WO2014024897A1 - Thiazolidinedione and pyrrolidinedione derivatives, and germicide having same as active ingredients thereof - Google Patents

Thiazolidinedione and pyrrolidinedione derivatives, and germicide having same as active ingredients thereof Download PDF

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WO2014024897A1
WO2014024897A1 PCT/JP2013/071289 JP2013071289W WO2014024897A1 WO 2014024897 A1 WO2014024897 A1 WO 2014024897A1 JP 2013071289 W JP2013071289 W JP 2013071289W WO 2014024897 A1 WO2014024897 A1 WO 2014024897A1
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group
carbon atoms
phenyl
alkyl group
substituted
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Japanese (ja)
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伸三 利部
泰司 三宅
憲太朗 山本
聡 畠山
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Ｍｅｉｊｉ Ｓｅｉｋａファルマ株式会社
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Publication of WO2014024897A1 publication Critical patent/WO2014024897A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D277/34—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D277/36—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • 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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • the present invention relates to a thiazolidinedione and a pyrrolidinedione derivative, and a fungicide containing these as active ingredients.
  • Non-Patent Document 1 discloses certain thiazolidinedione derivatives and their antibacterial activity.
  • Non-Patent Document 1 Some of thiazolidinedione derivatives are known for use as pharmaceuticals, but none of these pharmaceuticals are used for antibacterial activity. In addition, the thiazolidinedione derivative described in Non-Patent Document 1 has only been investigated for antibacterial activity against a small number of fungi such as a fungus causing rice blast and a fungus causing rice blight (non-patent literature). 1). There are no known thiazolidinedione derivatives that are widely effective against pathogens causing soil diseases, pathogens causing seed diseases, and pathogens causing foliage diseases.
  • fungicides used in the agricultural field bacteria that have acquired drug resistance have emerged as a result of continuing to use specific drugs.
  • the currently used bactericides are limited in the number of pathogenic bacteria that can exert their effects, and the creation of drugs having activity against a wider range of pathogenic bacteria is required.
  • the main object of the present invention is to provide a drug having a broad antibacterial activity against pathogenic bacteria causing soil diseases, pathogenic bacteria causing seed diseases, and pathogenic bacteria causing foliage diseases.
  • the present inventors have examined in detail the chemical structure and physiological activity of a large number of thiazolidinedione derivatives and further a large number of pyrrolidinedione derivatives. As a result, a compound having excellent antibacterial activity was found and the present invention was completed.
  • the present invention provides a compound represented by the following formula (A) and a fungicide containing the compound as an active ingredient.
  • X represents CH 2 , an oxygen atom or a sulfur atom
  • R represents a phenyl group, a pyridyl group, a thienyl group, a furanyl group, a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenoxyphenyl group.
  • the phenyl group, pyridyl group, thienyl group, furanyl group and phenoxyphenyl group are selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group and a hydroxy group. It may be substituted with a substituent.
  • Y represents an oxygen atom or a sulfur atom
  • W represents a hydrogen atom, an alkyl group, a benzyl group, a phenyl group, a pyridyl group, an alkyloxycarbonylalkyl group, or an alkylaminocarbonylalkyl group.
  • the alkyl group, benzyl group, phenyl group, pyridyl group, alkyloxycarbonylalkyl group, and alkylaminocarbonylalkyl group are a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and It may be substituted with a substituent selected from alkylamine groups.
  • a broken line represents a single bond or a double bond.
  • One preferred embodiment is a compound represented by the following formula (A1- (I)) and a bactericidal agent containing it as an active ingredient.
  • X represents CH 2 or a sulfur atom
  • R 1 represents a phenyl group, a pyridyl group or a furanyl group.
  • the phenyl group, pyridyl group and furanyl group are substituted with a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group and a hydroxy group. May be.
  • Another preferred embodiment is a compound represented by the following formula (A1- (II)) and a fungicide containing it as an active ingredient.
  • X represents CH 2 or a sulfur atom
  • R 2 represents a triphenylphosphoranylidene group.
  • the three phenyl groups constituting the triphenylphosphoranylidene group may each independently be substituted with a substituent selected from a halogen atom and an alkyl group having 1 to 4 carbon atoms.
  • Another preferred embodiment is a compound represented by the following formula (A1- (XI)) and a fungicide containing it as an active ingredient.
  • X represents CH 2 or a sulfur atom
  • R 11 represents a phenyl group, a pyridyl group or a phenoxyphenyl group
  • R 12 represents an alkyl group, a phenyl group, a benzyl group or a pyridyl group.
  • the phenyl group, pyridyl group and phenoxyphenyl group are substituted with a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group and a hydroxy group. It may be.
  • Another preferred embodiment is a compound represented by the following formula (A1- (XII)) and a fungicide containing it as an active ingredient.
  • X represents CH 2 or a sulfur atom
  • R 13 represents an alkyloxycarbonylalkyl group or an alkylaminocarbonylalkyl group.
  • the alkyloxycarbonylalkyl group and the alkylaminocarbonylalkyl group may be substituted with a halogen atom.
  • R 14 represents a phenyl group or a thienyl group.
  • Another preferred embodiment is a compound represented by the following formula (A2- (I)) and a fungicide containing it as an active ingredient.
  • R 1a represents a hydroxy group or —NR 3 R 4 , wherein R 3 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 2 carbon atoms.
  • R 3 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 2 carbon atoms.
  • R 4 is an alkyl group having 2 to 6 carbon atoms or a phenyl group, R 3 and R 4 may combine to form a ring.
  • R 2a represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group.
  • R 3 alkyl group and phenyl group having 1 to 6 carbon atoms R 4 alkyl group and phenyl group having 2 to 6 carbon atoms
  • Another preferred embodiment is a compound represented by the following formula (A2- (II)) and a fungicide containing it as an active ingredient.
  • R 1b represents an alkoxy group having 1 to 6 carbon atoms
  • R 2b represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
  • the alkoxy group having 1 to 6 carbon atoms of R 1b and the alkyl group having 1 to 6 carbon atoms of R 2b are each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms.
  • Another preferred embodiment is a compound represented by the following formula (A2- (III)) and a fungicide containing it as an active ingredient.
  • R 2a represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group.
  • the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms of R 2a are each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, It may be substituted with a substituent selected from an alkylcarbonyloxy group having 1 to 4 carbon atoms, a nitro group and a phenyl group.
  • the phenyl group of R 2a may be unsubstituted or substituted.
  • Another preferred embodiment is a compound represented by the following formula (A2- (IV)) and a fungicide containing it as an active ingredient.
  • R 5 represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms or —NR 8 R 9 , and R 8 and R 9 each independently represent 1 to An alkyl group having 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkenyl group having 3 to 8 carbon atoms, or a phenyl group, and R 8 and R 9 may combine to form a ring.
  • R 6 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group.
  • the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms of R 5 are each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, It may be substituted with a substituent selected from an alkylcarbonyloxy group having 1 to 4 carbon atoms, a nitro group and a phenyl group.
  • the phenyl group of R 5 may be unsubstituted or substituted.
  • Another preferred embodiment is a compound represented by the following formula (A2- (V)) and a fungicide containing it as an active ingredient.
  • R 2a represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group.
  • the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms of R 2a are each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, It may be substituted with a substituent selected from an alkylcarbonyloxy group having 1 to 4 carbon atoms, a nitro group and a phenyl group.
  • the phenyl group of R 2a may be unsubstituted or substituted.
  • the present invention is a compound represented by the following formula (A1- (III)) and a fungicide containing the compound as an active ingredient.
  • R 7 represents a pyridyl group or a furanyl group, where the pyridyl group and the furanyl group are a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. And may be substituted with a substituent selected from an alkoxy group, a benzyloxy group and a hydroxy group.
  • the compound according to the present invention has a remarkable effect as a bactericide having antibacterial activity widely against pathogenic bacteria causing soil diseases, pathogenic bacteria causing seed diseases and pathogenic bacteria causing foliage diseases.
  • the fungicide according to the present invention contains a compound represented by the following formula (A) (hereinafter referred to as “the compound of the present invention”) as an active ingredient.
  • X represents CH 2 , an oxygen atom or a sulfur atom
  • R represents a phenyl group, a pyridyl group, a thienyl group, a furanyl group, a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenoxyphenyl group.
  • the phenyl group, pyridyl group, thienyl group, furanyl group and phenoxyphenyl group are selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group and a hydroxy group. It may be substituted with a substituent.
  • Y represents an oxygen atom or a sulfur atom
  • W represents a hydrogen atom, an alkyl group, a benzyl group, a phenyl group, a pyridyl group, an alkyloxycarbonylalkyl group, or an alkylaminocarbonylalkyl group.
  • the alkyl group, benzyl group, phenyl group, pyridyl group, alkyloxycarbonylalkyl group, and alkylaminocarbonylalkyl group are a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and It may be substituted with a substituent selected from alkylamine groups.
  • a broken line represents a single bond or a double bond.
  • Compound A1- (I) Compound A1- (I) is represented by the following formula (A1- (I)).
  • X of compound A1- (I) is CH 2 or a sulfur atom, and R 1 is a phenyl group, a pyridyl group, or a furanyl group.
  • the phenyl group, pyridyl group and furanyl group are substituted with a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group and a hydroxy group. May be.
  • the number of substituents may be one or two or more. When the number of substituents is two or more, each of the substituents may be the same or different. .
  • the phenyl group is unsubstituted or substituted by a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group, and a hydroxy group It is preferable.
  • the pyridyl group is preferably unsubstituted.
  • the pyridyl group may be bonded at any of the 1-position, 2-position, 3-position and 4-position, but it is preferably bonded at the 3-position carbon atom.
  • the furanyl group is preferably unsubstituted.
  • the furanyl group may be bonded at any of the carbon atoms at the 1-position, 2-position, and 3-position, but is preferably bonded at the 2-position carbon atom.
  • halogen atom examples include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. Among them, a chlorine atom is preferable.
  • the alkyl group having 1 to 4 carbon atoms may be linear, branched or cyclic.
  • Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, and a cyclopropyl group. Of these, a methyl group is preferable.
  • alkoxy group having 1 to 4 carbon atoms examples include a methoxy group, an ethoxy group, a propoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, and a cyclopentoxy group, and among them, a methoxy group is preferable.
  • R 1 is preferably an unsubstituted phenyl group, an unsubstituted pyridyl group or an unsubstituted furanyl group, and a substituent selected from a halogen atom, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group, and a hydroxy group A phenyl group substituted by As the halogen atom, a chlorine atom is preferable.
  • the alkoxy group having 1 to 4 carbon atoms is preferably a methoxy group. When the number of substituents in R 1 is 2 or more, each of the substituents may be the same or different.
  • R 1 is particularly preferably a phenyl group, 3-pyridyl group, 2-furanyl group, 4-chlorophenyl group, 4-methoxyphenyl group, 4-benzyloxyphenyl group, 2-hydroxyphenyl group, 3-hydroxyphenyl group or 4-hydroxyphenyl group.
  • R 1 is preferably selected from an unsubstituted phenyl group, an unsubstituted pyridyl group or an unsubstituted furanyl group, or a halogen atom and an alkoxy group having 1 to 4 carbon atoms.
  • the halogen atom a chlorine atom is preferable.
  • the alkoxy group having 1 to 4 carbon atoms is preferably a methoxy group.
  • R 1 is particularly preferably a phenyl group, a 3-pyridyl group, a 2-furanyl group, a 4-chlorophenyl group, or a 4-methoxyphenyl group.
  • X is CH 2 and R 1 is an unsubstituted phenyl group, an unsubstituted pyridyl group or an unsubstituted furanyl group, or a halogen atom and a carbon number of 1
  • R 1 is an unsubstituted phenyl group, an unsubstituted pyridyl group or an unsubstituted furanyl group, or a halogen atom and a carbon number of 1
  • X is a sulfur atom and R 1 is selected from a benzyloxy group and a hydroxy group
  • X is CH 2 and R 1 is an unsubstituted phenyl group, an unsubstituted pyridyl group or an unsubstituted furanyl group, or a chlorine atom and a methoxy group
  • X is CH 2 and R 1 is an unsubstituted phenyl group, an unsubstituted pyridyl group or an unsubstituted furanyl group, or a chlorine atom and a methoxy group
  • R 1 is an unsubstituted phenyl group, an unsubstituted pyridyl group or an unsubstituted furanyl group, or a chlorine atom and a methoxy group
  • X being a sulfur atom and R 1 being selected from a benzyloxy group and a hydroxy group
  • X is CH 2 and R 1 is a phenyl group, a 3-pyridyl group, a 2-furanyl group, a 4-chlorophenyl group or a 4-methoxyphenyl group.
  • R 1 is a compound wherein X is a sulfur atom and R 1 has a 4-benzyloxyphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group or a 4-hydroxyphenyl group.
  • compound A1- (I) is a pyrrolidinedione derivative represented by the following formula (A1- (IV)).
  • X is a sulfur atom
  • the compound A1- (I) is a thiazolidinedione derivative represented by the following formula (A1- (V)).
  • Compound A1- (I) can be produced, for example, according to the production method of compound A1- (III) described later.
  • Compound A1- (II) is represented by the following formula (A1- (II)).
  • X of compound A1- (II) is CH 2 or a sulfur atom. Among them, X is preferably is CH 2.
  • R 2 is a triphenylphosphoranylidene group.
  • the three phenyl groups constituting the triphenylphosphoranylidene group may each independently be substituted with a substituent selected from a halogen atom and an alkyl group having 1 to 4 carbon atoms.
  • the number of substituents may be one or two or more. When the number of substituents is two or more, each of the substituents may be the same or different. .
  • halogen atom examples include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. Among them, a chlorine atom is preferable.
  • the alkyl group having 1 to 4 carbon atoms may be linear, branched or cyclic.
  • Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, and a cyclopropyl group. Of these, a methyl group is preferable.
  • (ix) X is CH 2 or a sulfur atom
  • R 2 is an unsubstituted triphenylphosphoranylidene group
  • (x) X is CH 2
  • R 2 is a compound having a triphenylphosphoranylidene group which may be substituted with a substituent.
  • the compound A1- (II) is a compound in which X is CH 2 and R 2 has an unsubstituted triphenylphosphoranylidene group.
  • Compound A1- (II) can be produced, for example, according to the reference: T. Boettcher S. A. Sieber: J. Am. Chem. Soc. 132 (20), 6964-6972, 2010. it can.
  • Compound A1- (XI) is represented by the following formula (A1- (XI)).
  • X of compound A1- (XI) is CH 2 or a sulfur atom
  • R 11 is a phenyl group, a pyridyl group or a phenoxyphenyl group
  • R 12 is an alkyl group, a phenyl group, a benzyl group or a pyridyl group. is there.
  • the phenyl group, benzyl group, pyridyl group and phenoxyphenyl group are a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group and a hydroxy group. May be substituted.
  • the number of substituents may be one or two or more. When the number of substituents is two or more, each of the substituents may be the same or different. .
  • the phenyl group is unsubstituted or substituted by a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group, and a hydroxy group It is preferable.
  • a halogen atom a chlorine atom is preferable.
  • the alkoxy group having 1 to 4 carbon atoms is preferably a methoxy group.
  • the benzyl group is unsubstituted or substituted by a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group and a hydroxy group It is preferable.
  • a halogen atom a chlorine atom is preferable.
  • the alkoxy group having 1 to 4 carbon atoms is preferably a methoxy group.
  • the pyridyl group is preferably unsubstituted or substituted with a halogen atom.
  • the pyridyl group may be bonded at any of the 1-position, 2-position, 3-position and 4-position, but it is preferably bonded at the 3-position carbon atom.
  • the phenoxyphenyl group is unsubstituted or substituted by a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group, and a hydroxy group. Preferably it is.
  • a halogen atom a chlorine atom is preferable.
  • the alkoxy group having 1 to 4 carbon atoms is preferably a methoxy group.
  • the phenoxyphenyl group may be bonded at any of the 2-position, the 3-position and the 4-position, but is preferably bonded at the 3-position carbon atom.
  • X is a sulfur atom and R 11 is selected from an unsubstituted phenyl group, an unsubstituted pyridyl group or an unsubstituted phenoxyphenyl group, or a chlorine atom and a methoxy group a one phenyl group substituted with substituents, a compound having a pyridyl group R 12 is an alkyl group, a benzyl group is substituted with a phenyl group or a halogen atom.
  • X is a sulfur atom
  • R 11 is a phenyl group, a 3-pyridyl group, or a 3-phenoxyphenyl group
  • R 12 is a methyl group, a benzyl group, a phenyl group, Or a compound having a 2,6-dichloro-4-pyridyl group.
  • X of compound A1- (XII) represents CH 2 or a sulfur atom
  • R 13 represents an alkyloxycarbonylalkyl group or an alkylaminocarbonylalkyl group.
  • the alkoxy group or alkylamino group of the alkyloxycarbonylalkyl group or alkylaminocarbonylalkyl group has 1 to 6 carbon atoms and may be substituted with a halogen atom.
  • R 14 represents a phenyl group or a thienyl group.
  • the alkyl of an alkyloxycarbonylalkyl group or an alkylaminocarbonylalkyl group represents an alkyl having 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, t-butyl, and cyclopropyl. Ethyl is preferred.
  • the above-mentioned alkyloxy group represents an alkyloxy group having 1 to 4 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a propoxy group, and among them, a methoxy group is preferable.
  • the above alkylamino group represents an alkylamino group having 1 to 6 carbon atoms, and may be a cyclic amino group, such as a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentaamino group, 1- Examples include a piperidyl group and a dimethylamino group.
  • R 1a in compound A2- (I) is a hydroxy group or —NR 3 R 4 .
  • R 3 is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkenyl group having 3 to 8 carbon atoms, A heterocycloalkyl group having 3 to 8 carbon atoms or a phenyl group, and R 4 is an alkyl group having 2 to 6 carbon atoms or a phenyl group.
  • the alkyl group having 1 to 6 carbon atoms of R 3 may be linear or branched. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a t-butyl group.
  • the alkyl group having 1 to 6 carbon atoms of R 3 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
  • the alkynyl group having 2 to 6 carbon atoms of R 3 may be linear or branched.
  • Examples of the alkynyl group having 2 to 6 carbon atoms include ethynyl group, propynyl group, butynyl group, and the like.
  • the alkenyl group having 2 to 6 carbon atoms of R 3 may be linear or branched.
  • Examples of the alkenyl group having 2 to 6 carbon atoms include an ethenyl group, a propenyl group, and a butenyl group.
  • Examples of the cycloalkyl group having 3 to 8 carbon atoms of R 3 include a cyclopropyl group and a cyclobutyl group.
  • Examples of the cycloalkenyl group having 3 to 8 carbon atoms of R 3 include a cyclopropenyl group and a cyclobutenyl group.
  • R 3 and R 4 may combine to form a ring.
  • Examples of —NR 3 R 4 in which R 3 and R 4 are bonded to form a ring include a pyrrolidine ring and a piperidine ring.
  • alkyl group and phenyl group having 1 to 6 carbon atoms of R 3 and the alkyl group and phenyl group having 2 to 6 carbon atoms of R 4 are each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, It may be substituted with a substituent selected from an alkoxy group having 1 to 4 carbon atoms, an alkylcarbonyloxy group having 1 to 4 carbon atoms, a nitro group, and a phenyl group.
  • the number of substituents may be one or two or more. When the number of substituents is two or more, each of the substituents may be the same or different. .
  • Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.
  • Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, and a propyl group.
  • Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group and an ethoxy group.
  • Examples of the alkylcarbonyloxy group having 1 to 4 carbon atoms include an acetoxy group.
  • R 1a Preferred as R 1a, R 3 is attached is a -NR 3 R 4 (R 3 and R 4 alkyl group and R 4 having 1 to 3 carbon atoms is an alkyl group or a phenyl group having 2 to 4 carbon atoms Which may form a ring), or a hydroxy group.
  • R 1a is more preferably —NR 3 R 4 , wherein R 3 is a methyl group and R 4 is a phenyl group, and R 3 and R 4 are bonded to form a pyrrolidine ring or a piperidine ring. 3 R 4 or a hydroxy group.
  • R 2a in compound A2- (I) is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group.
  • halogen atom for R 2a examples include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom, and among them, a chlorine atom is preferable.
  • the alkyl group having 1 to 6 carbon atoms of R 2a may be linear, branched or cyclic.
  • Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, and a cyclopropyl group. Of these, a methyl group is preferable.
  • Examples of the alkoxy group having 1 to 6 carbon atoms of R 2a include a methoxy group, an ethoxy group, and a propoxy group, and among them, a methoxy group is preferable.
  • the alkyl group having 1 to 6 carbon atoms or the alkoxy group having 1 to 6 carbon atoms of R 2a is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms. And may be substituted with a substituent selected from an alkylcarbonyloxy group, a nitro group and a phenyl group.
  • the number of substituents may be one or two or more. When the number of substituents is two or more, each of the substituents may be the same or different. .
  • substituents in the alkyl group and phenyl group having 1 to 6 carbon atoms of R 3 and the alkyl group and phenyl group having 2 to 6 carbon atoms in R 4 are the same as the definition of the substituents in the alkyl group and phenyl group having 1 to 6 carbon atoms of R 3 and the alkyl group and phenyl group having 2 to 6 carbon atoms in R 4 .
  • the phenyl group of R 2a may be unsubstituted or substituted.
  • substituent for the phenyl group of R 2a include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a benzyloxy group, a hydroxy group, a nitro group, and a phenyl group.
  • the substituent for the phenyl group of R 2a is preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group or a hydroxy group, more preferably a halogen atom or carbon An alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms.
  • the halogen atom is preferably a chlorine atom
  • the alkyl group having 1 to 6 carbon atoms is preferably a methyl group
  • the alkoxy group having 1 to 6 carbon atoms is preferably a methoxy group.
  • R 2a is a phenyl group having a substituent
  • the substituent may be bonded to any position of the ortho position, the meta position, and the para position of the benzene ring, but at the para position of the benzene ring. Bonding is preferred.
  • R 2a is preferably an unsubstituted phenyl group and a phenyl group substituted by a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.
  • R 2a is more preferably an unsubstituted phenyl group and a phenyl group substituted by a chlorine atom, a methyl group or a methoxy group.
  • R 2a is more preferably a phenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, and a 4-methoxyphenyl group.
  • R 1a is a hydroxy group
  • R 3 is an alkyl group having 1 to 3 carbon atoms
  • R 4 is an alkyl group having 2 to 4 carbon atoms, or a phenyl group— NR 3 R 4 (R 3 and R 4 may combine to form a ring)
  • R 2a is an unsubstituted phenyl group, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or This is a compound having a phenyl group substituted with an alkoxy group having 1 to 3 carbon atoms.
  • R 1a is a hydroxy group
  • R 3 is a methyl group
  • R 4 is a phenyl group, or —NR 3 R 4 , or R 3 and R 4 are bonded to form a pyrrolidine ring
  • the compound is -NR 3 R 4 forming a piperidine ring
  • R 2a is a phenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, or a 4-methoxyphenyl group.
  • the compound A2- (I) is represented by the following formula A2- (VI).
  • R 1a is —NR 3 R 4
  • the compound A2- (I) is represented by the following formula A2- (VII).
  • a compound represented by the following formula A2- (VI) is referred to as “compound A2- (VI)”
  • a compound represented by the following formula A2- (VII) is referred to as “compound A2- (VII)”.
  • R 1b of compound A2- (II) is an alkoxy group having 1 to 6 carbon atoms.
  • the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group.
  • the alkoxy group having 1 to 6 carbon atoms of R 1b is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylcarbonyloxy group having 1 to 4 carbon atoms, a nitro group, and It may be substituted with a substituent selected from a phenyl group.
  • the number of substituents may be one or two or more.
  • each of the substituents may be the same or different.
  • the definition of these substituents is the same as the definition of the substituents in the alkyl group and phenyl group having 1 to 6 carbon atoms of R 3 and the alkyl group and phenyl group having 2 to 6 carbon atoms in R 4 .
  • R 1b is preferably an alkoxy group having 1 to 3 carbon atoms. R 1b is more preferably a methoxy group.
  • R 2b in compound A2- (II) is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
  • halogen atom of R 2b and the alkyl group having 1 to 6 carbon atoms is the same as the definition of R 2a .
  • the alkyl group having 1 to 6 carbon atoms of R 2b is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylcarbonyloxy group having 1 to 4 carbon atoms, a nitro group, and a phenyl group. It may be substituted with a substituent selected from The number of substituents may be one or two or more. When the number of substituents is two or more, each of the substituents may be the same or different. .
  • the phenyl group of R 2b may be unsubstituted or substituted.
  • substituent for the phenyl group of R 2b include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a benzyloxy group, a hydroxy group, a nitro group, and a phenyl group.
  • the substituent for the phenyl group of R 2b is preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group or a hydroxy group, more preferably a halogen atom or carbon An alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms.
  • a chlorine atom is preferable.
  • the alkoxy group having 1 to 6 carbon atoms is preferably a methoxy group.
  • R 2b is a phenyl group having a substituent
  • the substituent may be bonded to any position of the ortho position, the meta position, and the para position of the benzene ring, but in the para position of the benzene ring. Bonding is preferred.
  • R 2b is preferably an unsubstituted phenyl group and a phenyl group substituted by a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.
  • R 2b is more preferably an unsubstituted phenyl group and a phenyl group substituted with a chlorine atom, a methyl group or a methoxy group.
  • R 2b is more preferably a phenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, or a 4-methoxyphenyl group.
  • R 2a in compound A2- (III) is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group.
  • the definition of the halogen atom of R 2a , the alkyl group having 1 to 6 carbon atoms, and the alkoxy group having 1 to 6 carbon atoms is the same as the definition of R 2a .
  • the alkyl group having 1 to 6 carbon atoms or the alkoxy group having 1 to 6 carbon atoms of R 2a is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms. And may be substituted with a substituent selected from an alkylcarbonyloxy group, a nitro group and a phenyl group.
  • the number of substituents may be one or two or more. When the number of substituents is two or more, each of the substituents may be the same or different. .
  • the phenyl group of R 2a may be unsubstituted or substituted.
  • substituent for the phenyl group of R 2a include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a benzyloxy group, a hydroxy group, a nitro group, and a phenyl group.
  • the substituent for the phenyl group of R 2a is preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group or a hydroxy group, more preferably a halogen atom or carbon An alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms.
  • the halogen atom is preferably a chlorine atom
  • the alkyl group having 1 to 6 carbon atoms is preferably a methyl group
  • the alkoxy group having 1 to 6 carbon atoms is preferably a methoxy group.
  • R 2a is a phenyl group having a substituent
  • the substituent may be bonded to any position of the ortho position, the meta position, and the para position of the benzene ring, but at the para position of the benzene ring. Bonding is preferred.
  • R 2a is preferably an unsubstituted phenyl group and a phenyl group substituted by a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.
  • R 2a is more preferably a phenyl group substituted by a chlorine atom, a methyl group or a methoxy group.
  • R 2a is more preferably a 4-chlorophenyl group, a 4-methylphenyl group, and a 4-methoxyphenyl group.
  • R 5 of the compound A2- (IV) is a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or —NR 8 R 9 .
  • R 8 and R 9 are each independently an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a carbon number 3 to 8 cycloalkenyl groups or phenyl groups, and R 8 and R 9 may combine to form a ring.
  • R 6 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group.
  • the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms of R 6 are each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 carbon atom. It may be substituted with a substituent selected from alkylcarbonyloxy group, nitro group and phenyl group.
  • the phenyl group of R 6 may be unsubstituted or substituted.
  • R 6 is preferably an unsubstituted phenyl group and a phenyl group substituted by a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.
  • R 2a is more preferably an unsubstituted phenyl group and a phenyl group substituted by a chlorine atom, a methyl group or a methoxy group.
  • the alkyl group having 1 to 6 carbon atoms of R 8 and R 9 may be linear or branched. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a t-butyl group.
  • the alkyl group having 1 to 6 carbon atoms of R 8 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
  • the alkyl group having 1 to 6 carbon atoms of R 9 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
  • R 8 and R 9 may be the same or different from each other.
  • the alkynyl group having 2 to 6 carbon atoms of R 8 and R 9 may be linear or branched.
  • Examples of the alkynyl group having 2 to 6 carbon atoms include an ethynyl group, a propynyl group, and a butynyl group.
  • the alkenyl group having 2 to 6 carbon atoms of R 8 and R 9 may be linear or branched.
  • Examples of the alkenyl group having 2 to 6 carbon atoms include an ethenyl group, a propenyl group, and a butenyl group.
  • Examples of the cycloalkyl group having 3 to 8 carbon atoms of R 8 and R 9 include a cyclopropyl group and a cyclobutyl group.
  • Examples of the C3-C8 cycloalkenyl group of R 8 and R 9 include a cyclopropenyl group and a cyclobutenyl group.
  • R 8 and R 9 may combine to form a ring.
  • Examples of —NR 8 R 9 in which R 8 and R 9 are bonded to form a ring include a pyrrolidine ring and a piperidine ring.
  • alkyl group having 1 to 6 carbon atoms and the phenyl group of R 8 and R 9 are each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, 4 may be substituted with a substituent selected from an alkylcarbonyloxy group, a nitro group and a phenyl group.
  • the number of substituents may be one or two or more. When the number of substituents is two or more, each of the substituents may be the same or different. .
  • substituents in the alkyl group and phenyl group having 1 to 6 carbon atoms of R 3 and the alkyl group and phenyl group having 2 to 6 carbon atoms in R 4 are the same as the definition of the substituents in the alkyl group and phenyl group having 1 to 6 carbon atoms of R 3 and the alkyl group and phenyl group having 2 to 6 carbon atoms in R 4 .
  • R 8 is bonded to the -NR 8 R 9 (R 8 and R 9 alkyl group and R 9 having 1 to 3 carbon atoms is an alkyl group or phenyl group having 1 to 3 carbon atoms Which may form a ring), a hydroxy group, or an alkoxy group having 1 to 3 carbon atoms.
  • R 5 form a pyrrolidine ring or a piperidine ring
  • R 8 are bonded with each -NR 8 R 9, R 8 and R 9 and R 9 is a methyl group is a methyl group or a phenyl group -NR 8 R 9 , a hydroxy group, or a methoxy group.
  • R 2a in compound A2- (V) is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group.
  • halogen atom for R 2a examples include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom, and among them, a chlorine atom is preferable.
  • the alkyl group having 1 to 6 carbon atoms of R 2a may be linear, branched or cyclic.
  • Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, and a cyclopropyl group. Of these, a methyl group is preferable.
  • Examples of the alkoxy group having 1 to 6 carbon atoms of R 2a include a methoxy group, an ethoxy group, and a propoxy group, and among them, a methoxy group is preferable.
  • the phenyl group of R 2a may be unsubstituted or substituted.
  • substituent for the phenyl group of R 2a include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a benzyloxy group, a hydroxy group, a nitro group, and a phenyl group.
  • the substituent for the phenyl group of R 2a is preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group or a hydroxy group, more preferably a halogen atom or carbon An alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms.
  • a halogen atom a chlorine atom is preferable.
  • the alkoxy group having 1 to 4 carbon atoms is preferably a methoxy group.
  • R 2a is a phenyl group having a substituent
  • the substituent may be bonded to any position of the ortho position, the meta position, and the para position of the benzene ring, but at the para position of the benzene ring. Bonding is preferred.
  • R 2a is preferably an unsubstituted phenyl group and a phenyl group substituted by a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a benzyloxy group.
  • R 2a is more preferably an unsubstituted phenyl group and a phenyl group substituted by a chlorine atom, a methyl group, a methoxy group or a benzyloxy group.
  • R 2a is more preferably a phenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, a 4-methoxyphenyl group, and a 4-benzyloxyphenyl group.
  • Compound A1- (III) (pyrrolidinedione derivative) Compound A1- (III) is represented by the following formula (A1- (III)).
  • R 7 in compound A1- (III) represents a pyridyl group or a furanyl group.
  • the pyridyl group and furanyl group may be substituted with a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group, and a hydroxy group.
  • the definition of the substituent of the pyridyl group and furanyl group is the same as the definition of the pyridyl group or furanyl group of R 1 .
  • R 7 is preferably an unsubstituted pyridyl group or an unsubstituted furanyl group.
  • R 7 is more preferably a 3-pyridyl group or a 2-furanyl group.
  • the pyridyl group is preferably unsubstituted.
  • the pyridyl group may be bonded at any of the 2nd, 3rd and 4th positions, but is preferably bonded at the 3rd carbon atom.
  • the furanyl group is preferably unsubstituted.
  • the furanyl group may be bonded at any of the 2-position and 3-position carbon atoms, but is preferably bonded at the 2-position carbon atom.
  • solvent used is not particularly limited.
  • the solvent include halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane; aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as petroleum ether, hexane and methylcyclohexane; N, N -Amides such as dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidinone; Ethers such as diethyl ether, tetrahydrofuran and dioxane; Alcohols such as methanol and ethanol.
  • halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • aliphatic hydrocarbons such as petroleum ether, hexane and methylcyclohexane
  • N, N -Amides such as dimethyl
  • examples of the solvent include water, carbon disulfide, acetonitrile, ethyl acetate, pyridine, dimethyl sulfoxide, and acetone. These solvents can be used as a mixture of two or more.
  • a solvent composition comprising a solvent that does not form a uniform layer with each other can be mentioned.
  • the reaction can be carried out by adding a phase transfer catalyst such as a quaternary ammonium salt, a crown ether, or an analog of crown ether to the reaction mixture.
  • the solvent is not particularly limited, but benzene, chloroform, dichloromethane, hexane, toluene, tetrahydrofuran and the like can be used as the oil phase.
  • quaternary ammonium salt tetrabutylammonium salt, trimethylbenzylammonium salt, triethylbenzylammonium salt and the like are used.
  • Base A base may be added to the solvent.
  • the base that can be used is not particularly limited.
  • Preferred bases include, for example, alkali metal carbonates such as sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate; alkaline earth metal carbonates such as calcium carbonate and barium carbonate; sodium hydroxide and potassium hydroxide.
  • Alkali metal hydroxides such as lithium, sodium and potassium; Alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide; Sodium hydride, potassium hydride and lithium hydride, etc.
  • Alkali metal hydrides such as n-butyllithium; alkali metal amides such as lithium diisopropylamide; and triethylamine, pyridine, 4-dimethylaminopyridine, N, N-di Chiruanirin and 1,8-diazabicyclo-7- [5.4.0] Organic amines such as undecene, and the like.
  • Compound A2- (VII ′) is obtained by, for example, reacting a thiazolidinedione derivative represented by the following formula (a) with a compound represented by the following general formula (b) as shown in the following reaction formula (1). It can manufacture by making it react in presence.
  • the thiazolidinedione derivative represented by the general formula (a) is referred to as “compound (a)”
  • the compound represented by the general formula (b) is referred to as “compound (b)”.
  • R 2a ′ of compound (a) is the same as the substituent in the case where R 2a of compound A2- (I) described above is a substituted phenyl group. Also, R 3 and R 4 of the compound (b) is identical to R 3 and R 4 of the compounds described above A2- (I).
  • the amount of the compound (b) added is preferably 1.0 to 2.0 times the mole of the compound (a).
  • the base is not particularly limited but is preferably an alkali metal hydride such as sodium hydride (NaH); carbonates such as potassium carbonate (K 2 CO 3 ) and sodium carbonate (Na 2 CO 3 ); potassium hydroxide ( Alkali metal hydroxides such as KOH) and sodium hydroxide (NaOH); tertiary amines such as triethylamine; and organic bases such as pyridine can be used.
  • alkali metal hydride such as sodium hydride (NaH)
  • carbonates such as potassium carbonate (K 2 CO 3 ) and sodium carbonate (Na 2 CO 3 )
  • potassium hydroxide Alkali metal hydroxides such as KOH) and sodium hydroxide (NaOH)
  • tertiary amines such as triethylamine
  • organic bases such as pyridine can be used.
  • the solvent is not particularly limited.
  • amides such as dimethylformamide (DMF) and dimethylacetamide
  • nitriles such as acetonitrile
  • ketones such as acetone and methyl ethyl ketone
  • alcohols such as ethanol
  • ethers such as tetrahydrofuran
  • the reaction can proceed without using a solvent.
  • the reaction temperature is preferably 0 to 100 ° C.
  • the reaction time can be appropriately determined in consideration of temperature conditions, pressure conditions, etc., but is preferably in the range of 0.5 to 24 hours.
  • Compound A2- (VI ′) can be produced, for example, by reacting a thiazolidinedione derivative represented by the following general formula (c) in the presence of an acid or alkali as shown in the following reaction formula (2). it can.
  • a thiazolidinedione derivative represented by the general formula (c) is referred to as “compound (c)”.
  • R 2a ′ of compound (c) is the same as the substituent when R 2a of compound A2- (I) described above is a substituted phenyl group.
  • R 10 of the compound (c) is an alkyl group, for example, an alkyl group having 1 to 10 carbon atoms. Further, one to a plurality of double bonds or triple bonds between carbon atoms may be contained in the alkyl chain having 3 to 10 carbon atoms.
  • the acid is not particularly limited, and for example, hydrochloric acid and sulfuric acid can be used.
  • the alkali is not particularly limited, and for example, alkali metal hydroxide such as NaOH and KOH can be used.
  • the solvent is not particularly limited.
  • amides such as dimethylformamide (DMF) and dimethylacetamide
  • nitriles such as acetonitrile
  • alcohols such as ethanol
  • ethers such as tetrahydrofuran
  • one kind of solvent such as water
  • two or more types can be used in appropriate combination.
  • the reaction can proceed without using a solvent.
  • the reaction temperature is preferably ⁇ 10 to 100 ° C.
  • the reaction time can be appropriately determined in consideration of temperature conditions, pressure conditions, etc., but is preferably in the range of 0.5 to 24 hours.
  • Compound A2- (II ′) is obtained by, for example, reacting a thiazolidinedione derivative represented by the following general formula (d) with a compound represented by the following general formula (e) as shown in the following reaction formula (3). It can manufacture by making it react in presence of.
  • the thiazolidinedione derivative represented by the general formula (d) is referred to as “compound (d)”
  • the compound represented by the general formula (e) is referred to as “compound (e)”.
  • R 2b ′ of compound (d) is the same as the substituent in the case where R 2b of compound A2- (II) described above is a substituted phenyl group.
  • R 1b of compound (e) is the same as R 1b of compound A2- (II) described above.
  • the amount of the compound (e) added is preferably 1 to 2 moles compared to the compound (d).
  • the base is not particularly limited but is preferably an alkali metal hydride such as sodium hydride (NaH); carbonates such as potassium carbonate (K 2 CO 3 ) and sodium carbonate (Na 2 CO 3 ); potassium hydroxide ( Alkali metal hydroxides such as KOH) and sodium hydroxide (NaOH) can be used.
  • alkali metal hydride such as sodium hydride (NaH)
  • carbonates such as potassium carbonate (K 2 CO 3 ) and sodium carbonate (Na 2 CO 3 )
  • potassium hydroxide Alkali metal hydroxides such as KOH) and sodium hydroxide (NaOH) can be used.
  • the solvent is not particularly limited, and examples thereof include amides such as dimethylformamide (DMF) and dimethylacetamide; nitriles such as acetonitrile; ethers such as diethyl ether and tetrahydrofuran (THF); ketones such as acetone and methyl ethyl ketone; One or two or more kinds of solvents can be used in appropriate combination.
  • amides such as dimethylformamide (DMF) and dimethylacetamide
  • nitriles such as acetonitrile
  • ethers such as diethyl ether and tetrahydrofuran (THF)
  • ketones such as acetone and methyl ethyl ketone
  • One or two or more kinds of solvents can be used in appropriate combination.
  • R 2c of the compound (f) is the same as the substituent when R 2a of the compound A2- (III) described above is a substituted phenyl group.
  • the amount of compound (g) to be added is preferably 1 to 2 moles compared to compound (f).
  • the conditions for the base and the solvent are the same as in Production Method 1 for Compound A2- (I) described above.
  • R 7 of the compound (h) is identical to R 7 of the compound A1- (III) described above.
  • the amount of compound (h) added is preferably 1.0 to 2.0 moles compared to Compound A1- (II) -1.
  • the solvent is not particularly limited, and examples thereof include alcohols such as methanol and ethanol; amides such as dimethylformamide (DMF) and dimethylacetamide; nitriles such as acetonitrile; and ethers such as diethyl ether and tetrahydrofuran (THF).
  • alcohols such as methanol and ethanol
  • amides such as dimethylformamide (DMF) and dimethylacetamide
  • nitriles such as acetonitrile
  • ethers such as diethyl ether and tetrahydrofuran (THF).
  • One or two or more kinds of solvents can be used in appropriate combination. Can be used.
  • the reaction temperature is preferably 20 to 100 ° C.
  • the reaction time can be appropriately determined in consideration of temperature conditions, pressure conditions, etc., but is preferably in the range of 0.5 to 24 hours.
  • the compound of the present invention can be used alone or in combination with agricultural and horticulturally acceptable solid carriers, liquid carriers, and formulation aids such as surfactants, stabilizers, excipients, etc. It can be used as various preparations such as granules, granules, emulsions or flowables.
  • These preparations desirably contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight, more preferably 2 to 80% by weight, of the compound of the present invention as an active ingredient.
  • talc kaolin, bentonite, diatomaceous earth, white carbon, clay and the like
  • liquid diluent water, xylene, toluene, chlorobenzene, cyclohexane, cyclohexanone, dimethyl sulfoxide, dimethylformamide, alcohol and the like can be used.
  • the surfactant is preferably used depending on its effect, and as the emulsifier, polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan monolaurate or the like can be used, and as the dispersant, lignin sulfonate, dibutylnaphthalene.
  • a sulfonic acid salt or the like can be used.
  • wetting agent an alkyl sulfonic acid salt, an alkylphenyl sulfonic acid salt, or the like can be used.
  • Preparations include those that are used as they are and those that are diluted or dispersed to a predetermined concentration with a diluent such as water.
  • concentration of the compound of the present invention is preferably in the range of 0.001 to 1.0%.
  • the amount of the compound of the present invention used is 20 to 5000 g, more preferably 50 to 2000 g, per 1 ha of agricultural or horticultural land such as a field, a rice field, an orchard, or a greenhouse.
  • the concentration and amount used vary depending on the dosage form, use period, method, place of use, target crop, etc., and can be increased or decreased without being limited to the above range.
  • the compound according to the present invention contains other active ingredients such as fungicides, insecticides, acaricides, nematicides, plant growth regulators and / or herbicides as exemplified below. It may be used in combination with these. Thereby, the performance as a disinfectant, especially an agricultural and horticultural agent can be improved.
  • ⁇ Antimicrobial substances Acibenzora S methyl, 2-phenylphenol (OPP), azaconazole, azoxystrobin, amisulbrom, bixaphene, benalaxyl, benomyl, bench avaricarb-isopropyl, bicarbonate, biphenyl, viteltanol, blasticidin-S, borax, bordeaux, boscalid, Bromuconazole, bronopol, bupirimate, secbutyramine, calcium polysulfide, captafor, captan, carbendazim, carboxin, carpropamide, quinomethionate, chloronebu, chloropicrin, chlorothalonil, clozolinate, cyazofamide, cyflufenamide, simoxanil, cyproconil, cyprodiazole Dazomet, debacarb, diclofuranide, diclocimet, dicromedi , Dichlorane,
  • ⁇ Insecticide / acaricide / nematicide> Abamectin, Acephate, Acrinathrin, Alanicarb, Aldicarb, Alletrin, Amitraz, Avermectin, Azadirachtin, Azamethifos, Azinphos-ethyl, Azinphos-methyl, Azocycline, Aphidopiropen, Bacillus films, Bacillus subtilis, Bacillus subtilis , Bensultap, benzoximate, biphenazeite, bifenthrin, bioalletrin, bioresmethrin, bistriflurone, buprofezin, butcarboxyne, butoxycarboxyl, kazusafos, carbaryl, carbofuran, carbosulfan, cartap, CGA 50439, chlordeine, chloretifos, Chlorfenapyr, chlorfenvin foss, Chlorfluazuron
  • ⁇ Plant growth regulator > Ansimidol, 6-Benzylaminopurine, Paclobutrazol, Diclobutrazole, Uniconazole, Methylcyclopropene, Mepiquat chloride, Ecephone, Chlormequat chloride, Inabenfide, Prohexadione and its salts, Trinexapack Ethyl etc. Plant hormones include jasmonic acid, brassinosteroids, and gibberellins.
  • the compounds of the present invention have a plant disease control effect and can be used as, for example, agricultural and horticultural agents (see also Examples).
  • the compounds of the present invention exhibit a controlling effect against a wide range of plant diseases including foliage diseases, seed infectious diseases and soil infectious diseases. Therefore, the compound according to the present invention as an active ingredient can be used for a wide variety of plant diseases including foliage diseases, seed-borne diseases and soil-borne diseases. That is, the compound according to the present invention can be used in the form of agricultural and horticultural agents, foliars for foliage diseases, bactericides for seed infectious diseases or bactericides for soil infectious diseases.
  • Examples of applicable diseases include the following (in parentheses indicate the scientific name of the fungus causing the disease): wheat leaf blight (Septoria tritici), soybean rust (Phakopsora pachyrhizi, Phakopsora meibomiae), rice blast (Pyricularia) oryzae), rice sesame leaf blight (Cochliobolus miyabeanus), rice white blight (Xanthomonas oryzae), rice blight (Rhizoctonia solani), rice black rot (Helminthosporium sigmoideun), rice blast seedling (Gibberella fujikuroi) Rice seedling blight (Pythium aphanidermatum, Pythium graminicola, Rhizopus oryzae), apple powdery mildew (Podosphaera leucotricha), apple black spot disease (Venturia inaequalis), apple morinaria disease (Monilinia mali), apple
  • Examples of applicable plants include wild plants, plant cultivars, plants and plant cultivars obtained by conventional breeding such as crossbreeding or protoplast fusion, genetically modified plants and plant cultivars obtained by genetic manipulation.
  • Examples of genetically modified plants and plant cultivars include herbicide-tolerant crops, pest-tolerant crops incorporating insecticidal protein production genes, disease-resistant crops incorporating resistance-inducing substance production genes against diseases, food-enhancing crops, and preservation Examples include improved crops and yield-enhanced crops.
  • Specific examples of genetically modified plant cultivars include those containing registered trademarks such as ROUNDUP READY, LIBERTY LINK, CLEARFIELD, YIELDGARD, HERCULEX, and BOLLGARD.
  • Table 9 shows the spectrum data of the synthesized derivatives.
  • formulation examples and test examples are shown.
  • the carrier (diluent) and auxiliary agent, and the mixing ratio thereof can be changed within a wide range.
  • Parts in each formulation example represents parts by weight.
  • DMSO dimethyl sulfoxide
  • PDA potato-dextrose-agar medium
  • a test bacterium previously cultured on a plate medium was punched with a cork borer having a diameter of 4 mm and inoculated on a plate medium containing the above compound. After inoculation, the cells are cultured for 1 to 14 days (see Table 8) at the optimal temperature for growth of each fungus (see, for example, LIST OF CULTURES 1996 microorganisms 10th edition, literature from the Institute for Fermentation, etc.). Evaluation was made by measuring the diameter of the fungus. The growth degree of the fungus obtained on the plate medium containing the compound was compared with the growth degree of the fungus without the addition of the compound, and the hyphal elongation inhibition rate was determined by the following formula.
  • R represents the hyphal elongation inhibition rate (%)
  • dc represents the diameter of the fungus on the untreated plate
  • dt represents the diameter of the fungus on the drug-treated plate.
  • ⁇ Test Example 2 Antibacterial test against pathogenic bacteria> The antibacterial properties of the compounds of the present invention against various phytopathogenic fungi were tested in the same manner as in Test Example 1. The results were evaluated in three stages according to the criteria shown in Table 11. The results obtained for each bacterial species are shown in Table 21 to Table 39.
  • R represents the hyphal elongation inhibition rate (%)
  • dc represents the absorbance in the drug-free group
  • dt represents the absorbance in the drug-added group.
  • R 100 (dc ⁇ dt) / dc
  • ⁇ Test Example 4 Wheat red mold control effect test by foliar spray treatment> Each compound made into a wettable powder as in Formulation Example 1 was diluted with water to 500 mg / L and sprayed at a rate of 1,000 L / ha on the wheat ears at the flowering stage (variety: Norin 61). . After the head was air-dried, it was spray-inoculated with spores of wheat red mold fungus (adjusted to 2 ⁇ 10 5 cells / ml, containing Gramine S having a final concentration of 60 ppm), and kept at 20 ° C. under high humidity conditions. On the fifth day after inoculation, the severity of wheat red mold was evaluated according to the criteria shown in Table 41. The results are shown in Table 42.
  • Example 5 Wheat powdery mildew control effect test by foliar spray treatment> Each compound made into wettable powder as in Formulation Example 1 was diluted with water to a predetermined concentration in the second leaf wheat (variety: Norin 61) grown using a square plastic pot (6cm x 6cm) It was suspended and sprayed at a rate of 1,000 L / ha. After airing the sprayed leaves, wheat seedlings infected with wheat powdery mildew were sprinkled with powdery mildew fungus. On the 11th day after inoculation, the incidence of wheat powdery mildew was evaluated according to the criteria shown in Table 43. The results are shown in Table 44.
  • Example 6 Wheat red rust control effect test by foliar spray treatment> Each compound made into wettable powder as in Formulation Example 1 was diluted with water to a predetermined concentration in the second leaf wheat (variety: Norin 61) grown using a square plastic pot (6cm x 6cm) It was suspended and sprayed at a rate of 1,000 L / ha. The sprayed leaves were air-dried and then spray-inoculated with spores of wheat red rust fungus (adjusted to 200 cells / field of view, added with Grameen S to 60 ppm), and kept at 25 ° C. and high humidity for 48 hours. After that, it was managed in the greenhouse. On the 11th day after inoculation, the severity of wheat rust was evaluated according to the criteria shown in Table 43 above. The results are shown in Table 45.
  • Example 7 Wheat red rust control effect test> The compound of the present invention was dissolved in acetone and diluted 10 times with deionized water to prepare a diluted solution having a predetermined concentration. 1/1000 volume of neoesterin was added to this, and it was set as the spraying liquid. A sufficient amount was applied to 2.5-leaf wheat (variety: Norin 61). After air-drying, a conidial suspension of wheat rust (Puccinia recondita) prepared to 2 ⁇ 10 5 cells / mL was spray-inoculated. This was kept in a chamber at a temperature of 25 ° C. and a humidity of 100% for 24 hours and then managed in a greenhouse for 7 days.
  • Control value (height of lesion in untreated area ⁇ height of lesion in treated area) / height of lesion in untreated area ⁇ 100
  • the thiazolidinedione derivative and pyrrolidinedione derivative according to the present invention can be used as an active ingredient of an agricultural and horticultural agent for controlling pathogenic bacteria causing soil diseases, pathogenic bacteria causing seed diseases, and pathogenic bacteria causing foliage diseases.
  • the fungicide according to the present invention can be used in a method for controlling pathogenic bacteria that cause soil diseases, pathogenic bacteria that cause seed diseases, and pathogenic bacteria that cause foliage diseases.

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Abstract

This germicide contains a compound represented by formula (A) as an active ingredient thereof, and exhibits a wide-ranging controlling effect against pathogens which cause soil diseases, pathogens which cause seed diseases, and pathogens which cause stem and leaf diseases. (In the formula, X, Y, W and R represent prescribed substituent groups, and the dotted line represents a single bond or a double bond.)

Description

チアゾリジンジオンおよびピロリジンジオン誘導体、並びにそれらを有効成分としてなる殺菌剤Thiazolidinedione and pyrrolidinedione derivatives, and fungicides comprising them as active ingredients
　本発明は、チアゾリジンジオンおよびピロリジンジオン誘導体、並びにそれらを有効成分としてなる殺菌剤に関する。 The present invention relates to a thiazolidinedione and a pyrrolidinedione derivative, and a fungicide containing these as active ingredients.
　イプロジオンが、かんきつ灰色かび病、りんご斑点落葉病、なし黒斑病、および菌核病などの病害を防除するための農園芸用薬剤として用いられている。非特許文献１には、ある種のチアゾリジンジオン誘導体およびその抗菌活性が開示されている。 Iprodione is used as an agricultural and horticultural agent for controlling diseases such as citrus gray mold, apple spotted leaf disease, none black spot disease, and mycorrhizal disease. Non-Patent Document 1 discloses certain thiazolidinedione derivatives and their antibacterial activity.
　チアゾリジンジオン誘導体のいくつかは医薬としての使用が知られているが、それら医薬は何れも抗菌活性に関する用途では使用されていない。また、非特許文献１に記載のチアゾリジンジオン誘導体は、イネいもち病を引き起こす菌およびイネ紋枯病を引き起こす菌などのごく一部の菌に対する抗菌活性が調べられているのみである（非特許文献１参照）。土壌病害を引き起こす病原菌、種子病害を引き起こす病原菌および茎葉病害を引き起こす病原菌に広く効果を発揮するチアゾリジンジオン誘導体は知られていない。 Some of thiazolidinedione derivatives are known for use as pharmaceuticals, but none of these pharmaceuticals are used for antibacterial activity. In addition, the thiazolidinedione derivative described in Non-Patent Document 1 has only been investigated for antibacterial activity against a small number of fungi such as a fungus causing rice blast and a fungus causing rice blight (non-patent literature). 1). There are no known thiazolidinedione derivatives that are widely effective against pathogens causing soil diseases, pathogens causing seed diseases, and pathogens causing foliage diseases.
　農業用分野で用いられる殺菌剤では、特定の薬剤を使用し続けた結果、薬剤抵抗性を獲得した菌が出現している。また、現在用いられている殺菌剤は、効果を発揮できる病原菌が限られており、より広範な病原菌に対して活性を有する薬剤の創製が求められている。 In fungicides used in the agricultural field, bacteria that have acquired drug resistance have emerged as a result of continuing to use specific drugs. In addition, the currently used bactericides are limited in the number of pathogenic bacteria that can exert their effects, and the creation of drugs having activity against a wider range of pathogenic bacteria is required.
　そこで、本発明は、土壌病害を引き起こす病原菌、種子病害を引き起こす病原菌および茎葉病害を引き起こす病原菌に広く抗菌活性を示す薬剤を提供することを主な目的とする。 Therefore, the main object of the present invention is to provide a drug having a broad antibacterial activity against pathogenic bacteria causing soil diseases, pathogenic bacteria causing seed diseases, and pathogenic bacteria causing foliage diseases.
　上記課題解決のため、本発明者らは、多数のチアゾリジンジオン誘導体、さらには多数のピロリジンジオン誘導体について、その化学構造および生理活性を詳細に検討した。その結果、優れた抗菌活性を有する化合物を見出し、本発明を完成させるに至った。 In order to solve the above problems, the present inventors have examined in detail the chemical structure and physiological activity of a large number of thiazolidinedione derivatives and further a large number of pyrrolidinedione derivatives. As a result, a compound having excellent antibacterial activity was found and the present invention was completed.
　すなわち、本発明は、下記式（A）で示される化合物およびそれを有効成分として含有する殺菌剤を提供する。 That is, the present invention provides a compound represented by the following formula (A) and a fungicide containing the compound as an active ingredient.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
（式（A）中、Ｘは、ＣＨ２、酸素原子または硫黄原子を表し、
Ｒは、フェニル基、ピリジル基、チエニル基、フラニル基、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、またはフェノキシフェニル基を表す。ここで、フェニル基、ピリジル基、チエニル基、フラニル基およびフェノキシフェニル基は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基から選択される置換基により置換されていてもよい。
Ｙは、酸素原子または硫黄原子を表し、
Ｗは、水素原子、アルキル基、ベンジル基、フェニル基、ピリジル基、アルキルオキシカルボニルアルキル基、またはアルキルアミノカルボニルアルキル基を表す。ここで、アルキル基、ベンジル基、フェニル基、ピリジル基、アルキルオキシカルボニルアルキル基、およびアルキルアミノカルボニルアルキル基は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基およびアルキルアミン基から選択される置換基により置換されていてもよい。
破線は、単結合または二重結合を表す。）
　また、好ましい一態様は、下記式（A1-(I)）で示される化合物およびそれを有効成分として含有する殺菌剤である。 (In the formula (A), X represents CH 2 , an oxygen atom or a sulfur atom,
R represents a phenyl group, a pyridyl group, a thienyl group, a furanyl group, a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenoxyphenyl group. Here, the phenyl group, pyridyl group, thienyl group, furanyl group and phenoxyphenyl group are selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group and a hydroxy group. It may be substituted with a substituent.
Y represents an oxygen atom or a sulfur atom,
W represents a hydrogen atom, an alkyl group, a benzyl group, a phenyl group, a pyridyl group, an alkyloxycarbonylalkyl group, or an alkylaminocarbonylalkyl group. Here, the alkyl group, benzyl group, phenyl group, pyridyl group, alkyloxycarbonylalkyl group, and alkylaminocarbonylalkyl group are a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and It may be substituted with a substituent selected from alkylamine groups.
A broken line represents a single bond or a double bond. )
One preferred embodiment is a compound represented by the following formula (A1- (I)) and a bactericidal agent containing it as an active ingredient.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
（式（A1-(I））中、Ｘは、ＣＨ２または硫黄原子を表し、
Ｒ１は、フェニル基、ピリジル基またはフラニル基を表す。ここで、フェニル基、ピリジル基およびフラニル基は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基から選択される置換基により置換されていてもよい。）
　別の好ましい態様は、下記式（A1-(II））で示される化合物およびそれを有効成分として含有する殺菌剤である。 (In the formula (A1- (I)), X represents CH 2 or a sulfur atom,
R 1 represents a phenyl group, a pyridyl group or a furanyl group. Here, the phenyl group, pyridyl group and furanyl group are substituted with a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group and a hydroxy group. May be. )
Another preferred embodiment is a compound represented by the following formula (A1- (II)) and a fungicide containing it as an active ingredient.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
（式（A1-(II））中、Ｘは、ＣＨ２または硫黄原子を表し、
Ｒ２は、トリフェニルホスホラニリデン基を表す。ここで、トリフェニルホスホラニリデン基を構成している３つのフェニル基は、それぞれ独立に、ハロゲン原子および炭素数１～４のアルキル基から選択される置換基により置換されていてもよい。）
　別の好ましい態様は、下記式（A1-(XI））で示される化合物およびそれを有効成分として含有する殺菌剤である。 (In the formula (A1- (II)), X represents CH 2 or a sulfur atom,
R 2 represents a triphenylphosphoranylidene group. Here, the three phenyl groups constituting the triphenylphosphoranylidene group may each independently be substituted with a substituent selected from a halogen atom and an alkyl group having 1 to 4 carbon atoms. )
Another preferred embodiment is a compound represented by the following formula (A1- (XI)) and a fungicide containing it as an active ingredient.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
（式（A1-(XI））中、Ｘは、ＣＨ２または硫黄原子を表し、
Ｒ１１は、フェニル基、ピリジル基またはフェノキシフェニル基を表し、
Ｒ１２は、アルキル基、フェニル基、ベンジル基またはピリジル基を表す。ここで、フェニル基、ピリジル基およびフェノキシフェニル基は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基から選択される置換基により置換されていてもよい。）
　別の好ましい態様は、下記式（A1-(XII））で示される化合物およびそれを有効成分として含有する殺菌剤である。 (In the formula (A1- (XI)), X represents CH 2 or a sulfur atom,
R 11 represents a phenyl group, a pyridyl group or a phenoxyphenyl group,
R 12 represents an alkyl group, a phenyl group, a benzyl group or a pyridyl group. Here, the phenyl group, pyridyl group and phenoxyphenyl group are substituted with a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group and a hydroxy group. It may be. )
Another preferred embodiment is a compound represented by the following formula (A1- (XII)) and a fungicide containing it as an active ingredient.
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
（式（A1-(XII））中、Ｘは、ＣＨ２または硫黄原子を表し、
Ｒ１３は、アルキルオキシカルボニルアルキル基またはアルキルアミノカルボニルアルキル基を表す。ここで、アルキルオキシカルボニルアルキル基およびアルキルアミノカルボニルアルキル基は、ハロゲン原子で置換されていてもよい。
Ｒ１４は、フェニル基またはチエニル基を表す。）
　また、別の好ましい態様は、下記式（A2-(I））で示される化合物およびそれを有効成分として含有する殺菌剤である。 (In the formula (A1- (XII)), X represents CH 2 or a sulfur atom,
R 13 represents an alkyloxycarbonylalkyl group or an alkylaminocarbonylalkyl group. Here, the alkyloxycarbonylalkyl group and the alkylaminocarbonylalkyl group may be substituted with a halogen atom.
R 14 represents a phenyl group or a thienyl group. )
Another preferred embodiment is a compound represented by the following formula (A2- (I)) and a fungicide containing it as an active ingredient.
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
（式（A2-(I））中、Ｒ１ａは、ヒドロキシ基または－ＮＲ３Ｒ４を表し、Ｒ３は炭素数１～６のアルキル基、炭素数２～６のアルケニル基、炭素数２～６のアルキニル基、炭素数３～８のシクロアルキル基、炭素数３～８のシクロアルケニル基、またはフェニル基であり、Ｒ４は炭素数２～６のアルキル基、またはフェニル基であり、Ｒ３とＲ４とは結合して環を形成していてもよい。
Ｒ２ａは、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、またはフェニル基を表す。
ここで、Ｒ３の炭素数１～６のアルキル基およびフェニル基、Ｒ４の炭素数２～６のアルキル基およびフェニル基、Ｒ２ａの炭素数１～６のアルキル基および炭素数１～６のアルコキシ基は、それぞれ独立に、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、炭素数１～４のアルキルカルボニルオキシ基、ニトロ基およびフェニル基から選択される置換基により置換されていてもよい。Ｒ２ａのフェニル基は、無置換でもよいし、置換されていてもよい。）
　また、別の好ましい態様は、下記式（A2-(II））で示される化合物およびそれを有効成分として含有する殺菌剤である。 (In the formula (A2- (I)), R 1a represents a hydroxy group or —NR 3 R 4 , wherein R 3 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 2 carbon atoms. An alkynyl group having 6 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkenyl group having 3 to 8 carbon atoms, or a phenyl group, and R 4 is an alkyl group having 2 to 6 carbon atoms or a phenyl group, R 3 and R 4 may combine to form a ring.
R 2a represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group.
Here, R 3 alkyl group and phenyl group having 1 to 6 carbon atoms, R 4 alkyl group and phenyl group having 2 to 6 carbon atoms, R 2a alkyl group having 1 to 6 carbon atoms and 1 to 6 carbon atoms. Are independently selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylcarbonyloxy group having 1 to 4 carbon atoms, a nitro group, and a phenyl group. It may be substituted with a substituent. The phenyl group of R 2a may be unsubstituted or substituted. )
Another preferred embodiment is a compound represented by the following formula (A2- (II)) and a fungicide containing it as an active ingredient.
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
（式（A2-(II））中、Ｒ１ｂは、炭素数１～６のアルコキシ基を表し、
Ｒ２ｂは、水素原子、ハロゲン原子、炭素数１～６のアルキル基、またはフェニル基を表す。
ここで、Ｒ１ｂの炭素数１～６のアルコキシ基およびＲ２ｂの炭素数１～６のアルキル基は、それぞれ独立に、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、炭素数１～４のアルキルカルボニルオキシ基、ニトロ基およびフェニル基から選択される置換基により置換されていてもよい。Ｒ２ｂのフェニル基は、無置換でもよいし、置換されていてもよい。）
　また、別の好ましい態様は、下記式（A2-(III））で示される化合物およびそれを有効成分として含有する殺菌剤である。 (In the formula (A2- (II)), R 1b represents an alkoxy group having 1 to 6 carbon atoms,
R 2b represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
Here, the alkoxy group having 1 to 6 carbon atoms of R 1b and the alkyl group having 1 to 6 carbon atoms of R 2b are each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. It may be substituted with a substituent selected from an alkoxy group, an alkylcarbonyloxy group having 1 to 4 carbon atoms, a nitro group and a phenyl group. The phenyl group of R 2b may be unsubstituted or substituted. )
Another preferred embodiment is a compound represented by the following formula (A2- (III)) and a fungicide containing it as an active ingredient.
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
（式（A2-(III））中、Ｒ２ａは、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、またはフェニル基を表す。
ここで、Ｒ２ａの炭素数１～６のアルキル基および炭素数１～６のアルコキシ基は、それぞれ独立に、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、炭素数１～４のアルキルカルボニルオキシ基、ニトロ基およびフェニル基から選択される置換基により置換されていてもよい。Ｒ２ａのフェニル基は、無置換でもよいし、置換されていてもよい。）
　また、別の好ましい態様は、下記式（A2-(IV））で示される化合物およびそれを有効成分として含有する殺菌剤である。 In the formula (A2- (III)), R 2a represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group.
Here, the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms of R 2a are each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, It may be substituted with a substituent selected from an alkylcarbonyloxy group having 1 to 4 carbon atoms, a nitro group and a phenyl group. The phenyl group of R 2a may be unsubstituted or substituted. )
Another preferred embodiment is a compound represented by the following formula (A2- (IV)) and a fungicide containing it as an active ingredient.
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
（式（A2-(IV））中、Ｒ５は、ヒドロキシ基、炭素数１～６のアルコキシ基または－ＮＲ８Ｒ９を表し、Ｒ８およびＲ９は、それぞれ独立に、炭素数１～６のアルキル基、炭素数２～６のアルケニル基、炭素数２～６のアルキニル基、炭素数３～８のシクロアルキル基、炭素数３～８のシクロアルケニル基、またはフェニル基であり、Ｒ８とＲ９とは結合して環を形成していてもよい。
Ｒ６は、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、またはフェニル基を表す。
ここで、Ｒ５の炭素数１～６のアルキル基および炭素数１～６のアルコキシ基は、それぞれ独立に、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、炭素数１～４のアルキルカルボニルオキシ基、ニトロ基およびフェニル基から選択される置換基により置換されていてもよい。Ｒ５のフェニル基は、無置換でもよいし、置換されていてもよい。）
　また、別の好ましい態様は、下記式（A2-(V））で示される化合物およびそれを有効成分として含有する殺菌剤である。 (In the formula (A2- (IV)), R 5 represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms or —NR 8 R 9 , and R 8 and R 9 each independently represent 1 to An alkyl group having 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkenyl group having 3 to 8 carbon atoms, or a phenyl group, and R 8 and R 9 may combine to form a ring.
R 6 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group.
Here, the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms of R 5 are each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, It may be substituted with a substituent selected from an alkylcarbonyloxy group having 1 to 4 carbon atoms, a nitro group and a phenyl group. The phenyl group of R 5 may be unsubstituted or substituted. )
Another preferred embodiment is a compound represented by the following formula (A2- (V)) and a fungicide containing it as an active ingredient.
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
（式（A2-(V））中、Ｒ２ａは、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、またはフェニル基を表す。
ここで、Ｒ２ａの炭素数１～６のアルキル基および炭素数１～６のアルコキシ基は、それぞれ独立に、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、炭素数１～４のアルキルカルボニルオキシ基、ニトロ基およびフェニル基から選択される置換基により置換されていてもよい。Ｒ２ａのフェニル基は、無置換でもよいし、置換されていてもよい。）
　さらに、本発明は、下記式（A1-(III））で示される化合物およびそれを有効成分として含有する殺菌剤である。 (In the formula (A2- (V)), R 2a represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group.
Here, the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms of R 2a are each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, It may be substituted with a substituent selected from an alkylcarbonyloxy group having 1 to 4 carbon atoms, a nitro group and a phenyl group. The phenyl group of R 2a may be unsubstituted or substituted. )
Furthermore, the present invention is a compound represented by the following formula (A1- (III)) and a fungicide containing the compound as an active ingredient.
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
（式（A1-(III））中、Ｒ７は、ピリジル基またはフラニル基を表す。ここで、ピリジル基およびフラニル基は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基から選択される置換基により置換されていてもよい。） (In the formula (A1- (III)), R 7 represents a pyridyl group or a furanyl group, where the pyridyl group and the furanyl group are a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. And may be substituted with a substituent selected from an alkoxy group, a benzyloxy group and a hydroxy group.
　本発明に係る化合物は、土壌病害を引き起こす病原菌、種子病害を引き起こす病原菌および茎葉病害を引き起こす病原菌に広く抗菌活性を示す殺菌剤として顕著な効果を有する。 The compound according to the present invention has a remarkable effect as a bactericide having antibacterial activity widely against pathogenic bacteria causing soil diseases, pathogenic bacteria causing seed diseases and pathogenic bacteria causing foliage diseases.
　以下、本発明に係る殺菌剤の実施形態について説明する。 Hereinafter, embodiments of the disinfectant according to the present invention will be described.
　〔１．有効成分〕
　本発明に係る殺菌剤は、下記式（A）で示される化合物（以下、「本発明の化合物」と称する）を有効成分として含有する。 [1. Active ingredient)
The fungicide according to the present invention contains a compound represented by the following formula (A) (hereinafter referred to as “the compound of the present invention”) as an active ingredient.
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
（式（A）中、Ｘは、ＣＨ２、酸素原子または硫黄原子を表し、
Ｒは、フェニル基、ピリジル基、チエニル基、フラニル基、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、またはフェノキシフェニル基を表す。ここで、フェニル基、ピリジル基、チエニル基、フラニル基およびフェノキシフェニル基は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基から選択される置換基により置換されていてもよい。
Ｙは、酸素原子または硫黄原子を表し、
Ｗは、水素原子、アルキル基、ベンジル基、フェニル基、ピリジル基、アルキルオキシカルボニルアルキル基、またはアルキルアミノカルボニルアルキル基を表す。ここで、アルキル基、ベンジル基、フェニル基、ピリジル基、アルキルオキシカルボニルアルキル基、およびアルキルアミノカルボニルアルキル基は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基およびアルキルアミン基から選択される置換基により置換されていてもよい。
破線は、単結合または二重結合を表す。）
　〔２．化合物(A)〕
　本発明の化合物(A)は、以下のような化合物を包含する。 (In the formula (A), X represents CH 2 , an oxygen atom or a sulfur atom,
R represents a phenyl group, a pyridyl group, a thienyl group, a furanyl group, a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenoxyphenyl group. Here, the phenyl group, pyridyl group, thienyl group, furanyl group and phenoxyphenyl group are selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group and a hydroxy group. It may be substituted with a substituent.
Y represents an oxygen atom or a sulfur atom,
W represents a hydrogen atom, an alkyl group, a benzyl group, a phenyl group, a pyridyl group, an alkyloxycarbonylalkyl group, or an alkylaminocarbonylalkyl group. Here, the alkyl group, benzyl group, phenyl group, pyridyl group, alkyloxycarbonylalkyl group, and alkylaminocarbonylalkyl group are a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and It may be substituted with a substituent selected from alkylamine groups.
A broken line represents a single bond or a double bond. )
[2. Compound (A)
The compound (A) of the present invention includes the following compounds.
　（１）化合物A1-（I）
　化合物A1-（I）は、下記式（A1-（I））で示される。 (1) Compound A1- (I)
Compound A1- (I) is represented by the following formula (A1- (I)).
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
　化合物A1-（I）のＸは、ＣＨ２または硫黄原子であり、Ｒ１は、フェニル基、ピリジル基またはフラニル基である。 X of compound A1- (I) is CH 2 or a sulfur atom, and R 1 is a phenyl group, a pyridyl group, or a furanyl group.
　ここで、フェニル基、ピリジル基およびフラニル基は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基から選択される置換基により置換されていてもよい。置換基の数は１つであっても２つ以上であってもよく、置換基の数が２つ以上である場合、置換基のそれぞれは同一であってもよいし、異なっていてもよい。 Here, the phenyl group, pyridyl group and furanyl group are substituted with a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group and a hydroxy group. May be. The number of substituents may be one or two or more. When the number of substituents is two or more, each of the substituents may be the same or different. .
　フェニル基は、無置換であるか、またはハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基から選択される置換基により置換されていていることが好ましい。 The phenyl group is unsubstituted or substituted by a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group, and a hydroxy group It is preferable.
　ピリジル基は、無置換であることが好ましい。ピリジル基は、１位、２位、３位および４位の何れで結合していてもよいが、３位の炭素原子で結合していることが好ましい。 The pyridyl group is preferably unsubstituted. The pyridyl group may be bonded at any of the 1-position, 2-position, 3-position and 4-position, but it is preferably bonded at the 3-position carbon atom.
　フラニル基は、無置換であることが好ましい。フラニル基は、１位、２位および３位の何れの炭素原子で結合していてもよいが、２位の炭素原子で結合していることが好ましい。 The furanyl group is preferably unsubstituted. The furanyl group may be bonded at any of the carbon atoms at the 1-position, 2-position, and 3-position, but is preferably bonded at the 2-position carbon atom.
　ハロゲン原子としては、例えば、塩素原子、フッ素原子、臭素原子、およびヨウ素原子等が挙げられ、なかでも塩素原子が好ましい。 Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. Among them, a chlorine atom is preferable.
　炭素数１～４のアルキル基は、直鎖、分岐鎖および環状の何れであってもよい。炭素数１～４のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ｔ－ブチル基、およびシクロプロピル基等が挙げられ、なかでもメチル基が好ましい。 The alkyl group having 1 to 4 carbon atoms may be linear, branched or cyclic. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, and a cyclopropyl group. Of these, a methyl group is preferable.
　炭素数１～４のアルコキシ基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基およびシクロペントキシ基等が挙げられ、なかでもメトキシ基が好ましい。 Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, and a cyclopentoxy group, and among them, a methoxy group is preferable.
　Ｒ１として好ましくは、無置換のフェニル基、無置換のピリジル基または無置換のフラニル基、並びに、ハロゲン原子、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基から選択される置換基により置換されているフェニル基である。ハロゲン原子としては、塩素原子が好ましい。炭素数１～４のアルコキシ基としては、メトキシ基が好ましい。Ｒ１における置換基の数が２つ以上である場合、置換基のそれぞれは同一であってもよいし、異なっていてもよい。 R 1 is preferably an unsubstituted phenyl group, an unsubstituted pyridyl group or an unsubstituted furanyl group, and a substituent selected from a halogen atom, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group, and a hydroxy group A phenyl group substituted by As the halogen atom, a chlorine atom is preferable. The alkoxy group having 1 to 4 carbon atoms is preferably a methoxy group. When the number of substituents in R 1 is 2 or more, each of the substituents may be the same or different.
　Ｒ１として特に好ましくは、フェニル基、３－ピリジル基、２－フラニル基、４－クロロフェニル基、４－メトキシフェニル基、４－ベンジルオキシフェニル基、２－ヒドロキシフェニル基、３－ヒドロキシフェニル基または４－ヒドロキシフェニル基である。 R 1 is particularly preferably a phenyl group, 3-pyridyl group, 2-furanyl group, 4-chlorophenyl group, 4-methoxyphenyl group, 4-benzyloxyphenyl group, 2-hydroxyphenyl group, 3-hydroxyphenyl group or 4-hydroxyphenyl group.
　また、ＸがＣＨ２である場合、Ｒ１として好ましくは、無置換のフェニル基、無置換のピリジル基もしくは無置換のフラニル基、または、ハロゲン原子および炭素数１～４のアルコキシ基から選択される置換基により置換されているフェニル基である。ハロゲン原子としては、塩素原子が好ましい。炭素数１～４のアルコキシ基としては、メトキシ基が好ましい。 When X is CH 2 , R 1 is preferably selected from an unsubstituted phenyl group, an unsubstituted pyridyl group or an unsubstituted furanyl group, or a halogen atom and an alkoxy group having 1 to 4 carbon atoms. A phenyl group substituted by a substituent. As the halogen atom, a chlorine atom is preferable. The alkoxy group having 1 to 4 carbon atoms is preferably a methoxy group.
　ＸがＣＨ２である場合、Ｒ１として特に好ましくは、フェニル基、３－ピリジル基、２－フラニル基、４－クロロフェニル基または４－メトキシフェニル基である。 When X is CH 2 , R 1 is particularly preferably a phenyl group, a 3-pyridyl group, a 2-furanyl group, a 4-chlorophenyl group, or a 4-methoxyphenyl group.
　また、Ｘが硫黄原子である場合、Ｒ１として好ましくは、ベンジルオキシ基およびヒドロキシ基から選択される置換基により置換されているフェニル基である。Ｒ１としてさらに好ましくは、４－ベンジルオキシフェニル基、２－ヒドロキシフェニル基、３－ヒドロキシフェニル基または４－ヒドロキシフェニル基である。 When X is a sulfur atom, R 1 is preferably a phenyl group substituted with a substituent selected from a benzyloxy group and a hydroxy group. R 1 is more preferably a 4-benzyloxyphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group, or a 4-hydroxyphenyl group.
　化合物A1-（I）として好ましくは、（i）ＸがＣＨ２であって、Ｒ１が無置換のフェニル基、無置換のピリジル基もしくは無置換のフラニル基、または、ハロゲン原子および炭素数１～４のアルコキシ基から選択される置換基により置換されているフェニル基を有する化合物、および、（ii）Ｘが硫黄原子であって、Ｒ１がベンジルオキシ基およびヒドロキシ基から選択される置換基により置換されているフェニル基を有する化合物である。 Preferably as compound A1- (I), (i) X is CH 2 and R 1 is an unsubstituted phenyl group, an unsubstituted pyridyl group or an unsubstituted furanyl group, or a halogen atom and a carbon number of 1 A compound having a phenyl group substituted by a substituent selected from ˜4 alkoxy groups, and (ii) a substituent wherein X is a sulfur atom and R 1 is selected from a benzyloxy group and a hydroxy group A compound having a phenyl group substituted by
　化合物A1-（I）としてより好ましくは、（iii）ＸがＣＨ２であって、Ｒ１が無置換のフェニル基、無置換のピリジル基もしくは無置換のフラニル基、または、塩素原子およびメトキシ基から選択される置換基により置換されているフェニル基を有する化合物、および、（iv）Ｘが硫黄原子であって、Ｒ１がベンジルオキシ基およびヒドロキシ基から選択される置換基により置換されているフェニル基を有する化合物である。 More preferably as compound A1- (I), (iii) X is CH 2 and R 1 is an unsubstituted phenyl group, an unsubstituted pyridyl group or an unsubstituted furanyl group, or a chlorine atom and a methoxy group A compound having a phenyl group substituted by a substituent selected from: (iv) X is a sulfur atom, and R 1 is substituted by a substituent selected from a benzyloxy group and a hydroxy group It is a compound having a phenyl group.
　化合物A1-（I）としてさらに好ましくは、（v）ＸがＣＨ２であって、Ｒ１が無置換のフェニル基、無置換のピリジル基もしくは無置換のフラニル基、または、塩素原子およびメトキシ基から選択される１つの置換基により置換されているフェニル基を有する化合物、および、（vi）Ｘが硫黄原子であって、Ｒ１がベンジルオキシ基およびヒドロキシ基から選択される１つの置換基により置換されているフェニル基を有する化合物である。 More preferably as compound A1- (I), (v) X is CH 2 and R 1 is an unsubstituted phenyl group, an unsubstituted pyridyl group or an unsubstituted furanyl group, or a chlorine atom and a methoxy group A compound having a phenyl group substituted by one substituent selected from: and (vi) one substituent selected from X being a sulfur atom and R 1 being selected from a benzyloxy group and a hydroxy group A compound having a substituted phenyl group.
　化合物A1-（I）として特に好ましくは、（vii）ＸがＣＨ２であって、Ｒ１がフェニル基、３－ピリジル基、２－フラニル基、４－クロロフェニル基または４－メトキシフェニル基である化合物、および、（viii）Ｘが硫黄原子であって、Ｒ１が４－ベンジルオキシフェニル基、２－ヒドロキシフェニル基、３－ヒドロキシフェニル基または４－ヒドロキシフェニル基を有する化合物である。 Particularly preferably as compound A1- (I), (vii) X is CH 2 and R 1 is a phenyl group, a 3-pyridyl group, a 2-furanyl group, a 4-chlorophenyl group or a 4-methoxyphenyl group. And (viii) a compound wherein X is a sulfur atom and R 1 has a 4-benzyloxyphenyl group, a 2-hydroxyphenyl group, a 3-hydroxyphenyl group or a 4-hydroxyphenyl group.
　なお、ＸがＣＨ２である場合、化合物A1-(I)は下記式（A1-(IV)）で示されるピロリジンジオン誘導体である。また、Ｘが硫黄原子である場合、化合物A1-(I)は下記式（A1-(V)）で示されるチアゾリジンジオン誘導体である。 When X is CH 2 , compound A1- (I) is a pyrrolidinedione derivative represented by the following formula (A1- (IV)). When X is a sulfur atom, the compound A1- (I) is a thiazolidinedione derivative represented by the following formula (A1- (V)).
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
　また、化合物A1-(I)は、例えば、後述の化合物A1-(III)の製造方法に準じて製造することができる。 Compound A1- (I) can be produced, for example, according to the production method of compound A1- (III) described later.
　具体的な化合物A1-(I)として以下が例示される。 Specific examples of the compound A1- (I) include the following.
Figure JPOXMLDOC01-appb-T000037
Figure JPOXMLDOC01-appb-T000037
　（２）化合物A1-(II)
　化合物A1-(II)は、下記式（A1-(II)）で示される。 (2) Compound A1- (II)
Compound A1- (II) is represented by the following formula (A1- (II)).
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
　化合物A1-(II)のＸは、ＣＨ２または硫黄原子である。なかでも、Ｘは、ＣＨ２であることが好ましい。Ｒ２は、トリフェニルホスホラニリデン基である。 X of compound A1- (II) is CH 2 or a sulfur atom. Among them, X is preferably is CH 2. R 2 is a triphenylphosphoranylidene group.
　トリフェニルホスホラニリデン基を構成している３つのフェニル基は、それぞれ独立に、ハロゲン原子および炭素数１～４のアルキル基から選択される置換基により置換されていてもよい。置換基の数は１つであっても２つ以上であってもよく、置換基の数が２つ以上である場合、置換基のそれぞれは同一であってもよいし、異なっていてもよい。 The three phenyl groups constituting the triphenylphosphoranylidene group may each independently be substituted with a substituent selected from a halogen atom and an alkyl group having 1 to 4 carbon atoms. The number of substituents may be one or two or more. When the number of substituents is two or more, each of the substituents may be the same or different. .
　ハロゲン原子としては、例えば、塩素原子、フッ素原子、臭素原子、およびヨウ素原子等が挙げられ、なかでも塩素原子が好ましい。 Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. Among them, a chlorine atom is preferable.
　炭素数１～４のアルキル基は、直鎖、分岐鎖および環状の何れであってもよい。炭素数１～４のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ｔ－ブチル基、およびシクロプロピル基等が挙げられ、なかでもメチル基が好ましい。 The alkyl group having 1 to 4 carbon atoms may be linear, branched or cyclic. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, and a cyclopropyl group. Of these, a methyl group is preferable.
　トリフェニルホスホラニリデン基を構成している３つのフェニル基は、何れも無置換であることが好ましい。 It is preferable that all three phenyl groups constituting the triphenylphosphoranylidene group are unsubstituted.
　化合物A1-(II)として好ましくは、（ix）ＸがＣＨ２または硫黄原子であって、Ｒ２が無置換のトリフェニルホスホラニリデン基を有する化合物、および、（ｘ）ＸがＣＨ２であって、Ｒ２が置換基により置換されていてもよいトリフェニルホスホラニリデン基を有する化合物である。化合物A1-(II)としてより好ましくは、ＸがＣＨ２であって、Ｒ２が無置換のトリフェニルホスホラニリデン基を有する化合物である。 Preferably as compound A1- (II), (ix) X is CH 2 or a sulfur atom, R 2 is an unsubstituted triphenylphosphoranylidene group, and (x) X is CH 2 And R 2 is a compound having a triphenylphosphoranylidene group which may be substituted with a substituent. More preferably, the compound A1- (II) is a compound in which X is CH 2 and R 2 has an unsubstituted triphenylphosphoranylidene group.
　なお、化合物A1-(II)は、例えば、参考文献：T. Boettcher S. A. Sieber: J. Am. Chem. Soc. 132 (20), 6964-6972, 2010.に準じて製造することができる。 Compound A1- (II) can be produced, for example, according to the reference: T. Boettcher S. A. Sieber: J. Am. Chem. Soc. 132 (20), 6964-6972, 2010. it can.
　具体的な化合物A1-(II)として以下が例示される。 Specific examples of the compound A1- (II) include the following.
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
　（３）化合物A1-（XI）
　化合物A1-（XI）は、下記式（A1-（XI））で示される。 (3) Compound A1- (XI)
Compound A1- (XI) is represented by the following formula (A1- (XI)).
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
　化合物A1-(XI）のＸは、ＣＨ２または硫黄原子であり、Ｒ１１は、フェニル基、ピリジル基またはフェノキシフェニル基であり、Ｒ１２は、アルキル基、フェニル基、ベンジル基またはピリジル基である。 X of compound A1- (XI) is CH 2 or a sulfur atom, R 11 is a phenyl group, a pyridyl group or a phenoxyphenyl group, and R 12 is an alkyl group, a phenyl group, a benzyl group or a pyridyl group. is there.
　ここで、フェニル基、ベンジル基、ピリジル基およびフェノキシフェニル基は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基から選択される置換基により置換されていてもよい。置換基の数は１つであっても２つ以上であってもよく、置換基の数が２つ以上である場合、置換基のそれぞれは同一であってもよいし、異なっていてもよい。 Here, the phenyl group, benzyl group, pyridyl group and phenoxyphenyl group are a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group and a hydroxy group. May be substituted. The number of substituents may be one or two or more. When the number of substituents is two or more, each of the substituents may be the same or different. .
　フェニル基は、無置換であるか、またはハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基から選択される置換基により置換されていていることが好ましい。ハロゲン原子としては、塩素原子が好ましい。炭素数１～４のアルコキシ基としては、メトキシ基が好ましい。 The phenyl group is unsubstituted or substituted by a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group, and a hydroxy group It is preferable. As the halogen atom, a chlorine atom is preferable. The alkoxy group having 1 to 4 carbon atoms is preferably a methoxy group.
　ベンジル基は、無置換であるか、またはハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基から選択される置換基により置換されていていることが好ましい。ハロゲン原子としては、塩素原子が好ましい。炭素数１～４のアルコキシ基としては、メトキシ基が好ましい。 The benzyl group is unsubstituted or substituted by a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group and a hydroxy group It is preferable. As the halogen atom, a chlorine atom is preferable. The alkoxy group having 1 to 4 carbon atoms is preferably a methoxy group.
　ピリジル基は、無置換またはハロゲン原子で置換されていることが好ましい。ピリジル基は、１位、２位、３位および４位の何れで結合していてもよいが、３位の炭素原子で結合していることが好ましい。 The pyridyl group is preferably unsubstituted or substituted with a halogen atom. The pyridyl group may be bonded at any of the 1-position, 2-position, 3-position and 4-position, but it is preferably bonded at the 3-position carbon atom.
　フェノキシフェニル基は、無置換であるか、またはハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基から選択される置換基により置換されていていることが好ましい。ハロゲン原子としては、塩素原子が好ましい。炭素数１～４のアルコキシ基としては、メトキシ基が好ましい。フェノキシフェニル基は、２位、３位および４位の何れで結合していてもよいが、３位の炭素原子で結合していることが好ましい。 The phenoxyphenyl group is unsubstituted or substituted by a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group, and a hydroxy group. Preferably it is. As the halogen atom, a chlorine atom is preferable. The alkoxy group having 1 to 4 carbon atoms is preferably a methoxy group. The phenoxyphenyl group may be bonded at any of the 2-position, the 3-position and the 4-position, but is preferably bonded at the 3-position carbon atom.
　化合物A1-(XI）としてさらに好ましくは、Ｘが硫黄原子であって、Ｒ１１が無置換のフェニル基、無置換のピリジル基もしくは無置換のフェノキシフェニル基、または、塩素原子およびメトキシ基から選択される１つの置換基により置換されているフェニル基であって、Ｒ１２がアルキル基、ベンジル基、フェニル基、またはハロゲン原子で置換されているピリジル基を有する化合物である。 More preferably, as compound A1- (XI), X is a sulfur atom and R 11 is selected from an unsubstituted phenyl group, an unsubstituted pyridyl group or an unsubstituted phenoxyphenyl group, or a chlorine atom and a methoxy group a one phenyl group substituted with substituents, a compound having a pyridyl group R 12 is an alkyl group, a benzyl group is substituted with a phenyl group or a halogen atom.
　化合物A1-(XI）として特に好ましくは、Ｘが硫黄原子であって、Ｒ１１がフェニル基、３－ピリジル基、または３－フェノキシフェニル基であって、Ｒ１２がメチル基、ベンジル基、フェニル基、または２，６－ジクロロ－４－ピリジル基を有する化合物である。 Particularly preferably as compound A1- (XI), X is a sulfur atom, R 11 is a phenyl group, a 3-pyridyl group, or a 3-phenoxyphenyl group, and R 12 is a methyl group, a benzyl group, a phenyl group, Or a compound having a 2,6-dichloro-4-pyridyl group.
　具体的な化合物A1-（XI）として以下が例示される。 Specific examples of the compound A1- (XI) include the following.
Figure JPOXMLDOC01-appb-T000041
Figure JPOXMLDOC01-appb-T000041
　（４）化合物A1-（XII）
　化合物A1-（XII）は、下記式（A1-（XII））で示される。 (4) Compound A1- (XII)
Compound A1- (XII) is represented by the following formula (A1- (XII)).
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
　化合物A1-(XII）のＸは、ＣＨ２または硫黄原子であり、Ｒ１３は、アルキルオキシカルボニルアルキル基またはアルキルアミノカルボニルアルキル基を表す。ここで、アルキルオキシカルボニルアルキル基またはアルキルアミノカルボニルアルキル基のアルコキシ基またはアルキルアミノ基は、炭素数１～６を有し、ハロゲン原子により置換されていてもよい。また、Ｒ１４は、フェニル基またはチエニル基を表す。アルキルオキシカルボニルアルキル基またはアルキルアミノカルボニルアルキル基のアルキルとは、炭素数１～４のアルキルを表し、メチル、エチル、プロピル、イソプロピル、ｔ－ブチル、およびシクロプロピル等が挙げられ、なかでもメチルまたはエチルが好ましい。 X of compound A1- (XII) represents CH 2 or a sulfur atom, and R 13 represents an alkyloxycarbonylalkyl group or an alkylaminocarbonylalkyl group. Here, the alkoxy group or alkylamino group of the alkyloxycarbonylalkyl group or alkylaminocarbonylalkyl group has 1 to 6 carbon atoms and may be substituted with a halogen atom. R 14 represents a phenyl group or a thienyl group. The alkyl of an alkyloxycarbonylalkyl group or an alkylaminocarbonylalkyl group represents an alkyl having 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, propyl, isopropyl, t-butyl, and cyclopropyl. Ethyl is preferred.
　上記のアルキルオキシ基とは、炭素数１～４のアルキルオキシ基を表し、メトキシ基、エトキシ基およびプロポキシ基等が挙げられ、なかでもメトキシ基が好ましい。 The above-mentioned alkyloxy group represents an alkyloxy group having 1 to 4 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a propoxy group, and among them, a methoxy group is preferable.
　また、上記のアルキルアミノ基とは、炭素数１～６のアルキルアミノ基を表し、環状アミノ基でもよく、メチルアミノ基、エチルアミノ基、プロピルアミノ基、ブチルアミノ基、ペンタアミノ基、１－ピペリジル基、およびジメチルアミノ基等が挙げられる。 The above alkylamino group represents an alkylamino group having 1 to 6 carbon atoms, and may be a cyclic amino group, such as a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentaamino group, 1- Examples include a piperidyl group and a dimethylamino group.
　具体的な化合物A1-（XII）として以下が例示される。 Specific examples of the compound A1- (XII) include the following.
Figure JPOXMLDOC01-appb-T000043
Figure JPOXMLDOC01-appb-T000043
　（５）化合物A2-(I）
　化合物A2-(I）は、下記式（A2-(I））で示される。 (5) Compound A2- (I)
Compound A2- (I) is represented by the following formula (A2- (I)).
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
　化合物A2-(I)のＲ１ａは、ヒドロキシ基または－ＮＲ３Ｒ４である。Ｒ３は炭素数１～６のアルキル基、炭素数２～６のアルケニル基、炭素数２～６のアルキニル基、炭素数３～８のシクロアルキル基、炭素数３～８のシクロアルケニル基、炭素数３～８のヘテロシクロアルキル基、またはフェニル基であり、Ｒ４は炭素数２～６のアルキル基、またはフェニル基である。 R 1a in compound A2- (I) is a hydroxy group or —NR 3 R 4 . R 3 is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkenyl group having 3 to 8 carbon atoms, A heterocycloalkyl group having 3 to 8 carbon atoms or a phenyl group, and R 4 is an alkyl group having 2 to 6 carbon atoms or a phenyl group.
　Ｒ３の炭素数１～６のアルキル基は、直鎖および分岐鎖の何れであってもよい。炭素数１～６のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基またはｔ－ブチル基等が挙げられる。Ｒ３の炭素数１～６のアルキル基は、炭素数１～３のアルキル基であることが好ましく、メチル基であることがより好ましい。 The alkyl group having 1 to 6 carbon atoms of R 3 may be linear or branched. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a t-butyl group. The alkyl group having 1 to 6 carbon atoms of R 3 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
　Ｒ３の炭素数２～６のアルキニル基は、直鎖および分岐鎖の何れであってもよい。炭素数２～６のアルキニル基としては、例えば、エチニル基、プロピニル基またはブチニル基等が挙げられる。 The alkynyl group having 2 to 6 carbon atoms of R 3 may be linear or branched. Examples of the alkynyl group having 2 to 6 carbon atoms include ethynyl group, propynyl group, butynyl group, and the like.
　Ｒ３の炭素数２～６のアルケニル基は、直鎖および分岐鎖の何れであってもよい。炭素数２～６のアルケニル基としては、例えば、エテニル基、プロペニル基またはブテニル基等が挙げられる。 The alkenyl group having 2 to 6 carbon atoms of R 3 may be linear or branched. Examples of the alkenyl group having 2 to 6 carbon atoms include an ethenyl group, a propenyl group, and a butenyl group.
　Ｒ３の炭素数３～８のシクロアルキル基としては、例えば、シクロプロピル基およびシクロブチル基等が挙げられる。 Examples of the cycloalkyl group having 3 to 8 carbon atoms of R 3 include a cyclopropyl group and a cyclobutyl group.
　Ｒ３の炭素数３～８のシクロアルケニル基としては、例えば、シクロプロペニル基およびシクロブテニル基等が挙げられる。 Examples of the cycloalkenyl group having 3 to 8 carbon atoms of R 3 include a cyclopropenyl group and a cyclobutenyl group.
　Ｒ４の炭素数２～６のアルキル基は、直鎖、分岐鎖および環状の何れであってもよい。炭素数２～６のアルキル基としては、例えば、エチル基、プロピル基、イソプロピル基、ｔ－ブチル基またはシクロプロピル基等が挙げられる。Ｒ４の炭素数２～６のアルキル基は、炭素数２～４のアルキル基であることが好ましい。 The alkyl group having 2 to 6 carbon atoms of R 4 may be linear, branched or cyclic. Examples of the alkyl group having 2 to 6 carbon atoms include an ethyl group, a propyl group, an isopropyl group, a t-butyl group, and a cyclopropyl group. The alkyl group having 2 to 6 carbon atoms of R 4 is preferably an alkyl group having 2 to 4 carbon atoms.
　Ｒ３とＲ４とは結合して環を形成していてもよい。Ｒ３とＲ４とが結合して環を形成している－ＮＲ３Ｒ４としては、例えば、ピロリジン環およびピペリジン環等が挙げられる。 R 3 and R 4 may combine to form a ring. Examples of —NR 3 R 4 in which R 3 and R 4 are bonded to form a ring include a pyrrolidine ring and a piperidine ring.
　また、Ｒ３の炭素数１～６のアルキル基およびフェニル基、ならびにＲ４の炭素数２～６のアルキル基およびフェニル基は、それぞれ独立に、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、炭素数１～４のアルキルカルボニルオキシ基、ニトロ基およびフェニル基から選択される置換基により置換されていてもよい。置換基の数は１つであっても２つ以上であってもよく、置換基の数が２つ以上である場合、置換基のそれぞれは同一であってもよいし、異なっていてもよい。 Further, the alkyl group and phenyl group having 1 to 6 carbon atoms of R 3 and the alkyl group and phenyl group having 2 to 6 carbon atoms of R 4 are each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, It may be substituted with a substituent selected from an alkoxy group having 1 to 4 carbon atoms, an alkylcarbonyloxy group having 1 to 4 carbon atoms, a nitro group, and a phenyl group. The number of substituents may be one or two or more. When the number of substituents is two or more, each of the substituents may be the same or different. .
　ハロゲン原子としては、例えば、塩素原子、フッ素原子、臭素原子、およびヨウ素原子等が挙げられる。炭素数１～４のアルキル基としては、例えば、メチル基、エチル基、およびプロピル基等が挙げられる。炭素数１～４のアルコキシ基としては、例えば、メトキシ基、およびエトキシ基等が挙げられる。炭素数１～４のアルキルカルボニルオキシ基としては、例えば、アセトキシ基が挙げられる。 Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, and a propyl group. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group and an ethoxy group. Examples of the alkylcarbonyloxy group having 1 to 4 carbon atoms include an acetoxy group.
　Ｒ１ａとして好ましくは、Ｒ３が炭素数１～３のアルキル基かつＲ４が炭素数２～４のアルキル基もしくはフェニル基である－ＮＲ３Ｒ４（Ｒ３とＲ４とは結合して環を形成していてもよい）、またはヒドロキシ基である。また、Ｒ１ａとしてより好ましくは、Ｒ３がメチル基かつＲ４がフェニル基である－ＮＲ３Ｒ４、Ｒ３とＲ４とが結合してピロリジン環もしくはピペリジン環を形成している－ＮＲ３Ｒ４、またはヒドロキシ基である。 Preferred as R 1a, R 3 is attached is a -NR 3 R 4 (R 3 and R 4 alkyl group and R 4 having 1 to 3 carbon atoms is an alkyl group or a phenyl group having 2 to 4 carbon atoms Which may form a ring), or a hydroxy group. R 1a is more preferably —NR 3 R 4 , wherein R 3 is a methyl group and R 4 is a phenyl group, and R 3 and R 4 are bonded to form a pyrrolidine ring or a piperidine ring. 3 R 4 or a hydroxy group.
　化合物A2-(I)のＲ２ａは、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、またはフェニル基である。 R 2a in compound A2- (I) is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group.
　Ｒ２ａのハロゲン原子としては、例えば、塩素原子、フッ素原子、臭素原子、およびヨウ素原子等が挙げられ、なかでも塩素原子が好ましい。 Examples of the halogen atom for R 2a include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom, and among them, a chlorine atom is preferable.
　Ｒ２ａの炭素数１～６のアルキル基は、直鎖、分岐鎖および環状の何れであってもよい。炭素数１～６のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ｔ－ブチル基、およびシクロプロピル基等が挙げられ、なかでもメチル基が好ましい。 The alkyl group having 1 to 6 carbon atoms of R 2a may be linear, branched or cyclic. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, and a cyclopropyl group. Of these, a methyl group is preferable.
　Ｒ２ａの炭素数１～６のアルコキシ基としては、例えば、メトキシ基、エトキシ基、およびプロポキシ基等が挙げられ、なかでもメトキシ基が好ましい。 Examples of the alkoxy group having 1 to 6 carbon atoms of R 2a include a methoxy group, an ethoxy group, and a propoxy group, and among them, a methoxy group is preferable.
　また、Ｒ２ａの炭素数１～６のアルキル基または炭素数１～６のアルコキシ基は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、炭素数１～４のアルキルカルボニルオキシ基、ニトロ基およびフェニル基から選択される置換基により置換されていてもよい。置換基の数は１つであっても２つ以上であってもよく、置換基の数が２つ以上である場合、置換基のそれぞれは同一であってもよいし、異なっていてもよい。 In addition, the alkyl group having 1 to 6 carbon atoms or the alkoxy group having 1 to 6 carbon atoms of R 2a is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms. And may be substituted with a substituent selected from an alkylcarbonyloxy group, a nitro group and a phenyl group. The number of substituents may be one or two or more. When the number of substituents is two or more, each of the substituents may be the same or different. .
　これら置換基の定義は、上記Ｒ３の炭素数１～６のアルキル基およびフェニル基、ならびにＲ４の炭素数２～６のアルキル基およびフェニル基における置換基の定義と同じである。 The definition of these substituents is the same as the definition of the substituents in the alkyl group and phenyl group having 1 to 6 carbon atoms of R 3 and the alkyl group and phenyl group having 2 to 6 carbon atoms in R 4 .
　Ｒ２ａのフェニル基は、無置換でもよいし、置換されていてもよい。Ｒ２ａのフェニル基の置換基としては、例えば、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、ベンジルオキシ基、ヒドロキシ基、ニトロ基およびフェニル基が挙げられる。Ｒ２ａのフェニル基の置換基として好ましくは、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基であり、より好ましくは、ハロゲン原子、炭素数１～３のアルキル基および炭素数１～３のアルコキシ基である。ハロゲン原子としては、塩素原子が好ましく、炭素数１～６のアルキル基としては、メチル基が好ましく、炭素数１～６のアルコキシ基としては、メトキシ基が好ましい。 The phenyl group of R 2a may be unsubstituted or substituted. Examples of the substituent for the phenyl group of R 2a include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a benzyloxy group, a hydroxy group, a nitro group, and a phenyl group. The substituent for the phenyl group of R 2a is preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group or a hydroxy group, more preferably a halogen atom or carbon An alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms. The halogen atom is preferably a chlorine atom, the alkyl group having 1 to 6 carbon atoms is preferably a methyl group, and the alkoxy group having 1 to 6 carbon atoms is preferably a methoxy group.
　なお、Ｒ２ａが置換基を有するフェニル基である場合、当該置換基は、ベンゼン環のオルト位、メタ位、パラ位の何れの位置に結合していてもよいが、ベンゼン環のパラ位に結合していることが好ましい。 When R 2a is a phenyl group having a substituent, the substituent may be bonded to any position of the ortho position, the meta position, and the para position of the benzene ring, but at the para position of the benzene ring. Bonding is preferred.
　Ｒ２ａとして好ましくは、無置換のフェニル基、およびハロゲン原子、炭素数１～３のアルキル基または炭素数１～３のアルコキシ基により置換されたフェニル基である。また、Ｒ２ａとしてより好ましくは、無置換のフェニル基、および塩素原子、メチル基またはメトキシ基により置換されたフェニル基である。Ｒ２ａとしてさらに好ましくは、フェニル基、４－クロロフェニル基、４－メチルフェニル基、および４－メトキシフェニル基である。 R 2a is preferably an unsubstituted phenyl group and a phenyl group substituted by a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. R 2a is more preferably an unsubstituted phenyl group and a phenyl group substituted by a chlorine atom, a methyl group or a methoxy group. R 2a is more preferably a phenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, and a 4-methoxyphenyl group.
　また、化合物A2-(I)として好ましくは、Ｒ１ａが、ヒドロキシ基、またはＲ３が炭素数１～３のアルキル基かつＲ４が炭素数２～４のアルキル基、またはフェニル基である－ＮＲ３Ｒ４（Ｒ３とＲ４とは結合して環を形成していてもよい）であり、Ｒ２ａが、無置換のフェニル基、またはハロゲン原子、炭素数１～３のアルキル基もしくは炭素数１～３のアルコキシ基で置換されたフェニル基ある化合物である。化合物A2-(I)としてより好ましくは、Ｒ１ａが、ヒドロキシ基、Ｒ３がメチル基かつＲ４がフェニル基である－ＮＲ３Ｒ４、またはＲ３とＲ４とが結合してピロリジン環もしくはピペリジン環を形成している－ＮＲ３Ｒ４であり、Ｒ２ａが、フェニル基、４－クロロフェニル基、４－メチルフェニル基、または４－メトキシフェニル基である化合物である。 Further, as the compound A2- (I), preferably R 1a is a hydroxy group, or R 3 is an alkyl group having 1 to 3 carbon atoms and R 4 is an alkyl group having 2 to 4 carbon atoms, or a phenyl group— NR 3 R 4 (R 3 and R 4 may combine to form a ring), and R 2a is an unsubstituted phenyl group, a halogen atom, an alkyl group having 1 to 3 carbon atoms, or This is a compound having a phenyl group substituted with an alkoxy group having 1 to 3 carbon atoms. More preferably as compound A2- (I), R 1a is a hydroxy group, R 3 is a methyl group and R 4 is a phenyl group, or —NR 3 R 4 , or R 3 and R 4 are bonded to form a pyrrolidine ring Alternatively, the compound is -NR 3 R 4 forming a piperidine ring, and R 2a is a phenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, or a 4-methoxyphenyl group.
　なお、Ｒ１ａがヒドロキシ基である場合、化合物A2-(I)は下記式A2-(VI）で示される。また、Ｒ１ａが－ＮＲ３Ｒ４である場合、化合物A2-(I)は下記式A2-(VII）で示される。以下、下記式A2-(VI）で示される化合物を「化合物A2-(VI）」と称し、下記式A2-(VII）で示される化合物を「化合物A2-(VII）」と称する。 In addition, when R 1a is a hydroxy group, the compound A2- (I) is represented by the following formula A2- (VI). When R 1a is —NR 3 R 4 , the compound A2- (I) is represented by the following formula A2- (VII). Hereinafter, a compound represented by the following formula A2- (VI) is referred to as “compound A2- (VI)”, and a compound represented by the following formula A2- (VII) is referred to as “compound A2- (VII)”.
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
　具体的な化合物A2-(I)として以下が例示される。 Specific examples of the compound A2- (I) include the following.
Figure JPOXMLDOC01-appb-T000046
Figure JPOXMLDOC01-appb-T000046
　（６）化合物A2-(II）
　化合物A2-(II）は、下記式（A2-(II））で示される。 (6) Compound A2- (II)
Compound A2- (II) is represented by the following formula (A2- (II)).
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
　化合物A2-(II）のＲ１ｂは、炭素数１～６のアルコキシ基である。炭素数１～６のアルコキシ基としては、例えば、メトキシ基、エトキシ基、およびプロポキシ基等が挙げられる。また、Ｒ１ｂの炭素数１～６のアルコキシ基は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、炭素数１～４のアルキルカルボニルオキシ基、ニトロ基およびフェニル基から選択される置換基により置換されていてもよい。置換基の数は１つであっても２つ以上であってもよく、置換基の数が２つ以上である場合、置換基のそれぞれは同一であってもよいし、異なっていてもよい。これら置換基の定義は、上記Ｒ３の炭素数１～６のアルキル基およびフェニル基、ならびにＲ４の炭素数２～６のアルキル基およびフェニル基における置換基の定義と同じである。 R 1b of compound A2- (II) is an alkoxy group having 1 to 6 carbon atoms. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, and a propoxy group. In addition, the alkoxy group having 1 to 6 carbon atoms of R 1b is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylcarbonyloxy group having 1 to 4 carbon atoms, a nitro group, and It may be substituted with a substituent selected from a phenyl group. The number of substituents may be one or two or more. When the number of substituents is two or more, each of the substituents may be the same or different. . The definition of these substituents is the same as the definition of the substituents in the alkyl group and phenyl group having 1 to 6 carbon atoms of R 3 and the alkyl group and phenyl group having 2 to 6 carbon atoms in R 4 .
　Ｒ１ｂとして好ましくは、炭素数１～３のアルコキシ基である。また、Ｒ１ｂとしてより好ましくは、メトキシ基である。 R 1b is preferably an alkoxy group having 1 to 3 carbon atoms. R 1b is more preferably a methoxy group.
　化合物A2-(II）のＲ２ｂは、水素原子、ハロゲン原子、炭素数１～６のアルキル基、またはフェニル基である。 R 2b in compound A2- (II) is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
　Ｒ２ｂのハロゲン原子および炭素数１～６のアルキル基の定義は、Ｒ２ａの定義と同じである。 The definition of the halogen atom of R 2b and the alkyl group having 1 to 6 carbon atoms is the same as the definition of R 2a .
　Ｒ２ｂの炭素数１～６のアルキル基は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、炭素数１～４のアルキルカルボニルオキシ基、ニトロ基およびフェニル基から選択される置換基により置換されていてもよい。置換基の数は１つであっても２つ以上であってもよく、置換基の数が２つ以上である場合、置換基のそれぞれは同一であってもよいし、異なっていてもよい。これら置換基の定義は、上記Ｒ３の炭素数１～６のアルキル基およびフェニル基、ならびにＲ４の炭素数２～６のアルキル基およびフェニル基における置換基の定義と同じである。 The alkyl group having 1 to 6 carbon atoms of R 2b is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylcarbonyloxy group having 1 to 4 carbon atoms, a nitro group, and a phenyl group. It may be substituted with a substituent selected from The number of substituents may be one or two or more. When the number of substituents is two or more, each of the substituents may be the same or different. . The definition of these substituents is the same as the definition of the substituents in the alkyl group and phenyl group having 1 to 6 carbon atoms of R 3 and the alkyl group and phenyl group having 2 to 6 carbon atoms in R 4 .
　Ｒ２ｂのフェニル基は、無置換でもよいし、置換されていてもよい。Ｒ２ｂのフェニル基の置換基としては、例えば、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、ベンジルオキシ基、ヒドロキシ基、ニトロ基およびフェニル基が挙げられる。Ｒ２ｂのフェニル基の置換基として好ましくは、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基であり、より好ましくは、ハロゲン原子、炭素数１～３のアルキル基および炭素数１～３のアルコキシ基である。ハロゲン原子としては、塩素原子が好ましい。炭素数１～６のアルコキシ基としては、メトキシ基が好ましい。 The phenyl group of R 2b may be unsubstituted or substituted. Examples of the substituent for the phenyl group of R 2b include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a benzyloxy group, a hydroxy group, a nitro group, and a phenyl group. The substituent for the phenyl group of R 2b is preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group or a hydroxy group, more preferably a halogen atom or carbon An alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms. As the halogen atom, a chlorine atom is preferable. The alkoxy group having 1 to 6 carbon atoms is preferably a methoxy group.
　なお、Ｒ２ｂが置換基を有するフェニル基である場合、当該置換基は、ベンゼン環のオルト位、メタ位、パラ位の何れの位置に結合していてもよいが、ベンゼン環のパラ位に結合していることが好ましい。 In addition, when R 2b is a phenyl group having a substituent, the substituent may be bonded to any position of the ortho position, the meta position, and the para position of the benzene ring, but in the para position of the benzene ring. Bonding is preferred.
　Ｒ２ｂとして好ましくは、無置換のフェニル基、およびハロゲン原子、炭素数１～３のアルキル基または炭素数１～３のアルコキシ基により置換されたフェニル基である。また、Ｒ２ｂとしてより好ましくは、無置換のフェニル基、および塩素原子、メチル基またはメトキシ基により置換されたフェニル基である。Ｒ２ｂとしてさらに好ましくは、フェニル基、４－クロロフェニル基、４－メチルフェニル基、または４－メトキシフェニル基である。 R 2b is preferably an unsubstituted phenyl group and a phenyl group substituted by a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. R 2b is more preferably an unsubstituted phenyl group and a phenyl group substituted with a chlorine atom, a methyl group or a methoxy group. R 2b is more preferably a phenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, or a 4-methoxyphenyl group.
　具体的な化合物A2-(II)として以下が例示される。 Specific examples of the compound A2- (II) include the following.
Figure JPOXMLDOC01-appb-T000048
Figure JPOXMLDOC01-appb-T000048
　（７）化合物A2-(III）
　化合物A2-(III）は、下記式（A2-(III））で示される。 (7) Compound A2- (III)
Compound A2- (III) is represented by the following formula (A2- (III)).
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
　化合物A2-(III）のＲ２ａは、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、またはフェニル基である。Ｒ２ａのハロゲン原子、炭素数１～６のアルキル基および炭素数１～６のアルコキシ基の定義は、前記Ｒ２ａの定義と同じである。 R 2a in compound A2- (III) is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group. The definition of the halogen atom of R 2a , the alkyl group having 1 to 6 carbon atoms, and the alkoxy group having 1 to 6 carbon atoms is the same as the definition of R 2a .
　また、Ｒ２ａの炭素数１～６のアルキル基または炭素数１～６のアルコキシ基は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、炭素数１～４のアルキルカルボニルオキシ基、ニトロ基およびフェニル基から選択される置換基により置換されていてもよい。置換基の数は１つであっても２つ以上であってもよく、置換基の数が２つ以上である場合、置換基のそれぞれは同一であってもよいし、異なっていてもよい。 In addition, the alkyl group having 1 to 6 carbon atoms or the alkoxy group having 1 to 6 carbon atoms of R 2a is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms. And may be substituted with a substituent selected from an alkylcarbonyloxy group, a nitro group and a phenyl group. The number of substituents may be one or two or more. When the number of substituents is two or more, each of the substituents may be the same or different. .
　Ｒ２ａのフェニル基は、無置換でもよいし、置換されていてもよい。Ｒ２ａのフェニル基の置換基としては、例えば、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、ベンジルオキシ基、ヒドロキシ基、ニトロ基およびフェニル基が挙げられる。Ｒ２ａのフェニル基の置換基として好ましくは、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基であり、より好ましくは、ハロゲン原子、炭素数１～３のアルキル基および炭素数１～３のアルコキシ基である。ハロゲン原子としては、塩素原子が好ましく、炭素数１～６のアルキル基としては、メチル基が好ましく、炭素数１～６のアルコキシ基としては、メトキシ基が好ましい。 The phenyl group of R 2a may be unsubstituted or substituted. Examples of the substituent for the phenyl group of R 2a include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a benzyloxy group, a hydroxy group, a nitro group, and a phenyl group. The substituent for the phenyl group of R 2a is preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group or a hydroxy group, more preferably a halogen atom or carbon An alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms. The halogen atom is preferably a chlorine atom, the alkyl group having 1 to 6 carbon atoms is preferably a methyl group, and the alkoxy group having 1 to 6 carbon atoms is preferably a methoxy group.
　なお、Ｒ２ａが置換基を有するフェニル基である場合、当該置換基は、ベンゼン環のオルト位、メタ位、パラ位の何れの位置に結合していてもよいが、ベンゼン環のパラ位に結合していることが好ましい。 When R 2a is a phenyl group having a substituent, the substituent may be bonded to any position of the ortho position, the meta position, and the para position of the benzene ring, but at the para position of the benzene ring. Bonding is preferred.
　Ｒ２ａとして好ましくは、無置換のフェニル基、およびハロゲン原子、炭素数１～３のアルキル基または炭素数１～３のアルコキシ基により置換されたフェニル基である。また、Ｒ２ａとしてより好ましくは、塩素原子、メチル基またはメトキシ基により置換されたフェニル基である。Ｒ２ａとしてさらに好ましくは、４－クロロフェニル基、４－メチルフェニル基、および４－メトキシフェニル基である。 R 2a is preferably an unsubstituted phenyl group and a phenyl group substituted by a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. R 2a is more preferably a phenyl group substituted by a chlorine atom, a methyl group or a methoxy group. R 2a is more preferably a 4-chlorophenyl group, a 4-methylphenyl group, and a 4-methoxyphenyl group.
　具体的な化合物A2-(III）として以下が例示される。 Specific examples of the compound A2- (III) include the following.
Figure JPOXMLDOC01-appb-T000050
Figure JPOXMLDOC01-appb-T000050
　（８）化合物A2-(IV)
　化合物A2-(IV）は、下記式（A2-(IV））で示される。 (8) Compound A2- (IV)
Compound A2- (IV) is represented by the following formula (A2- (IV)).
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000051
　化合物A2-(IV）のＲ５は、ヒドロキシ基、炭素数１～６のアルコキシ基または－ＮＲ８Ｒ９である。Ｒ８およびＲ９は、それぞれ独立に、炭素数１～６のアルキル基、炭素数２～６のアルケニル基、炭素数２～６のアルキニル基、炭素数３～８のシクロアルキル基、炭素数３～８のシクロアルケニル基、またはフェニル基であり、Ｒ８とＲ９とは結合して環を形成していてもよい。Ｒ６は、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、またはフェニル基である。 R 5 of the compound A2- (IV) is a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or —NR 8 R 9 . R 8 and R 9 are each independently an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a carbon number 3 to 8 cycloalkenyl groups or phenyl groups, and R 8 and R 9 may combine to form a ring. R 6 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group.
　Ｒ６の炭素数１～６のアルキル基および炭素数１～６のアルコキシ基は、それぞれ独立に、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、炭素数１～４のアルキルカルボニルオキシ基、ニトロ基およびフェニル基から選択される置換基により置換されていてもよい。Ｒ６のフェニル基は、無置換でもよいし、置換されていてもよい。 The alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms of R 6 are each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 carbon atom. It may be substituted with a substituent selected from alkylcarbonyloxy group, nitro group and phenyl group. The phenyl group of R 6 may be unsubstituted or substituted.
　Ｒ６として好ましくは、無置換のフェニル基、およびハロゲン原子、炭素数１～３のアルキル基または炭素数１～３のアルコキシ基により置換されたフェニル基である。また、Ｒ２ａとしてより好ましくは、無置換のフェニル基、および塩素原子、メチル基またはメトキシ基により置換されたフェニル基である。 R 6 is preferably an unsubstituted phenyl group and a phenyl group substituted by a halogen atom, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. R 2a is more preferably an unsubstituted phenyl group and a phenyl group substituted by a chlorine atom, a methyl group or a methoxy group.
　Ｒ８およびＲ９の炭素数１～６のアルキル基は、直鎖および分岐鎖の何れであってもよい。炭素数１～６のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、およびｔ－ブチル基等が挙げられる。Ｒ８の炭素数１～６のアルキル基は、炭素数１～３のアルキル基であることが好ましく、メチル基であることがより好ましい。また、Ｒ９の炭素数１～６のアルキル基は、炭素数１～３のアルキル基であることが好ましく、メチル基であることがより好ましい。Ｒ８とＲ９とは、互いに同一の置換基であってもよいし、互いに異なる置換基であってもよい。 The alkyl group having 1 to 6 carbon atoms of R 8 and R 9 may be linear or branched. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a t-butyl group. The alkyl group having 1 to 6 carbon atoms of R 8 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. In addition, the alkyl group having 1 to 6 carbon atoms of R 9 is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group. R 8 and R 9 may be the same or different from each other.
　Ｒ８およびＲ９の炭素数２～６のアルキニル基は、直鎖および分岐鎖の何れであってもよい。炭素数２～６のアルキニル基としては、例えば、エチニル基、プロピニル基、およびブチニル基等が挙げられる。 The alkynyl group having 2 to 6 carbon atoms of R 8 and R 9 may be linear or branched. Examples of the alkynyl group having 2 to 6 carbon atoms include an ethynyl group, a propynyl group, and a butynyl group.
　Ｒ８およびＲ９の炭素数２～６のアルケニル基は、直鎖および分岐鎖の何れであってもよい。炭素数２～６のアルケニル基としては、例えば、エテニル基、プロペニル基、およびブテニル基等が挙げられる。 The alkenyl group having 2 to 6 carbon atoms of R 8 and R 9 may be linear or branched. Examples of the alkenyl group having 2 to 6 carbon atoms include an ethenyl group, a propenyl group, and a butenyl group.
　Ｒ８およびＲ９の炭素数３～８のシクロアルキル基としては、例えば、シクロプロピル基およびシクロブチル基等が挙げられる。 Examples of the cycloalkyl group having 3 to 8 carbon atoms of R 8 and R 9 include a cyclopropyl group and a cyclobutyl group.
　Ｒ８およびＲ９の炭素数３～８のシクロアルケニル基としては、例えば、シクロプロペニル基およびシクロブテニル基等が挙げられる。 Examples of the C3-C8 cycloalkenyl group of R 8 and R 9 include a cyclopropenyl group and a cyclobutenyl group.
　Ｒ８とＲ９とは結合して環を形成していてもよい。Ｒ８とＲ９とが結合して環を形成している－ＮＲ８Ｒ９としては、例えば、ピロリジン環およびピペリジン環等が挙げられる。 R 8 and R 9 may combine to form a ring. Examples of —NR 8 R 9 in which R 8 and R 9 are bonded to form a ring include a pyrrolidine ring and a piperidine ring.
　また、Ｒ８およびＲ９の炭素数１～６のアルキル基およびフェニル基は、それぞれ独立に、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、炭素数１～４のアルキルカルボニルオキシ基、ニトロ基およびフェニル基から選択される置換基により置換されていてもよい。置換基の数は１つであっても２つ以上であってもよく、置換基の数が２つ以上である場合、置換基のそれぞれは同一であってもよいし、異なっていてもよい。これら置換基の定義は、上記Ｒ３の炭素数１～６のアルキル基およびフェニル基、ならびにＲ４の炭素数２～６のアルキル基およびフェニル基における置換基の定義と同じである。 In addition, the alkyl group having 1 to 6 carbon atoms and the phenyl group of R 8 and R 9 are each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, 4 may be substituted with a substituent selected from an alkylcarbonyloxy group, a nitro group and a phenyl group. The number of substituents may be one or two or more. When the number of substituents is two or more, each of the substituents may be the same or different. . The definition of these substituents is the same as the definition of the substituents in the alkyl group and phenyl group having 1 to 6 carbon atoms of R 3 and the alkyl group and phenyl group having 2 to 6 carbon atoms in R 4 .
　Ｒ５として好ましくは、Ｒ８が炭素数１～３のアルキル基かつＲ９が炭素数１～３のアルキル基もしくはフェニル基である－ＮＲ８Ｒ９（Ｒ８とＲ９とは結合して環を形成していてもよい）、ヒドロキシ基、または炭素数１～３のアルコキシ基である。また、Ｒ５としてより好ましくは、Ｒ８がメチル基でありかつＲ９がメチル基もしくはフェニル基である－ＮＲ８Ｒ９、Ｒ８とＲ９とが結合してピロリジン環もしくはピペリジン環を形成している－ＮＲ８Ｒ９、ヒドロキシ基、またはメトキシ基である。 Preferred as R 5, R 8 is bonded to the -NR 8 R 9 (R 8 and R 9 alkyl group and R 9 having 1 to 3 carbon atoms is an alkyl group or phenyl group having 1 to 3 carbon atoms Which may form a ring), a hydroxy group, or an alkoxy group having 1 to 3 carbon atoms. Further, the more preferable as R 5, form a pyrrolidine ring or a piperidine ring R 8 are bonded with each -NR 8 R 9, R 8 and R 9 and R 9 is a methyl group is a methyl group or a phenyl group -NR 8 R 9 , a hydroxy group, or a methoxy group.
　具体的な化合物A2-(IV）として以下が例示される。 Specific examples of the compound A2- (IV) include the following.
Figure JPOXMLDOC01-appb-T000052
Figure JPOXMLDOC01-appb-T000052
　（９）化合物A2-(V)
　化合物A2-(V）は、下記式（A2-(V））で示される。 (9) Compound A2- (V)
Compound A2- (V) is represented by the following formula (A2- (V)).
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000053
　化合物A2-(V)のＲ２ａは、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、またはフェニル基である。 R 2a in compound A2- (V) is a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group.
　Ｒ２ａのハロゲン原子としては、例えば、塩素原子、フッ素原子、臭素原子、およびヨウ素原子等が挙げられ、なかでも塩素原子が好ましい。 Examples of the halogen atom for R 2a include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom, and among them, a chlorine atom is preferable.
　Ｒ２ａの炭素数１～６のアルキル基は、直鎖、分岐鎖および環状の何れであってもよい。炭素数１～６のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ｔ－ブチル基、およびシクロプロピル基等が挙げられ、なかでもメチル基が好ましい。 The alkyl group having 1 to 6 carbon atoms of R 2a may be linear, branched or cyclic. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, and a cyclopropyl group. Of these, a methyl group is preferable.
　Ｒ２ａの炭素数１～６のアルコキシ基としては、例えば、メトキシ基、エトキシ基、およびプロポキシ基等が挙げられ、なかでもメトキシ基が好ましい。 Examples of the alkoxy group having 1 to 6 carbon atoms of R 2a include a methoxy group, an ethoxy group, and a propoxy group, and among them, a methoxy group is preferable.
　Ｒ２ａのフェニル基は、無置換でもよいし、置換されていてもよい。Ｒ２ａのフェニル基の置換基としては、例えば、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、ベンジルオキシ基、ヒドロキシ基、ニトロ基およびフェニル基が挙げられる。Ｒ２ａのフェニル基の置換基として好ましくは、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基であり、より好ましくは、ハロゲン原子、炭素数１～３のアルキル基および炭素数１～３のアルコキシ基である。ハロゲン原子としては、塩素原子が好ましい。炭素数１～４のアルコキシ基としては、メトキシ基が好ましい。 The phenyl group of R 2a may be unsubstituted or substituted. Examples of the substituent for the phenyl group of R 2a include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a benzyloxy group, a hydroxy group, a nitro group, and a phenyl group. The substituent for the phenyl group of R 2a is preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group or a hydroxy group, more preferably a halogen atom or carbon An alkyl group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms. As the halogen atom, a chlorine atom is preferable. The alkoxy group having 1 to 4 carbon atoms is preferably a methoxy group.
　なお、Ｒ２ａが置換基を有するフェニル基である場合、当該置換基は、ベンゼン環のオルト位、メタ位、パラ位の何れの位置に結合していてもよいが、ベンゼン環のパラ位に結合していることが好ましい。 When R 2a is a phenyl group having a substituent, the substituent may be bonded to any position of the ortho position, the meta position, and the para position of the benzene ring, but at the para position of the benzene ring. Bonding is preferred.
　Ｒ２ａとして好ましくは、無置換のフェニル基、およびハロゲン原子、炭素数１～３のアルキル基、炭素数１～３のアルコキシ基またはベンジルオキシ基により置換されたフェニル基である。また、Ｒ２ａとしてより好ましくは、無置換のフェニル基、および塩素原子、メチル基、メトキシ基またはベンジルオキシ基により置換されたフェニル基である。Ｒ２ａとしてさらに好ましくは、フェニル基、４－クロロフェニル基、４－メチルフェニル基、４－メトキシフェニル基および４－ベンジルオキシフェニル基である。 R 2a is preferably an unsubstituted phenyl group and a phenyl group substituted by a halogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a benzyloxy group. R 2a is more preferably an unsubstituted phenyl group and a phenyl group substituted by a chlorine atom, a methyl group, a methoxy group or a benzyloxy group. R 2a is more preferably a phenyl group, a 4-chlorophenyl group, a 4-methylphenyl group, a 4-methoxyphenyl group, and a 4-benzyloxyphenyl group.
　具体的な化合物A2-(V）として以下が例示される。 Specific examples of the compound A2- (V) include the following.
Figure JPOXMLDOC01-appb-T000054
Figure JPOXMLDOC01-appb-T000054
　（１０）化合物A１-(III)（ピロリジンジオン誘導体）
　化合物A1-(III）は、下記式（A1-(III））で示される。 (10) Compound A1- (III) (pyrrolidinedione derivative)
Compound A1- (III) is represented by the following formula (A1- (III)).
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000055
　化合物A1-(III）のＲ７は、ピリジル基またはフラニル基を表す。ここで、ピリジル基およびフラニル基は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基から選択される置換基により置換されていてもよい。ピリジル基およびフラニル基の置換基の定義は、Ｒ１のピリジル基またはフラニル基の定義と同じである。 R 7 in compound A1- (III) represents a pyridyl group or a furanyl group. Here, the pyridyl group and furanyl group may be substituted with a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group, and a hydroxy group. . The definition of the substituent of the pyridyl group and furanyl group is the same as the definition of the pyridyl group or furanyl group of R 1 .
　Ｒ７は、無置換のピリジル基または無置換のフラニル基であることが好ましい。Ｒ７は、３－ピリジル基または２－フラニル基であることがより好ましい。 R 7 is preferably an unsubstituted pyridyl group or an unsubstituted furanyl group. R 7 is more preferably a 3-pyridyl group or a 2-furanyl group.
　ピリジル基は、無置換であることが好ましい。ピリジル基は、２位、３位および４位の何れで結合していてもよいが、３位の炭素原子で結合していることが好ましい。 The pyridyl group is preferably unsubstituted. The pyridyl group may be bonded at any of the 2nd, 3rd and 4th positions, but is preferably bonded at the 3rd carbon atom.
　フラニル基は、無置換であることが好ましい。フラニル基は、２位および３位の何れの炭素原子で結合していてもよいが、２位の炭素原子で結合していることが好ましい。 The furanyl group is preferably unsubstituted. The furanyl group may be bonded at any of the 2-position and 3-position carbon atoms, but is preferably bonded at the 2-position carbon atom.
　〔３．チアゾリジンジオン誘導体の製造方法〕
　化合物A2-(I）、A2-(II）およびA2-(III）の製造方法の一例について説明する。製造方法の各工程において使用される溶媒および塩基等としては、特に言及しない限り、以下のものを用いることができる。 [3. Method for producing thiazolidinedione derivative]
An example of a method for producing compounds A2- (I), A2- (II) and A2- (III) will be described. As the solvent and base used in each step of the production method, the following can be used unless otherwise specified.
　（１）溶媒
　使用される溶媒は、特に限定されない。溶媒としては、例えば、ジクロロメタン、クロロホルムおよびジクロロエタン等のハロゲン化炭化水素類；ベンゼン、トルエンおよびキシレン等の芳香族炭化水素類；石油エーテル、ヘキサンおよびメチルシクロヘキサン等の脂肪族炭化水素類；Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミドおよびＮ－メチル－２－ピロリジノン等のアミド類；ジエチルエーテル、テトラヒドロフランおよびジオキサン等のエーテル類；メタノールおよびエタノール等のアルコール類等が挙げられる。この他、溶媒としては、水、二硫化炭素、アセトニトリル、酢酸エチル、ピリジン、ジメチルスルホキシドおよびアセトン等が挙げられる。これらの溶媒は、２種類以上を混合して用いることができる。 (1) Solvent The solvent used is not particularly limited. Examples of the solvent include halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane; aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as petroleum ether, hexane and methylcyclohexane; N, N -Amides such as dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidinone; Ethers such as diethyl ether, tetrahydrofuran and dioxane; Alcohols such as methanol and ethanol. In addition, examples of the solvent include water, carbon disulfide, acetonitrile, ethyl acetate, pyridine, dimethyl sulfoxide, and acetone. These solvents can be used as a mixture of two or more.
　また、溶媒として、互いに均一な層を形成することのない溶媒からなる溶媒組成物が挙げられる。例えば、反応混合物中に、四級アンモニウム塩、クラウンエーテル、クラウンエーテルの類似物等の相間移動触媒を添加して反応を行うこともできる。この場合において、溶媒は、特に限定されないが、油相としてはベンゼン、クロロホルム、ジクロロメタン、ヘキサン、トルエン、テトラヒドロフラン等を用いることができる。なお、四級アンモニウム塩には、テトラブチルアンモニウム塩、トリメチルベンジルアンモニウム塩、トリエチルベンジルアンモニウム塩等が用いられる。 Further, as the solvent, a solvent composition comprising a solvent that does not form a uniform layer with each other can be mentioned. For example, the reaction can be carried out by adding a phase transfer catalyst such as a quaternary ammonium salt, a crown ether, or an analog of crown ether to the reaction mixture. In this case, the solvent is not particularly limited, but benzene, chloroform, dichloromethane, hexane, toluene, tetrahydrofuran and the like can be used as the oil phase. As the quaternary ammonium salt, tetrabutylammonium salt, trimethylbenzylammonium salt, triethylbenzylammonium salt and the like are used.
　（２）塩基
　溶媒には、塩基を添加してもよい。使用できる塩基は、特に限定されない。好ましい塩基としては、例えば、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウムおよび炭酸水素カリウム等のアルカリ金属の炭酸塩；炭酸カルシウムおよび炭酸バリウム等のアルカリ土類金属の炭酸塩；水酸化ナトリウムおよび水酸化カリウム等のアルカリ金属の水酸化物；リチウム、ナトリウムおよびカリウム等のアルカリ金属；ナトリウムメトキシド、ナトリウムエトキシドおよびカリウムｔ－ブトキシド等のアルカリ金属のアルコキシド；水素化ナトリウム、水素化カリウムおよび水素化リチウム等のアルカリ金属水素化合物；ｎ－ブチルリチウム等のアルカリ金属の有機金属化合物；リチウムジイソプロピルアミド等のアルカリ金属アミド類；ならびにトリエチルアミン、ピリジン、４－ジメチルアミノピリジン、Ｎ，Ｎ－ジメチルアニリンおよび１，８－ジアザビシクロ－７－［５．４．０］ウンデセン等の有機アミン類等が挙げられる。 (2) Base A base may be added to the solvent. The base that can be used is not particularly limited. Preferred bases include, for example, alkali metal carbonates such as sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate; alkaline earth metal carbonates such as calcium carbonate and barium carbonate; sodium hydroxide and potassium hydroxide. Alkali metal hydroxides such as lithium, sodium and potassium; Alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide; Sodium hydride, potassium hydride and lithium hydride, etc. Alkali metal hydrides such as n-butyllithium; alkali metal amides such as lithium diisopropylamide; and triethylamine, pyridine, 4-dimethylaminopyridine, N, N-di Chiruanirin and 1,8-diazabicyclo-7- [5.4.0] Organic amines such as undecene, and the like.
　（３）化合物A2-(I）の製造方法１
　まず、化合物A2-(I）に含まれる化合物のうち、化合物A2-(VII'）の製造方法について説明する。化合物A2-(VII'）は、例えば、下記反応式（１）に示すように、下記式（ａ）で示されるチアゾリジンジオン誘導体と、下記一般式（ｂ）で示される化合物とを、塩基の存在下で反応させることによって製造することができる。以下、一般式（ａ）で示されるチアゾリジンジオン誘導体を「化合物（ａ）」と、一般式（ｂ）で示される化合物を「化合物（ｂ）」と称する。 (3) Production method 1 of compound A2- (I)
First, among the compounds contained in Compound A2- (I), a method for producing Compound A2- (VII ′) will be described. Compound A2- (VII ′) is obtained by, for example, reacting a thiazolidinedione derivative represented by the following formula (a) with a compound represented by the following general formula (b) as shown in the following reaction formula (1). It can manufacture by making it react in presence. Hereinafter, the thiazolidinedione derivative represented by the general formula (a) is referred to as “compound (a)”, and the compound represented by the general formula (b) is referred to as “compound (b)”.
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000056
　化合物（ａ）のＲ２ａ'は、上記で説明した化合物A2-(I）のＲ２ａが置換されているフェニル基である場合の置換基と同一である。また、化合物（ｂ）のＲ３およびＲ４は、上記で説明した化合物A2-(I）のＲ３およびＲ４と同一である。 R 2a ′ of compound (a) is the same as the substituent in the case where R 2a of compound A2- (I) described above is a substituted phenyl group. Also, R 3 and R 4 of the compound (b) is identical to R 3 and R 4 of the compounds described above A2- (I).
　化合物（ｂ）の添加量は、化合物（ａ）に対して１．０～２．０倍モルであることが好ましい。 The amount of the compound (b) added is preferably 1.0 to 2.0 times the mole of the compound (a).
　塩基は、特に限定されないが、好適には水素化ナトリウム（ＮａＨ）等のアルカリ金属水素化物；炭酸カリウム（Ｋ２ＣＯ３）および炭酸ナトリウム（Ｎａ２ＣＯ３）等の炭酸塩；水酸化カリウム（ＫＯＨ）および水酸化ナトリウム（ＮａＯＨ）等のアルカリ金属水酸化物；トリエチルアミン等の第３級アミン類およびピリジン等の有機塩基などを用いることができる。 The base is not particularly limited but is preferably an alkali metal hydride such as sodium hydride (NaH); carbonates such as potassium carbonate (K 2 CO 3 ) and sodium carbonate (Na 2 CO 3 ); potassium hydroxide ( Alkali metal hydroxides such as KOH) and sodium hydroxide (NaOH); tertiary amines such as triethylamine; and organic bases such as pyridine can be used.
　溶媒は、特に限定されないが、例えば、ジメチルホルムアミド（ＤＭＦ）およびジメチルアセトアミド等のアミド類；アセトニトリル等のニトリル類；アセトンおよびメチルエチルケトン等のケトン類；エタノール等のアルコール類；テトラヒドロフラン等のエーテル類；水などの溶媒の中から１種類または２種類以上を適宜組み合わせて用いることができる。また、溶媒を用いないで反応を進めることができる場合もある。 The solvent is not particularly limited. For example, amides such as dimethylformamide (DMF) and dimethylacetamide; nitriles such as acetonitrile; ketones such as acetone and methyl ethyl ketone; alcohols such as ethanol; ethers such as tetrahydrofuran; Among these solvents, one kind or two or more kinds can be used in appropriate combination. In some cases, the reaction can proceed without using a solvent.
　反応温度は、０～１００℃が好ましい。反応時間は、温度条件および圧力条件等を考慮して適宜適当な時間とすることができるが、好適には０．５～２４時間の範囲である。 The reaction temperature is preferably 0 to 100 ° C. The reaction time can be appropriately determined in consideration of temperature conditions, pressure conditions, etc., but is preferably in the range of 0.5 to 24 hours.
　（４）化合物A2-(I）の製造方法２
　次に、化合物A2-(I）に含まれる化合物のうち、化合物A2-(VI'）の製造方法について説明する。化合物A2-(VI'）は、例えば、下記反応式（２）に示すように、下記一般式（ｃ）で示されるチアゾリジンジオン誘導体を酸またはアルカリの存在下で反応させることによって製造することができる。以下、一般式（ｃ）で示されるチアゾリジンジオン誘導体を「化合物（ｃ）」と称する。 (4) Production method 2 of compound A2- (I)
Next, among the compounds contained in Compound A2- (I), a method for producing Compound A2- (VI ′) will be described. Compound A2- (VI ′) can be produced, for example, by reacting a thiazolidinedione derivative represented by the following general formula (c) in the presence of an acid or alkali as shown in the following reaction formula (2). it can. Hereinafter, the thiazolidinedione derivative represented by the general formula (c) is referred to as “compound (c)”.
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000057
　化合物（ｃ）のＲ２ａ'は、上記で説明した化合物A2-(I）のＲ２ａが置換されているフェニル基である場合の置換基と同一である。また、化合物（ｃ）のＲ１０は、アルキル基であり、例えば、炭素数１～１０のアルキル基である。また、炭素数３～１０のアルキル鎖中に炭素原子同士の二重結合または三重結合を一個から複数個含んでもよい。 R 2a ′ of compound (c) is the same as the substituent when R 2a of compound A2- (I) described above is a substituted phenyl group. In addition, R 10 of the compound (c) is an alkyl group, for example, an alkyl group having 1 to 10 carbon atoms. Further, one to a plurality of double bonds or triple bonds between carbon atoms may be contained in the alkyl chain having 3 to 10 carbon atoms.
　酸は、特に限定されないが、例えば、塩酸および硫酸などを用いることができる。 The acid is not particularly limited, and for example, hydrochloric acid and sulfuric acid can be used.
　また、アルカリは特に限定されないが、例えば、ＮａＯＨおよびＫＯＨ等の水酸化アルカリ金属などを用いることができる。 The alkali is not particularly limited, and for example, alkali metal hydroxide such as NaOH and KOH can be used.
　溶媒は、特に限定されないが、例えば、ジメチルホルムアミド（ＤＭＦ）およびジメチルアセトアミド等のアミド類；アセトニトリル等のニトリル類；エタノール等のアルコール類；テトラヒドロフラン等のエーテル類；水などの溶媒の中から１種類または２種類以上を適宜組み合わせて用いることができる。また、溶媒を用いないで反応を進めることができる場合もある。 The solvent is not particularly limited. For example, amides such as dimethylformamide (DMF) and dimethylacetamide; nitriles such as acetonitrile; alcohols such as ethanol; ethers such as tetrahydrofuran; one kind of solvent such as water Alternatively, two or more types can be used in appropriate combination. In some cases, the reaction can proceed without using a solvent.
　反応温度は、－１０～１００℃が好ましい。反応時間は、温度条件および圧力条件等を考慮して適宜適当な時間とすることができるが、好適には０．５～２４時間の範囲である。 The reaction temperature is preferably −10 to 100 ° C. The reaction time can be appropriately determined in consideration of temperature conditions, pressure conditions, etc., but is preferably in the range of 0.5 to 24 hours.
　（５）化合物A2-(II）の製造方法
　化合物A2-(II）に含まれる化合物のうち、化合物A2-(II'）の製造方法について説明する。化合物A2-(II'）は、例えば、下記反応式（３）に示すように、下記一般式（ｄ）で示されるチアゾリジンジオン誘導体と、下記一般式（ｅ）で示される化合物とを、塩基の存在下で反応させることによって製造することができる。以下、一般式（ｄ）で示されるチアゾリジンジオン誘導体を「化合物（ｄ）」と、一般式（ｅ）で示される化合物を「化合物（e）」と称する。 (5) Method for Producing Compound A2- (II) Among the compounds contained in Compound A2- (II), a method for producing Compound A2- (II ′) will be described. Compound A2- (II ′) is obtained by, for example, reacting a thiazolidinedione derivative represented by the following general formula (d) with a compound represented by the following general formula (e) as shown in the following reaction formula (3). It can manufacture by making it react in presence of. Hereinafter, the thiazolidinedione derivative represented by the general formula (d) is referred to as “compound (d)”, and the compound represented by the general formula (e) is referred to as “compound (e)”.
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000058
　化合物（ｄ）のＲ２ｂ'は、上記で説明した化合物A2-(II）のＲ２ｂが置換されているフェニル基である場合の置換基と同一である。また、化合物（ｅ）のＲ１ｂは、上記で説明した化合物A2-(II）のＲ１ｂと同一である。 R 2b ′ of compound (d) is the same as the substituent in the case where R 2b of compound A2- (II) described above is a substituted phenyl group. In addition, R 1b of compound (e) is the same as R 1b of compound A2- (II) described above.
　化合物（ｅ）の添加量は、化合物（ｄ）に対して１～２倍モルであることが好ましい。 The amount of the compound (e) added is preferably 1 to 2 moles compared to the compound (d).
　塩基は、特に限定されないが、好適には水素化ナトリウム（ＮａＨ）等のアルカリ金属水素化物；炭酸カリウム（Ｋ２ＣＯ３）および炭酸ナトリウム（Ｎａ２ＣＯ３）等の炭酸塩；水酸化カリウム（ＫＯＨ）および水酸化ナトリウム（ＮａＯＨ）等のアルカリ金属水酸化物などを用いることができる。 The base is not particularly limited but is preferably an alkali metal hydride such as sodium hydride (NaH); carbonates such as potassium carbonate (K 2 CO 3 ) and sodium carbonate (Na 2 CO 3 ); potassium hydroxide ( Alkali metal hydroxides such as KOH) and sodium hydroxide (NaOH) can be used.
　溶媒は、特に限定されないが、例えば、ジメチルホルムアミド（ＤＭＦ）およびジメチルアセトアミド等のアミド類；アセトニトリル等のニトリル類；ジエチルエーテルおよびテトラヒドロフラン（ＴＨＦ）等のエーテル類；アセトンおよびメチルエチルケトン等のケトン類などの溶媒の中から１種類または２種類以上を適宜組み合わせて用いることができる。 The solvent is not particularly limited, and examples thereof include amides such as dimethylformamide (DMF) and dimethylacetamide; nitriles such as acetonitrile; ethers such as diethyl ether and tetrahydrofuran (THF); ketones such as acetone and methyl ethyl ketone; One or two or more kinds of solvents can be used in appropriate combination.
　反応温度は、０～１００℃が好ましい。反応時間は、温度条件および圧力条件等を考慮して適宜適当な時間とすることができるが、好適には０．５～２４時間の範囲である。 The reaction temperature is preferably 0 to 100 ° C. The reaction time can be appropriately determined in consideration of temperature conditions, pressure conditions, etc., but is preferably in the range of 0.5 to 24 hours.
　（６）化合物A2-(III）の製造方法
　化合物A2-(III）に含まれる化合物のうち、化合物A2-(III'）の製造方法について説明する。化合物A2-(III'）は、例えば、下記反応式（４）に示すように、下記一般式（ｆ）で示されるチアゾリジンジオン誘導体と、下記一般式（ｇ）で示される化合物とを、塩基の存在下で反応させることによって製造することができる。以下、一般式（ｆ）で示されるチアゾリジンジオン誘導体を「化合物（ｆ）」と、一般式（ｇ）で示される化合物を「化合物（ｇ）」と称する。 (6) Production method of compound A2- (III) Among the compounds contained in compound A2- (III), a production method of compound A2- (III ′) will be described. For example, as shown in the following reaction formula (4), the compound A2- (III ′) is obtained by reacting a thiazolidinedione derivative represented by the following general formula (f) with a compound represented by the following general formula (g). It can manufacture by making it react in presence of. Hereinafter, the thiazolidinedione derivative represented by the general formula (f) is referred to as “compound (f)”, and the compound represented by the general formula (g) is referred to as “compound (g)”.
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000059
　化合物（ｆ）のＲ２ｃは、上記で説明した化合物A2-(III）のＲ２ａが置換されているフェニル基である場合の置換基と同一である。 R 2c of the compound (f) is the same as the substituent when R 2a of the compound A2- (III) described above is a substituted phenyl group.
　化合物（ｇ）の添加量は、化合物（ｆ）に対して１～２倍モルであることが好ましい。塩基および溶媒の条件は、上記で説明した化合物A2-(I）の製造方法１と同様である。 The amount of compound (g) to be added is preferably 1 to 2 moles compared to compound (f). The conditions for the base and the solvent are the same as in Production Method 1 for Compound A2- (I) described above.
　〔４．ピロリジンジオン誘導体の製造方法〕
　化合物A1-(III)の製造方法の一例について説明する。化合物A1-(III)は、例えば、下記反応式（５）に示すように、化合物A1-(II)-1と、下記一般式（ｈ）で示されるアルデヒドとを、反応させることによって製造することができる。以下、一般式（ｈ）で示されるアルデヒドを「化合物（ｈ）」と称する。 [4. Method for producing pyrrolidinedione derivative]
An example of a method for producing compound A1- (III) will be described. Compound A1- (III) is produced, for example, by reacting compound A1- (II) -1 with an aldehyde represented by the following general formula (h) as shown in the following reaction formula (5). be able to. Hereinafter, the aldehyde represented by the general formula (h) is referred to as “compound (h)”.
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000060
　化合物（ｈ）のＲ７は、上記で説明した化合物A1-(III)のＲ７と同一である。 R 7 of the compound (h) is identical to R 7 of the compound A1- (III) described above.
　化合物（ｈ）の添加量は、化合物A1-(II)-1に対して１．０～２．０倍モルであることが好ましい。 The amount of compound (h) added is preferably 1.0 to 2.0 moles compared to Compound A1- (II) -1.
　溶媒は、特に限定されないが、例えば、メタノールおよびエタノール等のアルコール類；ジメチルホルムアミド（ＤＭＦ）およびジメチルアセトアミド等のアミド類；アセトニトリル等のニトリル類；ジエチルエーテルおよびテトラヒドロフラン（ＴＨＦ）等のエーテル類などの溶媒の中から１種類または２種類以上を適宜組み合わせて用いることができる。用いることができる。 The solvent is not particularly limited, and examples thereof include alcohols such as methanol and ethanol; amides such as dimethylformamide (DMF) and dimethylacetamide; nitriles such as acetonitrile; and ethers such as diethyl ether and tetrahydrofuran (THF). One or two or more kinds of solvents can be used in appropriate combination. Can be used.
　反応温度は、２０～１００℃が好ましい。反応時間は、温度条件および圧力条件等を考慮して適宜適当な時間とすることができるが、好適には０．５～２４時間の範囲である。 The reaction temperature is preferably 20 to 100 ° C. The reaction time can be appropriately determined in consideration of temperature conditions, pressure conditions, etc., but is preferably in the range of 0.5 to 24 hours.
　〔５．製剤〕
　本発明の化合物は、単独で、あるいは農園芸上許容される固体担体、液体担体、および界面活性剤、安定化剤、賦形剤等の製剤補助剤と混合して、粉剤、水和剤、粒剤、顆粒剤、乳剤、またはフロアブル剤などの種々の製剤として使用できる。 [5. Formulation]
The compound of the present invention can be used alone or in combination with agricultural and horticulturally acceptable solid carriers, liquid carriers, and formulation aids such as surfactants, stabilizers, excipients, etc. It can be used as various preparations such as granules, granules, emulsions or flowables.
　これらの製剤（殺菌剤）は、有効成分として本発明の化合物を０．１～９５重量％、好ましくは０．５～９０重量％、より好ましくは２～８０重量％を含むのが望ましい。 These preparations (bactericides) desirably contain 0.1 to 95% by weight, preferably 0.5 to 90% by weight, more preferably 2 to 80% by weight, of the compound of the present invention as an active ingredient.
　固体担体としては、タルク、カオリン、ベントナイト、珪藻土、ホワイトカーボン、クレーなどを用いることができる。液体希釈剤としては、水、キシレン、トルエン、クロロベンゼン、シクロヘキサン、シクロヘキサノン、ジメチルスルホキシド、ジメチルホルムアミド、アルコールなどを用いることができる。界面活性剤は、その効果により使い分けることが好ましく、乳化剤としては、ポリオキシエチレンアルキルアリールエーテル、ポリオキシエチレンソルビタンモノラウレートなどを用いることができ、分散剤としては、リグニンスルホン酸塩、ジブチルナフタリンスルホン酸塩などを用いることができ、湿潤剤としては、アルキルスルホン酸塩、アルキルフェニルスルホン酸塩などを用いることができる。 As the solid carrier, talc, kaolin, bentonite, diatomaceous earth, white carbon, clay and the like can be used. As the liquid diluent, water, xylene, toluene, chlorobenzene, cyclohexane, cyclohexanone, dimethyl sulfoxide, dimethylformamide, alcohol and the like can be used. The surfactant is preferably used depending on its effect, and as the emulsifier, polyoxyethylene alkylaryl ether, polyoxyethylene sorbitan monolaurate or the like can be used, and as the dispersant, lignin sulfonate, dibutylnaphthalene. A sulfonic acid salt or the like can be used. As the wetting agent, an alkyl sulfonic acid salt, an alkylphenyl sulfonic acid salt, or the like can be used.
　製剤としては、そのまま使用するものと水等の希釈剤で所定濃度に希釈あるいは分散して使用するものとがある。希釈して使用する場合、本発明の化合物の濃度は０．００１～１．０％の範囲であることが望ましい。また、本発明の化合物の使用量は、畑、田、果樹園、または温室などの農園芸地１ｈａあたり、２０～５０００ｇ、より好ましくは５０～２０００ｇである。使用濃度および使用量は、剤形、使用時期、使用方法、使用場所、および対象作物等によっても異なるため、上記の範囲に限定されることなく増減することが可能である。 Preparations include those that are used as they are and those that are diluted or dispersed to a predetermined concentration with a diluent such as water. When diluted and used, the concentration of the compound of the present invention is preferably in the range of 0.001 to 1.0%. The amount of the compound of the present invention used is 20 to 5000 g, more preferably 50 to 2000 g, per 1 ha of agricultural or horticultural land such as a field, a rice field, an orchard, or a greenhouse. The concentration and amount used vary depending on the dosage form, use period, method, place of use, target crop, etc., and can be increased or decreased without being limited to the above range.
　さらに、本発明に係る化合物は、他の有効成分、例えば以下に例示するような殺菌剤、殺虫剤、殺ダニ剤、殺線虫剤、植物成長調節剤、および／または除草剤などを含んでいてもよく、また、これらと組み合わせて使用してもよい。これにより、殺菌剤、特に農園芸用薬剤としての性能を高め得ることができる。 Further, the compound according to the present invention contains other active ingredients such as fungicides, insecticides, acaricides, nematicides, plant growth regulators and / or herbicides as exemplified below. It may be used in combination with these. Thereby, the performance as a disinfectant, especially an agricultural and horticultural agent can be improved.
　＜抗菌性物質＞
　アシベンゾラＳメチル、２－フェニルフェノール（ＯＰＰ）、アザコナゾール、アゾキシストロビン、アミスルブロム、ビキサフェン、ベナラキシル、ベノミル、ベンチアバリカルブ-イソプロピル、ビカルボネイト、ビフェニル、ビテルタノール、ブラスチシジン－Ｓ、ボラックス、ボルドー液、ボスカリド、ブロムコナゾール、ブロノポール、ブピリメート、セックブチラミン、カルシウムポリスルフィド、カプタフォル、キャプタン、カルベンダジム、カルボキシン、カルプロパミド、キノメチオネート、クロロネブ、クロロピクリン、クロロタロニル、クロゾリネート、シアゾファミド、シフルフェナミド、シモキサニル、シプロコナゾール、シプロジニル、ダゾメット、デバカルブ、ジクロフルアニド、ジクロシメット、ジクロメジン、ジクロラン、ジエトフェンカルブ、ジフェノコナゾール、ジフルメトリン、ジメトモルフ、ジニコナゾール、ジノカップ、ジフェニルアミン、ジチアノン、ドデモルフ、ドジン、エディフェンフォス、エポキシコナゾール、エタポキサム、エトキシキン、エトリジアゾール、エネストロブリン、ファモキサドン、フェナミドン、フェナリモル、フェンブコナゾール、フェンフラム、フェンヘキサミド、フェノキサニル、フェンピクロニル、フェンプロピジン、フェンプロピモルフ、フェンチン、フェンピラザミン、フェルバム、フェリムゾン、フルアジナム、フルジオキソニル、フルモルフ、フルオロミド、フルオキサストロビン、フルキンコナゾール、フルシラゾール、フルスルファミド、フルトラニル、フルトリアフォル、フォルペット、フォセチル－アルミニウム、フベリダゾール、フララキシル、フラメトピル、フルオピコリド、フルオピラム、グアザチン、ヘキサクロロベンゼン、ヘキサコナゾール、ヒメキサゾール、イマザリル、イミベンコナゾール、イミノクタジン、イプコナゾール、イプロベンフォス、イプロジオン、イプロバリカルブ、イソプロチオラン、イソピラザム、イソチアニル、イソフェタミド、カスガマイシン、銅調製物（例えば水酸化銅、ナフテン酸銅、オキシ塩化銅、硫酸銅、酸化銅、オキシン－銅）、クレゾキシムメチル、マンコカッパー、マンコゼブ、マネブ、マンジプロパミド、マンデストロビン、メパニピリム、メプロニル、メタラキシル、メトコナゾール、メチラム、メトミノスウトロビン、ミルジオマイシン、ミクロブタニル、ニトロタル－イソプロピル、ヌアリモル、オフレース、オキサジキシル、オキソリニック酸、オキスポコナゾール、オキシカルボキシン、オキシテトラサイクリン、オキサチアピプロリン、ペフラゾエート、オリサストロビン、ペンコナゾール、ペンシクロン、ペンチオピラド、ピリベンカルブ、ペンフルフェン、フサライド、ピコキシストロビン、ピペラリン、ポリオキシン、プロベナゾール、プロクロラズ、プロシミドン、プロパモカルブ、プロピコナゾール、プロピネブ、プロキナジド、プロチオコナゾール、ピラクロストロビン、ピラゾフォス、ピリフェノックス、ピリメタニル、ピロキロン、フルキサピロキサド、ピリオフェノン、キノキシフェン、キントゼン、シルチオファム、シメコナゾール、スピロキサミン、硫黄および硫黄調製物、テブコナゾール、テブフロキン、テクロフタラム、テクナゼン、テトラコナゾール、チアベンダゾール、チフルザミド、チオファネート－メチル、チラム、チアジニル、トルクロフォス－メチル、トリルフルアニド、トリアジメフォン、トリアジメノール、トリアゾキシド、トリシクラゾール、トリデモルフ、トリフロキシストロビン、トリフルミゾール、トリホリン、トリチコナゾール、トルプロカルブ、バリダマイシン、ビンクロゾリン、ジネブ、ジラム、ゾキサミド、アミスルブロム、セダキサン、フルチアニル、バリフェナル、アメトクトラジン、ジモキシストロビン、メトラフェノン、ヒドロキシイソキサゾール、メタスルホカルブなど。 <Antimicrobial substances>
Acibenzora S methyl, 2-phenylphenol (OPP), azaconazole, azoxystrobin, amisulbrom, bixaphene, benalaxyl, benomyl, bench avaricarb-isopropyl, bicarbonate, biphenyl, viteltanol, blasticidin-S, borax, bordeaux, boscalid, Bromuconazole, bronopol, bupirimate, secbutyramine, calcium polysulfide, captafor, captan, carbendazim, carboxin, carpropamide, quinomethionate, chloronebu, chloropicrin, chlorothalonil, clozolinate, cyazofamide, cyflufenamide, simoxanil, cyproconil, cyprodiazole Dazomet, debacarb, diclofuranide, diclocimet, dicromedi , Dichlorane, diethofencarb, diphenoconazole, diflumethrin, dimethomorph, diniconazole, dinocup, diphenylamine, dithianone, dodemorph, dodin, edifenphos, epoxiconazole, etapoxam, ethoxyquin, etridiazole, enestrobrin, famoxadone, fenamidone Nazole, fenflam, fenhexamide, phenoxanyl, fenpicuronyl, fenpropidin, fenpropimorph, fentin, fenpyrazamine, felbam, ferrimzone, fluazinam, fludioxonil, flumorph, fluoromido, fluoxastrobin, fluquinconazole, flusilazole, flusulfamide, flutolanil , Furtriafor, Forpe , Focetyl-aluminum, fuberidazole, flaxilil, furametopyr, fluopicolide, fluopyram, guazatine, hexachlorobenzene, hexaconazole, himexazole, imazalil, imibenconazole, iminoctazine, ipconazole, iprobenfos, iprodione, iprovalithiol, isoprolanthiol , Isophetamide, kasugamycin, copper preparations (eg copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper), crezooxime methyl, mancopper, mancozeb, maneb, mandipropamide, mandestrobin , Mepanipyrim, mepronil, metalaxyl, metconazole, methylam, metminosoutrobin, myrdiomycin, microbutanyl, Trotal-isopropyl, nuarimol, off-race, oxadixyl, oxolinic acid, oxpoconazole, oxycarboxyl, oxytetracycline, oxathiapiproline, pefazoate, orisatrobin, penconazole, pencyclon, penthiopyrado, pyribencarb, penflufen, fusaride, picoxist Robin, Piperalin, Polyoxin, Probenazole, Prochloraz, Procymidone, Propamocarb, Propiconazole, Propineb, Proquinazide, Prothioconazole, Pyraclostrobin, Pyrazophos, Pyrifenox, Pyrimethanyl, Pyroxylone, Floxapiloxado, Pyriphenone, Quinoxyphen, Quinoxyphene , Silthiofam, cimeconazole, spiroxamine, sulfur and sulfur Preparation, Tebuconazole, Tebufloquine, Teclophthalam, Technazene, Tetraconazole, Thiabendazole, Thifluzamide, Thiophanato-methyl, Tyram, Thiazinyl, Torcrophos-methyl, Tolylfuranide, Triadimephone, Triadimenol, Triazoxide, Tricyclazole, Tridemorph, Trifloxystrobin, Triflumizole, Trifolin, Triticonazole, Tolprocarb, Validamycin, Vinclozoline, Dinebu, Diram, Zoxamide, Amisulbrom, Sedaxane, Flutianyl, Variphenal, Amethoctrazine, Dimethostrobin, Metraphenone, Hydroxyisoxazole, Meta Sulfocarb etc.
　＜殺虫剤／殺ダニ剤／殺線虫剤＞
　アバメクチン、アセフェート、アクリナトリン、アラニカルブ、アルジカルブ、アレトリン、アミトラズ、アベルメクチン、アザジラクチン、アザメチフォス、アジンフォス－エチル、アジンフォス－メチル、アゾサイクロチン、アフィドピロペン、バシルス・フィルムス、バシルス・ズブチルス、バシルス・ツリンジエンシス、ベンジオカルブ、ベンフラカルブ、ベンスルタップ、ベンゾキシメイト、ビフェナゼイト、ビフェントリン、ビオアレトリン、ビオレスメトリン、ビストリフルロン、ブプロフェジン、ブトカルボキシン、ブトキシカルボキシン、カズサフォス、カルバリル、カルボフラン、カルボスルファン、カータップ、ＣＧＡ ５０４３９、クロルデイン、クロレトキシフォス、クロルフェナピル、クロルフェンビンフォス、クロルフルアズロン、クロルメフォス、クロルピリフォス、クロルピリフォスメチル、クロマフェノザイド、クロフェンテジン、クロチアニジン、クロラントラリニプロール、コウンパフォス、クリオライト、シアノフォス、シクロプロトリン、シフルトリン、シハロトリン、シヘキサチン、シペルメトリン、シフェノトリン、シロマジン、シアントラニルプロール、シクラニリプロール、シエノピラフェン、ＤＣＩＰ、ＤＤＴ、デルタメトリン、デメトン－Ｓ－メチル、ジアフェンチウロン、ジアジノン、ジクロロフェン、ジクロロプロペン、ジクロルボス、ジコフォル、ジクロトフォス、ジシクラニル、ジフルベンズロン、ジメトエート、ジメチルビンフォス、ジノブトン、ジノテフラン、エマメクチン、エンドスルファン、ＥＰＮ、エスフェンバレレート、エチオフェンカルブ、エチオン、エチプロール、エトフェンプロックス、エトプロフォス、エトキサゾール、ファムフル、フェナミフォス、フェナザキン、フェンブタチンオキシド、フェニトロチオン、フェノブカルブ、フェノチオカルブ、フェノキシカルブ、フェンプロパトリン、フェンピロキシメート、フェンチオン、フェンバレレート、フイプロニル、フロニカミド、フルアクロピリム、フルシクロクスロン、フルシトリネート、フルフェノクスロン、フルメトリン、フルバリネート、フルベンジアミド、フォルメタネート、フォスチアゼート、ハルフェンプロクス、フラチオカルブ、ハロヘノジド、フロメトキン、フルピラジフロン、フロエンスルホン、ガンマ－ＨＣＨ、ヘプテノフォス、ヘキサフルムロン、ヘキシチアゾックス、ヒドラメチルノン、イミダクロプリド、イミプロトリン、インドキサカルブ、イソプロカルブ、イソキサチオン、ルフェヌロン、マラチオン、メカルバム、メタム、メタミドフォス、メチダチオン、メチオカルブ、メトミル、メトプレン、メトスリン、メトキシフェノジド、メトルカルブ、ミルベメクチン、モノクロトフォス、ナレド、ニコチン、ニテンピラム、ノバルロン、ノビフルムロン、オメトエート、オキサミル、オキシデメトンメチル、パラチオン、パーメトリン、フェントエート、フォレート、フォサロン、フォスメット、フォスファミドン、フォキシム、ピリミカルブ、ピリミフォスメチル、プロフェノフォス、プロポクスル、プロチオフォス、ピメトロジン、ピラクロフォス、ピレスリン、ピリダベン、ピリダリル、ピリミジフェン、ピリプロキシフェン、ピリフルキナゾン、ピリプロール、ピフルブミド、キナルフォス、シラフルオフェン、スピノサド、スピロジクロフェン、スピロメシフェン、スピロテトラマット、スルフラミド、スルフォテップ、ＳＺＩ－１２１、テブフェノジド、テブフェンピラド、テブピリムフォス、テフルベンズロン、テフルトリン、テメフォス、テルブフォス、テトラクロルビンフォス、チアクロプリド、チアメトキサム、チオジカルブ、チオファノックス、チオメトン、トルフェンピラド、トラロメトリン、トラロピリル、トリアザメート、トリアゾフォス、トリクロルフオン、トリフルムロン、バミドチオン、バリフェナル、ＸＭＣ、キシリルカルブ、イミシアホス、レピメクチンなど。 <Insecticide / acaricide / nematicide>
Abamectin, Acephate, Acrinathrin, Alanicarb, Aldicarb, Alletrin, Amitraz, Avermectin, Azadirachtin, Azamethifos, Azinphos-ethyl, Azinphos-methyl, Azocycline, Aphidopiropen, Bacillus films, Bacillus subtilis, Bacillus subtilis , Bensultap, benzoximate, biphenazeite, bifenthrin, bioalletrin, bioresmethrin, bistriflurone, buprofezin, butcarboxyne, butoxycarboxyl, kazusafos, carbaryl, carbofuran, carbosulfan, cartap, CGA 50439, chlordeine, chloretifos, Chlorfenapyr, chlorfenvin foss, Chlorfluazuron, Chlormefos, Chlorpyrifos, Chlorpyrifosmethyl, Chromaphenoid, Chlofenthedin, Clothianidin, Chloranthriniprolol, Counpaphos, Cryolite, Cyanophos, Cycloproton, Cyfluthrin, Cyhalothrin, Cihexatin, Si Permethrin, ciphenothrin, cyromazine, cyantranylprol, cyclanilipol, sienopyrafen, DCIP, DDT, deltamethrin, demeton-S-methyl, diafenthiuron, diazinon, dichlorophen, dichloropropene, dichlorvos, dicofol, dicrotophos, dicyclanil , Diflubenzuron, dimethoate, dimethylvinphos, dinobutone, dinotefuran, emamectin, endosulfan, EPN, e Fenvalerate, etiophencarb, ethion, ethiprole, etofenprox, etofolfos, etoxazole, famflu, phenamiphos, phenazaquin, fenbutatin oxide, fenitrothion, fenocarb, phenothiocarb, phenoxycarb, fenpropatoline, fenpyroximate, fenthionyl, fenthionyl Flonicamid, fluaclopyrim, flucycloxuron, flucitrinate, flufenoxuron, flumethrin, fulvalinate, flubendiamide, formethanate, fostiazate, halfenprox, furthiocarb, halohenozide, flometoquine, flupiradifuron, furoenesulfone, gamma-HCH , Heptenophos, hexaflumuron, Xithiazox, hydramethylnon, imidacloprid, imiprothrin, indoxacarb, isoprocarb, isoxathion, lufenuron, malathion, mecarbam, metham, methamidophos, methidathion, methiocarb, methomyl, methoprene, methosrin, methoxyphenozide, metortocarb, milletol Nared, nicotine, nitenpyram, nobarulone, nobiflumuron, ometoate, oxamyl, oxydemetonmethyl, parathion, permethrin, phentoate, folate, fosalon, fosmet, phosphamidone, foxime, pirimicarb, pirimiphosmethyl, profenofos, propox, Prothiophos, pymetrozine, pyracrophos, pyrethrin, pyridaben, Pyridalyl, Pyrimidifen, Pyriproxyfen, Pyrifluquinazone, Pyriprole, Pifulbumide, Quinarfos, Silafluophene, Spinosad, Spirodiclofen, Spiromesifene, Spirotetramat, Sulfamide, Sulfotep, SZI-121, Tebufenozide, Tebufenpyrad, Tebupyrimfos, Teflupyrifos Temefos, terbufos, tetrachlorvinfos, thiacloprid, thiamethoxam, thiodicarb, thiophanox, thiometon, tolfenpyrad, tolomethrin, tralopyril, triazamate, triazophos, trichlorfon, triflumuron, bamidthione, varifenal, XMC, xylylcarb, mithiacarb
　＜植物成長調節剤＞
　アンシミドール、６－ベンジルアミノプリン、パクロブトラゾール、ジクロブトラゾール、ウニコナゾール、メチルシクロプロペン、メピコートクロリド、エセフォン、クロルメコートクロライド、イナベンフィド、プロヘキサジオンおよびその塩、トリネキサパックエチル等。また、植物ホルモンとして、ジャスモン酸、ブラシノステロイド、およびジベレリンなど。 <Plant growth regulator>
Ansimidol, 6-Benzylaminopurine, Paclobutrazol, Diclobutrazole, Uniconazole, Methylcyclopropene, Mepiquat chloride, Ecephone, Chlormequat chloride, Inabenfide, Prohexadione and its salts, Trinexapack Ethyl etc. Plant hormones include jasmonic acid, brassinosteroids, and gibberellins.
　〔６．殺菌剤の有用性〕
　本発明の化合物は植物病害防除効果を有しており、例えば、農園芸用薬剤として利用できる（実施例も参照）。特に、本発明の化合物は、茎葉病害、種子伝染病害および土壌伝染病害を含む広汎な植物病害に対して防除効果を示す。そのため、有効成分となる本発明に係る化合物は、茎葉病害、種子伝染病害および土壌伝染病害を含む広汎な植物病害に対して用いることができる。すなわち、本発明に係る化合物は、農園芸用薬剤、茎葉病害用殺菌剤、種子伝染病害用殺菌剤または土壌伝染病害用殺菌剤の形態で用いることができる。 [6. Usefulness of fungicides)
The compounds of the present invention have a plant disease control effect and can be used as, for example, agricultural and horticultural agents (see also Examples). In particular, the compounds of the present invention exhibit a controlling effect against a wide range of plant diseases including foliage diseases, seed infectious diseases and soil infectious diseases. Therefore, the compound according to the present invention as an active ingredient can be used for a wide variety of plant diseases including foliage diseases, seed-borne diseases and soil-borne diseases. That is, the compound according to the present invention can be used in the form of agricultural and horticultural agents, foliars for foliage diseases, bactericides for seed infectious diseases or bactericides for soil infectious diseases.
　適用病害の例として以下が挙げられる（括弧内は、その病気を引き起こす菌の学名を示す）：コムギ葉枯病（Septoria tritici）、ダイズさび病（Phakopsora pachyrhizi、Phakopsora meibomiae）、イネいもち病（Pyricularia oryzae）、イネごま葉枯病（Cochliobolus miyabeanus）、イネ白葉枯病（Xanthomonas oryzae）、イネ紋枯病（Rhizoctonia solani）、イネ小黒菌核病（Helminthosporium sigmoideun）、イネばか苗病（Gibberella fujikuroi）、イネ苗立枯病（Pythium aphanidermatum、Pythium graminicola 、Rhizopus oryzae）、リンゴうどんこ病（Podosphaera leucotricha）、リンゴ黒星病（Venturia inaequalis）、リンゴモリニア病（Monilinia mali）、リンゴ斑点落葉病（Alternaria alternata）、リンゴ腐乱病（Valsa mali）、ナシ黒斑病（Alternaria kikuchiana）、ナシうどんこ病（Phyllactinia pyri）、ナシ赤星病（Gymnosporangium asiaticum）、ナシ黒星病（Venturia nashicola）、ブドウうどんこ病（Uncinula necator）、ブドウべと病（Plasmopara viticola）、ブドウ晩腐病（Glomerella cingulata）、オオムギうどんこ病（Erysiphe graminis f. sp hordei）、オオムギ黒さび病（Puccinia graminis）、オオムギ黄さび病（Puccinia striiformis）、オオムギ斑葉病（Pyrenophora graminea）、オオムギ雲形病（Rhynchosporium secalis）、コムギうどんこ病（Erysiphe graminis f. sp tritici）、コムギ赤さび病（Puccinia recondita）、コムギ黄さび病（Puccinia striiformis）、コムギ眼紋病（Pseudocercosporella herpotrichoides）、コムギ赤かび病（Fusarium graminearum、Microdochium nivale）、コムギふ枯病（Phaeosphaeria nodorum）、ウリ類うどんこ病（Sphaerotheca fuliginea）、ウリ類炭疸病（Colletotrichum lagenarium）、キュウリべと病（Pseudoperonospora cubensis）、キュウリ灰色疫病（Phytophthora capsici）、トマトうどんこ病（Erysiphe cichoracearum）、トマト輪紋病（Alternaria solani）、ナスうどんこ病（Erysiphe cichoracearum）、イチゴうどんこ病（Sphaerotheca humuli）、タバコうどんこ病（Erysiphe cichoracearum）、テンサイ褐斑病（Cercospora beticola）、トウモロコシ黒穂病（Ustilago maydis）、核果類果樹の灰星病（Monilinia fructicola）、種々の作物をおかす灰色かび病（Botrytis cinerea）、菌核病（Sclerotinia sclerotiorum）、ブドウさび病（Phakopsora ampelopsidis）、スイカつる割病（Fusarium oxysporum f.sp.niveum）、キュウリつる割病（Fusarium oxysporum f.sp.cucumerinum）、ダイコン萎黄病（Fusarium oxysporum f.sp.raphani）、タバコ赤星病（Alternaria longipes）、ジャカイモ夏疫病（Alternaria solani）、ダイズ褐紋病（Septoria glycines）、ダイズ紫斑病（Cercospora kikuchii）、コムギ紅色雪腐病（Microdochium nivale）、コムギ立枯れ病（Gaeumannomyces graminis）、オオムギ裸黒穂病（Ustilago nuda）、カンキツ青かび病（Penicillium italicum）。 Examples of applicable diseases include the following (in parentheses indicate the scientific name of the fungus causing the disease): wheat leaf blight (Septoria tritici), soybean rust (Phakopsora pachyrhizi, Phakopsora meibomiae), rice blast (Pyricularia) oryzae), rice sesame leaf blight (Cochliobolus miyabeanus), rice white blight (Xanthomonas oryzae), rice blight (Rhizoctonia solani), rice black rot (Helminthosporium sigmoideun), rice blast seedling (Gibberella fujikuroi) Rice seedling blight (Pythium aphanidermatum, Pythium graminicola, Rhizopus oryzae), apple powdery mildew (Podosphaera leucotricha), apple black spot disease (Venturia inaequalis), apple morinaria disease (Monilinia mali), apple spotted leaf disease (Alternaria applesaltern tern) Rot disease (Valsa mali), pear black spot disease (Alternaria kikuchiana), pear powdery mildew (Phyllactinia pyri), pear red star disease (Gymnospor) angium asiaticum), pear black spot disease (Venturia nashicola), grape powdery mildew (Uncinula necator), grape downy mildew (Plasmopara viticola), grape late rot (Glomerella cingulata), barley powdery mildew (Erysiphe graminis f. sp hori ), Barley black rust (Puccinia graminis), barley yellow rust (Puccinia striiformis), barley leaf spot (Pyrenophora graminea), barley cloud (Rhynchosporium secalis), wheat powdery mildew (Erysiphe graminisf Wheat red rust (Puccinia recondita), Wheat yellow rust (Puccinia striiformis), Wheat eye spot disease (Pseudocercosporella herpotrichoides), Wheat red mold (Fusarium graminearum, Microdochium nivale), Wheat blight (Phaumosphaerian Disease (Sphaerotheca fuliginea), cucumber anthracnose (Colletotrichum lagenarium), cucumber downy mildew (Pseudoperonospora cube) nsis), cucumber gray plague (Phytophthora capsici), tomato powdery mildew (Erysiphe cichoracearum), tomato ringworm (Alternaria solani), eggplant powdery mildew (Erysiphe cichoracearum), strawberry powdery mildew (Sphaerotheca humuli), tobacco powdery mildew Disease (Erysiphe cichoracearum), sugar beet brown spot (Cercospora beticola), maize scab (Ustilago maydis), fruit tree fruit rot (Monilinia fructicola), gray mold disease (Botrytis cinerea) that kills various crops Disease (Sclerotinia sclerotiorum), grape rust (Phakopsora ampelopsidis), watermelon vine split disease (Fusarium oxysporum f.sp.niveum), cucumber vine split disease (Fusarium oxysporum f.sp.cucumerinum), radish sp.raphani), tobacco red star disease (Alternaria longipes), potato summer plague (Alternaria solani), soybean brown spot disease (Septoria glycines), soybean purple Disease (Cercospora kikuchii), wheat pink snow mold (Microdochium nivale), wheat take-all disease (Gaeumannomyces graminis), barley loose smut (Ustilago nuda), citrus blue mold disease (Penicillium italicum).
　適用植物の例としては、野生植物、植物栽培品種、異種交配もしくは原形質融合などの従来の生物育種によって得られる植物および植物栽培品種、遺伝子操作によって得られる遺伝子組み換え植物および植物栽培品種が挙げられる。遺伝子組み換え植物および植物栽培品種としては、例えば、除草剤耐性作物、殺虫性タンパク産生遺伝子を組み込んだ害虫耐性作物、病害に対する抵抗性誘導物質産生遺伝子を組み込んだ病害耐性作物、食味向上作物、保存性向上作物、および収量向上作物等が挙げられる。遺伝子組み換え植物栽培品種としては、具体的に、ROUNDUP READY、LIBERTY LINK、CLEARFIELD、YIELDGARD、HERCULEX、およびBOLLGARD等の登録商標を含むものが挙げられる。 Examples of applicable plants include wild plants, plant cultivars, plants and plant cultivars obtained by conventional breeding such as crossbreeding or protoplast fusion, genetically modified plants and plant cultivars obtained by genetic manipulation. . Examples of genetically modified plants and plant cultivars include herbicide-tolerant crops, pest-tolerant crops incorporating insecticidal protein production genes, disease-resistant crops incorporating resistance-inducing substance production genes against diseases, food-enhancing crops, and preservation Examples include improved crops and yield-enhanced crops. Specific examples of genetically modified plant cultivars include those containing registered trademarks such as ROUNDUP READY, LIBERTY LINK, CLEARFIELD, YIELDGARD, HERCULEX, and BOLLGARD.
　以下に実施例を示し、本発明の実施の形態についてさらに詳しく説明する。もちろん、本発明は以下の実施例に限定されるものではなく、細部については様々な態様が可能であることはいうまでもない。さらに、本発明は上述した実施形態に限定されるものではなく、請求項に示した範囲で種々の変更が可能であり、それぞれ開示された技術的手段を適宜組み合わせて得られる実施形態についても本発明の技術的範囲に含まれる。また、本明細書中に記載された文献の全てが参考として援用される。 Examples will be shown below, and the embodiments of the present invention will be described in more detail. Of course, the present invention is not limited to the following examples, and it goes without saying that various aspects are possible in detail. Further, the present invention is not limited to the above-described embodiments, and various modifications can be made within the scope shown in the claims, and the present invention is also applied to the embodiments obtained by appropriately combining the disclosed technical means. It is included in the technical scope of the invention. Moreover, all the literatures described in this specification are used as reference.
　製造例において、ＩＲスペクトル分析では、Perkin Elmer FTIR 1600 spectrometerを用いた。なお、以下の製造例等で使用される化合物は、適宜、市販品を用いることができる。 In the production example, Perkin Elmer FTIR 1600 spectrometer was used for IR spectrum analysis. In addition, the compound used by the following manufacture examples etc. can use a commercial item suitably.
　＜製造例１：３－（３－ピリジルメチリデニル）ピロリジン－２，５－ジオン（化合物A1-(I)-4）の製造＞
　５ｍｌのメタノールに溶解している３－トリフェニルホスホラニリデニルスクシンイミド（３５９ｍｇ）および３－ピリジンアルデヒド（１０７ｍｇ）の溶液を５時間還流させた。その後、反応容器を室温で数時間静置した。次いで、沈殿固体を濾過し、メタノールから再結晶化させた。
収量：１１２ｍｇ（収率：６０％）
IR νmax(KBr): 1750, 1723, 1660 cm-1
　＜製造例２：３－（２－フラニルメチリデニル）ピロリジン－２，５－ジオン（化合物A1-(I)-5）の製造＞
　２－フランカルボキシアルデヒドを用いた以外、化合物A1-(I)-4の場合と同様の方法により製造した。
収率：６５％
IR νmax(KBr): 1758, 1701, 1645 cm-1
　＜製造例３：２，４－ジオキソ－５－（フェニルメチル）－３－チアゾリジン酢酸メチルエステル（化合物A2-(II)-3）の製造＞
　アセトニトリルに溶解している、５－ベンジル－２，４－チアゾリジンジオン（１．１０ｇ）、ブロモ酢酸メチル（１．６２ｇ）および炭酸カリウム（１．４８ｇ）の混合物を２０時間還流させた。減圧下で溶媒と揮発させた後、残渣を酢酸エチルに溶解し、水で洗浄して、無水ＭｇＳＯ４上で乾燥した。次いで、溶媒を揮発させて、固体をメタノールから再結晶化させ、純粋なエステルとして得た。
収量：２７ｍｇ（収率：２％）、液体、IR νmax(KBr): 1750, 1698 cm-1
　＜製造例４：２，４－ジオキソ－５－（４－メチルフェニルメチル）－３－チアゾリジン酢酸メチルエステル（化合物A2-(II)-1）の製造＞
　５－（４－メチルベンジル）－２，４－チアゾリジンジオンを用いた以外、化合物A2-(II)-3の場合と同様の方法により製造した。
収率：３６％、液体、IR νmax (KBr): 1745, 1690 cm-1
　＜製造例５：２，４－ジオキソ－５－（４－クロロフェニルメチル）－３－チアゾリジン酢酸メチルエステル（化合物A2-(II)-2）の製造＞
　５－（４－クロロベンジル）－２，４－チアゾリジンジオンを用いた以外、化合物A2-(II)-3の場合と同様の方法により製造した。
収率：４５％、IR νmax (KBr): 1742, 1693 cm-1
　＜製造例６：２，４－ジオキソ－５－（フェニルメチル）－３－チアゾリジン酢酸（化合物A2-(I)-1）の製造＞
　１０ｍｌの酢酸に溶解している、２，４－ジオキソ－５－（フェニルメチル）－３－チアゾリジン酢酸メチルエステル（化合物A2-(II)-3）（２９１ｍｇ）および２ｍｌの濃塩酸の混合物を１３時間還流させた。次いで、酢酸を揮発させ、残渣を酢酸エチルで抽出した。その後、水で洗浄し、無水ＭｇＳＯ４上で乾燥した。酢酸エチルを揮発させて、固化した残渣をヘキサンで洗浄した。
収量：７０ｍｇ（収率：２４％）、IR νmax (KBr): 1715, 1689 cm-1
　＜製造例７：Ｎ，Ｎ－ジメチル－２，４－ジオキソ－５－（フェニルメチル）－３－チアゾリジンアセトアミド（化合物A2-(IV)-2）の製造＞
　１５ｍｌのアセトニトリルに溶解している、５－ベンジルチアゾリジン－２，４－ジオン化合物A2-(V)-4（２０６ｍｇ）、２－クロロ－Ｎ，Ｎ－ジメチルアセトアミド（１５５ｍｇ）および炭酸カリウム（２７６ｍｇ）の混合物を８時間還流させた。その後、反応混合物を冷却して濾過し、濾過液中のアセトニトリルを揮発させた。残渣をエーテル中で結晶化させ、濾過した固体をヘキサンで洗浄した。
収量：６４ｍｇ（収率：２２％）、液体、IR νmax(KBr): 1687, 1667 cm-1
　＜製造例８：Ｎ－メチル，Ｎ－フェニル－２，４－ジオキソ－５－（フェニルメチル）－３－チアゾリジンアセトアミド（化合物A2-(I)-7）の製造＞
　化合物A2-(IV)-2の場合と同様の方法により製造した。
収率：３１％、IR νmax (KBr): 1686, 1662 cm-1
　＜製造例９：Ｎ－｛１－［２，４－ジオキソ－５－（フェニルメチル）－３－チアゾリジニル］アセチル｝ピロリジン（化合物A2-(I)-2）の製造＞
　化合物A2-(IV)-2の場合と同様の方法により製造した。
収率：１０％、液体、IR νmax (KBr): 1684, 1661 cm-1
　＜製造例１０：Ｎ－｛１－［２，４－ジオキソ－５－（フェニルメチル）－３－チアゾリジニル］アセチル｝ピペリジン（化合物A2-(I)-3）の製造＞
　化合物A2-(IV)-2の場合と同様の方法により製造した。
収率：１４％、液体、IR νmax (KBr): 1689, 1661 cm-1
　＜製造例１１：Ｎ，Ｎ－ジメチル－２，４－ジオキソ－５－（４－メトキシフェニルメチル）－３－チアゾリジンアセトアミド（化合物A2-(III)-1）の製造＞
　化合物A2-(IV)-2の場合と同様の方法により製造した。
収率：７％、液体、IR νmax (KBr): 1689, 1660 cm-1
　＜製造例１２：Ｎ－メチル，Ｎ－フェニル－２，４－ジオキソ－５－（４－メトキシフェニルメチル）－３－チアゾリジンアセトアミド（化合物A2-(I)-4）の製造＞
　化合物A2-(IV)-2の場合と同様の方法により製造した。
収率：５２％、IR νmax (KBr): 1681, 1660 cm-1
　＜製造例１３：Ｎ，Ｎ－ジメチル－２，４－ジオキソ－５－（４－メチルフェニルメチル）－３－チアゾリジンアセトアミド（化合物A2-(III)-2）の製造＞
　化合物A2-(IV)-2の場合と同様の方法により製造した。
収率：２０％、IR νmax (KBr): 1682, 1662 cm-1
　＜製造例１４：Ｎ－メチル，Ｎ－フェニル－２，４－ジオキソ－５－（４－メチルフェニルメチル）－３－チアゾリジンアセトアミド（化合物A2-(I)-5）の製造＞
　化合物A2-(IV)-2の場合と同様の方法により製造した。
収率：３７％、IR νmax (KBr): 1683, 1656 cm-1
　＜製造例１５：Ｎ，Ｎ－ジメチル－２，４－ジオキソ－５－（４－クロロフェニルメチル）－３－チアゾリジンアセトアミド（化合物A2-(III)-3）の製造＞
　化合物A2-(IV)-2の場合と同様の方法により製造した。
収率：４９％、IR νmax (KBr): 1687, 1658 cm-1
　＜製造例１６：Ｎ－メチル，Ｎ－フェニル－２，４－ジオキソ－５－（４－クロロフェニルメチル）－３－チアゾリジンアセトアミド（化合物A2-(I)-6）の製造＞
　化合物A2-(IV)-2の場合と同様の方法により製造した。
収率：３０％、IR νmax (KBr): 1687, 1662 cm-1
　＜製造例１７：５－（４－クロロベンジリデニル）チアゾリジン－２，４－ジオン（化合物A1-(I)-10）の製造＞
　チアゾリジン－２，４－ジオン2.34g(0.02mol)をエタノール30mlに溶かし、４－クロロベンズアルデヒド2.81g(0.02mol)、ピペリジン1.36g(0.016mol)を加え、11時間加熱還流した。放冷し、生じた黄色結晶をろ集した。結晶を水、ヘキサンで洗浄した後、エタノールで再結晶し、目的物の淡黄色結晶を得た。
収量：3.49g(収率：73%)、融点：210-212℃、EIMS m/z (%)　239 (M+, 93), 168 (100)
　＜製造例１８：５－（２－クロロベンジリデニル）チアゾリジン－２，４－ジオン（化合物A1-(I)-11）の製造＞
　４－クロロベンズアルデヒドの代わりに２－クロロベンズアルデヒドを用い、化合物A1-(I)-10と同様の方法で製造した。
収率：7％、融点：187-189℃、EIMS m/z (%)　239 (M+, 20), 204 (85), 168 (100)
　＜製造例１９：５－（３－クロロベンジリデニル）チアゾリジン－２，４－ジオン（化合物A1-(I)-12）の製造＞
　４－クロロベンズアルデヒドの代わりに３－クロロベンズアルデヒドを用い、化合物A1-(I)-10と同様の方法で製造した。
収率：51％、融点：198-201℃、EIMS m/z (%)　239 (M+, 74), 168 (100)
　＜製造例２０：５－（４－メトキシベンジリデニル）チアゾリジン－２，４－ジオン（化合物A1-(I)-13）の製造＞
　４－クロロベンズアルデヒドの代わりに４－メトキシベンズアルデヒドを用い、化合物A1-(I)-10と同様の方法で製造した。
収率：54％、融点：230-232℃、EIMS m/z (%)　235 (M+, 83), 204 (10), 164 (100)
　＜製造例２１：５－（３－ピリジルメチリデニル）チアゾリジン－２，４－ジオン（化合物A1-(I)-14）の製造＞
　４－クロロベンズアルデヒドの代わりに３－ピリジンアルデヒドを用い、化合物A1-(I)-10と同様の方法で製造した。
収率52％、融点：247-249℃、EIMS m/z (%)　206 (M+, 43), 135 (100)
　＜製造例２２：５－（２－クロロベンジリデニル）チアゾリジン－２，４－ジオン（化合物A1-(I)-15）の製造＞
　４－クロロベンズアルデヒドの代わりに４－メチルベンズアルデヒドを用い、化合物A1-(I)-10と同様の方法で製造した。
収率：74％、融点：190-193℃、EIMS m/z (%)　219 (M+, 13), 167 (43), 148 (100)
　＜製造例２３：５－（３－ベンジルオキシベンジリデニル）チアゾリジン－２，４－ジオン（化合物A1-(I)-16）の製造＞
　チアゾリジン－２，４－ジオン587mg(5mmol)をトルエン5mlに溶かし、３－ヒドロキシベンズアルデヒド610mg(5mmol)、安息香酸733mg(6mmol)、ピペリジン426mg(5mmol)を加え、6時間加熱還流した。放冷し、生じた結晶をろ集した。結晶をメタノール：水=1：1の溶液で洗浄し、５－（３－ヒドロキシベンジリデニル）チアゾリジン－２，４－ジオンを得た。収量：945ｍg(収率：85%)
　得られた５－（３－ヒドロキシベンジリデニル）チアゾリジン－２，４－ジオン664mg(3mmol)をアセトニトリルに溶かし、塩化ベンジル380mg(3mmol)、炭酸カリウム497mg(3.6mmol)を加え11時間加熱還流した。放冷後、濃縮し、水を加え酢酸エチルで抽出した。有機層を硫酸マグネシウムで乾燥後ろ過、濃縮した。残渣を薄層クロマトグラフィー（クロロホルム：メタノール＝30：1）で精製し、目的物を得た。
収量：30mg(収率：3%)、融点：207-209℃、EIMS m/z (%)　311 (M+, 100), 184 (27)
　＜製造例２４：Ｎ－メチル－５－ベンジリデニルチアゾリジン－２，４－ジオン（化合物A1-(XI)-1）の製造＞
　５－ベンジリデニルチアゾリジン－２，４－ジオン205mg(1mmol)をアセトニトリルに溶かし、炭酸カリウム276mg(2mmol)、ヨウ化メチル170mg(1.2mmol)を加え、50℃で1.5時間撹拌した。ろ過し、ろ液を濃縮後、残渣をエーテルで洗浄し目的物を得た。
収量：126mg(収率：58%)、融点：134-136℃、EIMS m/z (%)　219 (M+, 83), 134 (100)
　＜製造例２５：Ｎ－メチル－５－(３－フェノキシベンジリデニル)チアゾリジン－２，４－ジオン（化合物A1-(XI)-2）の製造＞
　５－ベンジリデニルチアゾリジン－２，４－ジオンの代わりに５－（３－フェノキシベンジリデニル）チアゾリジン－２，４－ジオン（５－（４－クロロベンジリデニル）チアゾリジン－２，４－ジオンと同様の方法で合成）を用いて、化合物A1-(XI)-1と同様の方法で製造した。
収率：74%、融点：166-168℃、EIMS m/z (%)　311 (M+, 88), 226 (100)
　＜製造例２６：Ｎ－ベンジル－５－ベンジリデニルチアゾリジン－２，４－ジオン（化合物A1-(XI)-3）の製造＞
　ヨウ化メチルの代わりに塩化ベンジルを用いて、化合物A1-(XI)-1と同様の方法で製造した。
収率：59%、融点：138-141℃、EIMS m/z (%)　295 (M+, 78), 134 (100), 91 (90)
　＜製造例２７：Ｎ－フェニル－５－ベンジリデニルチアゾリジン－２，４－ジオン（化合物A1-(XI)-4)）の製造＞
　チオグリコール酸エチル1.80g(15mmol)をトルエン10mlに溶かしフェニルイソシアネイト2.03g(15mmol)を加えた後、金属ナトリウム20mgを加え13.5時間加熱還流した。放冷し、生じた結晶をろ集した。結晶をエタノールに溶かし活性炭を加え、熱時ろ過した。放冷し生じたＮ－フェニルチアゾリジン－２，４－ジオンの結晶をろ集した。収量：1.17g (収率：41%)
　得られたＮ－フェニルチアゾリジン－２，４－ジオン288mg(1.5mmol)をエタノール20mlに溶かし、ベンズアルデヒド、ピペリジン102mg(1.2mmol)を加え12時間加熱還流した。放冷し、生じた結晶をろ集し、結晶をヘキサンで洗浄し目的物を得た。
収量：71mg(収率17%)、融点：218-220℃、EIMS m/z (%)　281 (M+, 88), 134 (100)
　＜製造例２８：Ｎ－（２，６－ジクロロ－４－ピリジルメチル）－５－ベンジリデニルチアゾリジン－２，４－ジオン（化合物A1-(XI)-5）の製造＞
　ヨウ化メチルの代わりに２，６－ジクロロ－４－ピリジルメチルクロライドを用いて、化合物A1-(XI)-1と同様の方法で製造した。
収率：26%、融点：190-192℃、EIMS m/z (%)　364 (M+, 80), 134 (100)
　＜製造例２９：５－ベンジリデニルロダニン－３－酢酸メチルエステル（化合物A1-(XII)-2）の製造＞
　80℃に熱した酢酸20mlへベンズアルデヒド1.06g(10mmol)、ロダニン1.33g(10mmol)を加え30分撹拌した後、無水酢酸ナトリウム2.87g(35mmol)を加え1時間撹拌した。放冷し、200mlの水にあけ、生じた結晶をろ集した。結晶を水：エタノール＝1：1の溶液で洗浄し、５－ベンジリデニルロダニンを得た。収量：1.66g(収率：75%)、融点：212-214℃
　得られた５－ベンジリデニルロダニン221mg(1mmol)をDMF10mlに溶かし、水素化ナトリウム(60%)48mg(1.2mmol)を加え、室温で30分間撹拌した。この懸濁液にブロモ酢酸メチル184mg(1.2mmol)を加え、80℃で13時間撹拌した。DMFを留去し、水を加え、酢酸エチルで抽出した。有機層を水で洗浄し、硫酸マグネシウムで乾燥後、ろ過、濃縮し目的物を得た。
収量：150mg(収率：51%)、融点：139-141℃、EIMS m/z (%)　293 (M+, 85), 162 (80), 134 (100)
　＜製造例３０：５－ベンジリデニルロダニン－３－酢酸メチルエステル（化合物A1-(XII)-1）の製造＞
　ベンズアルデヒドの代わりに３－チオフェンアルデヒドを用いて、化合物A1-(XII)-2と同様の方法で製造した。
収率：70%、融点：157-159℃、EIMS m/z (%)　299 (M+, 22), 226 (31), 140 (100)
　＜製造例３１：３－（２－オキソ－２－（ピペリジン－１－イル）エチル）－５－（３－チエニルメチリデン）ロダニン（化合物A1-(XII)-3）の製造＞
　ロダニン－３－酢酸をジクロロメタン15mlに溶かし、１－エチル－３－（３－ジメチルアミノプロピル）カルボジイミド塩酸塩192mg(1mmol)、４－ジメチルアミノピリジン122mg(1mmol)、ピペリジン85mg(1mmol)を加え室温で13時間撹拌した。反応溶液を飽和重曹水、1％HCl、水で洗浄し、硫酸マグネシウムで乾燥後、ろ過、濃縮した。残渣をメタノールで再結晶し、３－（２－オキソ－２－（ピペリジン－１－イル）エチル）－ロダニンを得た。収量：46mg(収率：18%)、融点：173-175℃
　酢酸3mlを80℃に加熱し、３－チオフェンアルデヒド56mg(0.5mmol)、３－（２－オキソ－２－（ピペリジン－１－イル）エチル）－ロダニン129mg(0.5mmol)を加え、30分間撹拌した。その後無水酢酸ナトリウム148mg(1.8mmol)を加え18時間撹拌した。放冷し、50mlの水にあけ、生じた結晶をろ集し、水：エタノール＝1：1で洗浄し目的物を得た。
収量：86mg(収率：48%)、融点：213-215℃、EIMS m/z (%)　352 (M+, 8), 250 (100), 140 (59)
　＜製造例３２：３－（２－オキソ－２－（ピペリジン－１－イル）エチル）－５－ベンジリデンロダニン（化合物A1-(XII)-4）の製造＞
　３－チオフェンアルデヒドの代わりにベンズアルデヒドを用いて、化合物A1-(XII)-3と同様の方法で製造した。
収率：17%、融点：180-182℃、EIMS m/z (%)　346 (M+, 12), 134 (72), 84 (100)
　＜製造例３３：３－（２－オキソ－３－（ピペリジン－１－イル）プロピル）－５－（３－チエニルメチリデン）ロダニン（化合物A1-(XII)-5）の製造＞
　ロダニン－３－酢酸の代わりにロダニン－３－プロピオン酸を用いて、化合物A1-(XII)-3と同様の方法で製造した。
収率：12%、EIMS m/z (%)　366 (M+, 1), 283 (17), 140 (70), 84 (100)
　＜製造例３４：３－（２－オキソ－３－（ピペリジン－１－イル）プロピル）－５－ベンジリデンロダニン（化合物A1-(XII)-6）の製造＞
　ロダニン－３－酢酸の代わりにロダニン－３－プロピオン酸を用い、３－チオフェンアルデヒドの代わりにベンズアルデヒドを用いて、化合物A1-(XII)-3と同様の方法で製造した。
収率：4%、融点：148-150℃、EIMS m/z (%)　366 (M+, 1), 283 (17), 140 (70), 84 (100)
　＜製造例３５：N，N－ジメチル－５－（３－チエニルメチリデン）－３－ロダニンアセトアミド（化合物A1-(XII)-7）の製造＞
　ピペリジンの代わりにジメチルアミン塩酸塩を用いて、化合物A1-(XII)-3と同様の方法で製造した。
収率：17%、融点：198-200℃、EIMS m/z (%)　312 (M+, 16), 269 (22), 140 (100)
　＜製造例３６：N，N－ジメチル－５－ベンジリデン－３－ロダニンアセトアミドの製造＞
　ピペリジンの代わりにジメチルアミン塩酸塩を用い、３－チオフェンアルデヒドの代わりにベンズアルデヒドを用いて、化合物A1-(XII)-3と同様の方法で製造した。
収率：12%、融点：204-206℃、EIMS m/z (%)　306 (M+, 19), 134 (100)
　＜参考製造例１：３－ベンジリデニルピロリジン－２，５－ジオン（化合物A1-(I)-1）の製造＞
　参考文献：Y. Luo, L. Ma, H. Zheng, L. Chen, R. Li, C. He, S. Yang, X. Ye, Z. Chen, Z. Li, Y. Gao, J. Han, G. He, L. Yang, and Y. Wei: J. Med. Chem. 53, 273-281 (2010) に従って製造した。 <Production Example 1: Production of 3- (3-pyridylmethylidenyl) pyrrolidine-2,5-dione (Compound A1- (I) -4)>
A solution of 3-triphenylphosphoranylidenyl succinimide (359 mg) and 3-pyridine aldehyde (107 mg) dissolved in 5 ml of methanol was refluxed for 5 hours. Thereafter, the reaction vessel was allowed to stand at room temperature for several hours. The precipitated solid was then filtered and recrystallized from methanol.
Yield: 112 mg (Yield: 60%)
IR νmax (KBr): 1750, 1723, 1660 cm -1
<Production Example 2: Production of 3- (2-furanylmethylidenyl) pyrrolidine-2,5-dione (Compound A1- (I) -5)>
It was produced by the same method as for compound A1- (I) -4 except that 2-furancarboxaldehyde was used.
Yield: 65%
IR νmax (KBr): 1758, 1701, 1645 cm -1
<Production Example 3: Production of 2,4-dioxo-5- (phenylmethyl) -3-thiazolidineacetic acid methyl ester (compound A2- (II) -3)>
A mixture of 5-benzyl-2,4-thiazolidinedione (1.10 g), methyl bromoacetate (1.62 g) and potassium carbonate (1.48 g) dissolved in acetonitrile was refluxed for 20 hours. After evaporating with solvent under reduced pressure, the residue was dissolved in ethyl acetate, washed with water and dried over anhydrous MgSO 4 . The solvent was then evaporated and the solid was recrystallized from methanol to give the pure ester.
Yield: 27 mg (Yield: 2%), liquid, IR νmax (KBr): 1750, 1698 cm −1
<Production Example 4: Production of 2,4-dioxo-5- (4-methylphenylmethyl) -3-thiazolidineacetic acid methyl ester (compound A2- (II) -1)>
Prepared by a method similar to that for compound A2- (II) -3 except that 5- (4-methylbenzyl) -2,4-thiazolidinedione was used.
Yield: 36%, liquid, IR νmax (KBr): 1745, 1690 cm -1
<Production Example 5: Production of 2,4-dioxo-5- (4-chlorophenylmethyl) -3-thiazolidineacetic acid methyl ester (compound A2- (II) -2)>
Prepared by a method similar to that for compound A2- (II) -3, except that 5- (4-chlorobenzyl) -2,4-thiazolidinedione was used.
Yield: 45%, IR νmax (KBr): 1742, 1693 cm -1
<Production Example 6: Production of 2,4-dioxo-5- (phenylmethyl) -3-thiazolidineacetic acid (Compound A2- (I) -1)>
13 of a mixture of 2,4-dioxo-5- (phenylmethyl) -3-thiazolidineacetic acid methyl ester (compound A2- (II) -3) (291 mg) and 2 ml concentrated hydrochloric acid dissolved in 10 ml acetic acid. Reflux for hours. The acetic acid was then evaporated and the residue was extracted with ethyl acetate. Thereafter, it was washed with water and dried over anhydrous MgSO 4 . Ethyl acetate was evaporated and the solidified residue was washed with hexane.
Yield: 70 mg (Yield: 24%), IR νmax (KBr): 1715, 1689 cm −1
<Production Example 7: Production of N, N-dimethyl-2,4-dioxo-5- (phenylmethyl) -3-thiazolidineacetamide (Compound A2- (IV) -2)>
5-benzylthiazolidine-2,4-dione compound A2- (V) -4 (206 mg), 2-chloro-N, N-dimethylacetamide (155 mg) and potassium carbonate (276 mg) dissolved in 15 ml of acetonitrile Was refluxed for 8 hours. Thereafter, the reaction mixture was cooled and filtered, and acetonitrile in the filtrate was volatilized. The residue was crystallized in ether and the filtered solid was washed with hexane.
Yield: 64 mg (Yield: 22%), liquid, IR νmax (KBr): 1687, 1667 cm −1
<Production Example 8: Production of N-methyl, N-phenyl-2,4-dioxo-5- (phenylmethyl) -3-thiazolidineacetamide (Compound A2- (I) -7)>
Prepared by a method similar to that for compound A2- (IV) -2.
Yield: 31%, IR νmax (KBr): 1686, 1662 cm -1
<Production Example 9: Production of N- {1- [2,4-dioxo-5- (phenylmethyl) -3-thiazolidinyl] acetyl} pyrrolidine (Compound A2- (I) -2)>
Prepared by a method similar to that for compound A2- (IV) -2.
Yield: 10%, liquid, IR νmax (KBr): 1684, 1661 cm -1
<Production Example 10: Production of N- {1- [2,4-dioxo-5- (phenylmethyl) -3-thiazolidinyl] acetyl} piperidine (Compound A2- (I) -3)>
Prepared by a method similar to that for compound A2- (IV) -2.
Yield: 14%, liquid, IR νmax (KBr): 1689, 1661 cm -1
<Production Example 11: Production of N, N-dimethyl-2,4-dioxo-5- (4-methoxyphenylmethyl) -3-thiazolidineacetamide (Compound A2- (III) -1)>
Prepared by a method similar to that for compound A2- (IV) -2.
Yield: 7%, liquid, IR νmax (KBr): 1689, 1660 cm -1
<Production Example 12: Production of N-methyl, N-phenyl-2,4-dioxo-5- (4-methoxyphenylmethyl) -3-thiazolidineacetamide (Compound A2- (I) -4)>
Prepared by a method similar to that for compound A2- (IV) -2.
Yield: 52%, IR νmax (KBr): 1681, 1660 cm -1
<Production Example 13: Production of N, N-dimethyl-2,4-dioxo-5- (4-methylphenylmethyl) -3-thiazolidineacetamide (Compound A2- (III) -2)>
Prepared by a method similar to that for compound A2- (IV) -2.
Yield: 20%, IR νmax (KBr): 1682, 1662 cm -1
<Production Example 14: Production of N-methyl, N-phenyl-2,4-dioxo-5- (4-methylphenylmethyl) -3-thiazolidineacetamide (Compound A2- (I) -5)>
Prepared by a method similar to that for compound A2- (IV) -2.
Yield: 37%, IR νmax (KBr): 1683, 1656 cm -1
<Production Example 15: Production of N, N-dimethyl-2,4-dioxo-5- (4-chlorophenylmethyl) -3-thiazolidineacetamide (Compound A2- (III) -3)>
Prepared by a method similar to that for compound A2- (IV) -2.
Yield: 49%, IR νmax (KBr): 1687, 1658 cm -1
<Production Example 16: Production of N-methyl, N-phenyl-2,4-dioxo-5- (4-chlorophenylmethyl) -3-thiazolidineacetamide (Compound A2- (I) -6)>
Prepared by a method similar to that for compound A2- (IV) -2.
Yield: 30%, IR νmax (KBr): 1687, 1662 cm -1
<Production Example 17: Production of 5- (4-chlorobenzylidenyl) thiazolidine-2,4-dione (Compound A1- (I) -10)>
Thiazolidine-2,4-dione (2.34 g, 0.02 mol) was dissolved in ethanol (30 ml), 4-chlorobenzaldehyde (2.81 g (0.02 mol)) and piperidine (1.36 g (0.016 mol)) were added, and the mixture was heated to reflux for 11 hours. The mixture was allowed to cool and the resulting yellow crystals were collected by filtration. The crystals were washed with water and hexane, and then recrystallized with ethanol to obtain the desired pale yellow crystals.
Yield: 3.49 g (Yield: 73%), Melting point: 210-212 ° C, EIMS m / z (%) 239 (M +, 93), 168 (100)
<Production Example 18: Production of 5- (2-chlorobenzylidenyl) thiazolidine-2,4-dione (Compound A1- (I) -11)>
The compound was produced in the same manner as for compound A1- (I) -10 using 2-chlorobenzaldehyde instead of 4-chlorobenzaldehyde.
Yield: 7%, Melting point: 187-189 ° C, EIMS m / z (%) 239 (M +, 20), 204 (85), 168 (100)
<Production Example 19: Production of 5- (3-chlorobenzylidenyl) thiazolidine-2,4-dione (Compound A1- (I) -12)>
The compound was prepared by a method similar to that for compound A1- (I) -10 using 3-chlorobenzaldehyde in place of 4-chlorobenzaldehyde.
Yield: 51%, melting point: 198-201 ° C, EIMS m / z (%) 239 (M +, 74), 168 (100)
<Production Example 20: Production of 5- (4-methoxybenzylidenyl) thiazolidine-2,4-dione (Compound A1- (I) -13)>
4-methoxybenzaldehyde was used in place of 4-chlorobenzaldehyde, and production was carried out in the same manner as for compound A1- (I) -10.
Yield: 54%, melting point: 230-232 ° C, EIMS m / z (%) 235 (M +, 83), 204 (10), 164 (100)
<Production Example 21: Production of 5- (3-pyridylmethylidenyl) thiazolidine-2,4-dione (Compound A1- (I) -14)>
The compound was produced in the same manner as for compound A1- (I) -10 using 3-pyridinealdehyde in place of 4-chlorobenzaldehyde.
Yield 52%, Melting point: 247-249 ° C, EIMS m / z (%) 206 (M +, 43), 135 (100)
<Production Example 22: Production of 5- (2-chlorobenzylidenyl) thiazolidine-2,4-dione (Compound A1- (I) -15)>
The compound was produced in the same manner as for compound A1- (I) -10 using 4-methylbenzaldehyde in place of 4-chlorobenzaldehyde.
Yield: 74%, Melting point: 190-193 ° C, EIMS m / z (%) 219 (M +, 13), 167 (43), 148 (100)
<Production Example 23: Production of 5- (3-benzyloxybenzylidenyl) thiazolidine-2,4-dione (Compound A1- (I) -16)>
587 mg (5 mmol) of thiazolidine-2,4-dione was dissolved in 5 ml of toluene, 610 mg (5 mmol) of 3-hydroxybenzaldehyde, 733 mg (6 mmol) of benzoic acid, and 426 mg (5 mmol) of piperidine were added, and the mixture was heated to reflux for 6 hours. The mixture was allowed to cool and the resulting crystals were collected by filtration. The crystal was washed with a solution of methanol: water = 1: 1 to obtain 5- (3-hydroxybenzylidenyl) thiazolidine-2,4-dione. Yield: 945 mg (Yield: 85%)
664 mg (3 mmol) of the obtained 5- (3-hydroxybenzylidenyl) thiazolidine-2,4-dione was dissolved in acetonitrile, 380 mg (3 mmol) of benzyl chloride and 497 mg (3.6 mmol) of potassium carbonate were added, and the mixture was heated to reflux for 11 hours. . After allowing to cool, the mixture was concentrated, water was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, filtered and concentrated. The residue was purified by thin layer chromatography (chloroform: methanol = 30: 1) to obtain the desired product.
Yield: 30 mg (Yield: 3%), Melting point: 207-209 ° C, EIMS m / z (%) 311 (M +, 100), 184 (27)
<Production Example 24: Production of N-methyl-5-benzylidenylthiazolidine-2,4-dione (Compound A1- (XI) -1)>
5-Benzylidenylthiazolidine-2,4-dione (205 mg, 1 mmol) was dissolved in acetonitrile, potassium carbonate (276 mg, 2 mmol) and methyl iodide (170 mg, 1.2 mmol) were added, and the mixture was stirred at 50 ° C. for 1.5 hours. After filtration, the filtrate was concentrated, and the residue was washed with ether to obtain the desired product.
Yield: 126 mg (Yield: 58%), Melting point: 134-136 ° C., EIMS m / z (%) 219 (M +, 83), 134 (100)
<Production Example 25: Production of N-methyl-5- (3-phenoxybenzylidenyl) thiazolidine-2,4-dione (Compound A1- (XI) -2)>
5- (3-phenoxybenzylidenyl) thiazolidine-2,4-dione (5- (4-chlorobenzylidenyl) thiazolidine-2,4-dione instead of 5-benzylidenylthiazolidine-2,4-dione In the same manner as compound A1- (XI) -1.
Yield: 74%, Melting point: 166-168 ° C, EIMS m / z (%) 311 (M +, 88), 226 (100)
<Production Example 26: Production of N-benzyl-5-benzylidenylthiazolidine-2,4-dione (Compound A1- (XI) -3)>
It was prepared in the same manner as in compound A1- (XI) -1, using benzyl chloride instead of methyl iodide.
Yield: 59%, melting point: 138-141 ° C, EIMS m / z (%) 295 (M +, 78), 134 (100), 91 (90)
<Production Example 27: Production of N-phenyl-5-benzylidenylthiazolidine-2,4-dione (Compound A1- (XI) -4))>
1.80 g (15 mmol) of ethyl thioglycolate was dissolved in 10 ml of toluene, 2.03 g (15 mmol) of phenyl isocyanate was added, 20 mg of sodium metal was added, and the mixture was heated to reflux for 13.5 hours. The mixture was allowed to cool and the resulting crystals were collected by filtration. The crystals were dissolved in ethanol, activated carbon was added, and the mixture was filtered while hot. The crystals of N-phenylthiazolidine-2,4-dione that were allowed to cool were collected by filtration. Yield: 1.17 g (Yield: 41%)
The obtained N-phenylthiazolidine-2,4-dione (288 mg, 1.5 mmol) was dissolved in ethanol (20 ml), benzaldehyde and piperidine (102 mg, 1.2 mmol) were added, and the mixture was heated to reflux for 12 hours. The mixture was allowed to cool, and the resulting crystals were collected by filtration, and the crystals were washed with hexane to obtain the desired product.
Yield: 71 mg (17% yield), melting point: 218-220 ° C., EIMS m / z (%) 281 (M +, 88), 134 (100)
<Production Example 28: Production of N- (2,6-dichloro-4-pyridylmethyl) -5-benzylidenylthiazolidine-2,4-dione (Compound A1- (XI) -5)>
Prepared in the same manner as for compound A1- (XI) -1, using 2,6-dichloro-4-pyridylmethyl chloride in place of methyl iodide.
Yield: 26%, melting point: 190-192 ° C, EIMS m / z (%) 364 (M +, 80), 134 (100)
<Production Example 29: Production of 5-benzylidenylrhodanine-3-acetic acid methyl ester (Compound A1- (XII) -2)>
To 20 ml of acetic acid heated to 80 ° C., 1.06 g (10 mmol) of benzaldehyde and 1.33 g (10 mmol) of rhodanine were added and stirred for 30 minutes, and then 2.87 g (35 mmol) of anhydrous sodium acetate was added and stirred for 1 hour. The mixture was allowed to cool, poured into 200 ml of water, and the resulting crystals were collected by filtration. The crystals were washed with a solution of water: ethanol = 1: 1 to obtain 5-benzylidenylrhodanine. Yield: 1.66 g (Yield: 75%), Melting point: 212-214 ° C
The obtained 5-benzylidenylrhodanine (221 mg, 1 mmol) was dissolved in DMF (10 ml), sodium hydride (60%) (48 mg, 1.2 mmol) was added, and the mixture was stirred at room temperature for 30 minutes. To this suspension, 184 mg (1.2 mmol) of methyl bromoacetate was added and stirred at 80 ° C. for 13 hours. DMF was distilled off, water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate, filtered and concentrated to obtain the desired product.
Yield: 150 mg (Yield: 51%), Melting point: 139-141 ° C., EIMS m / z (%) 293 (M +, 85), 162 (80), 134 (100)
<Production Example 30: Production of 5-benzylidenylrhodanine-3-acetic acid methyl ester (Compound A1- (XII) -1)>
The compound was produced in the same manner as for compound A1- (XII) -2 using 3-thiophenaldehyde instead of benzaldehyde.
Yield: 70%, Melting point: 157-159 ° C, EIMS m / z (%) 299 (M +, 22), 226 (31), 140 (100)
<Production Example 31: Production of 3- (2-oxo-2- (piperidin-1-yl) ethyl) -5- (3-thienylmethylidene) rhodanine (Compound A1- (XII) -3)>
Rhodanine-3-acetic acid was dissolved in 15 ml of dichloromethane, and 192 mg (1 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, 122 mg (1 mmol) of 4-dimethylaminopyridine and 85 mg (1 mmol) of piperidine were added at room temperature. For 13 hours. The reaction solution was washed with saturated aqueous sodium hydrogen carbonate, 1% HCl and water, dried over magnesium sulfate, filtered and concentrated. The residue was recrystallized from methanol to give 3- (2-oxo-2- (piperidin-1-yl) ethyl) -rhodanine. Yield: 46 mg (Yield: 18%), Melting point: 173-175 ° C
3 ml of acetic acid was heated to 80 ° C., and 56 mg (0.5 mmol) of 3-thiophenaldehyde and 129 mg (0.5 mmol) of 3- (2-oxo-2- (piperidin-1-yl) ethyl) -rhodanine were added and stirred for 30 minutes. did. Thereafter, 148 mg (1.8 mmol) of anhydrous sodium acetate was added and stirred for 18 hours. The mixture was allowed to cool, poured into 50 ml of water, and the resulting crystals were collected by filtration and washed with water: ethanol = 1: 1 to obtain the desired product.
Yield: 86 mg (yield: 48%), melting point: 213-215 ° C, EIMS m / z (%) 352 (M +, 8), 250 (100), 140 (59)
<Production Example 32: Production of 3- (2-oxo-2- (piperidin-1-yl) ethyl) -5-benzylidenerhodanine (Compound A1- (XII) -4)>
It was prepared in the same manner as for compound A1- (XII) -3 using benzaldehyde instead of 3-thiophenaldehyde.
Yield: 17%, Melting point: 180-182 ° C, EIMS m / z (%) 346 (M +, 12), 134 (72), 84 (100)
<Production Example 33: Production of 3- (2-oxo-3- (piperidin-1-yl) propyl) -5- (3-thienylmethylidene) rhodanine (Compound A1- (XII) -5)>
It was produced in the same manner as for compound A1- (XII) -3, using rhodanine-3-propionic acid instead of rhodanine-3-acetic acid.
Yield: 12%, EIMS m / z (%) 366 (M +, 1), 283 (17), 140 (70), 84 (100)
<Production Example 34: Production of 3- (2-oxo-3- (piperidin-1-yl) propyl) -5-benzylidenerhodanine (Compound A1- (XII) -6)>
It was prepared in the same manner as Compound A1- (XII) -3 using rhodanine-3-propionic acid in place of rhodanine-3-acetic acid and benzaldehyde in place of 3-thiophenealdehyde.
Yield: 4%, melting point: 148-150 ° C, EIMS m / z (%) 366 (M +, 1), 283 (17), 140 (70), 84 (100)
<Production Example 35: Production of N, N-dimethyl-5- (3-thienylmethylidene) -3-rhodanine acetamide (Compound A1- (XII) -7)>
It was prepared in the same manner as in compound A1- (XII) -3, using dimethylamine hydrochloride instead of piperidine.
Yield: 17%, Melting point: 198-200 ° C, EIMS m / z (%) 312 (M +, 16), 269 (22), 140 (100)
<Production Example 36: Production of N, N-dimethyl-5-benzylidene-3-rhodanine acetamide>
Prepared in the same manner as for compound A1- (XII) -3, using dimethylamine hydrochloride instead of piperidine and benzaldehyde instead of 3-thiophenaldehyde.
Yield: 12%, melting point: 204-206 ° C, EIMS m / z (%) 306 (M +, 19), 134 (100)
<Reference Production Example 1: Production of 3-benzylidenylpyrrolidine-2,5-dione (Compound A1- (I) -1)>
References: Y. Luo, L. Ma, H. Zheng, L. Chen, R. Li, C. He, S. Yang, X. Ye, Z. Chen, Z. Li, Y. Gao, J. Han , G. He, L. Yang, and Y. Wei: J. Med. Chem. 53, 273-281 (2010).
　＜参考製造例２：３－（４－クロロベンジリデニル）ピロリジン－２，５－ジオン（化合物A1-(I)-2）の製造＞
　参考文献：Y. Luo, L. Ma, H. Zheng, L. Chen, R. Li, C. He, S. Yang, X. Ye, Z. Chen, Z. Li, Y. Gao, J. Han, G. He, L. Yang, and Y. Wei: J. Med. Chem. 53, 273-281 (2010) に従って製造した。 <Reference Production Example 2: Production of 3- (4-chlorobenzylidenyl) pyrrolidine-2,5-dione (Compound A1- (I) -2)>
References: Y. Luo, L. Ma, H. Zheng, L. Chen, R. Li, C. He, S. Yang, X. Ye, Z. Chen, Z. Li, Y. Gao, J. Han , G. He, L. Yang, and Y. Wei: J. Med. Chem. 53, 273-281 (2010).
　＜参考製造例３：３－（４－メトキシベンジリデニル）ピロリジン－２，５－ジオン（化合物A1-(I)-3）の製造＞
　参考文献：Y. Luo, L. Ma, H. Zheng, L. Chen, R. Li, C. He, S. Yang, X. Ye, Z. Chen, Z. Li, Y. Gao, J. Han, G. He, L. Yang, and Y. Wei: J. Med. Chem. 53, 273-281 (2010) に従って製造した。 <Reference Production Example 3: Production of 3- (4-methoxybenzylidenyl) pyrrolidine-2,5-dione (Compound A1- (I) -3)>
References: Y. Luo, L. Ma, H. Zheng, L. Chen, R. Li, C. He, S. Yang, X. Ye, Z. Chen, Z. Li, Y. Gao, J. Han , G. He, L. Yang, and Y. Wei: J. Med. Chem. 53, 273-281 (2010).
　＜参考製造例４：５－（２－ヒドロキシベンジリデニル）チアゾリジン－２，４－ジオン（化合物A1-(I)-6）の製造＞
　参考文献：S. Venkatesan and R. Singh: Int. J. Chem. Pharm. Sci. 1, 17-23 (2010) に従って製造した。 <Reference Production Example 4: Production of 5- (2-hydroxybenzylidenyl) thiazolidine-2,4-dione (Compound A1- (I) -6)>
Reference: S. Venkatesan and R. Singh: Int. J. Chem. Pharm. Sci. 1, 17-23 (2010).
　＜参考製造例５：５－（３－ヒドロキシベンジリデニル）チアゾリジン－２，４－ジオン（化合物A1-(I)-7）の製造＞
　参考文献：Y. Luo, L. Ma, H. Zheng, L. Chen, R. Li, C. He, S. Yang, X. Ye, Z. Chen, Z. Li, Y. Gao, J. Han, G. He, L. Yang, and Y. Wei: J. Med. Chem. 53, 273-281 (2010) に従って製造した。 <Reference Production Example 5: Production of 5- (3-hydroxybenzylidenyl) thiazolidine-2,4-dione (Compound A1- (I) -7)>
References: Y. Luo, L. Ma, H. Zheng, L. Chen, R. Li, C. He, S. Yang, X. Ye, Z. Chen, Z. Li, Y. Gao, J. Han , G. He, L. Yang, and Y. Wei: J. Med. Chem. 53, 273-281 (2010).
　＜参考製造例６：５－（４－ヒドロキシベンジリデニル）チアゾリジン－２，４－ジオン（化合物A1-(I)-8）の製造＞
　参考文献：Y. Luo, L. Ma, H. Zheng, L. Chen, R. Li, C. He, S. Yang, X. Ye, Z. Chen, Z. Li, Y. Gao, J. Han, G. He, L. Yang, and Y. Wei: J. Med. Chem. 53, 273-281 (2010) 、および、参考文献：D. Rakowitz, R. Maccari, R. Ottana, M. G. Vigorita: Bioorg. Med. Chem. 14, 567-574 (2006) に従って製造した。 <Reference Production Example 6: Production of 5- (4-hydroxybenzylidenyl) thiazolidine-2,4-dione (Compound A1- (I) -8)>
References: Y. Luo, L. Ma, H. Zheng, L. Chen, R. Li, C. He, S. Yang, X. Ye, Z. Chen, Z. Li, Y. Gao, J. Han , G. He, L. Yang, and Y. Wei: J. Med. Chem. 53, 273-281 (2010) and references: D. Rakowitz, R. Maccari, R. Ottana, MG Vigorita: Bioorg Med. Chem. 14, 567-574 (2006).
　＜参考製造例７：５－（４－ベンジルオキシベンジリデニル）チアゾリジン－２，４－ジオン（化合物A1-(I)-9）の製造＞
　参考文献：R. G. Giles, N. J. Lewis, J. K. Quick, M. J. Sasse, M. W. J. Urquhart and L. Yousef: Tetrahedron, 56, 4531-4537 (2000) 、および、参考文献：D. Rakowitz, R. Maccari, R. Ottana, M. G. Vigorita: Bioorg. Med. Chem. 14, 567-574 (2006) に従って製造した。 <Reference Production Example 7: Production of 5- (4-benzyloxybenzylidenyl) thiazolidine-2,4-dione (Compound A1- (I) -9)>
References: RG Giles, NJ Lewis, JK Quick, MJ Sasse, MWJ Urquhart and L. Yousef: Tetrahedron, 56, 4531-4537 (2000), and reference: D. Rakowitz, R. Maccari, R. Ottana, Prepared according to MG Vigorita: Bioorg. Med. Chem. 14, 567-574 (2006).
　＜参考製造例８：３－トリフェニルホスホラニリデニルスクシンイミド（化合物A1-(II)-1）の製造＞
　参考文献：T. Boettcher and S.A. Sieber: J. Am. Chem. Soc., 132, 6964-6972 (2010) に従って製造した。 <Reference Production Example 8: Production of 3-triphenylphosphoranylidenyl succinimide (Compound A1- (II) -1)>
Reference: Prepared according to T. Boettcher and SA Sieber: J. Am. Chem. Soc., 132, 6964-6972 (2010).
　＜参考製造例９：５－ベンジルチアゾリジン－２，４－ジオン（化合物A2-(V)-4）の製造＞
　参考文献：R. G. Giles, N. J. Lewis, J. K. Quick, M. J. Sasse, M. W. J. Urquhart and L. Yousef: Tetrahedron, 56, 4531-4537 (2000) に従って製造した。 <Reference Production Example 9: Production of 5-benzylthiazolidine-2,4-dione (Compound A2- (V) -4)>
Reference: Prepared according to R. G. Giles, N. J. Lewis, J. K. Quick, M. J. Sasse, M. W. J. Urquhart and L. Yousef: Tetrahedron, 56, 4531-4537 (2000).
　＜参考製造例１０：２，４－ジオキソ－５－（４－メトキシフェニルメチル）－３－チアゾリジン酢酸メチルエステル（化合物A2-(IV)-1）の製造＞
　参考文献：D. Rakowitz, R. Maccari, R. Ottana, M. G. Vigorita: Bioorg. Med. Chem. 14, 567-574 (2006) に従って製造した。 <Reference Production Example 10: Production of 2,4-dioxo-5- (4-methoxyphenylmethyl) -3-thiazolidineacetic acid methyl ester (Compound A2- (IV) -1)>
Reference: Prepared according to D. Rakowitz, R. Maccari, R. Ottana, M. G. Vigorita: Bioorg. Med. Chem. 14, 567-574 (2006).
　＜参考製造例１１：５－（４－メトキシベンジル）チアゾリジン－２，４－ジオン（化合物A2-(V)-1）の製造＞
　参考文献：R. G. Giles, N. J. Lewis, J. K. Quick, M. J. Sasse, M. W. J. Urquhart and L. Yousef: Tetrahedron, 56, 4531-4537 (2000) 、および、参考文献：D. Rakowitz, R. Maccari, R. Ottana, M. G. Vigorita: Bioorg. Med. Chem. 14, 567-574 (2006) に従って製造した。 <Reference Production Example 11: Production of 5- (4-methoxybenzyl) thiazolidine-2,4-dione (Compound A2- (V) -1)>
References: RG Giles, NJ Lewis, JK Quick, MJ Sasse, MWJ Urquhart and L. Yousef: Tetrahedron, 56, 4531-4537 (2000), and reference: D. Rakowitz, R. Maccari, R. Ottana, Prepared according to MG Vigorita: Bioorg. Med. Chem. 14, 567-574 (2006).
　＜参考製造例１２：５－（４－ベンジルオキシベンジル）チアゾリジン－２，４－ジオン（化合物A2-(V)-5）の製造＞
　参考文献：R. G. Giles, N. J. Lewis, J. K. Quick, M. J. Sasse, M. W. J. Urquhart and L. Yousef: Tetrahedron, 56, 4531-4537 (2000) 、および、参考文献：D. Rakowitz, R. Maccari, R. Ottana, M. G. Vigorita: Bioorg. Med. Chem. 14, 567-574 (2006) に従って製造した。 <Reference Production Example 12: Production of 5- (4-benzyloxybenzyl) thiazolidine-2,4-dione (Compound A2- (V) -5)>
References: RG Giles, NJ Lewis, JK Quick, MJ Sasse, MWJ Urquhart and L. Yousef: Tetrahedron, 56, 4531-4537 (2000), and reference: D. Rakowitz, R. Maccari, R. Ottana, Prepared according to MG Vigorita: Bioorg. Med. Chem. 14, 567-574 (2006).
　＜参考製造例１３：５－（４－クロロベンジル）チアゾリジン－２，４－ジオン（化合物A2-(V)-3）の製造＞
　参考文献：T. Sohda, K. Mizuno, E. Imamiya, H. Tawada, K. Meguro, Y. Kawamatsu, and Y. Yamamoto: Chem. Pharm. Bull. 30, 3601-3616 (1982) に従って製造した。 <Reference Production Example 13: Production of 5- (4-chlorobenzyl) thiazolidine-2,4-dione (Compound A2- (V) -3)>
Reference: T. Sohda, K. Mizuno, E. Imamiya, H. Tawada, K. Meguro, Y. Kawamatsu, and Y. Yamamoto: Chem. Pharm. Bull. 30, 3601-3616 (1982).
　＜参考製造例１４：５－（４－メチルベンジル）チアゾリジン－２，４－ジオン（化合物A2-(V)-2）の製造＞
　参考文献：T. Sohda, K. Mizuno, T. Hirata, Y. Maki, Y. Kawamatsu: Chem. Pharm. Bull. 31 (2), 560-569 (1983) に従って製造した。
収率：２２％、融点：８１～８４℃。 <Reference Production Example 14: Production of 5- (4-methylbenzyl) thiazolidine-2,4-dione (Compound A2- (V) -2)>
Reference: T. Sohda, K. Mizuno, T. Hirata, Y. Maki, Y. Kawamatsu: Chem. Pharm. Bull. 31 (2), 560-569 (1983).
Yield: 22%, melting point: 81-84 ° C.
　上記の合成した誘導体のスペクトルデータを表９に示す。 Table 9 shows the spectrum data of the synthesized derivatives.
Figure JPOXMLDOC01-appb-T000061
Figure JPOXMLDOC01-appb-T000061
　次に、製剤例および試験例を示す。なお、担体（希釈剤）および助剤、その混合比は広い範囲で変更し得るものとする。各製剤例の「部」は重量部を表す。 Next, formulation examples and test examples are shown. The carrier (diluent) and auxiliary agent, and the mixing ratio thereof can be changed within a wide range. “Parts” in each formulation example represents parts by weight.
　＜製剤例１：水和剤＞
化合物A1-(I)-4　　　　　５０　部
リグニンスルホン酸塩　　　５　部
アルキルスルホン酸塩　　　３　部
珪藻土　　　　　　　　　４２　部
を粉砕混合して水和剤とし、水に分散して使用した。 <Formulation example 1: wettable powder>
Compound A1- (I) -4 50 parts lignin sulfonate 5 parts alkyl sulfonate 3 parts diatomaceous earth 42 parts were pulverized and mixed to obtain a wettable powder, and dispersed in water for use.
　＜製剤例２：粉剤＞
化合物A1-(I)-4　　　　　　３　部
クレー　　　　　　　　　４０　部
タルク　　　　　　　　　５７　部
を粉砕混合し、散粉として使用した。 <Formulation Example 2: Powder>
Compound A1- (I) -4 3 parts Clay 40 parts Talc 57 parts were ground and mixed and used as dust.
　＜製剤例３：粒剤＞
化合物A1-(I)-4　　　　　　５　部
ベントナイト　　　　　　４３　部
クレー　　　　　　　　　４５　部
リグニンスルホン酸塩　　　７　部
を均一に混合しさらに水を加えて練り合わせ、押し出し式造粒機で粒状に加工乾燥して粒剤とした。 <Formulation Example 3: Granule>
Compound A1- (I) -4 5 parts Bentonite 43 parts Clay 45 parts Lignin sulfonate 7 parts are mixed uniformly, kneaded with water, processed into granules in an extrusion granulator and dried into granules. .
　＜製剤例４：乳剤＞
化合物A1-(I)-4　　　　　　　　　　　　　　　２０　部
ポリオキシエチレンアルキルアリールエーテル　１０　部
ポリオキシエチレンソルビタンモノラウレート　　３　部
キシレン　　　　　　　　　　　　　　　　　　６７　部
を均一に混合溶解して乳剤とした。 <Formulation Example 4: Emulsion>
Compound A1- (I) -4 20 parts polyoxyethylene alkyl aryl ether 10 parts polyoxyethylene sorbitan monolaurate 3 parts Xylene 67 parts were mixed and dissolved uniformly to give an emulsion.
　＜製剤例５：水和剤＞
化合物A2-(I)-1　　　　　５０　部
リグニンスルホン酸塩　　　５　部
アルキルスルホン酸塩　　　３　部
珪藻土　　　　　　　　　４２　部
を粉砕混合して水和剤とし、水に分散して使用した。 <Formulation example 5: wettable powder>
Compound A2- (I) -1 50 parts lignin sulfonate 5 parts alkyl sulfonate 3 parts diatomaceous earth 42 parts were pulverized and mixed to obtain a wettable powder, and dispersed in water for use.
　＜製剤例６：粉剤＞
化合物A2-(I)-1　　　　　　３　部
クレー　　　　　　　　　４０　部
タルク　　　　　　　　　５７　部
を粉砕混合し、散粉として使用した。 <Formulation Example 6: Powder>
Compound A2- (I) -1 3 parts Clay 40 parts Talc 57 parts were ground and mixed and used as dust.
　＜製剤例７：粒剤＞
化合物A2-(I)-1　　　　　　５　部
ベントナイト　　　　　　４３　部
クレー　　　　　　　　　４５　部
リグニンスルホン酸塩　　　７　部
を均一に混合しさらに水を加えて練り合わせ、押し出し式造粒機で粒状に加工乾燥して粒剤とした。 <Formulation Example 7: Granule>
Compound A2- (I) -1 5 parts Bentonite 43 parts Clay 45 parts Lignin sulfonate 7 parts are mixed uniformly, kneaded with water and processed into granules by an extrusion granulator to form granules .
　＜製剤例８：乳剤＞
化合物A2-(I)-1　　　　　　　　　　　　　　　２０　部
ポリオキシエチレンアルキルアリールエーテル　１０　部
ポリオキシエチレンソルビタンモノラウレート　　３　部
キシレン　　　　　　　　　　　　　　　　　　６７　部
を均一に混合溶解して乳剤とした。 <Formulation Example 8: Emulsion>
Compound A2- (I) -1 20 parts polyoxyethylene alkyl aryl ether 10 parts polyoxyethylene sorbitan monolaurate 3 parts Xylene 67 parts were mixed and dissolved uniformly to prepare an emulsion.
　＜試験例１：病原菌に対する抗菌性試験＞
　本試験例では、各種植物病原性糸状菌に対する本発明の化合物の抗菌性を試験した。 <Test Example 1: Antibacterial test against pathogenic bacteria>
In this test example, the antibacterial properties of the compounds of the present invention against various phytopathogenic fungi were tested.
　各化合物をジメチルスルホキシド（ＤＭＳＯ）に溶解し、６０℃前後のＰＤＡ培地（ポテト－デキストロース－アガー培地）に加えた。三角フラスコ内でよく混合した後、シャーレ内に流し固化させて、所定の濃度の化合物を含む平板培地（薬剤処理平板培地）を作製した。 Each compound was dissolved in dimethyl sulfoxide (DMSO) and added to a PDA medium (potato-dextrose-agar medium) at around 60 ° C. After mixing well in an Erlenmeyer flask, it was poured into a petri dish and solidified to prepare a plate medium (drug-treated plate medium) containing a compound of a predetermined concentration.
　一方、予め平板培地上で培養した供試菌を直径４ｍｍのコルクボーラーで打ち抜き、上記の化合物を含む平板培地上に接種した。接種後、各菌の生育適温（例えば、LIST OF CULTURES 1996 microorganisms 10th edition、財団法人発酵研究所等の文献を参照）にて１～１４日間培養（表８参照）し、菌の生育の状態を菌そう直径の測定により評価した。化合物を含む平板培地上で得られた菌の生育程度を、化合物無添加における菌の生育程度と比較して、下記式により菌糸伸長抑制率を求めた。なお、下記式中、Ｒは菌糸伸長抑制率（％）、ｄｃは無処理平板上菌そう直径、ｄｔは薬剤処理平板上菌そう直径を示している。
Ｒ（％）＝１００×（ｄｃ－ｄｔ）／ｄｃ On the other hand, a test bacterium previously cultured on a plate medium was punched with a cork borer having a diameter of 4 mm and inoculated on a plate medium containing the above compound. After inoculation, the cells are cultured for 1 to 14 days (see Table 8) at the optimal temperature for growth of each fungus (see, for example, LIST OF CULTURES 1996 microorganisms 10th edition, literature from the Institute for Fermentation, etc.). Evaluation was made by measuring the diameter of the fungus. The growth degree of the fungus obtained on the plate medium containing the compound was compared with the growth degree of the fungus without the addition of the compound, and the hyphal elongation inhibition rate was determined by the following formula. In the following formula, R represents the hyphal elongation inhibition rate (%), dc represents the diameter of the fungus on the untreated plate, and dt represents the diameter of the fungus on the drug-treated plate.
R (%) = 100 × (dc−dt) / dc
Figure JPOXMLDOC01-appb-T000062
Figure JPOXMLDOC01-appb-T000062
　結果を、表１１に示す基準にしたがって３段階評価した。抗菌性指数が大きいほど、抗菌性に優れていることを示す。 The results were evaluated in three stages according to the criteria shown in Table 11. It shows that it is excellent in antibacterial property, so that an antibacterial index is large.
Figure JPOXMLDOC01-appb-T000063
Figure JPOXMLDOC01-appb-T000063
　各菌種について得られた結果を表１２～表２０に示す。 The results obtained for each bacterial species are shown in Tables 12 to 20.
Figure JPOXMLDOC01-appb-T000064
Figure JPOXMLDOC01-appb-T000064
Figure JPOXMLDOC01-appb-T000065
Figure JPOXMLDOC01-appb-T000065
Figure JPOXMLDOC01-appb-T000066
Figure JPOXMLDOC01-appb-T000066
Figure JPOXMLDOC01-appb-T000067
Figure JPOXMLDOC01-appb-T000067
Figure JPOXMLDOC01-appb-T000068
Figure JPOXMLDOC01-appb-T000068
Figure JPOXMLDOC01-appb-T000069
Figure JPOXMLDOC01-appb-T000069
Figure JPOXMLDOC01-appb-T000070
Figure JPOXMLDOC01-appb-T000070
Figure JPOXMLDOC01-appb-T000071
Figure JPOXMLDOC01-appb-T000071
Figure JPOXMLDOC01-appb-T000072
Figure JPOXMLDOC01-appb-T000072
　＜試験例２：病原菌に対する抗菌性試験＞
　試験例１と同様の方法により、各種植物病原性糸状菌に対する本発明の化合物の抗菌性を試験した。その結果を、表１１に示す基準にしたがって３段階評価した。各菌種について得られた結果を表２１～表３９に示す。 <Test Example 2: Antibacterial test against pathogenic bacteria>
The antibacterial properties of the compounds of the present invention against various phytopathogenic fungi were tested in the same manner as in Test Example 1. The results were evaluated in three stages according to the criteria shown in Table 11. The results obtained for each bacterial species are shown in Table 21 to Table 39.
Figure JPOXMLDOC01-appb-T000073
Figure JPOXMLDOC01-appb-T000073
Figure JPOXMLDOC01-appb-T000074
Figure JPOXMLDOC01-appb-T000074
Figure JPOXMLDOC01-appb-T000075
Figure JPOXMLDOC01-appb-T000075
Figure JPOXMLDOC01-appb-T000076
Figure JPOXMLDOC01-appb-T000076
Figure JPOXMLDOC01-appb-T000077
Figure JPOXMLDOC01-appb-T000077
Figure JPOXMLDOC01-appb-T000078
Figure JPOXMLDOC01-appb-T000078
Figure JPOXMLDOC01-appb-T000079
Figure JPOXMLDOC01-appb-T000079
Figure JPOXMLDOC01-appb-T000080
Figure JPOXMLDOC01-appb-T000080
Figure JPOXMLDOC01-appb-T000081
Figure JPOXMLDOC01-appb-T000081
Figure JPOXMLDOC01-appb-T000082
Figure JPOXMLDOC01-appb-T000082
Figure JPOXMLDOC01-appb-T000083
Figure JPOXMLDOC01-appb-T000083
Figure JPOXMLDOC01-appb-T000084
Figure JPOXMLDOC01-appb-T000084
Figure JPOXMLDOC01-appb-T000085
Figure JPOXMLDOC01-appb-T000085
Figure JPOXMLDOC01-appb-T000086
Figure JPOXMLDOC01-appb-T000086
Figure JPOXMLDOC01-appb-T000087
Figure JPOXMLDOC01-appb-T000087
Figure JPOXMLDOC01-appb-T000088
Figure JPOXMLDOC01-appb-T000088
Figure JPOXMLDOC01-appb-T000089
Figure JPOXMLDOC01-appb-T000089
Figure JPOXMLDOC01-appb-T000090
Figure JPOXMLDOC01-appb-T000090
Figure JPOXMLDOC01-appb-T000091
Figure JPOXMLDOC01-appb-T000091
　＜試験例３：病原菌に対する抗菌性試験＞
　本試験例では、Pyricularia oryzae（P.o）に対する抗菌性を試験した。ジメチルスルホキシド（ＤＭＳＯ）に化合物を溶解し、その薬液１μｌを平底９６穴マイクロプレートに添加後、イネいもち病菌（Pyricularia oryzae）の胞子懸濁液（約１×１０５ｃｅｌｌｓ／ｍｌ）を９９μｌ加え、よく攪拌した（化合物の終濃度１０ｍｇ／Ｌ）。薬剤を含まないＤＭＳＯを１μｌ添加した薬剤無添加区も設けた。２０℃で約４日間培養した後、吸光度（５９５ｎｍ）を測定し、下記式により菌糸伸長抑制率を求めた。 <Test Example 3: Antibacterial test against pathogenic bacteria>
In this test example, antibacterial activity against Pyricularia oryzae (Po) was tested. Dissolve the compound in dimethyl sulfoxide (DMSO), add 1 μl of the drug solution to a flat-bottom 96-well microplate, add 99 μl of a spore suspension (about 1 × 10 5 cells / ml) of rice blast fungus (Pyricularia oryzae), and stir well. (Final concentration of compound 10 mg / L). A non-drug-added section with 1 μl of DMSO containing no drug was also provided. After culturing at 20 ° C. for about 4 days, the absorbance (595 nm) was measured, and the mycelial elongation suppression rate was determined by the following formula.
　なお、下記式中、Ｒは菌糸伸長抑制率（％）、ｄｃは薬剤無添加区の吸光度、ｄｔは薬剤添加区の吸光度を示している。
Ｒ＝１００（ｄｃ－ｄｔ）／ｄｃ
　結果を、上記の表１１に示す基準にしたがって３段階で評価した。結果を表４０に示す。 In the following formula, R represents the hyphal elongation inhibition rate (%), dc represents the absorbance in the drug-free group, and dt represents the absorbance in the drug-added group.
R = 100 (dc−dt) / dc
The results were evaluated in three stages according to the criteria shown in Table 11 above. The results are shown in Table 40.
Figure JPOXMLDOC01-appb-T000092
Figure JPOXMLDOC01-appb-T000092
　＜試験例４：茎葉散布処理によるコムギ赤かび病防除効果試験＞
　開花期のコムギ穂部（品種：農林６１号）に、製剤例１のような水和剤にした各化合物を、水で５００ｍｇ／Ｌに希釈懸濁し、１，０００Ｌ／ｈａの割合で散布した。穂部を風乾した後、コムギ赤かび病菌の胞子（２×１０５個／ｍｌに調整、終濃度６０ｐｐｍのグラミンＳを含む）を噴霧接種し、２０℃、高湿度条件下に保持した。接種後、５日目にコムギ赤かび病の発病度を表４１に示す基準により評価した。その結果を表４２に示した。 <Test Example 4: Wheat red mold control effect test by foliar spray treatment>
Each compound made into a wettable powder as in Formulation Example 1 was diluted with water to 500 mg / L and sprayed at a rate of 1,000 L / ha on the wheat ears at the flowering stage (variety: Norin 61). . After the head was air-dried, it was spray-inoculated with spores of wheat red mold fungus (adjusted to 2 × 10 5 cells / ml, containing Gramine S having a final concentration of 60 ppm), and kept at 20 ° C. under high humidity conditions. On the fifth day after inoculation, the severity of wheat red mold was evaluated according to the criteria shown in Table 41. The results are shown in Table 42.
Figure JPOXMLDOC01-appb-T000093
Figure JPOXMLDOC01-appb-T000093
Figure JPOXMLDOC01-appb-T000094
Figure JPOXMLDOC01-appb-T000094
　＜試験例５：茎葉散布処理によるコムギうどんこ病防除効果試験＞
　角型プラスチックポット（６ｃｍ×６ｃｍ）を用いて栽培した第２葉期のコムギ（品種：農林６１号）に、製剤例１のような水和剤にした各化合物を、水で所定濃度に希釈懸濁し、１，０００Ｌ／ｈａの割合で散布した。散布葉を風乾した後、コムギうどんこ病に感染したコムギ苗から、うどんこ病菌をふりかけ接種した。接種後、１１日目にコムギうどんこ病の発病度を表４３に示す基準により評価した。その結果を表４４に示した。 <Test Example 5: Wheat powdery mildew control effect test by foliar spray treatment>
Each compound made into wettable powder as in Formulation Example 1 was diluted with water to a predetermined concentration in the second leaf wheat (variety: Norin 61) grown using a square plastic pot (6cm x 6cm) It was suspended and sprayed at a rate of 1,000 L / ha. After airing the sprayed leaves, wheat seedlings infected with wheat powdery mildew were sprinkled with powdery mildew fungus. On the 11th day after inoculation, the incidence of wheat powdery mildew was evaluated according to the criteria shown in Table 43. The results are shown in Table 44.
Figure JPOXMLDOC01-appb-T000095
Figure JPOXMLDOC01-appb-T000095
Figure JPOXMLDOC01-appb-T000096
Figure JPOXMLDOC01-appb-T000096
　＜試験例６：茎葉散布処理によるコムギ赤さび病防除効果試験＞
　角型プラスチックポット（６ｃｍ×６ｃｍ）を用いて栽培した第２葉期のコムギ（品種：農林６１号）に、製剤例１のような水和剤にした各化合物を、水で所定濃度に希釈懸濁し、１，０００Ｌ／ｈａの割合で散布した。散布葉を風乾した後、コムギ赤さび病菌の胞子（２００個／視野に調整、６０ｐｐｍとなるようにグラミンＳを添加）を噴霧接種し、２５℃、高湿度条件下に４８時間保った。その後は温室内で管理した。接種後、１１日目にコムギ赤さび病の発病度を上記の表４３に示す基準により評価した。その結果を表４５に示す。 <Test Example 6: Wheat red rust control effect test by foliar spray treatment>
Each compound made into wettable powder as in Formulation Example 1 was diluted with water to a predetermined concentration in the second leaf wheat (variety: Norin 61) grown using a square plastic pot (6cm x 6cm) It was suspended and sprayed at a rate of 1,000 L / ha. The sprayed leaves were air-dried and then spray-inoculated with spores of wheat red rust fungus (adjusted to 200 cells / field of view, added with Grameen S to 60 ppm), and kept at 25 ° C. and high humidity for 48 hours. After that, it was managed in the greenhouse. On the 11th day after inoculation, the severity of wheat rust was evaluated according to the criteria shown in Table 43 above. The results are shown in Table 45.
Figure JPOXMLDOC01-appb-T000097
Figure JPOXMLDOC01-appb-T000097
　＜試験例７：コムギ赤さび病の防除効果試験＞
　本発明の化合物をアセトンで溶解し、脱イオン水で１０倍に希釈して所定の濃度の希釈液を調製した。これに１／１０００容のネオエステリンを添加し、散布液とした。２．５葉期のコムギ（品種：農林６１号）に十分な量を散布した。自然乾燥させた後、２×１０５個／ｍＬに調製したコムギ赤さび病菌（Puccinia recondita）の分生子懸濁液を噴霧接種した。これを温度２５℃、湿度１００％のチャンバー内に２４時間保持した後、温室内で７日間管理した。第二葉に形成された病斑数を指標に下記の基準で発病の強さを目視で判定した後、式１および式２を用いて防除価を算出した。その結果、化合物A1-(I)-11およびA1-(I)-12が２００ｐｐｍで、それぞれ防除価９３、７１であった。
（発病の強さ）
　０：病斑を認めない
　１：病斑数が無処理の１０％未満
　２：病斑数が無処理の１０％以上３０％未満
　３：病斑数が無処理の３０％以上６０％未満
　４：病斑数が無処理の６０％以上９０％未満
　５：病斑数が無処理の９０％以上
（式１）
　発病度＝（発病の強さの平均値×１００）／３
（式２）
　防除価＝（無処理区の発病度－処理区の発病度）／無処理区の発病度×１００
　＜試験例８：イネ紋枯病の防除効果試験＞
　本発明の化合物をアセトンで溶解し、脱イオン水で１０倍に希釈して所定の濃度の希釈液を調製した。これに１／２０００容のネオエステリンを添加し、散布液とした。５葉期のイネ（品種：コシヒカリ）に十分な量を散布した。自然乾燥させた後、イネ紋枯病菌（Rhizoctonia solani AG-1）の菌叢が形成されたＰＳＡ（Potato Sucurose Agar）培地片をイネの地際部に静置し、温度３０℃、湿度８０％で５日間管理し、イネに形成された病斑の高さを指標に式３を用いて防除価を算出した。病斑の形成が認められない場合は病斑の高さを０とした。その結果、化合物A1-(I)-12およびA1-(I)-13が２００ｐｐｍで、それぞれ防除価７３、１００であった。
（式３）
　防除価＝（無処理区の病斑の高さ－処理区の病斑の高さ）／無処理区の病斑の高さ×１００ <Test Example 7: Wheat red rust control effect test>
The compound of the present invention was dissolved in acetone and diluted 10 times with deionized water to prepare a diluted solution having a predetermined concentration. 1/1000 volume of neoesterin was added to this, and it was set as the spraying liquid. A sufficient amount was applied to 2.5-leaf wheat (variety: Norin 61). After air-drying, a conidial suspension of wheat rust (Puccinia recondita) prepared to 2 × 10 5 cells / mL was spray-inoculated. This was kept in a chamber at a temperature of 25 ° C. and a humidity of 100% for 24 hours and then managed in a greenhouse for 7 days. Using the number of lesions formed on the second leaf as an index, the intensity of the disease was visually determined according to the following criteria, and then the control value was calculated using Equation 1 and Equation 2. As a result, the compounds A1- (I) -11 and A1- (I) -12 were 200 ppm, and the control values were 93 and 71, respectively.
(Strength of disease)
0: No lesion found 1: Less than 10% of lesions untreated 2: No more than 10% of lesions not more than 30% 3: No more than 30% of lesions less than 60% 4 : 60% or more and less than 90% of lesions untreated 5: 90% or more of lesions untreated (Formula 1)
Disease severity = (average value of disease intensity × 100) / 3
(Formula 2)
Control value = (morbidity of untreated area−morbidity of treated area) / morbidity of untreated area × 100
<Test Example 8: Control effect test of rice blight disease>
The compound of the present invention was dissolved in acetone and diluted 10 times with deionized water to prepare a diluted solution having a predetermined concentration. 1/2000 volume of neoesterin was added to this to make a spray solution. A sufficient amount was sprayed on rice (variety: Koshihikari) at the 5-leaf stage. After being naturally dried, a piece of PSA (Potato Sucurose Agar) medium in which the flora of rice rot fungus (Rhizoctonia solani AG-1) is formed is allowed to stand on the subsurface of rice, at a temperature of 30 ° C and a humidity of 80 %, And the control value was calculated using Formula 3 using the height of lesions formed in rice as an index. When no lesion formation was observed, the height of the lesion was set to zero. As a result, the compounds A1- (I) -12 and A1- (I) -13 were 200 ppm, and the control values were 73 and 100, respectively.
(Formula 3)
Control value = (height of lesion in untreated area−height of lesion in treated area) / height of lesion in untreated area × 100
　本発明に係るチアゾリジンジオン誘導体およびピロリジンジオン誘導体は、土壌病害を引き起こす病原菌、種子病害を引き起こす病原菌および茎葉病害を引き起こす病原菌を防除する農園芸用薬剤の有効成分として利用することができる。また、本発明に係る殺菌剤は、土壌病害を引き起こす病原菌、種子病害を引き起こす病原菌および茎葉病害を引き起こす病原菌を防除するための方法に利用することができる。 The thiazolidinedione derivative and pyrrolidinedione derivative according to the present invention can be used as an active ingredient of an agricultural and horticultural agent for controlling pathogenic bacteria causing soil diseases, pathogenic bacteria causing seed diseases, and pathogenic bacteria causing foliage diseases. In addition, the fungicide according to the present invention can be used in a method for controlling pathogenic bacteria that cause soil diseases, pathogenic bacteria that cause seed diseases, and pathogenic bacteria that cause foliage diseases.

Claims (22)

  1. 　下記式（A）で示される化合物を有効成分として含有する殺菌剤。
    Figure JPOXMLDOC01-appb-C000001
     （式（A）中、Ｘは、ＣＨ２、酸素原子または硫黄原子を表し、
    Ｒは、フェニル基、ピリジル基、チエニル基、フラニル基、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、またはフェノキシフェニル基を表す。ここで、フェニル基、ピリジル基、チエニル基、フラニル基およびフェノキシフェニル基は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基から選択される置換基により置換されていてもよい。
    Ｙは、酸素原子または硫黄原子を表し、
    Ｗは、水素原子、アルキル基、ベンジル基、フェニル基、ピリジル基、アルキルオキシカルボニルアルキル基、またはアルキルアミノカルボニルアルキル基を表す。ここで、アルキル基、ベンジル基、フェニル基、ピリジル基、アルキルオキシカルボニルアルキル基、およびアルキルアミノカルボニルアルキル基は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基およびアルキルアミン基から選択される置換基により置換されていてもよい。
    破線は、単結合または二重結合を表す。）     A fungicide containing a compound represented by the following formula (A) as an active ingredient.
    Figure JPOXMLDOC01-appb-C000001
     (In the formula (A), X represents CH 2 , an oxygen atom or a sulfur atom,
    R represents a phenyl group, a pyridyl group, a thienyl group, a furanyl group, a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenoxyphenyl group. Here, the phenyl group, pyridyl group, thienyl group, furanyl group and phenoxyphenyl group are selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group and a hydroxy group. It may be substituted with a substituent.
    Y represents an oxygen atom or a sulfur atom,
    W represents a hydrogen atom, an alkyl group, a benzyl group, a phenyl group, a pyridyl group, an alkyloxycarbonylalkyl group, or an alkylaminocarbonylalkyl group. Here, the alkyl group, benzyl group, phenyl group, pyridyl group, alkyloxycarbonylalkyl group, and alkylaminocarbonylalkyl group are a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and It may be substituted with a substituent selected from alkylamine groups.
    A broken line represents a single bond or a double bond. )
  2. 　下記式（A1-(I)）で示される化合物を有効成分として含有する殺菌剤。
    Figure JPOXMLDOC01-appb-C000002
     （式（A1-(I））中、Ｘは、ＣＨ２または硫黄原子を表し、
    Ｒ１は、フェニル基、ピリジル基またはフラニル基を表す。ここで、フェニル基、ピリジル基およびフラニル基は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基から選択される置換基により置換されていてもよい。）     A fungicide containing a compound represented by the following formula (A1- (I)) as an active ingredient.
    Figure JPOXMLDOC01-appb-C000002
     (In the formula (A1- (I)), X represents CH 2 or a sulfur atom,
    R 1 represents a phenyl group, a pyridyl group or a furanyl group. Here, the phenyl group, pyridyl group and furanyl group are substituted with a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group and a hydroxy group. May be. )
  3. 　下記式（A1-(II））で示される化合物を有効成分として含有する殺菌剤。
    Figure JPOXMLDOC01-appb-C000003
     （式（A1-(II））中、Ｘは、ＣＨ２または硫黄原子を表し、
    Ｒ２は、トリフェニルホスホラニリデン基を表す。ここで、トリフェニルホスホラニリデン基を構成している３つのフェニル基は、それぞれ独立に、ハロゲン原子および炭素数１～４のアルキル基から選択される置換基により置換されていてもよい。）     A bactericide containing a compound represented by the following formula (A1- (II)) as an active ingredient.
    Figure JPOXMLDOC01-appb-C000003
     (In the formula (A1- (II)), X represents CH 2 or a sulfur atom,
    R 2 represents a triphenylphosphoranylidene group. Here, the three phenyl groups constituting the triphenylphosphoranylidene group may each independently be substituted with a substituent selected from a halogen atom and an alkyl group having 1 to 4 carbon atoms. )
  4. 　下記式（A1-(XI））で示される化合物を有効成分として含有する殺菌剤。
    Figure JPOXMLDOC01-appb-C000004
     （式（A1-(XI））中、Ｘは、ＣＨ２または硫黄原子を表し、
    Ｒ１１は、フェニル基、ピリジル基またはフェノキシフェニル基を表し、
    Ｒ１２は、アルキル基、フェニル基、ベンジル基またはピリジル基を表す。ここで、フェニル基、ピリジル基およびフェノキシフェニル基は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基から選択される置換基により置換されていてもよい。）     A fungicide containing a compound represented by the following formula (A1- (XI)) as an active ingredient.
    Figure JPOXMLDOC01-appb-C000004
     (In the formula (A1- (XI)), X represents CH 2 or a sulfur atom,
    R 11 represents a phenyl group, a pyridyl group or a phenoxyphenyl group,
    R 12 represents an alkyl group, a phenyl group, a benzyl group or a pyridyl group. Here, the phenyl group, pyridyl group and phenoxyphenyl group are substituted with a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group and a hydroxy group. It may be. )
  5. 　下記式（A1-(XII））で示される化合物を有効成分として含有する殺菌剤。
    Figure JPOXMLDOC01-appb-C000005
     （式（A1-(XII））中、Ｘは、ＣＨ２または硫黄原子を表し、
    Ｒ１３は、アルキルオキシカルボニルアルキル基またはアルキルアミノカルボニルアルキル基を表す。ここで、アルキルオキシカルボニルアルキル基およびアルキルアミノカルボニルアルキル基は、ハロゲン原子で置換されていてもよい。
    Ｒ１４は、フェニル基またはチエニル基を表す。）     A fungicide containing a compound represented by the following formula (A1- (XII)) as an active ingredient.
    Figure JPOXMLDOC01-appb-C000005
     (In the formula (A1- (XII)), X represents CH 2 or a sulfur atom,
    R 13 represents an alkyloxycarbonylalkyl group or an alkylaminocarbonylalkyl group. Here, the alkyloxycarbonylalkyl group and the alkylaminocarbonylalkyl group may be substituted with a halogen atom.
    R 14 represents a phenyl group or a thienyl group. )
  6. 　下記式（A2-(I））で示される化合物を有効成分として含有する殺菌剤。
    Figure JPOXMLDOC01-appb-C000006
     （式（A2-(I））中、Ｒ１ａは、ヒドロキシ基または－ＮＲ３Ｒ４を表し、Ｒ３は炭素数１～６のアルキル基、炭素数２～６のアルケニル基、炭素数２～６のアルキニル基、炭素数３～８のシクロアルキル基、炭素数３～８のシクロアルケニル基、またはフェニル基であり、Ｒ４は炭素数２～６のアルキル基、またはフェニル基であり、Ｒ３とＲ４とは結合して環を形成していてもよい。
    Ｒ２ａは、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、またはフェニル基を表す。
    ここで、Ｒ３の炭素数１～６のアルキル基およびフェニル基、Ｒ４の炭素数２～６のアルキル基およびフェニル基、Ｒ２ａの炭素数１～６のアルキル基および炭素数１～６のアルコキシ基は、それぞれ独立に、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、炭素数１～４のアルキルカルボニルオキシ基、ニトロ基およびフェニル基から選択される置換基により置換されていてもよい。Ｒ２ａのフェニル基は、無置換でもよいし、置換されていてもよい。）     A bactericide containing a compound represented by the following formula (A2- (I)) as an active ingredient.
    Figure JPOXMLDOC01-appb-C000006
     (In the formula (A2- (I)), R 1a represents a hydroxy group or —NR 3 R 4 , wherein R 3 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 2 carbon atoms. An alkynyl group having 6 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkenyl group having 3 to 8 carbon atoms, or a phenyl group, and R 4 is an alkyl group having 2 to 6 carbon atoms or a phenyl group, R 3 and R 4 may combine to form a ring.
    R 2a represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group.
    Here, R 3 alkyl group and phenyl group having 1 to 6 carbon atoms, R 4 alkyl group and phenyl group having 2 to 6 carbon atoms, R 2a alkyl group having 1 to 6 carbon atoms and 1 to 6 carbon atoms. Are independently selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylcarbonyloxy group having 1 to 4 carbon atoms, a nitro group, and a phenyl group. It may be substituted with a substituent. The phenyl group of R 2a may be unsubstituted or substituted. )
  7. 　下記式（A2-(II））で示される化合物を有効成分として含有する殺菌剤。
    Figure JPOXMLDOC01-appb-C000007
     （式（A2-(II））中、Ｒ１ｂは、炭素数１～６のアルコキシ基を表し、
    Ｒ２ｂは、水素原子、ハロゲン原子、炭素数１～６のアルキル基、またはフェニル基を表す。
    ここで、Ｒ１ｂの炭素数１～６のアルコキシ基およびＲ２ｂの炭素数１～６のアルキル基は、それぞれ独立に、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、炭素数１～４のアルキルカルボニルオキシ基、ニトロ基およびフェニル基から選択される置換基により置換されていてもよい。Ｒ２ｂのフェニル基は、無置換でもよいし、置換されていてもよい。）     A fungicide containing a compound represented by the following formula (A2- (II)) as an active ingredient.
    Figure JPOXMLDOC01-appb-C000007
     (In the formula (A2- (II)), R 1b represents an alkoxy group having 1 to 6 carbon atoms,
    R 2b represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
    Here, the alkoxy group having 1 to 6 carbon atoms of R 1b and the alkyl group having 1 to 6 carbon atoms of R 2b are each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. It may be substituted with a substituent selected from an alkoxy group, an alkylcarbonyloxy group having 1 to 4 carbon atoms, a nitro group and a phenyl group. The phenyl group of R 2b may be unsubstituted or substituted. )
  8. 　下記式（A2-(III））で示される化合物を有効成分として含有する殺菌剤。
    Figure JPOXMLDOC01-appb-C000008
     （式（A2-(III））中、Ｒ２ａは、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、またはフェニル基を表す。
    ここで、Ｒ２ａの炭素数１～６のアルキル基および炭素数１～６のアルコキシ基は、それぞれ独立に、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、炭素数１～４のアルキルカルボニルオキシ基、ニトロ基およびフェニル基から選択される置換基により置換されていてもよい。Ｒ２ａのフェニル基は、無置換でもよいし、置換されていてもよい。）     A fungicide containing a compound represented by the following formula (A2- (III)) as an active ingredient.
    Figure JPOXMLDOC01-appb-C000008
     In the formula (A2- (III)), R 2a represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group.
    Here, the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms of R 2a are each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, It may be substituted with a substituent selected from an alkylcarbonyloxy group having 1 to 4 carbon atoms, a nitro group and a phenyl group. The phenyl group of R 2a may be unsubstituted or substituted. )
  9. 　下記式（A2-(IV））で示される化合物を有効成分として含有する殺菌剤。
    Figure JPOXMLDOC01-appb-C000009
     （式（A2-(IV））中、Ｒ５は、ヒドロキシ基、炭素数１～６のアルコキシ基または－ＮＲ８Ｒ９を表し、Ｒ８およびＲ９は、それぞれ独立に、炭素数１～６のアルキル基、炭素数２～６のアルケニル基、炭素数２～６のアルキニル基、炭素数３～８のシクロアルキル基、炭素数３～８のシクロアルケニル基、またはフェニル基であり、Ｒ８とＲ９とは結合して環を形成していてもよい。
    Ｒ６は、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、またはフェニル基を表す。
    ここで、Ｒ６の炭素数１～６のアルキル基および炭素数１～６のアルコキシ基は、それぞれ独立に、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、炭素数１～４のアルキルカルボニルオキシ基、ニトロ基およびフェニル基から選択される置換基により置換されていてもよい。Ｒ６のフェニル基は、無置換でもよいし、置換されていてもよい。）     A fungicide containing a compound represented by the following formula (A2- (IV)) as an active ingredient.
    Figure JPOXMLDOC01-appb-C000009
     (In the formula (A2- (IV)), R 5 represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms or —NR 8 R 9 , and R 8 and R 9 each independently represent 1 to An alkyl group having 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkenyl group having 3 to 8 carbon atoms, or a phenyl group, and R 8 and R 9 may combine to form a ring.
    R 6 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group.
    Here, the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms of R 6 are each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, It may be substituted with a substituent selected from an alkylcarbonyloxy group having 1 to 4 carbon atoms, a nitro group and a phenyl group. The phenyl group of R 6 may be unsubstituted or substituted. )
  10. 　下記式（A2-(V））で示される化合物を有効成分として含有する殺菌剤。
    Figure JPOXMLDOC01-appb-C000010
     （式（A2-(V））中、Ｒ２ａは、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、またはフェニル基を表す。
    ここで、Ｒ２ａの炭素数１～６のアルキル基および炭素数１～６のアルコキシ基は、それぞれ独立に、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、炭素数１～４のアルキルカルボニルオキシ基、ニトロ基およびフェニル基から選択される置換基により置換されていてもよい。Ｒ２ａのフェニル基は、無置換でもよいし、置換されていてもよい。）     A fungicide containing a compound represented by the following formula (A2- (V)) as an active ingredient.
    Figure JPOXMLDOC01-appb-C000010
     (In the formula (A2- (V)), R 2a represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group.
    Here, the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms of R 2a are each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, It may be substituted with a substituent selected from an alkylcarbonyloxy group having 1 to 4 carbon atoms, a nitro group and a phenyl group. The phenyl group of R 2a may be unsubstituted or substituted. )
  11. 　下記式（A1-(III））で示される化合物を有効成分として含有する殺菌剤。
    Figure JPOXMLDOC01-appb-C000011
     （式（A1-(III））中、Ｒ７は、ピリジル基またはフラニル基を表す。ここで、ピリジル基およびフラニル基は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基から選択される置換基により置換されていてもよい。）     A fungicide containing a compound represented by the following formula (A1- (III)) as an active ingredient.
    Figure JPOXMLDOC01-appb-C000011
     (In the formula (A1- (III)), R 7 represents a pyridyl group or a furanyl group, where the pyridyl group and the furanyl group are a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. And may be substituted with a substituent selected from an alkoxy group, a benzyloxy group and a hydroxy group.
  12. 　下記式（A）で示される化合物。
    Figure JPOXMLDOC01-appb-C000012
     （式（A）中、Ｘは、ＣＨ２、酸素原子または硫黄原子を表し、
    Ｒは、フェニル基、ピリジル基、チエニル基、フラニル基、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、またはフェノキシフェニル基を表す。ここで、フェニル基、ピリジル基、チエニル基、フラニル基およびフェノキシフェニル基は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基から選択される置換基により置換されていてもよい。
    Ｙは、酸素原子または硫黄原子を表し、
    Ｗは、水素原子、アルキル基、ベンジル基、フェニル基、ピリジル基、アルキルオキシカルボニルアルキル基、またはアルキルアミノカルボニルアルキル基を表す。ここで、アルキル基、ベンジル基、フェニル基、ピリジル基、アルキルオキシカルボニルアルキル基、およびアルキルアミノカルボニルアルキル基は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基およびアルキルアミン基から選択される置換基により置換されていてもよい。
    破線は、単結合または二重結合を表す。）     A compound represented by the following formula (A).
    Figure JPOXMLDOC01-appb-C000012
     (In the formula (A), X represents CH 2 , an oxygen atom or a sulfur atom,
    R represents a phenyl group, a pyridyl group, a thienyl group, a furanyl group, a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenoxyphenyl group. Here, the phenyl group, pyridyl group, thienyl group, furanyl group and phenoxyphenyl group are selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group and a hydroxy group. It may be substituted with a substituent.
    Y represents an oxygen atom or a sulfur atom,
    W represents a hydrogen atom, an alkyl group, a benzyl group, a phenyl group, a pyridyl group, an alkyloxycarbonylalkyl group, or an alkylaminocarbonylalkyl group. Here, the alkyl group, benzyl group, phenyl group, pyridyl group, alkyloxycarbonylalkyl group, and alkylaminocarbonylalkyl group are a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and It may be substituted with a substituent selected from alkylamine groups.
    A broken line represents a single bond or a double bond. )
  13. 　下記式（A1-(I)）で示される化合物。
    Figure JPOXMLDOC01-appb-C000013
     （式（A1-(I））中、Ｘは、ＣＨ２または硫黄原子を表し、
    Ｒ１は、フェニル基、ピリジル基またはフラニル基を表す。ここで、フェニル基、ピリジル基およびフラニル基は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基から選択される置換基により置換されていてもよい。）     A compound represented by the following formula (A1- (I)).
    Figure JPOXMLDOC01-appb-C000013
     (In the formula (A1- (I)), X represents CH 2 or a sulfur atom,
    R 1 represents a phenyl group, a pyridyl group or a furanyl group. Here, the phenyl group, pyridyl group and furanyl group are substituted with a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group and a hydroxy group. May be. )
  14. 　下記式（A1-(II））で示される化合物。
    Figure JPOXMLDOC01-appb-C000014
     （式（A1-(II））中、Ｘは、ＣＨ２または硫黄原子を表し、
    Ｒ２は、トリフェニルホスホラニリデン基を表す。ここで、トリフェニルホスホラニリデン基を構成している３つのフェニル基は、それぞれ独立に、ハロゲン原子および炭素数１～４のアルキル基から選択される置換基により置換されていてもよい。）     A compound represented by the following formula (A1- (II)).
    Figure JPOXMLDOC01-appb-C000014
     (In the formula (A1- (II)), X represents CH 2 or a sulfur atom,
    R 2 represents a triphenylphosphoranylidene group. Here, the three phenyl groups constituting the triphenylphosphoranylidene group may each independently be substituted with a substituent selected from a halogen atom and an alkyl group having 1 to 4 carbon atoms. )
  15. 　下記式（A1-(XI））で示される化合物。
    Figure JPOXMLDOC01-appb-C000015
     （式（A1-(XI））中、Ｘは、ＣＨ２または硫黄原子を表し、
    Ｒ１１は、フェニル基、ピリジル基またはフェノキシフェニル基を表し、
    Ｒ１２は、アルキル基、フェニル基、ベンジル基またはピリジル基を表す。ここで、フェニル基、ピリジル基およびフェノキシフェニル基は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基から選択される置換基により置換されていてもよい。）     A compound represented by the following formula (A1- (XI)).
    Figure JPOXMLDOC01-appb-C000015
     (In the formula (A1- (XI)), X represents CH 2 or a sulfur atom,
    R 11 represents a phenyl group, a pyridyl group or a phenoxyphenyl group,
    R 12 represents an alkyl group, a phenyl group, a benzyl group or a pyridyl group. Here, the phenyl group, pyridyl group and phenoxyphenyl group are substituted with a substituent selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a benzyloxy group and a hydroxy group. It may be. )
  16. 　下記式（A1-(XII））で示される化合物。
    Figure JPOXMLDOC01-appb-C000016
     （式（A1-(XII））中、Ｘは、ＣＨ２または硫黄原子を表し、
    Ｒ１３は、アルキルオキシカルボニルアルキル基またはアルキルアミノカルボニルアルキル基を表す。ここで、アルキルオキシカルボニルアルキル基およびアルキルアミノカルボニルアルキル基は、ハロゲン原子で置換されていてもよい。
    Ｒ１４は、フェニル基またはチエニル基を表す。）     A compound represented by the following formula (A1- (XII)).
    Figure JPOXMLDOC01-appb-C000016
     (In the formula (A1- (XII)), X represents CH 2 or a sulfur atom,
    R 13 represents an alkyloxycarbonylalkyl group or an alkylaminocarbonylalkyl group. Here, the alkyloxycarbonylalkyl group and the alkylaminocarbonylalkyl group may be substituted with a halogen atom.
    R 14 represents a phenyl group or a thienyl group. )
  17. 　下記式（A2-(I））で示される化合物。
    Figure JPOXMLDOC01-appb-C000017
     （式（A2-(I））中、Ｒ１ａは、ヒドロキシ基または－ＮＲ３Ｒ４を表し、Ｒ３は炭素数１～６のアルキル基、炭素数２～６のアルケニル基、炭素数２～６のアルキニル基、炭素数３～８のシクロアルキル基、炭素数３～８のシクロアルケニル基、またはフェニル基であり、Ｒ４は炭素数２～６のアルキル基、またはフェニル基であり、Ｒ３とＲ４とは結合して環を形成していてもよい。
    Ｒ２ａは、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、またはフェニル基を表す。
    ここで、Ｒ３の炭素数１～６のアルキル基およびフェニル基、Ｒ４の炭素数２～６のアルキル基およびフェニル基、Ｒ２ａの炭素数１～６のアルキル基および炭素数１～６のアルコキシ基は、それぞれ独立に、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、炭素数１～４のアルキルカルボニルオキシ基、ニトロ基およびフェニル基から選択される置換基により置換されていてもよい。Ｒ２ａのフェニル基は、無置換でもよいし、置換されていてもよい。）     A compound represented by the following formula (A2- (I)).
    Figure JPOXMLDOC01-appb-C000017
     (In the formula (A2- (I)), R 1a represents a hydroxy group or —NR 3 R 4 , wherein R 3 represents an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or 2 carbon atoms. An alkynyl group having 6 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkenyl group having 3 to 8 carbon atoms, or a phenyl group, and R 4 is an alkyl group having 2 to 6 carbon atoms or a phenyl group, R 3 and R 4 may combine to form a ring.
    R 2a represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group.
    Here, R 3 alkyl group and phenyl group having 1 to 6 carbon atoms, R 4 alkyl group and phenyl group having 2 to 6 carbon atoms, R 2a alkyl group having 1 to 6 carbon atoms and 1 to 6 carbon atoms. Are independently selected from a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylcarbonyloxy group having 1 to 4 carbon atoms, a nitro group, and a phenyl group. It may be substituted with a substituent. The phenyl group of R 2a may be unsubstituted or substituted. )
  18. 　下記式（A2-(II））で示される化合物。
    Figure JPOXMLDOC01-appb-C000018
     （式（A2-(II））中、Ｒ１ｂは、炭素数１～６のアルコキシ基を表し、
    Ｒ２ｂは、水素原子、ハロゲン原子、炭素数１～６のアルキル基、またはフェニル基を表す。
    ここで、Ｒ１ｂの炭素数１～６のアルコキシ基およびＲ２ｂの炭素数１～６のアルキル基は、それぞれ独立に、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、炭素数１～４のアルキルカルボニルオキシ基、ニトロ基およびフェニル基から選択される置換基により置換されていてもよい。Ｒ２ｂのフェニル基は、無置換でもよいし、置換されていてもよい。）     A compound represented by the following formula (A2- (II)).
    Figure JPOXMLDOC01-appb-C000018
     (In the formula (A2- (II)), R 1b represents an alkoxy group having 1 to 6 carbon atoms,
    R 2b represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.
    Here, the alkoxy group having 1 to 6 carbon atoms of R 1b and the alkyl group having 1 to 6 carbon atoms of R 2b are each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. It may be substituted with a substituent selected from an alkoxy group, an alkylcarbonyloxy group having 1 to 4 carbon atoms, a nitro group and a phenyl group. The phenyl group of R 2b may be unsubstituted or substituted. )
  19. 　下記式（A2-(III））で示される化合物。
    Figure JPOXMLDOC01-appb-C000019
     （式（A2-(III））中、Ｒ２ａは、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、またはフェニル基を表す。
    ここで、Ｒ２ａの炭素数１～６のアルキル基および炭素数１～６のアルコキシ基は、それぞれ独立に、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、炭素数１～４のアルキルカルボニルオキシ基、ニトロ基およびフェニル基から選択される置換基により置換されていてもよい。Ｒ２ａのフェニル基は、無置換でもよいし、置換されていてもよい。）     A compound represented by the following formula (A2- (III)).
    Figure JPOXMLDOC01-appb-C000019
     In the formula (A2- (III)), R 2a represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group.
    Here, the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms of R 2a are each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, It may be substituted with a substituent selected from an alkylcarbonyloxy group having 1 to 4 carbon atoms, a nitro group and a phenyl group. The phenyl group of R 2a may be unsubstituted or substituted. )
  20. 　下記式（A2-(IV））で示される化合物を有効成分として含有する殺菌剤。
    Figure JPOXMLDOC01-appb-C000020
     （式（A2-(IV））中、Ｒ５は、ヒドロキシ基、炭素数１～６のアルコキシ基または－ＮＲ８Ｒ９を表し、Ｒ８およびＲ９は、それぞれ独立に、炭素数１～６のアルキル基、炭素数２～６のアルケニル基、炭素数２～６のアルキニル基、炭素数３～８のシクロアルキル基、炭素数３～８のシクロアルケニル基、またはフェニル基であり、Ｒ８とＲ９とは結合して環を形成していてもよい。
    Ｒ６は、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、またはフェニル基を表す。
    ここで、Ｒ６の炭素数１～６のアルキル基および炭素数１～６のアルコキシ基は、それぞれ独立に、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、炭素数１～４のアルキルカルボニルオキシ基、ニトロ基およびフェニル基から選択される置換基により置換されていてもよい。Ｒ６のフェニル基は、無置換でもよいし、置換されていてもよい。）     A fungicide containing a compound represented by the following formula (A2- (IV)) as an active ingredient.
    Figure JPOXMLDOC01-appb-C000020
     (In the formula (A2- (IV)), R 5 represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms or —NR 8 R 9 , and R 8 and R 9 each independently represent 1 to An alkyl group having 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a cycloalkenyl group having 3 to 8 carbon atoms, or a phenyl group, and R 8 and R 9 may combine to form a ring.
    R 6 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group.
    Here, the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms of R 6 are each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, It may be substituted with a substituent selected from an alkylcarbonyloxy group having 1 to 4 carbon atoms, a nitro group and a phenyl group. The phenyl group of R 6 may be unsubstituted or substituted. )
  21. 　下記式（A2-(V））で示される化合物。
    Figure JPOXMLDOC01-appb-C000021
     （式（A2-(V））中、Ｒ２ａは、水素原子、ハロゲン原子、炭素数１～６のアルキル基、炭素数１～６のアルコキシ基、またはフェニル基を表す。
    ここで、Ｒ２ａの炭素数１～６のアルキル基および炭素数１～６のアルコキシ基は、それぞれ独立に、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、炭素数１～４のアルキルカルボニルオキシ基、ニトロ基およびフェニル基から選択される置換基により置換されていてもよい。Ｒ２ａのフェニル基は、無置換でもよいし、置換されていてもよい。）     A compound represented by the following formula (A2- (V)).
    Figure JPOXMLDOC01-appb-C000021
     (In the formula (A2- (V)), R 2a represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group.
    Here, the alkyl group having 1 to 6 carbon atoms and the alkoxy group having 1 to 6 carbon atoms of R 2a are each independently a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, It may be substituted with a substituent selected from an alkylcarbonyloxy group having 1 to 4 carbon atoms, a nitro group and a phenyl group. The phenyl group of R 2a may be unsubstituted or substituted. )
  22. 　下記一般式（A1-(III)）で示される化合物。
    Figure JPOXMLDOC01-appb-C000022
     （式（A1-(III））中、Ｒ７は、ピリジル基またはフラニル基を表す。ここで、ピリジル基およびフラニル基は、ハロゲン原子、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、ベンジルオキシ基およびヒドロキシ基から選択される置換基により置換されていてもよい。）     A compound represented by the following general formula (A1- (III)).
    Figure JPOXMLDOC01-appb-C000022
     (In the formula (A1- (III)), R 7 represents a pyridyl group or a furanyl group, where the pyridyl group and the furanyl group are a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. And may be substituted with a substituent selected from an alkoxy group, a benzyloxy group and a hydroxy group.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019510787A (en) * 2016-04-05 2019-04-18 イミューン センサー リミテッド ライアビリティ カンパニー cGAS antagonist compound

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58183603A (en) * 1982-04-19 1983-10-26 Mitsubishi Chem Ind Ltd Fungicide for soil blight
JPH0377875A (en) * 1989-08-18 1991-04-03 Kaken Pharmaceut Co Ltd Thiazolidine-2,4-dione derivative and its production
JP2004507501A (en) * 2000-08-31 2004-03-11 オックスフォード・グリコサイエンシーズ・（ユーケイ）・リミテッド Benzylidenthiazolidinedione and their use as antifungal agents

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58183603A (en) * 1982-04-19 1983-10-26 Mitsubishi Chem Ind Ltd Fungicide for soil blight
JPH0377875A (en) * 1989-08-18 1991-04-03 Kaken Pharmaceut Co Ltd Thiazolidine-2,4-dione derivative and its production
JP2004507501A (en) * 2000-08-31 2004-03-11 オックスフォード・グリコサイエンシーズ・（ユーケイ）・リミテッド Benzylidenthiazolidinedione and their use as antifungal agents

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
"International Journal of Pharmacy and Pharmaceutical Sciences", INTERNATIONAL JOURNAL OF PHARMACY AND PHARMACEUTICAL SCIENCES, vol. 4, no. 3, June 2012 (2012-06-01), pages 273 - 276 *
"Journal of Pestcide Science", JOURNAL OF PESTCIDE SCIENCE, vol. 33, no. 4, 2008, pages 357 - 363 *
"Journal of the Pharmaceutical Society of Japan", JOURNAL OF THE PHARMACEUTICAL SOCIETY OF JAPAN, vol. 76, no. 2, 1956, pages 154 - 157 *
BIOORGANIC & MEDICINAL CHEMISTRY, vol. 14, 2006, pages 567 - 574 *
FARMATSEVTICHNII ZHURNAL (KIEV), 1990, pages 40 - 43 *
TETRAHEDRON, vol. 24, 1968, pages 2241 - 2254 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019510787A (en) * 2016-04-05 2019-04-18 イミューン センサー リミテッド ライアビリティ カンパニー cGAS antagonist compound
JP2022105091A (en) * 2016-04-05 2022-07-12 イミューン センサー リミテッド ライアビリティ カンパニー cGAS ANTAGONIST COMPOUNDS
JP7116422B2 (en) 2016-04-05 2022-08-10 イミューン センサー リミテッド ライアビリティ カンパニー cGAS antagonist compounds
US11597707B2 (en) 2016-04-05 2023-03-07 Immunesensor Therapeutics, Inc. CGAS antagonist compounds
JP7530068B2 (en) 2016-04-05 2024-08-07 イミューン センサー リミテッド ライアビリティ カンパニー cGAS antagonist compounds
US12065416B2 (en) 2016-04-05 2024-08-20 Immunesensor Therapeutics, Inc. cGAS antagonist compounds

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