilled under reduced pressure. The residue was purified by silica gel column chromatography to give 2-bromo-4-methyl-6- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl]oxy aniline (700 mg, yield: 54 ).
[0516] 1H NMR (400 MHz, CDCl3 / TMS) (ppm): 7.13 (1H, d), 6.67 (1H, d), 5.83 (1H, s), 4.11 (2H, br s), 3.82 (3H, s), 2.21 (3H, s)
[0517] 2) N-(2-bromo-4-methyl-6- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5- yl]oxy phenyl)acetamide
[0518] 2-Bromo-4-methyl-6- [1-methyl-3-(trifluoromethyl)-1H-pyrazol-5- yl]oxy aniline (400 mg, 1.14 mmol) was dissolved in dichloromethane (10 mL), triethylamine (0.48 mL, 3.42 mmol) and acetyl chloride (0.16 mL, 2.24 mmol) were added, and the mixture was stirred at 20 °C for 16 hours. The reaction solution was poured into water and extracted with dichloromethane. The organic layer was washed sequentially with water and saturated brine, the organic layer was dried with anhydrous magnesium sulfate, and the solvent was distilled under reduced press...
Claims
1. An azolyloxy heterocyclic compound represented by general formula[I] or a salt thereof,[Chem. 1]R3wherein,when A1 is a nitrogen atom, A3 represents an oxygen atom or a sulfur atom, and when A3 is a nitrogen atom, A1 represents an oxygen atom or a sulfur atom,A4, A5, A6 and A7 each independently represent a nitrogen atom, C-H, or C-R4,R1 represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C6 cycloalkyl group, or a C3-C6 halocycloalkyl group,R2 represents a hydrogen atom, a halogen atom, an azido group, a cyano group, a cyanato group, an isocyanato group, a thiocyanato group, an isothiocyanato group, a nitro group, a C1-C6 alkyl group (the C1-C6 alkyl group may be substituted with one or more substituents selected from R7 substituents), a C2-C6 alkenyl group (the C2-C6 alkenyl group may be substituted with one or more substituents selected from R7 substituents), a C2-C6 alkynyl group (the C2-C6 alkynyl group may be substituted with one or more substituents selected from R7 substituents), a C3-C6 cycloalkyl group (the C3-C6 cycloalkyl group may be substituted with one or more substituents selected from R7 substituents), a heterocyclyl group (the heterocyclyl group may be substituted with one or more substituents selected from R5 substituents), a C6-C12 aryl group (the C6-C12 aryl group may be substituted with one or more substituents selected from R5 substituents), a heteroaryl group (the heteroaryl group may be substituted with one or more substituents selected from R5 substituents), a C7-C14 aralkyl group (the C7-C14 aralkyl group may be substituted with one or more substituents selected from R5 substituents), a heteroaralkyl group (the heteroaralkyl group may be substituted with one or more substituents selected from R5 substituents), a hydroxy group, a C1-C6 alkoxy group (the C1-C6 alkoxy group may be substituted with one or more substituents selected from R7 substituents), a C2-C6alkenyloxy group (the C2-C6 alkenyloxy group may be substituted with one or more substituents selected from R7 substituents), a C2-C6 alkynyloxy group (the C2-C6 alkynyloxy group may be substituted with one or more substituents selected from R7 substituents), a C3-C6 cycloalkyloxy group (the C3-C6 cycloalkyloxy group may be substituted with one or more substituents selected from R7 substituents), a C6-C12 aryloxy group (the C6-C12 aryloxy group may be substituted with one or more substituents selected from R5 substituents), a heteroaryloxy group (the heteroaryloxy group may be substituted with one or more substituents selected from R5 substituents), a C7-C14 aralkyloxy group (the C7-C14 aralkyloxy group may be substituted with one or more substituents selected from R5 substituents), a heteroaralkyloxy group (the heteroaralkyloxy group may be substituted with one or more substituents selected from R5 substituents), a sulfanyl group, a pentahalosulfanyl group, a formylthio group, a C1-C6 alkylcarbonylthio group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylthio group, a C1-C6 haloalkylsulfinyl group, a C1-C6 haloalkylsulfonyl group, a C3-C6 cycloalkylthio group, a C3-C6 cycloalkylsulfinyl group, a C3-C6 cycloalkylsulfonyl group, a C3-C6 halocycloalkylthio group, a C3-C6 halocycloalkylsulfinyl group, a C3-C6 halocycloalkylsulfonyl group, a C6-C12 arylthio group, a C6-C12 arylsulfinyl group, a C6-C12 arylsulfonyl group, a heteroarylthio group, a heteroarylsulfinyl group, a heteroarylsulfonyl group, a carboxyl group, a C1-C6 alkoxycarbonyl group, an aminocarbonyl group (the nitrogen atom of the aminocarbonyl group may be substituted with one or more substituents selected from R6 substituents), an aminothiocarbonyl group (the nitrogen atom of the aminothiocarbonyl group may be substituted with one or more substituents selected from R6 substituents), an amino group (the amino group may be substituted with one or more substituents selected from R6 substituents), or a (di (C1-C6 alkyl) sulfinylidene) amino group,R3 represents a hydrogen atom, a halogen atom, an azido group, a cyano group, a nitro group, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 halocycloalkyl group, a phenyl group, a pentahalosulfanyl group, or a C1-C6 alkoxycarbonyl group,R4 each independently represents a halogen atom, an azido group, a cyano group, a nitro group, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 haloalkyl group, a hydroxy group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a pentahalosulfanyl group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylthio group, a C1-C6 haloalkylsulfinyl group, a C1-C6 haloalkylsulfonyl group, a formyl group, a carboxyl group, an aminocarbonyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylcarbonylgroup, an amino group, a mono (C1-C6 alkyl) amino group, or a di (C1-C6 alkyl) amino group,R5 represents a halogen atom, an azido group, a cyano group, a nitro group, a hydroxy group, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a pentahalosulfanyl group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylthio group, a C1-C6 haloalkylsulfinyl group, a C1-C6 haloalkylsulfonyl group, a carboxyl group, a C1-C6 alkoxycarbonyl group, an aminocarbonyl group, a mono (C1-C6 alkyl) aminocarbonyl group, a di (C1-C6 alkyl) aminocarbonyl group, an amino group, a mono (C1-C6 alkyl) amino group, or a di (C1-C6 alkyl) amino group,R6 represents a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, or a hydroxyl group, and R6 may form a 3 to 7membered heterocyclic ring together with a nitrogen atom bound thereto,R7 represents a halogen atom, a cyano group, a nitro group, a hydroxy group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 halocycloalkyl group, a cyano C3-C6 cycloalkyl group, a pentahalosulfanyl group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylthio group, a C1-C6 haloalkylsulfinyl group, or a C1-C6 haloalkylsulfonyl group.
2. A pesticide composition comprising the azolyloxy heterocyclic compound or the salt thereof according to claim 1 as an active ingredient.
3. The pesticide composition according to claim 2, further comprising a surfactant.
4. A herbicide comprising the azolyloxy heterocyclic compound or the salt thereof according to claim 1 as an active ingredient.
5. The herbicide according to claim 4, which has a herbicidal activity on a weed growing in a dry field, a paddy field, an orchard, a lawn, a non-crop land, a greenhouse, a seedling raising facility, or a plant factory where a useful plant having agricultural, horticultural and industrial uses is cultured.
6. The herbicide according to claim 5, wherein the useful plant having agricultural, horticultural and industrial uses is a plant transformed in culturing by a breeding method or a gene recombination technique.
7. A method for controlling weeds using an active ingredient amount of the azolyloxy heterocyclic compound or the salt thereof according to claim 1.
8. A method for controlling weeds, wherein the pesticide composition according to claim 2 or 3 is simultaneously or dividedly applied to a useful plant having agricultural, horticultural and industrial uses or a place where a useful plant having agricultural, horticultural and industrial uses is to be grown or is growing.
9. A method for controlling weeds, wherein the place to which the control method according to claim 7 is applied is a paddy field, a dry field, a lawn, an orchard, a non-crop land, a greenhouse, a seedling raising facility, or a plant factory.
10. A method for controlling weeds, wherein the place to which the control method according to claim 8 is applied is a paddy field, a dry field, a lawn, an orchard, a non-crop land, a greenhouse, a seedling raising facility, or a plant factory.
11. A method of using a herbicide, wherein the herbicide according to any one of claims 4 to 6 is used for controlling weeds on a useful plant having agricultural, horticultural and industrial uses.
12. A compound which is a production intermediate of the compound represented by the general formula [I] or the salt thereof according to claim 1, represented by general formula [VI],[Chem. 2]wherein,A1 represents an oxygen atom or a sulfur atom,A4, A5, A6 and A7 each independently represent a nitrogen atom, C-H, orC-R4,R1 represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C6 cycloalkyl group, or a C3-C6 halocycloalkyl group,R3 represents a hydrogen atom, a halogen atom, an azido group, a cyano group, a nitro group, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 halocycloalkyl group, a phenyl group, a pentahalosulfanyl group, or a C1-C6 alkoxycarbonyl group,R4 each independently represents a halogen atom, an azido group, a cyano group, a nitro group, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 haloalkyl group, a hydroxy group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a pentahalosulfanyl group, a C1-C6 alkylthio group, a C1-C6 alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylthio group, a C1-C6 haloalkylsulfinyl group, a C1-C6 haloalkylsulfonyl group, a formyl group, a carboxyl group, an aminocarbonyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylcarbonyl group, an amino group, a mono (C1-C6 alkyl) amino group, or a di (C1-C6 alkyl) amino group.
13. A compound which is a production intermediate of the compound represented by the general formula [I] or the salt thereof according to claim 1, represented by general formula [IX],[Chem. 3]wherein,A3 represents an oxygen atom or a sulfur atom,A4, A5, A6 and A7 each independently represent a nitrogen atom, C-H, or C-R4,R1 represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C6 cycloalkyl group, or a C3-C6 halocycloalkyl group,R3 represents a hydrogen atom, a halogen atom, an azido group, a cyano group, a nitro group, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C3-C6 cycloalkyl group, a C3-C6 halocycloalkyl group, a phenylgroup, a pentahalosulfanyl group, or a C1-C6 alkoxycarbonyl group,R4 each independently represents a halogen atom, an azido group, a cyano group, a nitro group, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C1-C6 haloalkyl group, a hydroxy group, a C1-C6 alkoxy group, a C1-C6 haloalkoxy group,5 a C3-C6 cycloalkyl group, a pentahalosulfanyl group, a C1-C6 alkylthio group, a C1-C6alkylsulfinyl group, a C1-C6 alkylsulfonyl group, a C1-C6 haloalkylthio group, a C1-C6 haloalkylsulfinyl group, a C1-C6 haloalkylsulfonyl group, a formyl group, a carboxyl group, an aminocarbonyl group, a C1-C6 alkoxycarbonyl group, a C1-C6 alkylcarbonyl group, an amino group, a mono (C1-C6 alkyl) amino group, or a di (C1-C6 alkyl) amino10 group.