WO2011070771A1 - Azole derivatives, methods for producing the same, intermediate thereof, agro-horticultural agents - Google Patents

Azole derivatives, methods for producing the same, intermediate thereof, agro-horticultural agents Download PDF

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Publication number
WO2011070771A1
WO2011070771A1 PCT/JP2010/007118 JP2010007118W WO2011070771A1 WO 2011070771 A1 WO2011070771 A1 WO 2011070771A1 JP 2010007118 W JP2010007118 W JP 2010007118W WO 2011070771 A1 WO2011070771 A1 WO 2011070771A1
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group
compound
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formula
degrees
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PCT/JP2010/007118
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English (en)
French (fr)
Inventor
Nobuyuki Araki
Toru Yamazaki
Nobuyuki Kusano
Eiyu Imai
Hisashi Kanno
Masaru Mori
Taiji Miyake
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Kureha Corporation
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Priority to UAA201208247A priority Critical patent/UA108867C2/uk
Priority to ES10798835.4T priority patent/ES2524376T3/es
Priority to BR112012013201A priority patent/BR112012013201B1/pt
Priority to CN201080055788.6A priority patent/CN102639509B/zh
Priority to US13/508,269 priority patent/US8710090B2/en
Priority to DK10798835.4T priority patent/DK2509958T3/da
Priority to JP2012524809A priority patent/JP5831990B2/ja
Priority to EA201290460A priority patent/EA023393B1/ru
Priority to EP10798835.4A priority patent/EP2509958B1/en
Priority to AU2010329332A priority patent/AU2010329332B2/en
Priority to KR1020127017557A priority patent/KR101464421B1/ko
Application filed by Kureha Corporation filed Critical Kureha Corporation
Priority to PL10798835T priority patent/PL2509958T3/pl
Priority to CA2783552A priority patent/CA2783552C/en
Publication of WO2011070771A1 publication Critical patent/WO2011070771A1/en
Priority to ZA2012/02988A priority patent/ZA201202988B/en
Priority to US14/213,240 priority patent/US9162966B2/en
Priority to US14/213,043 priority patent/US9145351B2/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/10—Aromatic or araliphatic carboxylic acids, or thio analogues thereof; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/60—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated

Definitions

  • the present invention relates to a novel azole derivative. It also relates to an agro-horticultural agent and an industrial material protecting agent containing the derivative as an active ingredient as well as method for producing the derivatives.
  • a certain 2-substituted-benzyl-1-azolylmethylcyclopentanol derivative is known to have a biocidal activity (for example, see Patent Literatures 1 and 2).
  • Patent Literature 3 contains no description with regard to agro-horticultural agents and industrial material protecting agents, and no specific disclosure of the compounds encompassed by the invention.
  • an agro-horticultural pesticide having a low toxicity to humans and animals, capable of being handled safely, and exhibiting a high controlling effect on a wide range of plant diseases has been desired. Also, there has been a need for a plant growth regulator which regulates the growth of a variety of crops and horticultural plants thereby exhibiting yield-increasing and quality-improving effects, or an industrial material protecting agent which protects an industrial material from a wide range of hazardous microorganisms which invade such materials.
  • the present invention aims primarily at providing an agro-horticultural agent and an industrial material which fulfill the need described above.
  • an azole derivative according to the invention has a structure represented by Formula (I): wherein each of R a and R b independently denotes a hydrogen atom, or a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group or a C 2 -C 6 alkynyl group; provided that R a and R b are not hydrogen atoms at the same time, and the hydrogen atoms of the alkyl group, the alkenyl group and the alkynyl group may be substituted with X a or X b ; each of X a and X b denotes a halogen atom; n a denotes 0 or the number of X a -substituted hydrogen atoms among the hydrogen atoms in R a ; n b denotes 0 or the number of X b -substituted hydrogen atoms among the hydrogen atoms in R b ; provided that "n
  • the azole derivative according to the invention is advantageous in exhibiting an excellent biocidal effect on a large number of microorganisms which induce diseases in plants.
  • each of the alkyl group, the alkenyl group and the alkynyl group in R a and R b in Formula (I) described above denotes a C 1 -C 4 alkyl group, a C 2 -C 4 alkenyl group and a C 2 -C 4 alkynyl group; each of X a and X b denotes a fluorine atom, a chlorine atom or a bromine atom; each of n a and n b denotes 0 to 5; each Y denotes a halogen atom, a C 1 -C 3 alkyl group, a C 1 -C 3 haloalkyl group, a C 1 -C 3 alkoxy group or a C 1 -C 3 haloalkoxy group; m denotes 0 to 3; and A denotes a nitrogen atom.
  • the azole derivative according to the invention is preferable when the alkyl group in R a and R b in Formula (I) described above denotes a C 1 -C 3 alkyl group; each of X a and X b denotes a chlorine atom or a bromine atom; each of n a and n b denotes 0 to 3; each Y denotes a halogen atom, a C 1 -C 2 haloalkyl group or a C 1 -C 2 haloalkoxy group; and m denotes 0 to 2.
  • n a , n b and m in Formula (I) described above denote 0 to 1 and Y is a halogen atom.
  • the invention also includes the following intermediates of the azole derivatives.
  • the intermediate compound of the azole derivatives according to the invention is a 3-hydroxymethyl-2-oxocyclopentane carboxylic acid ester derivative represented by Formula (XI): wherein R 1 denotes a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group or a C 2 -C 6 alkynyl group; and R 2 denotes a C 1 -C 4 alkyl group.
  • the intermediate compound of the azole derivatives according to the invention is an oxetane compound represented by Formula (XVI):
  • the intermediate of the azole derivatives according to the invention is an oxetane sulfone ester derivative represented by Formula (XX): wherein R 3 denotes a lower alkyl group, or an optionally substituted phenyl group or naphthyl group.
  • the invention further includes the following inventions as methods for producing the azole derivatives shown above.
  • a method for producing the azole derivative according to the invention comprises a step for substituting a halogen atom-substitutable leaving group in an intermediate compound represented by Formula (II) with a halogen atom thereby obtaining a compound represented by Formula (Ia): wherein each of R a and R b may be substituted with X a , X b , L a , L b or Z; Z denotes a halogen atom; each of L a and L b denotes a halogen atom-substitutable leaving group; "n a1 +p a " denotes 0 or the number of hydrogen atoms substituted with X a or L a or Z among the hydrogen atoms in R a ; "n b1 +p b " denotes 0 or the number of hydrogen atoms substituted with X b or L b or Z among the hydrogen atoms in R b ; "p a +p b " de
  • a method for producing the azole derivative according to the invention comprises a step for subjecting a carbonyl compound represented by Formula (V) to conversion into an oxirane thereby obtaining an oxirane derivative represented by Formula (III) which is then reacted with a compound represented by Formula (IV): wherein M denotes a hydrogen atom or an alkaline metal.
  • a method for producing the azole derivative according to the invention comprises a step for subjecting an oxetane compound represented by Formula (XVI) to ring opening using a halogenic acid.
  • the invention further includes the following inventions as methods for producing intermediate compounds for the azole derivatives.
  • a method for producing an intermediate compound according to the invention comprises a step for reacting a 2-oxocyclopentane carboxylic acid ester derivative represented by Formula (XII) with formaldehyde or an equivalent thereof.
  • a method for producing an intermediate compound according to the invention comprises a step for subjecting a 2,2-bishydroxymethyl cyclopentanol derivative represented by Formula (XIX) to conversion into an oxetane ring while converting into a sulfone ester.
  • a method for producing an intermediate compound for an azole derivative according to the invention comprises a step for reducing the sulfone ester of an oxetane sulfone ester derivative represented by Formula (XX) to obtain an intermediate compound represented by Formula (XXI).
  • the invention also encompasses an agro-horticultural agent or an industrial material protecting agent containing as an active ingredient an azole derivative according to the invention.
  • An azole derivative according to the invention has an excellent biocidal effect on a large number of microorganisms which induce diseases in plants. Therefore, an agro-horticultural agent containing the azole derivative according to the invention as an active ingredient can advantageously exhibit a high controlling effect on a wide range of plant diseases.
  • the agro-horticultural agent containing the azole derivative according to the invention as an active ingredient can advantageously regulate the growth of a variety of crops and horticultural plants thereby increasing their yields while improving their qualities.
  • an industrial material protecting agent containing the azole derivative according to the invention as an active ingredient can further advantageously protect an industrial material from a wide range of hazardous microorganisms which invade such materials.
  • X a , X b , n a and n b may for example be a halogen atom.
  • the halogen atom may for example be a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among these, a fluorine atom, a chlorine atom and a bromine atom are preferred, with a chlorine atom being especially preferred.
  • n a denotes 0 or the number of X a -substituted hydrogen atoms in R a .
  • n b denotes 0 or the number of X b -substituted hydrogen atoms in R b .
  • n a and n b are preferably within the range of 0 to 5, more preferably 0 to 3, especially 0 to 1. Nevertheless, "n a +n b " is an integer of 1 or more. When n a is 2 or more, then each X a may be same or different. When n b is 2 or more, then each X b may be same or different.
  • R a and R b are not hydrogen atoms at the same time.
  • R a is a hydrogen atom, R a is not substituted with X a .
  • This understanding is not limited to R a , and is applicable also to R b .
  • C 1 -C 6 Alkyl group specifically, a methyl group, an ethyl group, a (1-methyl)ethyl group, a n-propyl group, a 1-methylpropyl group, 2-methylpropyl group, a n-butyl group, a 1-methylbutyl group, 2-methylbutyl group, a 1-ethylpropyl group and a 1,1-dimethylethyl group can be exemplified.
  • a C 1 -C 4 alkyl group is preferred, with C 1 -C 3 alkyl group being especially preferred.
  • C 2 -C 6 Alkenyl group specifically, an ethenyl group, a 1,2-dimethylethenyl group, a 4-methyl-1,3-butadienyl group, a 1-propenyl group, a 2-propenyl group, a 2-methyl-2-propenyl group, a 3-methyl-2-propenyl group, a 2-butenyl group, a 3-butenyl group and 3-methyl-3-butenyl group can be exemplified.
  • a C 2 -C 4 alkenyl group is preferred.
  • C 2 -C 6 Alkynyl group specifically, an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group and a 2-butynyl group can be exemplified. Among these, a C 2 -C 4 alkynyl group is preferred.
  • C 1 -C 6 Alkyl group specifically, a halogen-substituted C 1 -C 6 alkyl group, such as a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a 2-chloroethyl group, a 1-chloroethyl group, a 2,2-dichloroethyl group, a 1,2-dichloroethyl group, a 2,2,2-trichloroethyl group, a 3-chloropropyl group, a 2,3-dichloropropyl group, a 1-chloro-1-methylethyl group, 2-chloro-1-methylethyl group, a 2-chloropropyl group, a 4-chlorobutyl group, a 5-chloropentyl group, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2-fluoroethyl group, a
  • C 2 -C 6 Alkenyl group specifically, a halogen-substituted C 2 -C 6 alkenyl group, such as a 2-chloroethenyl group, a 2,2-dichloroethenyl group, a 2-chloro-2-propenyl group, a 3,3-dichloro-2-propenyl group, a 2,3-dichloro-2-propenyl group, a 3,3-dichloro-2-methyl-2-propenyl group, a 3-chloro-2-butenyl group, a 2-fluoroethenyl group, a 2,2-difluoroethenyl group, a 2-fluoro-2-propenyl group, a 3,3-difluoro-2-propenyl group, a 2,3-difluoro-2-propenyl group, a 3,3-difluoro-2-methyl-2-propenyl group, a 3-fluoro
  • C 2 -C 6 Alkynyl group specifically, a halogen-substituted C 2 -C 6 alkynyl group, such as a 2-fluoroethynyl group, a 2-chloroethynyl group, a 3-fluoro-2-propynyl group, a 3-chloro-2-propynyl group, a 3-bromo-2-propynyl group and the like can be exemplified. Among these, a C 2 -C 4 alkynyl group is preferred.
  • Halogen atom specifically, a chlorine atom, a fluorine atom, a bromine atom and an iodine atom can be exemplified.
  • C 1 -C 4 Alkyl group specifically, a methyl group, an ethyl group, a n-propyl group, a 1-methylethyl group, 2-methylpropyl group, a n-butyl group, a 1,1-dimethylethyl group and the like can be exemplified.
  • C 1 -C 4 Haloalkyl group specifically, a trifluoromethyl group, a 1,1,2,2,2-pentafluoroethyl group, a chloromethyl group, a trichloromethyl group, a bromomethyl group and the like can be exemplified.
  • C 1 -C 4 Alkoxy group specifically, a methoxy group, an ethoxy group, a n-propoxy group and the like can be exemplified.
  • C 1 -C 4 Haloalkoxy group specifically, a trifluoromethoxy group, a difluoromethoxy group, a 1,1,2,2,2-pentafluoroethoxy group, a 2,2,2-trifluoroethoxy group and the like can be exemplified.
  • Y may also be a phenyl group, a cyano group or a nitro group.
  • Y is preferably a halogen atom, a C 1 -C 3 haloalkyl group, a C 1 -C 3 haloalkoxy group, a C 1 -C 3 alkyl group and a C 1 -C 3 alkoxy group, with a halogen atom, a C 1 -C 2 haloalkyl group and a C 1 -C 2 haloalkoxy group being especially preferred.
  • n denotes an integer of 0 to 5.
  • each Y may be same or different.
  • m is preferably 0 to 3, and more preferably 0 to 2.
  • a nitrogen atom or a methyne group can be exemplified as A. More preferably, A is a nitrogen atom.
  • Stereoisomers Compound (I) exists as a stereoisomer represented by Formula (I-C) or (I-T) (type C or type T). Compound (I) may be either one of the isomers, or a mixture thereof.
  • the relative steric configuration of a cis type between the hydroxyl group in 1-position and the benzyl group in 5-position is referred to as (I-C)
  • the relative steric configuration of a trans type is referred to as (I-T).
  • R b is a hydrogen atom
  • the hydrogen atom-deficient carbon atom on the left end of (R b )X b n b serves to the binding to the cyclopentane ring in Compound (I) .
  • Columns of Ym "- (hyphen) " indicates a non-substitution (m 0). The number before "-" indicates the binding position when regarding the carbon atom binding to the carbon atom binding to the cyclopentane ring as being in 1-position in the case having a substituent on a phenyl ring.
  • solvents While the solvent employed is not limited particularly unless it is involved in a reaction, it may usually be ethers such as diethyl ether, tetrahydrofuran, dioxane and the like, alcohols such as methanol, ethanol, isopropanol and the like, aromatic hydrocarbons such as benzene, toluene, xylene and the like, aliphatic hydrocarbons such as petroleum ether, hexane, methylcyclohexane and the like, amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidinone and the like.
  • ethers such as diethyl ether, tetrahydrofuran, dioxane and the like
  • alcohols such as methanol, ethanol, isopropanol and the like
  • aromatic hydrocarbons such as benzene, toluene, xylene and the like
  • solvents may for example be water, acetonitrile, ethyl acetate, acetic anhydride, acetic acid, pyridine, dimethyl sulfoxide and the like. Two or more of these solvents may be employed in combination.
  • One which may also be exemplified as a solvent is a solvent composition consisting of solvents which do not form a homogenous layer with each other.
  • a phase transfer catalyst such as a customary employed quaternary ammonium salt or a crown ether can be added to the reaction system.
  • the base employed is not limited particularly.
  • the base may for example be a carbonate of an alkaline metal such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate and the like; a carbonate of an alkaline earth metal such as calcium carbonate, barium carbonate and the like; a hydroxide of an alkaline metal such as sodium hydroxide, potassium hydroxide and the like; an alkaline metal such as lithium, sodium, potassium and the like; an alkoxide of an alkaline metal such as sodium methoxide, sodium ethoxide, potassium t-butoxide and the like; an alkaline metal hydride such as sodium hydride, potassium hydride, lithium hydride and the like; an organic metal compound of an alkaline metal such as n-butyl lithium and the like; an alkaline metal such as sodium, potassium, lithium and the like; an alkaline metal amide such as lithium diisopropyl amide and the like; and an organic amine such as triethyl
  • the acid employed is not limited particularly.
  • the acid may for example be an inorganic acid such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid and the like, an organic acid such as formic acid, acetic acid, butyric acid, trifluoroacetic acid, p-toluenesulfonic acid and the like, a Lewis acid such as lithium chloride, lithium bromide, rhodium chloride, aluminum chloride, boron trifluoride and the like.
  • an inorganic acid such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid and the like
  • an organic acid such as formic acid, acetic acid, butyric acid, trifluoroacetic acid, p-toluenesulfonic acid and the like
  • a Lewis acid such as lithium chloride, lithium bromide, rhodium chloride, aluminum chloride, boron trifluoride and the like.
  • halogenic acid refers to hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid.
  • the halogenic acid may be a gas, a liquid, or an aqueous solution. It is also possible to use as a solution formed by dissolving it in a suitable organic solvent.
  • Step 1A a production method according to the invention is described below.
  • One embodiment of this production method comprises a step for substituting a certain functional group in a compound represented by Formula (II) shown below with a halogen atom to obtain a 2-(halogenated hydrocarbon-substituted)-5-benzyl-1-azolylmethylcyclopentanol derivative represented by Formula (Ia) shown below (Step 1A) (see Scheme (1) shown below).
  • the compound represented by Formula (II) shown below is a compound having a leaving group on the substituent in 2-position of the cyclopentane ring.
  • the compound represented by Formula (II) is referred to as "Compound (II)"
  • the compound represented by Formula (Ia) is referred to as "Compound (Ia)”.
  • Y, m, and A are as described above.
  • X a1 and X b1 have similar meanings as X a and X b .
  • Z denotes a halogen atom.
  • the halogen atom may for example be a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • a fluorine atom, a chlorine atom and a bromine atom are preferred, with a chlorine atom being especially preferred.
  • Each of R a1 and R b1 independently denotes a hydrogen atom, or a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group or a C 2 -C 6 alkynyl group.
  • the C 1 -C 6 alkyl group, C 2 -C 6 alkenyl group and C 2 -C 6 alkynyl group may be substituted with X a1 , X b1 , L a , L b , and z.
  • Each of L a and L b denotes a halogen atom-substitutable leaving group.
  • n a1 and n b1 denote the numbers of X a1 and X b1 on R a1 and R b1 .
  • p a and p b denote the number of L a and L b on R a1 and R b1 .
  • n a1 +p a denotes 0 or the number of hydrogen atoms substituted with X a1 or L a or Z among the hydrogen atoms in R a1 .
  • n b1 +p b denotes 0 or the number of hydrogen atoms substituted with X b1 or L b or Z among the hydrogen atoms in R b1 .
  • p a +p b denotes an integer of 1 or more.
  • n a1 denotes 2 or more then each X a1 may be same or different.
  • n b1 denotes 2 or more then each X b1 may be same or different.
  • the method for substituting the leaving group with the halogen atom may for example be (a) a method for substituting a compound having a substituted sulfonyloxy group such as a p-toluenesulfonyloxy group or a methanesulfonyloxy group in a solvent with a halogenated salt, (b) a method for substituting a hydroxyl group or an alkoxy group using hydrochloric acid or hydrobromic acid, (c) a method for substituting a hydroxyl group using a halogenated phosphorus, and (d) a method for reacting a hydroxyl group with a thionyl halide.
  • substitution method indicated as (a) is preferred.
  • substitution method indicated as (a) is detailed below.
  • the reaction in the method indicated as (a) is usually conducted by mixing Compound (II) with a halogenated salt such as potassium fluoride, cesium fluoride, lithium chloride, potassium chloride, lithium bromide, magnesium bromide, and sodium iodide and the like in a solvant.
  • a halogenated salt such as potassium fluoride, cesium fluoride, lithium chloride, potassium chloride, lithium bromide, magnesium bromide, and sodium iodide and the like in a solvant.
  • the amount of the halogenated salt employed per mole of Compound (II) is usually 0.1 to 100 moles, and preferably 0.8 to 20 moles.
  • the reaction temperature is usually 0 to 250 degrees C, and preferably room temperature to 200 degrees C.
  • the reaction time is usually 0.1 hour to several days, and preferably 0.2 hour to 2 days.
  • Step 1B A compound represented by Formula (IIa) employed in Step 1A (hereinafter referred to as "Compound (IIa)”) is obtained by a step for reacting a compound represented by Formula (VI) ("Compound (VI)") with a substituted sulfonyl chloride represented by Formula (XV) ("Compound (XV)”) ("Step 1B") (see Scheme (2) shown below).
  • Compound (IIa) is a 5-benzyl-1-azolylmethylcyclopentanol derivative having a substituted sulfonyloxy group-substituted substituent in 2-position.
  • Compound (VI) is a 5-benzyl-1-azolylmethylcyclopentanol derivative having a hydroxyl group-substituted substituent in 2-position.
  • Y, m and A are as described above.
  • X a2 and X b2 have similar meanings as X a and X b , respectively.
  • L a1 denotes a halogen atom-substitutable substituted sulfonyloxy group.
  • Each of R a2 and R b2 independently denotes a hydrogen atom, or a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group or a C 2 -C 6 alkynyl group.
  • the C 1 -C 6 alkyl group, C 2 -C 6 alkenyl group and C 2 -C 6 alkynyl group may be substituted with X a2 , X b2 or a hydroxyl group.
  • n a2 and n b2 denote the numbers of X a2 and X b2 on R a2 and R b2 .
  • p a1 and p b1 denote the number of the hydroxyl groups and L a1 on R a2 and R b2 .
  • "n a2 +p a1 denotes 0 or the number of X a2 -, hydroxyl group- or L a1 -substituted hydrogen atoms among the hydrogen atoms in R a2 .
  • n b2 +p b1 denotes 0 or the number of X b2 -, hydroxyl group- or L a1 -substituted hydrogen atoms among the hydrogen atoms in R b2 .
  • p a1 +p b1 denotes an integer of 1 or more. When n a2 denotes 2 or more then each X a2 may be same or different. When n b2 denotes 2 or more then each X b2 may be same or different.
  • R in Formula (XV) denotes a lower alkyl group, a phenyl group, or a naphthyl group.
  • the lower alkyl group may for example be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a trifluoromethyl group and the like.
  • the phenyl group and the naphthyl group may be substituted.
  • the optionally substituted phenyl group and naphthyl group may for example be a 4-methylphenyl group, a 2-nitrophenyl group, and a 5-dimethylaminonaphthyl group. Among these, the methyl group and the 4-methylphenyl group are preferred.
  • the amount of Compound (XV) employed per mole of Compound (VI) is usually 0.5 to 10 moles, and preferably 0.8 to 5 moles. While the reaction may proceed without any added base, it is preferable to add a base for removing hydrogen chloride generated. In such a case, the amount of the base employed per mole of Compound (VI) is usually 0 to 5 moles or less (excluding 0), preferably 0.5 to 3 moles.
  • the base employed is not limited particularly.
  • the base may for example be an alkaline metal hydride such as sodium hydride, potassium hydride, lithium hydride and the like; and an organic amine such as triethylamine, pyridine, 4-dimethylaminopyridine, N,N-dimethylaniline and the like.
  • the reaction temperature may appropriately be selected depending on the types of the solvent, the base and the like which are employed.
  • the reaction temperature is preferably -50 degrees C to 200 degrees C, and more preferably -20 degrees C to 150 degrees C.
  • the reaction time may appropriately be selected depending on the types of the solvent, the base and the like which are employed.
  • the reaction time is preferably 0.1 hour to several days, and more preferably 0.5 hour to 1 day.
  • Step 1C Compound (VI) employed in Step 1B may be produced by a known method (for example, see Patent Literature 4). However, Compound (VIa) having a hydroxymethyl group and an alkyl group in 2-position is preferably produced using the synthetic method shown below.
  • R 1 denotes a C 1 -C 6 alkyl group, a C 2 -C 6 alkenyl group or a C 2 -C 6 alkynyl group. Specific examples of these C 1 -C 6 alkyl group, C 2 -C 6 alkenyl group and C 2 -C 6 alkynyl group are the same as the specific examples in R a and R b described above, and accordingly are not specified here in detail.
  • G denotes a protective group, and is not limited particularly as long as Compound (VIa) can be produced from Compound (VII).
  • the protective group can for example be an alkoxymethyl group such as a methoxymethyl group and an ethoxymethyl group, a lower alkyl group such as a t-butyl group and a methyl group as well as a substituted or unsubstituted benzyl group and the like.
  • M denotes a hydrogen atom or an alkaline metal.
  • Step 1C1 A step for subjecting Compound (IX) to conversion into an oxirane to obtain Compound (VIII) (Step 1C1) in this Step 1C is described below.
  • a method involving reacting Compound (IX) with a sulfur ylide including sulfonium methylides such as dimetylsulfonium methylide and the like or sulfoxonium methylides such as dimethyl sulfoxonium methylide and the like in a solvent can be exemplified.
  • the sulfonium methylides and the sulfoxonium methylides employed can be produced by reacting, in a solvent, a sulfonium salt (for example, trimethylsulfonium iodide, trimethylsulfonium bromide and the like) or a sulfoxonium salt (for example, trimethylsulfoxonium iodide, trimethylsulfoxonium bromide and the like) with a base.
  • a sulfonium salt for example, trimethylsulfonium iodide, trimethylsulfonium bromide and the like
  • a sulfoxonium salt for example, trimethylsulfoxonium iodide, trimethylsulfoxonium bromide and the like
  • the amount of such a sulfonium methylide and sulfoxonium methylide per mole of Compound (IX) described above is preferably 0.5 to 5 moles, and more preferably 0.8 to 2 moles.
  • the solvent employed is not limited particularly.
  • the solvent can for example be dimethyl sulfoxide, amides such as N-methylpyrrolidone, N,N-dimethylformamide and the like, ethers such as tetrahydrofuran, dioxane and the like, as well as a solvent mixture thereof.
  • the base employed for producing sulfonium methylides and sulfoxonium methylides is not limited particularly.
  • the base can for example be a metal hydride such as sodium hydride and the like, an alkoxide of an alkaline metal such as sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium t-butoxide and the like.
  • the reaction temperature and the reaction time may appropriately be selected depending on the types of the solvent, Compound (IX), sulfonium salt or sulfoxonium salt, base and the like which are employed.
  • the reaction temperature is preferably -100 degrees C to 200 degrees C, and more preferably -50 degrees C to 150 degrees C.
  • the reaction time is preferably 0.1 hour to several days, and more preferably 0.5 hour to 2 days.
  • the base is not limited particularly.
  • the base may for example be sodium hydroxide.
  • the samarium iodide employed can be produced by reacting a metal samarium with 1,2-diiodoethane or diiodomethane in an anhydrous solvent.
  • the solvent employed is not limited particularly and may for example be an ether such as tetrahydrofuran and the like.
  • the amount of the base per mole of Compound (IX) is not limited particularly, it is preferably 0.5 to 10 moles in usual cases, and more preferably 0.8 to 6 moles.
  • an aqueous solution of sodium hydroxide may for example be employed since no anhydrous system is required.
  • the reaction temperature and the reaction time may appropriately be selected depending on the types of the solvent, Compound (IX), base and the like which are employed.
  • the reaction temperature is preferably -100 degrees C to 150 degrees C, and more preferably -50 degrees C to 100 degrees C.
  • the reaction time is preferably 0.1 hour to several days, and more preferably 0.5 hour to 2 days.
  • Step 1C2 a step for reacting Compound (VIII) and Compound (IV) to obtain Compound (VII) (Step 1C2) in this Step 1C is described below.
  • Compound (VII) is produced by mixing Compound (VIII) with Compound (IV) in a solvent to form a carbon-nitrogen bond between the carbon atom constituting an oxirane ring in an oxirane derivative (Compound (VIII)) and the nitrogen atom in 1,2,4-triazole or imidazole.
  • solvent employed is not limited particularly, and can for example be amides such as N-methylpyrrolidone and N,N-dimethylformamide and the like.
  • the amount of Compound (IV) employed per mole of Compound (VIII) is preferably 0.5 to 10 moles in usual cases, and more preferably 0.8 to 5 moles.
  • a base may be added if necessary.
  • the amount of the base employed per mole of Compound (IV) is preferably 0 to 5 moles (excluding 0) in usual cases, and more preferably 0.5 to 2 moles.
  • the reaction temperature may appropriately be selected depending on the types of the solvent, the base and the like which are employed.
  • the reaction temperature is preferably 0 degrees C to 250 degrees C, and more preferably 10 degrees C to 150 degrees C.
  • the reaction time may appropriately be selected depending on the types of the solvent, the base and the like which are employed.
  • the reaction time is preferably 0.1 hour to several days, and more preferably 0.5 hour to 2 days.
  • Y, m, A, R 1 , G and M are as described above.
  • the solvent employed here is not limited particularly.
  • a polar solvent having an amide bond such as N-methylpyrrolidone and N,N-dimethylformamide and the like, or dimethyl sulfoxide, or a solvent mixture of a polar solvent with an alcohol can be exemplified.
  • the alcohol may be t-butanol.
  • the base employed for producing sulfonium methylides and sulfoxonium methylides are not limited particularly.
  • the base can for example be a metal hydride such as sodium hydride and the like, an alkoxide of an alkaline metal such as sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium t-butoxide and the like.
  • an alkaline metal salt of 1,2,4-triazole or imidazole may also be used.
  • the reaction temperature may appropriately be selected depending on the types of the solvent, Compound (IX), sulfonium salt or sulfoxonium salt, base and the like which are employed.
  • the reaction temperature is preferably -100 degrees C to 250 degrees C, and more preferably -50 degrees C to 200 degrees C.
  • the reaction time may appropriately be selected depending on the types of the solvent, Compound (IX), sulfonium salt or sulfoxonium salt, base and the like which are employed.
  • the reaction time is preferably 0.1 hour to several days, more preferably 0.5 hour to 2 days.
  • the number of times when a trimethyl sulfonium halide or a trimethyl sulfonium halide and a base are added intermittently is not limited particularly as long as it is the number of times allowing a predetermined aim to be accomplished. A preferred number of times may usually be 2 to 20 times, with 3 to 15 times being more preferable.
  • the total amount of a trimethylsulfonium salt or a trimethylsulfoxonium salt employed per mole of Compound (IX) is preferably 0.5 to 5 moles, more preferably 0.8 to 2 moles.
  • the amount of Compound (IV) employed per mole of Compound (IX) is preferably 0.5 to 10 moles in usual cases, and more preferably 0.8 to 5 moles. It is preferable to use Compound (IV) in which M is an alkaline metal salt.
  • Patent Literature 5 For details of the steps for conducting the conversion into an azole while allowing the oxirane derivative to be produced in the production of the azolylmethylcycloalkanol derivative, see Patent Literature 5.
  • Step 1C3 a step for deprotecting the protective group of Compound (VII) to obtain Compound (VIa) (Step 1C3) in this Step 1C is described below.
  • a preferred condition differs depending on the type of the protective group, in the cases, for example, of using an alkoxymethyl group such as a methoxymethyl group or an ethoxyethyl group or a lower alkyl group such as a t-butyl group or a methyl group, the deprotection is conducted preferably in a solvent under an acidic condition involving hydrogen chloride or sulfuric acid and the like.
  • the acid employed here is preferably a halogenated hydrogen such as hydrogen chloride or an inorganic acid such as sulfuric acid. While the amount employed is not limited particularly, the amount of the acid employed per mole of Compound (VII) is usually 0.5 to 100 moles, and preferably 0.8 to 20 moles.
  • the reaction temperature is preferably 0 degrees C to 200 degrees C in usual cases, and more preferably room temperature to 100 degrees C.
  • the reaction time is preferably 0.1 hour to several days in usual cases, more preferably 0.5 hour to 2 days.
  • Step 1D Compound (XII) employed in Step 1C can preferably be synthesized by the method shown below.
  • a keto ester compound represented by Formula (XII) shown below (hereinafter referred to as "Compound (XII)") is hydroxymethylated to obtain a compound represented by Formula (XI) shown below (“Compound (XI)”).
  • a protective group such as a methoxymethyl group or a t-butyl group and the like is introduced into the hydroxyl group in Compound (XI) to effect derivatization into a compound represented by Formula (X) shown below (“Compound (X)”).
  • Compound (X) is hydrolyzed/decarbonated to obtain a carbonyl compound represented by Formula (XI) shown below (“Compound (XI)”).
  • Step 1D is represented by Scheme (5) shown below.
  • Y, m, R 1 and G are as described above.
  • R 2 denotes a C1-C4 alkyl group.
  • the specific examples of the alkyl groups in R 2 are the same as the specific examples in R a and R b described above, and accordingly are not specified here in detail.
  • Step 1D1 in the step for obtaining Compound (XI) by hydroxymethylating Compound (XII), a method involving a reaction with formaldehyde in the presence of a base in a solvent may be employed.
  • the amount of formaldehyde employed per mole of Compound (XII) is usually 0.5 to 20 moles, and preferably 0.8 to 10 moles.
  • the base can for example be, but not limited to, a carbonate of an alkaline metal such as sodium carbonate, potassium carbonate and the like as well as a hydroxide of an alkaline metal such as sodium hydroxide and the like.
  • the amount of the base employed per mole of Compound (XII) is usually 0.1 to 10 moles, and preferably 0.2 to 5 moles.
  • the reaction temperature is preferably 0 degrees C to 250 degrees C in usual cases, and more preferably 0 to 100 degrees C.
  • the reaction time is preferably 0.1 hour to several days in usual cases, and more preferably 0.5 hour to 2 days.
  • Compound (XII) employed here may be produced by a known method (for example, the method disclosed in Patent Literature 1).
  • Step 1D2 a step for introducing a protective group into the hydroxyl group in Compound (XI) to obtain Compound (X) (Step 1D2) in this Step 1D is described below.
  • the protective group for protecting the hydroxyl group is not limited particularly, those employed preferably are an alkoxymethyl group such as a methoxymethyl group and an ethoxymethyl group, and a lower alkyl group such as a t-butyl group and the like.
  • Introduction of these protective group is conducted preferably by (a) an acetal exchange of the hydroxyl group in Compound (XII) using a formaldehyde dialkylacetal in the case of introduction of an alkoxymethyl group.
  • (b) Addition of the hydroxyl group in Compound (XII) using isobutene is utilized preferably in the case of introduction of a t-butyl group.
  • an inorganic acid such as hydrochloric acid, phosphoric acid (including a compound allowing an acidic group to be generated by addition of an alcohol or water, such as diphosphorus pentoxide) and sulfuric acid, and an organic acid such as p-toluenesulfonic acid and the like are employed.
  • a formaldehyde dialkylacetal is employed preferably in a solvent or in a solvent-free system. It is further preferred to add a compound allowing any generated alcohol to be removed, such as diphosphorus pentoxide.
  • the amount of the formaldehyde dialkylacetal employed per mole of Compound (XI) is usually 0.5 to 50 moles, and preferably 0.8 to 10 moles.
  • the amount of the acid employed per mole of Compound (XI) is usually 0.01 to 10 moles, and preferably 0.05 to 5 moles.
  • the reaction temperature is preferably 0 degrees C to 250 degrees C in usual cases, and more preferably 0 degrees C to 150 degrees C.
  • the reaction time is preferably 0.1 hour to several days in usual cases, and more preferably 0.5 hour to 2 days.
  • the amount of isobutene employed per mole of Compound (XI) is usually 0.5 to 100 moles, and preferably 0.8 to 20 moles.
  • the amount of the acid employed per mole of Compound (XI) is usually 0.01 to 10 moles, and preferably 0.05 to 5 moles.
  • the reaction temperature is preferably 0 degrees C to 200 degrees C in usual cases, and more preferably 0 degrees C to 100 degrees C.
  • the reaction time is preferably 0.1 hour to several days in usual cases, and more preferably 0.5 hour to 2 days.
  • Step 1D3 a step for hydrolyzing/decarbonating Compound (X) to obtain Compound (IX) (Step 1D3) in this Step 1D is described below.
  • the reaction is conducted preferably in the presence of a base in a solvent.
  • the base employed usually includes an alkaline metal base such as sodium hydroxide, potassium hydroxide and the like.
  • the amount of base employed per mole of Compound (X) is usually 0.1 to 50 moles, and preferably 0.2 to 20 moles.
  • the solvent may usually be water, as well as water combined with an alcohol and the like, a solvent mixture consisting of solvents which do not form a homogenous layer with each other (such as water-toluene) (in such a case it may sometimes be preferable to use a phase transfer catalyst, such as a customary quaternary ammonium salt, in the reaction system).
  • a phase transfer catalyst such as a customary quaternary ammonium salt
  • the reaction temperature is preferably 0 degrees C to reflux temperature in usual cases, and more preferably room temperature to reflux temperature.
  • the reaction time is preferably 0.1 hour to several days in usual cases, and more preferably 0.5 hour to 24 hours.
  • Step 2A Another embodiment of the production method according to the invention is described.
  • This embodiment comprises a step for subjecting a carbonyl compound represented by Formula (V) shown below to conversion into an oxirane thereby obtaining an oxirane derivative represented by Formula (III) shown below which is then reacted with a compound represented by Formula (IV) shown below to obtain Compound (I) (Step 2A) (see Scheme (6) shown below).
  • the carbonyl compound represented by Formula (V) is referred to as "Compound (V)”
  • the oxirane derivative represented by Formula (III) is referred to as "Compound (III)”.
  • R a , R b , X a , X b , n a , n b , Y, m, A and M are as described above.
  • Step 2A1 a step for converting Compound (V) into an oxirane to obtain Compound (III) (Step 2A1) is described below.
  • a method involving reacting Compound (V) with a sulfur ylide including sulfonium methylides such as dimetylsulfonium methylide and the like or sulfoxonium methylides such as dimethyl sulfoxonium methylide and the like in a solvent can be exemplified.
  • the sulfonium methylides or the sulfoxonium methylides can be produced by reacting, in a solvent, a sulfonium salt (for example, trimethylsulfonium iodide, trimethylsulfonium bromide and the like) or a sulfoxonium salt (for example, trimethylsulfoxonium iodide, trimethylsulfoxonium bromide and the like) with a base.
  • a sulfonium salt for example, trimethylsulfonium iodide, trimethylsulfonium bromide and the like
  • a sulfoxonium salt for example, trimethylsulfoxonium iodide, trimethylsulfoxonium bromide and the like
  • the base is not limited particularly, those employed preferably include a metal hydride such as sodium hydride and the like, an alkoxide of an alkaline metal such as sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium t-butoxide and the like.
  • a metal hydride such as sodium hydride and the like
  • an alkoxide of an alkaline metal such as sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium t-butoxide and the like.
  • the amount of such a sulfonium methylide and sulfoxonium methylide per mole of Compound (V) is 0.5 to 5 moles, and preferably 0.8 to 2 moles.
  • the solvent employed is not limited particularly, it may for example be dimethyl sulfoxide, amides such as N-methylpyrrolidone and N,N-dimethylformamide and the like, ethers such as tetrahydrofuran, dioxane and the like, as well as a solvent mixture thereof.
  • reaction temperature may appropriately be selected depending on the types of the solvent, Compound (V), sulfonium salt or sulfoxonium salt, base and the like which are employed, it is preferably -100 degrees C to 200 degrees C, and more preferably -50 degrees C to 150 degrees C.
  • reaction time may appropriately be selected depending on the types of the solvent, Compound (V), sulfonium salt or sulfoxonium salt, base and the like which are employed, it is preferably 0.1 hour to several days, and more preferably 0.5 hour to 2 days.
  • a method involving reacting Compound (V) with samarium iodide and diiodomethane in a solvent and then treating it with a base can be exemplified.
  • the base employed is not limited particularly and may for example be sodium hydroxide.
  • the amount of samarium iodide per mole of Compound (V) is usually 0.5 to 10 moles, and preferably 1 to 6 moles.
  • the amount of diiodomethane per mole of Compound (V) is usually 0.5 to 10 moles, and preferably 0.8 to 5 moles.
  • the samarium iodide can be produced by reacting a metal samarium with 1,2-diiodoethane or diiodomethane in an anhydrous solvent.
  • the amount of the base per mole of Compound (V) is not limited particularly, it is preferably 0.5 to 10 moles in usual cases, and more preferably 0.8 to 6 moles.
  • an aqueous solution of sodium hydroxide may for example be employed since no anhydrous system is required.
  • the reaction temperature and the reaction time may appropriately be selected depending on the types of the solvent, Compound (V), base and the like which are employed.
  • the reaction temperature is preferably -100 degrees C to 150 degrees C, and more preferably -50 degrees C to 100 degrees C.
  • the reaction time is preferably 0.1 hour to several days, and more preferably 0.5 hour to 2 days.
  • Step 2A2 a step for obtaining Compound (I) from Compound (III) and Compound (IV) (Step 2A2) is described below.
  • Compound (I) is produced by mixing Compound (III) with Compound (IV) in a solvent to form a carbon-nitrogen bond between the carbon atom constituting an oxirane ring in an oxirane derivative and the nitrogen atom in 1,2,4-triazole or imidazole.
  • the solvent employed is not limited particularly, it can for example be amides such as N-methylpyrrolidone and N,N-dimethylformamide and the like.
  • the amount of Compound (IV) employed per mole of Compound (III) is preferably 0.5 to 10 moles in usual cases, and more preferably 0.8 to 5 moles.
  • a base may be added if necessary.
  • the amount of the base employed per mole of Compound (IV) is preferably 0 to 5 moles (excluding 0) in usual cases, and more preferably 0.5 to 2 moles.
  • the reaction temperature may appropriately be selected depending on the types of the solvent, the base and the like which are employed.
  • the reaction temperature is preferably 0 degrees C to 250 degrees C, and more preferably 10 degrees C to 150 degrees C.
  • the reaction time may appropriately be selected depending on the types of the solvent, the base and the like which are employed.
  • the reaction time is preferably 0.1 hour to several days, and more preferably 0.5 hour to 2 days.
  • Step 2B While for Compound (V) employed in Step 2A it is possible to use a compound which can be synthesized by a conventional technology, Compound (Va) is preferably produced by the following synthetic method.
  • R 1 , R 2 , Y and m are as described above.
  • R a1 , X a1 and n a1 have similar meanings as R a , X a and n a , respectively.
  • Step 2B1 a step for reacting Compound (XII) in the presence of a base with Compound (XIX) to obtain Compound (XIII) (Step 2B1) is described below.
  • the base is not limited particularly, and includes alkaline metal hydrides such as sodium hydride and the like, and alkaline metal carbonates such as sodium carbonate, potassium carbonate and the like.
  • the amount of the base per mole of Compound (XII) is preferably 0.5 to 5 moles, and more preferably 0.8 to 2 moles.
  • the amount of Compound (XIV) per mole of Compound (XII) is preferably 0.5 to 10 moles, and more preferably 0.8 to 5 moles.
  • reaction temperature may appropriately be selected depending on the types of the solvent, Compound (XII), Compound (XIV), base and the like which are employed, it is preferably 0 degrees C to 250 degrees C, and more preferably room temperature to 150 degrees C.
  • reaction time may appropriately be selected depending on the types of the solvent, Compound (XII), Compound (XIV), base and the like which are employed, it is preferably 0.1 hour to several days, and more preferably 0.5 hour to 24 hours.
  • Step 2B2 a step for hydrolyzing/decarbonating Compound (XIII) (Step 2B2) is described below.
  • This reaction can be conducted in a solvent under both of a basic condition and an acidic condition.
  • the base When conducting hydrolysis under the basic condition, the base is usually an alkaline metal base such as sodium hydroxide, potassium hydroxide and the like.
  • the solvent is usually water, as well as water combined with alcohols.
  • the acid catalyst is an inorganic acid such as hydrochloric acid, hydrobromic acid, sulfuric acid and the like.
  • the solvent is usually water, or water combined with an organic acid such as acetic acid.
  • the reaction temperature is preferably 0 degrees C to reflux temperature in usual cases, and more preferably room temperature to reflux temperature.
  • the reaction time is usually 0.1 hour to several days, and preferably 0.5 hour to 24 hours.
  • Step 3A Another embodiment of the production method according to the invention is described.
  • This embodiment comprises a step for reacting a compound represented by Formula (VIb) shown below (“Compound VIb") with a substituted sulfonyl chloride group represented by Formula (XV) shown below (“Compound (XV)”) to obtain an oxetane compound represented by Formula (XVI) shown below (“Compound (XVI)”).
  • a step for subjecting Compound (XVI) to ring opening using any halogenic acid to obtain Compound (Ib) (Step 3A; see Scheme (8) shown below).
  • R a , X a , n a , R, Y, m and X b are as described above.
  • Step 3A1 a step for subjecting Compound (VIb) to ring closing to obtain an oxetane compound (XVI) (Step 3A1) is described below.
  • the sulfonyl chloride may for example be p-toluenesulfonyl chloride and methanesulfonyl chloride and the like.
  • p-toluenesulfonyl chloride is employed preferably.
  • the base is not limited particularly, those employed preferably include a metal hydride such as sodium hydride and the like, an alkoxide of an alkaline metal such as sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium t-butoxide and the like.
  • the amount of the sulfonyl chloride per mole of Compound (VIb) is preferably 0.5 to 5 moles, and more preferably 0.8 to 2 moles.
  • the amount of the base is preferably 1.5 to 5 moles, and more preferably 1.8 to 3 moles.
  • the solvent is not limited particularly, it includes amides such as N-methylpyrrolidone and N,N-dimethylformamide and the like, ethers such as tetrahydrofuran and dioxane and the like, or dimethyl sulfoxide as well as solvent mixtures thereof.
  • reaction temperature may appropriately be selected depending on the types of the solvent, Compound (VIb), sulfonyl chloride, base and the like which are employed, it is preferably -100 degrees C to 200 degrees C, and more preferably -50 degrees C to 150 degrees C.
  • reaction time may appropriately be selected depending on the types of the solvent, Compound (VIb), sulfonyl chloride, base and the like which are employed, it is preferably 0.1 hour to several days, and more preferably 0.5 hour to 2 days.
  • Step 3A2 Next, a step for obtaining Compound (Ib) from Compound (XVI) (Step 3A2) is described below.
  • Compound (Ib) can be produced preferably by mixing Compound (XVI) with Compound H-X b in a solvent to effect ring opening of the oxetane ring possessed by Compound (XVI) thereby producing a halogenated methyl group and a tertiary hydroxyl group.
  • H-X b denotes a halogenic acid, such as hydrogen chloride, hydrogen bromide, hydrogen iodide and the like.
  • the halogenic acid may be introduced also as a gas, and it may be added as being dissolved in an organic solvent solution. It is possible to add a halogenic acid salt and an acid irrelevant to the halogenic acid salt (such as toluenesulfonic acid, methanesulfonic acid and the like) thereby obtaining Compound (Ib) from Compound (XVI).
  • the solvent employed is not limited particularly, it may for example be amides such as N-methylpyrrolidone and N,N-dimethylformamide and the like, alcohols such as methanol and ethanol, and ethers such as tetrahydrofuran, dioxane and the like.
  • the amount of Compound H-X b employed per mole of Compound (XVI) is usually 0.5 to 50 moles, and preferably 1 to 20 moles.
  • reaction temperature may appropriately be selected depending on the types of the solvent, base and the like which are employed, it is preferably -20 degrees C to 250 degrees C, and more preferably -10 degrees C to 150 degrees C.
  • reaction time may appropriately be selected depending on the types of the solvent, base and the like which are employed, it is preferably 0.1 hour to several days, and more preferably 0.5 hour to 2 days.
  • Step 3A1 Compound (VIb) employed in Step 3A1 can be synthesized by the method similar to Step 1C and Step 1D described in the first production method. The entire steps of the third production method involving the step for synthesizing Compound (VIb) is indicated in Scheme (9) shown below.
  • Step 4A Another embodiment of the production method according to the invention is described.
  • Y, m, A and X b are as described above.
  • R 3 denotes a lower alkyl group, a phenyl group or a naphthyl group.
  • the lower alkyl group may for example be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a trifluoromethyl group.
  • the phenyl group and the naphthyl group may be substituted.
  • the phenyl group and the naphthyl group which may be substituted may for example be a 4-methylphenyl group, a 2-nitrophenyl group and a 5-dimethylaminonaphthyl group. Among these, the methyl group or the 4-methylphenyl group is employed preferably.
  • Step 4A1 a step for converting Compound (XIX) into an oxetane while sulfonylating it to obtain Compound (XX) (Step 4A1) is described below.
  • the sulfonyl chloride may for example be p-toluenesulfonyl chloride, methanesulfonyl chloride and the like. Among these, p-toluenesulfonyl chloride is employed preferably. While the base is not limited particularly, those employed preferably include a metal hydride such as sodium hydride and the like, and an alkoxide of an alkaline metal such as sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium t-butoxide and the like.
  • a metal hydride such as sodium hydride and the like
  • an alkoxide of an alkaline metal such as sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium t-butoxide and the like.
  • the amount of the sulfonyl chloride per mole of Compound (XIX) is preferably 1.8 to 10 moles, and more preferably 2 to 5 moles.
  • the amount of the base is preferably 2.5 to 10 moles, and more preferably 2.8 to 6 moles.
  • the solvent is not limited particularly, it includes amides such as N-methylpyrrolidone and N,N-dimethylformamide and the like, ethers such as tetrahydrofuran and dioxane and the like, or dimethyl sulfoxide as well as solvent mixtures thereof.
  • reaction temperature may appropriately be selected depending on the types of the solvent, Compound (XIX), sulfonyl chloride, base and the like which are employed, it is preferably -100 degrees C to 200 degrees C, and more preferably -50 degrees C to 150 degrees C.
  • reaction time may appropriately be selected depending on the types of the solvent, Compound (XIX), sulfonyl chloride, base and the like which are employed, it is preferably 0.1 hour to several days, and more preferably 0.5 hour to 2 days.
  • Step 4A2 a step for obtaining Compound (XXI) from Compound (XX) (Step 4A2) is described below.
  • the reducing agent can for example be a metal, a hydride type reducing agent, a hydrogen/catalytic hydrogenation catalyst and the like.
  • the metal includes an iron powder, a zinc powder, a combination of a zinc powder and NaI and the like.
  • the hydride type reducing agent includes sodium borohydride, lithium borohydride, lithium aluminum hydride and the like.
  • the catalytic hydrogenation catalyst includes a palladium/carbon, a palladium hydroxide/carbon, a platinum/carbon, a Raney nickel and the like.
  • the metal powder is employed preferably, with a combination of the zinc powder and NaI being more preferred.
  • the solvent is not limited particularly, and may appropriately be selected depending on the type of the reducing agent.
  • the solvent may be an ether based solvent such as tetrahydrofuran, diethyl ether and the like, an alcohol based solvent such as methanol, ethanol and the like, or a protic solvent having a high polar ratio such as dimethyl sulfoxide, dimethyl formamide and the like.
  • the amount of the reducing agent employed per mole of Compound (XX) is usually 0.5 to 50 moles, and preferably 1 to 20 moles.
  • reaction temperature may appropriately be selected depending on the types of the solvent, base and the like which are employed, it is preferably -20 degrees C to 250 degrees C, and more preferably -10 degrees C to 150 degrees C.
  • reaction time may appropriately be selected depending on the types of the solvent, base and the like which are employed, it is preferably 0.1 hour to several days, and more preferably 0.5 hour to 3 days.
  • Step 4A3 a step for obtaining Compound (Id) from Compound (XXI) (Step 4A3) is described below.
  • Compound (Id) can be produced by mixing Compound (XXI) with Compound H-X b in a solvent to effect ring opening of the oxetane ring possessed by Compound (XXI) thereby producing a halogenated methyl group and a tertiary hydroxyl group.
  • H-X b denotes a halogenic acid, such as hydrogen chloride, hydrogen bromide, hydrogen iodide and the like.
  • the halogenic acid may be introduced also as a gas, and it may be added as being dissolved in an organic solvent solution. It is possible to add an acid irrelevant to the halogenic acid salt (such as toluenesulfonic acid, methanesulfonic acid and the like) thereby obtaining Compound (Id) from Compound (XXI).
  • the solvent employed is not limited particularly, it may for example be amides such as N-methylpyrrolidone and N,N-dimethylformamide and the like, alcohols such as methanol and ethanol, and ethers such as tetrahydrofuran, dioxane and the like.
  • the amount of Compound H-X b employed per mole of Compound (XXI) is usually 0.5 to 50 moles, and preferably 1 to 20 moles.
  • reaction temperature may appropriately be selected depending on the types of the solvent, H-X b and the like which are employed, it is preferably -20 degrees C to 250 degrees C, and more preferably -10 degrees C to 150 degrees C.
  • reaction time may appropriately be selected depending on the types of the solvent, base and the like which are employed, it is preferably 0.1 hour to several days, and more preferably 0.5 hour to 2 days.
  • Step 4B Compound (XIX) employed in Step 4A may be produced preferably by the following method.
  • Y, m, A and M are as described above.
  • G 2 denotes a protective group, and is not limited particularly as long as Compound (XIX) can be produced from Compound (XXIV).
  • the protective group can for example be an alkoxymethyl group such as a methoxymethyl group and an ethoxymethyl group, a lower alkyl group such as a t-butyl group and a methyl group as well as a substituted or unsubstituted benzyl group and the like.
  • Two G 2 s may also be taken together to form a ring, in which case the protective group may for example be methylene acetal, isopropylidene ketal and the like.
  • Step 4B1 A step for subjecting Compound (XXII) to conversion into an oxirane to obtain Compound (XXIII) (Step 4B1) in this Step 4B is described below.
  • a method involving reacting Compound (XXII) with a sulfur ylide in a solvent can be exemplified.
  • the sulfur ylide may for example be sulfonium methylides such as dimetylsulfonium methylide and the like or sulfoxonium methylides such as dimethyl sulfoxonium methylide and the like.
  • the sulfonium methylides or the sulfoxonium methylides employed can be produced by reacting, in a solvent, a sulfonium salt (for example, trimethylsulfonium iodide, trimethylsulfonium bromide and the like) or a sulfoxonium salt (for example, trimethylsulfoxonium iodide, trimethylsulfoxonium bromide and the like) with a base.
  • a sulfonium salt for example, trimethylsulfonium iodide, trimethylsulfonium bromide and the like
  • a sulfoxonium salt for example, trimethylsulfoxonium iodide, trimethylsulfoxonium bromide and the like
  • the amount of such a sulfonium methylide or sulfoxonium methylide employed per mole of Compound (XXII) described above is preferably 0.5 to 5 moles, and more preferably 0.8 to 2 moles.
  • the solvent employed is not limited particularly, it can for example be amides such as N-methylpyrrolidone and N,N-dimethylformamide and the like, ethers such as tetrahydrofuran, dioxane and the like, as well as a solvent mixture thereof.
  • the base employed for producing sulfonium methylides and sulfoxonium methylides are not limited particularly.
  • the base can for example be a metal hydride such as sodium hydride and the like, and an alkoxide of an alkaline metal such as sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium t-butoxide and the like.
  • the reaction temperature and the reaction time are appropriately selected depending on the types of the solvent, Compound (XXII), sulfonium salt or sulfoxonium salt, base and the like which are employed.
  • the reaction temperature is preferably -100 degrees C to 200 degrees C, and more preferably -50 degrees C to 150 degrees C.
  • the reaction time is preferably 0.1 hour to several days, and more preferably 0.5 hour to 2 days.
  • Compound (XXIII) can be produced by reacting Compound (XXII) with samarium iodide and diiodomethane in a solvent, and then treating the reactant with a base.
  • the base is not limited particularly, and may for example be sodium hydroxide.
  • the samarium iodide employed can be produced by reacting a metal samarium with 1,2-diiodoethane or diiodomethane in an anhydrous solvent.
  • the solvent employed is not limited particularly and may for example be an ether such as tetrahydrofuran and the like.
  • the amount of the base per mole of Compound (XXII) is not limited particularly, it is preferably 0.5 to 10 moles in usual cases, and more preferably 0.8 to 6 moles.
  • an aqueous solution of sodium hydroxide may for example be employed since no anhydrous system is required.
  • the reaction temperature and the reaction time may appropriately be selected depending on the types of the solvent, Compound (XXII), base and the like which are employed.
  • the reaction temperature is preferably -100 degrees C to 150 degrees C, and more preferably -50 degrees C to 100 degrees C.
  • the reaction time is preferably 0.1 hour to several days, and more preferably 0.5 hour to 2 days.
  • Step 4B2 a step for reacting Compound (XXIII) and Compound (IV) to obtain Compound (XXIV) (Step 4B2) in this Step 4B is described below.
  • Compound (XXIV) is produced by mixing Compound (XXIII) with Compound (IV) in a solvent to form a carbon-nitrogen bond between the carbon atom constituting an oxirane ring in an oxirane derivative (Compound (XXIII)) and the nitrogen atom in 1,2,4-triazole or imidazole (Compound (IV)).
  • solvent employed is not limited particularly, and can for example be amides such as N-methylpyrrolidone and N,N-dimethylformamide and the like.
  • the amount of Compound (IV) employed per mole of Compound (XXIII) is preferably 0.5 to 10 moles in usual cases, and more preferably 0.8 to 5 moles.
  • a base may be added if necessary.
  • the amount of the base employed per mole of Compound (IV) is preferably 0 to 5 moles (excluding 0) in usual cases, and more preferably 0.5 to 2 moles.
  • reaction temperature may appropriately be selected depending on the types of the solvent, the base and the like which are employed, it is preferably 0 degrees C to 250 degrees C, and more preferably 10 degrees C to 150 degrees C.
  • reaction time may also appropriately be selected depending on the types of the solvent, the base and the like which are employed, it is preferably 0.1 hour to several days, and more preferably 0.5 hour to 2 days.
  • Y, m, A, G 2 and M are as described above.
  • Compound (XXII) and Compound (IV) are dissolved in a polar solvent having an amide bond, or dimethyl sulfoxide, or a solvent mixture of a polar solvent with an alcohol. Then, to this, a trimethylsulfonium salt or a trimethylsulfoxonium salt and a base are added intermittently to produce sulfonium methylides such as dimetylsulfonium methylide and the like or sulfoxonium methylides such as dimethyl sulfoxonium methylide and the like in the reaction system, thereby effecting the conversion into an azole while allowing Compound (XXIII) to be produced.
  • the solvent employed here is not limited particularly.
  • the solvent may for example be a polar solvent having an amide bond such as N-methylpyrrolidone and N,N-dimethylformamide and the like, or dimethyl sulfoxide.
  • the alcohol in the solvent mixture may for example be t-butanol.
  • the base employed for producing sulfonium methylides or sulfoxonium methylides is not limited particularly.
  • the base can for example be a metal hydride such as sodium hydride and the like, an alkoxide of an alkaline metal such as sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium t-butoxide and the like. It is possible to use an alkaline metal salt of 1,2,4-triazole or imidazole.
  • the reaction temperature may appropriately be selected depending on the types of the solvent, Compound (XXII), sulfonium salt or sulfoxonium salt, base and the like which are employed.
  • the reaction temperature is preferably -100 degrees C to 250 degrees C, and more preferably -50 degrees C to 200 degrees C.
  • the reaction time may appropriately be selected depending on the types of the solvent, Compound (XXII), sulfonium salt or sulfoxonium salt, base and the like which are employed.
  • the reaction time is preferably 0.1 hour to several days, and more preferably 0.5 hour to 2 days.
  • the number of times when a trimethyl sulfonium halide or a trimethyl sulfonium halide and a base are added intermittently is not limited particularly as long as it is the number of times allowing a predetermined aim to be accomplished.
  • a preferred number of times is 2 to 20 times, with 3 to 15 times being more preferable.
  • the total amount of a trimethylsulfonium salt or a trimethylsulfoxonium salt employed per mole of Compound (XXII) is preferably 0.5 to 5 moles, and more preferably 0.8 to 2 moles.
  • the amount of Compound (IV) employed per mole of Compound (XXII) is preferably 0.5 to 10 moles in usual cases, and more preferably 0.8 to 5 moles. It is preferable to use Compound (IV) in which M is an alkaline metal salt.
  • Patent Literature 4 for the details of the steps for conducting conversion into an azole while allowing an oxirane derivative to be produced in the production of a certain azolylmethylcycloalkanol derivative.
  • Step 4B3 a step for deprotecting the protective group of Compound (XXIV) to obtain Compound (XIX) (Step 4B3) in this Step 4B is described below.
  • a preferred condition of the deprotection differs depending on the type of the protective group. Nevertheless, in the cases of using an alkoxymethyl group such as a methoxymethyl group, an ethoxyethyl group and the like, or a lower alkyl group such as a t-butyl group, a methyl group and the like, or a cyclic acetal or ketal protective group such as methylene acetal, isopropylidene ketal and the like, the deprotection is conducted preferably in a solvent under an acidic condition involving hydrogen chloride or sulfuric acid and the like.
  • the acid employed preferably in the deprotection may be a halogenated hydrogen such as hydrogen chloride or an inorganic acid such as sulfuric acid. While the amount employed is not limited particularly, the amount of the acid employed per mole of Compound (XXIV) is usually 0.5 to 100 moles, and preferably 0.8 to 20 moles.
  • the reaction temperature is preferably 0 degrees C to 200 degrees C in usual cases, and more preferably room temperature to 100 degrees C.
  • the reaction time is preferably 0.1 hour to several days in usual cases, and more preferably 0.5 hour to 2 days.
  • Step 4C Compound (XXII) employed in Step 4B can preferably be synthesized by the method shown below.
  • a keto ester compound represented by Formula (XXV) shown below (hereinafter referred to as "Compound (XXV)") is hydroxymethylated to obtain a compound represented by Formula (XXVI) shown below (“Compound (XXVI)").
  • a protective group such as a methoxymethyl group, a t-butyl group and the like is introduced into the hydroxyl group in Compound (XXVI) to effect derivatization into a compound represented by Formula (XXVII) shown below (“Compound (XXVII)”).
  • Compound (XXVII) is hydrolyzed/decarbonated to obtain a carbonyl compound represented by Formula (XXII) shown below (“Compound (XXII)”).
  • a series of these reaction procedures (Step 4C) is represented by Scheme (13) shown below.
  • Y, m, R 2 and G 2 are as described above.
  • Step 4C1 A step for bishydroxymethylating Compound (XXV) to obtain Compound (XXVI) (Step 4C1) in this Step 4C is described below.
  • Compound (XXVI) can be produced by reacting Compound (XXV) with formaldehyde in the presence of a base in a solvent.
  • the amount of formaldehyde employed per mole of Compound (XXV) is preferably 0.5 to 20 moles in usual cases, and more preferably 0.8 to 10 moles.
  • the base can for example be, but not limited to, a carbonate of an alkaline metal such as sodium carbonate, potassium carbonate and the like as well as a hydroxide of an alkaline metal such as sodium hydroxide and the like.
  • the amount of the base employed per mole of Compound (XXV) is preferably 0.1 to 10 moles in usual cases, and more preferably 0.2 to 5 moles.
  • the reaction temperature is preferably 0 degrees C to 250 degrees C in usual cases, and more preferably 0 degrees C to 100 degrees C.
  • the reaction time is preferably 0.1 hour to several days in usual cases, and more preferably 0.5 hour to 2 days.
  • Compound (XII) employed may be a compound produced by a known method (for example, the method disclosed in Patent Literature 1).
  • Step 4C2 a step for introducing a protective group into the hydroxyl group in Compound (XXVI) to obtain Compound (XXVII) (Step 4C2) in this Step 4C is described below.
  • the protective group for protecting the hydroxyl group is not limited particularly.
  • the protective group is preferably an alkoxymethyl group such as a methoxymethyl group, an ethoxymethyl group and the like, or a lower alkyl group such as a t-butyl group and the like. Introduction of these protective groups is conducted under an acidic condition. Nevertheless, a method involving (a) an acetal exchange of the hydroxyl group in Compound (XXVI) using a formaldehyde dialkylacetal in the case of introduction of an alkoxymethyl group is preferred. (b) Introduction of the protective group to the hydroxyl group in Compound (XXVI) using isobutene is utilized preferably in the case of introduction of a t-butyl group. (c) A suitable aldehyde or ketone is employed preferably under an acidic catalyst when protecting 2 hydroxyl groups with acetal and ketal at the same time.
  • hydrochloric acid including a compound allowing an acidic group to be generated by addition of an alcohol or water, such as diphosphorus pentoxide
  • an inorganic acid such as sulfuric acid, an organic acid such as p-toluenesulfonic acid and the like
  • the formaldehyde dialkylacetal is employed preferably in the presence of an acid in a solvent or in a solvent-free system. It is further preferred to add a compound allowing any generated alcohol to be removed (for example, diphosphorus pentoxide).
  • the amount of the formaldehyde dialkylacetal employed per mole of Compound (XXVI) is preferably 0.5 to 50 moles in usual cases, and more preferably 0.8 to 10 moles.
  • the amount of the acid employed per mole of Compound (XXVI) is preferably 0.01 to 10 moles in usual cases, and more preferably 0.05 to 5 moles.
  • the reaction temperature is preferably 0 degrees C to 250 degrees C in usual cases, and more preferably 0 degrees C to 150 degrees C.
  • the reaction time is preferably 0.1 hour to several days in usual cases, and more preferably 0.5 hour to 2 days.
  • the protective group is a t-butyl group (in the case of (b))
  • the amount of isobutene employed per mole of Compound (XXVI) is preferably 0.5 to 100 moles in usual cases, and more preferably 0.8 to 20 moles.
  • the amount of the acid employed per mole of Compound (XXVI) is preferably 0.01 to 10 moles in usual cases, and more preferably 0.05 to 5 moles.
  • the reaction temperature is preferably 0 degrees C to 200 degrees C in usual cases, and more preferably 0 to 100 degrees C.
  • the reaction time is preferably 0.1 to several days in usual cases, and more preferably 0.5 hour to 2 days.
  • the protective group is isopropylidene ketal (in the case of (c))
  • the amount of acetone dimethyl acetal employed per mole of Compound (XXVI) is preferably 0.5 to 100 moles in usual cases, and more preferably 0.8 to 20 moles.
  • the amount of the acid employed per mole of Compound (XXVI) is preferably 0.01 to 10 moles in usual cases, and more preferably 0.05 to 5 moles.
  • the reaction temperature is preferably 0 degrees C to 200 degrees C in usual cases, and more preferably 0 to 100 degrees C.
  • the reaction time is preferably 0.1 hour to several days in usual cases, and more preferably 0.5 hour to 2 days.
  • Step 4C3 a reaction for hydrolyzing/decarbonating Compound (XXVII) to obtain Compound (XXII) (Step 4C3) in this Step 4C is described below.
  • the reaction indicated as Step 4C4 is conducted preferably in the presence of a base in a solvent.
  • the base employed usually includes an alkaline metal base such as sodium hydroxide, potassium hydroxide and the like.
  • the amount of base employed per mole of Compound (XXVII) is preferably 0.1 to 50 moles in usual cases, and more preferably 0.2 to 20 moles.
  • the solvent may usually be water, as well as water combined with an alcohol and the like, a solvent composition consisting of solvents which do not form a homogenous layer with each other (such as water-toluene).
  • a solvent composition consisting of solvents which do not form a homogenous layer with each other (such as water-toluene).
  • a phase transfer catalyst for example a customary quaternary ammonium salt
  • the reaction temperature is preferably 0 degrees C to reflux temperature in usual cases, and more preferably room temperature to reflux temperature.
  • the reaction time is preferably 0.1 hour to several days in usual cases, and more preferably 0.5 hour to 24 hours.
  • Agro-horticultural agents and industrial material protecting agents The utilities of a 2-(halogenated hydrocarbon-substituted)-5-benzyl-1-azolylmethylcyclopentanol derivatives according to the invention (Compound (I)) as an agro-horticultural agent and an industrial material protecting agent (hereinafter also referred to as "agro-horticultural agent and the like") are described below.
  • Compound (I) Since Compound (I) has a 1,2,4-triazolyl group or an imidazolyl group, it forms an acid addition salt of an inorganic acid or an organic acid, as well as a metal complex. Accordingly, Compound (I) can be employed also in the form of such an acid addition salt or the metal complex.
  • Compound (I) may have at least three asymmetric carbon atoms unless (R a )X a n a and (R b )X b n b are the same substituents.
  • it may be a stereoisomer mixture (enantiomer or diastereomer) or either one of the stereoisomers. Accordingly, at least one of these stereoisomers can be employed also as an active ingredient of an agro-horticultural agent and the like.
  • Plant disease controlling effects Compound (I) of the invention exhibits a controlling effect on a broad range of plant diseases. Applicable diseases are exemplified below.
  • Soybean rust (Phakopsora pachyrhizi, Phakopsora meibomiae), rice blast (Pyricularia grisea), rice brown spot (Cochliobolus miyabeanus), rice leaf blight (Xanthomonas oryzae), rice sheath blight (Rhizoctonia solani), rice stem rot (Helminthosporium sigmoideun), rice bakanae disease (Gibberella fujikuroi), rice bacterial seedling blight (Pythium aphanidermatum), apple powdery mildew (Podosphaera leucotricha), apple scab (Venturia inaequalis), apple blossom blight (Monilinia mali), apple alternaria blotch (Alternaria alternata), apple valsa canker (Valsa mali), pear black spot (Alternaria kikuchiana), pear powdery mildew (Phyllact
  • Examples of applicable plants may be wild plants, cultivated plant varieties, plants and cultivated plant varieties obtained by conventional biological breeding such as heterologous mating or plasma fusion, and plants and cultivated plant varieties obtained by gene engineering.
  • the gene-engineered plants and the cultivated plant varieties may for example be herbicide-resistant crops, vermin-resistant crops having insecticidal protein-producing genes integrated therein, disease-resistant crops having disease resistance inducer-producing genes integrated therein, palatably improved crops, productively improved crops, preservably improved crops, productively improved crops and the like.
  • the gene-engineered cultivated plant varieties may for example be those involving trade marks such as ROUNDUP READY, LIVERTY LINK, CLEARFIELD, YIELDGARD, HERCULEX, BLLGARD and the like.
  • Compound (I) exhibits yield-increasing effects and quality-improving effects on a broad range of crops and horticultural plants by regulating the growth.
  • crops may for example be those listed below.
  • Compound (I) exhibits an excellent ability of protecting an industrial material from a broad spectrum of hazardous microorganisms which invade such a material. Examples of such microorganisms are listed below.
  • Paper/pulp deteriorating microorganisms such as Aspergillus sp., Trichoderma sp., Penicillium sp., Geotrichum sp., Chaetomium sp., Cadophora sp., Ceratostomella sp., Cladosporium sp., Corticium sp., Lentinus sp., Lezites sp., Phoma sp., Polysticus sp., Pullularia sp., Stereum sp., Trichosporium sp., Aerobacter sp., Bacillus sp., Desulfovibrio sp., Pseudomonas sp., Flavobacterium sp.
  • Fiber-deteriorating microorganisms such as Aspergillus sp.,Penicillium sp., Chaetomium sp., Myrothecium sp., Curvularia sp., Gliomastix sp., Memnoniella sp., Sarcopodium sp., Stachybotrys sp., Stemphylium sp., Zygorhynchus sp., Bacillus sp.
  • fiber-deteriorating microorganisms such as Aspergillus sp.,Penicillium sp., Chaetomium sp., Myrothecium sp., Curvularia sp., Gliomastix sp., Memnoniella sp., Sarcopodium sp., Stachybotrys sp., Stemphylium sp., Zygorhynchus
  • Lumber-deteriorating fungi such as Tyromyces palustris, Coriolus versicolor, Aspergillus sp., Penicillium sp., Rhizopus sp., Aureobasidium sp., Gliocladium sp., Cladosporium sp., Chaetomium sp.
  • leather-deteriorating microorganisms such as Aspergillus sp., Penicillium sp., Chaetomium sp., Cladosporium sp., Mucor sp., Paecilomyces sp., Pilobus sp., Pullularia sp., Trichosporon sp.
  • paint-deteriorating microorganisms such as Aspergillus sp., Penicillium sp., Cladosporium sp., Aureobasidium sp., Gliocladium sp., Botryodiplodia sp., Macrosporium sp., Monilia sp., Phoma sp., Pullularia sp., Sporotrichum sp., Trichoderma sp., Bacillus sp., Proteus sp., Pseudomonas sp. and Serratia sp..
  • An agro-horticultural formulation containing Compound (I) as an active ingredient may contain various components other than Compound (I).
  • the agro-horticultural formulation containing Compound (I) as an active ingredient can be mixed with a solid carrier, a liquid carrier, a surfactant, and other formulation auxiliary agents.
  • the dosage form of the agro-horticultural formulation containing Compound (I) as an active ingredient may for example be a powder, wettable powder, granule, emulsifiable concentrate and the like.
  • the agro-horticultural formulation may contain Compound (I) as an active ingredient in an amount of 0.1 to 95% by weight based on the total amount of the agro-horticultural formulation.
  • Compound (I) as an active ingredient is contained preferably in an amount of 0.5 to 90% by weight, and more preferably 2 to 80% by weight.
  • Carriers, diluents and surfactants employed as formulation auxiliary agents are exemplified below.
  • the solid carriers include talc, kaolin, bentonite, diatomaceous earth, white carbon, clay and the like.
  • the liquid carriers include water, xylene, toluene, chlorobenzene, cyclohexane, cyclohexanone, dimethyl sulfoxide, dimethyl formamide, alcohols and the like.
  • the surfactant may appropriately be selected for an intended effect.
  • the emulsifier may for example be polyoxiethylene alkylaryl ether, polyoxyethylene sorbitan monolaurate and the like
  • the dispersing agent may for example be lignin sulfonate, dibutylnaphthalene sulfonate and the like
  • the wetting agent may for example be an alkyl sulfonate, alkylphenyl sulfonate and the like.
  • the formulation may be used as it is, or used as being diluted in a diluent such as water to a certain concentration.
  • concentration of Compound (I) when used as being diluted is preferably 0.001% to 1.0%.
  • the amount of Compound (I) for 1 ha of the agro-horticultural field such as a farm, paddy field, orchard, greenhouse and the like is 20 to 5000 g, and more preferably 50 to 2000 g. Since these concentration and amount to be used may vary depending on the dosage form, timing of use, method of use, place of use, subject crop and the like, they can be increased or decreased regardless of the ranges mentioned above.
  • Compound (I) can be combined with other active ingredients, including bactericides, insecticides, acaricides, herbicides and the like, such as those listed below, thereby enabling the use as an agro-horticultural agent having an enhanced performance.
  • active ingredients including bactericides, insecticides, acaricides, herbicides and the like, such as those listed below, thereby enabling the use as an agro-horticultural agent having an enhanced performance.
  • ⁇ Anti-bacterial substances Acibenzolar-S-methyl, 2-phenylphenol (OPP), azaconazole, azoxystrobin, amisulbrom, bixafen, benalaxyl, benomyl, benthiavalicarb-isopropyl, bicarbonate, biphenyl, bitertanol, blasticidin-S, borax, Bordeaux mixture, boscalid, bromuconazole, bronopol, bupirimate, sec-butylamine, calcium polysulphide, captafol, captan, carbendazim, carboxin, carpropamid, quinomethionate, chloroneb, chloropicrin, chlorothalonil, chlozolinate, cyazofamid, cyflufenamid, cymoxanil, cyproconazole, cyprodinil, dazomet, debacarb, dichlofluanid, dic
  • plant hormones jasmonic acid, brassinosteoid, gibberellin and the like.
  • An industrial material protecting agents containing Compound (I) as an active ingredient may contain various components other than Compound (I).
  • the industrial material protecting agents containing Compound (I) as an active ingredient can be used as being dissolved or dispersed in a suitable liquid carrier or as being mixed with a solid carrier.
  • the industrial material protecting agents containing Compound (I) as an active ingredient may further contain an emulsifier, dispersing agent, spreading agent, penetrating agent, wetting agent, stabilizer and the like.
  • the dosage form of the industrial material protecting agents containing Compound (I) as an active ingredient may for example be a wettable powder, powder, granule, tablet, paste, suspension, spray and the like.
  • the industrial material protecting agents containing Compound (I) as an active ingredient may contain other biocides, insecticides, deterioration-preventing agent and the like.
  • the liquid carrier may be any liquid as long as it does not react with an active ingredient.
  • the liquid carrier may for example be water, alcohols (for example, methyl alcohol, ethyl alcohol, ethylene glycol, cellosolve and the like), ketones (for example, acetone, methylethylketone and the like), ethers (for example, dimethyl ether, diethyl ether, dioxane, tetrahydrofuran and the like), aromatic hydrocarbons (for example, benzene, toluene, xylene, methylnaphthalene and the like), aliphatic hydrocarbons (for example, gasoline, kerosene, paraffin oil, machine oil, fuel oil and the like), acid amides (for example, dimethyl formamide, N-methylpyrrolidone and the like), halogenated hydrocarbons (for example, chloroform, carbon tetrachloride and the like), esters (for example, acetic acid ethyl este
  • the solid carrier may for example be a microparticle or a granule of kaolin clay, bentonite, acid clay, pyrophylite, talc, diatomaceous earth, calcite, urea, ammonium sulfate and the like.
  • the emulsifiers and the dispersing agents may for example be soaps, alkyl sulfonates, alkylaryl sulfonates, dialkyl sulfosuccinates, quaternary ammonium salts, oxyalkylamines, fatty acid esters, polyalkylene oxide-based, anhydrosorbitol-based surfactants.
  • Compound (I) When Compound (I) is contained as an active ingredient in a formulation, it is added in such an amount that the concentration becomes 0.1 to 99.9% by weight based on the entire amount of the formulation, although the content may vary depending on the dosage form and the purpose of use. Upon being used practically, it is combined appropriately with a solvent, diluent, extender and the like so that the treatment concentration is usually 0.005 to 5% by weight, and preferably 0.01 to 1% by weight.
  • an azole derivative represented by Compound (I) exhibits an excellent biocidal effect on a large number of microorganisms which induce diseases in plants.
  • an agro-horticultural disease controlling agent containing Compound (I) as an active ingredient has a low toxicity to humans and animals, are capable of being handled safely, and exhibits a high controlling effect on a wide range of plant diseases.
  • Lithium chloride (10.4 mg, 0.245 mmol) was added, and stirring was conducted for 1.5 hours at 100 degrees C.
  • ethyl acetate (2 ml) was added, washed with saturated brine (0.5 ml x 5).
  • the organic layer was dried over anhydrous sodium sulfate, and then concentrated.
  • Compound (I) can also be produced from Intermediate (XVI) as shown below in accordance with the third production method described above. As an example, the production of I-1 is shown below.
  • Lithium chloride (9.2 mg, 0.216 mmol) was added, and stirring was conducted for 3 hours at 100 degrees C.
  • ethyl acetate (2 ml) was added, and washing with saturated brine (0.5 ml x 5) was conducted.
  • the organic layer was dried over anhydrous sodium sulfate, and then concentrated.
  • reaction solution was poured into a solution mixture of an aqueous solution of NaOH (NaOH (1.1 g) dissolved in 10 ml of water) and THF (10 ml), and stirring was continued for 30 minutes at room temperature.
  • This reaction solution was combined with ice, neutralized with a 1N aqueous solution of hydrochloric acid, and then extracted with hexane.
  • the organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate.
  • the solvent was distilled away under reduced pressure.
  • the aqueous layer was extracted with ethyl acetate (50 ml), and then the organic layer was washed with saturated brine (50 ml), and then dried over anhydrous sodium sulfate, and concentrated.
  • the organic layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate, the solvent was distilled away, and the residue was recrystallized from hexane/ethyl acetate for purification to obtain the desired substance.
  • methanesulfonyl chloride (0.0246 ml, 0.341 mmol) was added dropwise, and stirring was conducted for 3 hours while warming to room temperature. After completion of the reaction, water was added and extraction with ethyl acetate was conducted. This was washed with a dilute aqueous solution of sodium hydroxide and saturated brine and dried over anhydrous sodium sulfate. The solvent was distilled away, and the residue was dried in vacuum to obtain a crude intended substance.
  • the intermediate compounds (VI) employed above can be produced by Reference Production Example 7 described below and analogous methods as well as methods known in references.
  • R b is a hydrogen atom
  • the hydrogen atom-deficient carbon atom on the left end of (R b2 )X b2 n b2 (OH)p b1 serves to the binding to the cyclopentane ring in Compound (VI).
  • the number before "-" indicates the binding position when the carbon atom binding to the carbon atom binding to the cyclopentane ring is regarded as being in 1-position in the case of having a substituent on a phenyl ring.
  • the intermediate compounds (XVI) are produced also as described below.
  • the intermediate (XXI) for producing Compound No.I-1 can otherwise be synthesized according to the method described in Reference Production Example 10 described below.
  • This Compound (XXI) has a meaning identical to the abovementioned Compound (XVI)-1 and the NMR spectra were in complete agreement.
  • the intermediate (XIX) employed here can be synthesized in accordance with Reference Production Example 11 described below.
  • Example 1 Efficacy test against Cucumber gray mold > Onto a cucumber (variety:SHARP1) plant in its cotyledon phase grown using a square plastic pot (6cm x 6cm), a wettable formulation such as Formulation Example 1 which was diluted and suspended in water at a certain concentrations (100 mg/L and 50mg/L) was sprayed at a rate of 1,000L/ha. The sprayed leaves were air-dried, and loaded with a paper disc (8 mm in diameter) soaked in a spore suspension of Botrytis cinerea, and kept at 20 degrees C and a high humidity. Four days after inoculation, the cucumber gray mold lesion degree was investigated, and the protective value was calculated by the following equation.
  • Example 3 Efficacy test against Wheat fusarium head blight > Onto a head of a wheat plant (variety: NORIN No.61) grown to the blooming phase, a wettable formulations such as Formulation Example 1 which was diluted and suspended in water at certain concentrations (500mg/L and 100mg/L) was sprayed at a rate of 1,000L/ha.
  • the head was air-dried, and inoculated with spore suspension of Fusarium graminearum (adjusted at 2 x 10 5 spores/ml, containing Gramin S at a final concentration of 60 ppm and sucrose at a final concentration of 0.5%) by spraying, and kept at 20 degrees C and a high humidity.
  • the wheat fusarium head blight lesion degree was investigated, and the protective value was calculated by the following equation.
  • compounds I-1, I-25, I-36, I-73, I-74, I-77, I-80, I-86, I-88, I-101, I-104, I-115, I-601, I-602 for example, showed protective values of 80% or higher at 100mg/L.
  • Example 4 Microplate test of biocidal effect on Wheat Septoria blotch (Septoria tritici) > A spore suspension of wheat Septoria blotch (Septoria tritici) (spore concentration: 1 x 10 6 cells/ml) was prepared, and subjected to 100-fold dilution with a PD medium. A flat 96-well microplate was provided and 1 microlitre of the test compound solution formed by dissolution in dimethyl sulfoxide (DMSO) at a concentration 100 times the test concentration was dispensed to the microplate, and then 100 microlitre of the medium containing the spore was added and stirred thoroughly.
  • DMSO dimethyl sulfoxide
  • a non-inoculated control zone was provided by adding 1 microlitre of DMSO, and after cultivating at 20 degrees C for about 10 days, the absorbance (550 nm) was measured and % mycelium growth inhibitions were calculated according to the following equation to obtain the activity level (EC 80 ).
  • I-1, I-15, I-25, I-36, I-73, I-74, I-77, I-79, I-80, I-86, I-88, I-97, I-101, I-104, I-203, I-244, I-301, I-601, I-602 showed an activity level as high as 0.2 mg/L or less, in contrast to the following comparative compound (I) described in Patent Literature 1 (JPA01-93574) whose activity was 0.4 mg/L.
  • Example 5 Assay for fungicidal effect on various pathogenic microorganism and hazardous microorganisms>
  • the fungicidal effects of the inventive compounds on various phytopathogenic fungi for plants and hazardous microorganism for industrial materials were examined by the methods described below.
  • Each inventive compound was dissolved in 2 ml of dimethyl sulfoxide. 0.6 ml of this solution was added to 60 ml of a PDA medium (potato dextrose agar medium) at about 60 degrees C, which was mixed thoroughly in a 100-ml conical flask, and poured into a dish, where it was solidified, thereby obtaining a plate medium containing the inventive compound at 50 mg/L and 5 mg/L.
  • PDA medium potato dextrose agar medium
  • a subject microorganism previously cultured on a plate medium was cut out using a cork borer whose diameter was 4 mm, and inoculated to the test compound-containing plate medium described above. After inoculation, the dish was grown at the optimum growth temperatures for respective microorganisms (for this growth temperature, see, for example, a reference LIST OF CULTURES 1996 microorganisms 10th edition, Institute for Fermentation (foundation)) for 1 to 3 days, and the mycelial growth was measured as a diameter of its flora. The growth degree of the microorganism on the test compound-containing plate medium thus observed was compared with the growth degree of the microorganism in the untreated group, and % mycelial growth inhibition was calculated by the following equation.
  • Example 6 Rice elongation prevention assay> 36 mg of a test compound was dissolved in 3.6 ml of DMSO, and applied to 180 g of rice seeds in a vial. After soaking the seeds and promoting germination, the seeds were seeded to seedling boxes at a rate of 180 g/box, allowed to germinate in the seedling boxes, and then cultivated in a greenhouse at 35 degrees C. 20 Days after seeding, the plant height of the seedlings in each treatment group was surveyed in 10 locations, and the % plant height suppression was calculated by the following Equation 6.
  • Each inventive compound was dissolved in 2 ml of dimethyl sulfoxide to obtain a prescribed concentration. 0.6 ml of the each solution was added to 60 ml of a PDA medium (potato dextrose agar medium) at about 60 degrees C, which was mixed thoroughly in a 100-ml conical flask, and poured into a dish, where it was solidified, thereby obtaining medium plates containing the inventive compound at 0.02 mg/L.
  • PDA medium potato dextrose agar medium
  • the subject microorganism previously cultured on a plate medium was cut out using a cork borer whose diameter was 4 mm, and inoculated to the test compound-containing plate medium described above. After inoculation, the dish was incubated at the optimum growth temperatures for the microorganism (for this growth temperature, see, for example, a reference LIST OF CULTURES 1996 microorganisms 10th edition, Institute for Fermentation (foundation)) for 10 days, and the mycelial growth was measured as a diameter of its flora.
  • the growth degree of the microorganism on the test compound-containing plate medium thus observed was compared with the growth degree of the microorganism in the untreated group, and % mycelial growth inhibition was calculated by the following equation.
  • Example 9 Assay for fungicidal effect on Septoria tritici>
  • the fungicidal effects of the inventive compounds on Septoria tritici were examined by the methods described in the Experimental Example 5.
  • the inventive compounds were diluted at 1.25 mg/L.
  • An azole derivative according to the invention can preferably be utilized as an active ingredient of agro-horticultural bactericides, plant growth regulators and industrial material protecting agents.

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UAA201208247A UA108867C2 (uk) 2009-12-08 2010-07-12 Похідні азолу, спосіб їх одержання (варіанти), проміжні продукти, засіб для сільського господарства і садівництва
KR1020127017557A KR101464421B1 (ko) 2009-12-08 2010-12-07 아졸 유도체, 그의 제조 방법, 그의 중간체, 농원예용 약제
AU2010329332A AU2010329332B2 (en) 2009-12-08 2010-12-07 Azole derivatives, methods for producing the same, intermediate thereof, agro-horticultural agents
US13/508,269 US8710090B2 (en) 2009-12-08 2010-12-07 Azole derivatives, methods for producing the same, intermediate thereof, agro-horticultural agents
BR112012013201A BR112012013201B1 (pt) 2009-12-08 2010-12-07 derivado de azol, métodos para produzir o mesmo e agente de agro-horticultura ou um agente protetor de material industrial
JP2012524809A JP5831990B2 (ja) 2009-12-08 2010-12-07 アゾール誘導体およびその製造方法、該誘導体の中間体化合物、ならびに農園芸用薬剤
EA201290460A EA023393B1 (ru) 2009-12-08 2010-12-07 Производные азола, способы их получения, промежуточные продукты, средства для сельского хозяйства и садоводства
ES10798835.4T ES2524376T3 (es) 2009-12-08 2010-12-07 Derivados de azol, métodos para producirlos, compuestos intermedios de los mismos, agentes agrohortícolas
CN201080055788.6A CN102639509B (zh) 2009-12-08 2010-12-07 唑衍生物、其制造方法、该唑衍生物的中间体、农业园艺试剂
DK10798835.4T DK2509958T3 (da) 2009-12-08 2010-12-07 Azolderivater, fremgangsmåder til fremstilling af disse, mellemprodukter deraf, midler til landbrug og gartnerier
EP10798835.4A EP2509958B1 (en) 2009-12-08 2010-12-07 Azole derivatives, methods for producing the same, intermediates thereof, agro-horticultural agents
PL10798835T PL2509958T3 (pl) 2009-12-08 2010-12-07 Pochodna azolu, sposoby ich wytwarzania, ich produkty pośrednie, środki do stosowania w rolnictwie i ogrodnictwie
CA2783552A CA2783552C (en) 2009-12-08 2010-12-07 Azole derivatives, methods for producing the same, intermediate thereof, agro-horticultural agents
ZA2012/02988A ZA201202988B (en) 2009-12-08 2012-04-24 Azole derivatives, methods for producing the same, intermediate thereof, agro-horticultural agents
US14/213,240 US9162966B2 (en) 2009-12-08 2014-03-14 Azole derivatives, methods for producing the same, intermediate thereof, agro-horticultural agents
US14/213,043 US9145351B2 (en) 2009-12-08 2014-03-14 Azole derivatives, methods for producing the same, intermediate thereof, agro-horticultural agents

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JPH05271197A (ja) 1992-03-24 1993-10-19 Kureha Chem Ind Co Ltd 新規（ヒドロキシアルキル）アゾリルメチルシクロペンタノール誘導体

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