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WO2024005209A1 - Dérivé de 1,4-cinéol et intermédiaire de celui-ci, herbicide le contenant en tant que principe actif, procédé d'utilisation d'un herbicide et procédé de préparation d'une composition agrochimique - Google Patents

Dérivé de 1,4-cinéol et intermédiaire de celui-ci, herbicide le contenant en tant que principe actif, procédé d'utilisation d'un herbicide et procédé de préparation d'une composition agrochimique Download PDF

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Publication number
WO2024005209A1
WO2024005209A1 PCT/JP2023/024517 JP2023024517W WO2024005209A1 WO 2024005209 A1 WO2024005209 A1 WO 2024005209A1 JP 2023024517 W JP2023024517 W JP 2023024517W WO 2024005209 A1 WO2024005209 A1 WO 2024005209A1
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group
methyl
isopropyl
oxabicyclo
alkyl group
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PCT/JP2023/024517
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English (en)
Japanese (ja)
Inventor
潤 鈴木
聡仁 大▲高▼
達也 平野
熟人 小川
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Hokko Chemical Industry Co Ltd
Meiji University
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Hokko Chemical Industry Co Ltd
Meiji University
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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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P13/00—Herbicides; Algicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/08—Bridged systems

Definitions

  • the present invention relates to 1,4-cineole derivatives and intermediates thereof, herbicides and herbicides containing the above derivatives as active ingredients and having extremely excellent control effects against harmful weeds in agricultural and horticultural cultivation settings and non-agricultural lands. It relates to methods of use and methods of preparing agrochemical compositions.
  • An object of the present invention is to provide 1,4-cineole derivatives and intermediates thereof, and herbicides having excellent herbicidal activity and crop selectivity. It is also an object of the present invention to provide a method for using a herbicide and a method for preparing an agrochemical composition.
  • a 1,4-cineole derivative represented by the following general formula (1), (1'), (2) or (2') (hereinafter sometimes referred to as "the compound of the present invention” in this specification).
  • R 1 is each independently a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C2-C6 alkenyl group, a C2-C6 alkynyl group, a C3-C6 cycloalkyl group (the group is a halogen atom, a C1-C6 alkyl group) or a C1-C6 haloalkyl group), a C3-C6 cycloalkyl C1-C6 alkyl group (the group may be substituted by a halogen atom, a C1-C6 alkyl group, or a C1-C6 haloalkyl group) ), a C1-C6 alkoxy C1-C6 alkyl group, a phenyl group (the group may be mono- or polysubstituted by a halogen atom, a C1-C6 alkyl group
  • R 2 and R 3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 alkoxy C1-C6 alkoxy group, a C1-C6 represents an alkylcarbonyloxy group, a C1-C6 alkoxycarbonyloxy group, a C1-C6 alkylthiocarbonyloxy group, a C1-C6 alkylthiothiocarbonyloxy group, a C1-C6 alkylsulfonyloxy group, or a C1-C6 haloalkylsulfonyloxy group, and at least Either one is a substituent other than a hydrogen atom.
  • the two adjacent substituents R 2 and R 3 together with the carbon to which they are bonded form a 3- to 6-membered carbon ring, or independently from the oxygen, sulfur, and nitrogen atoms.
  • a 3- to 6-membered heterocycle having 1 to 4 selected heteroatoms is formed, and the ring formed here may have one or more substituents.
  • X represents an oxygen atom, a sulfur atom, CR 4 R 5 or NR 6 .
  • R 4 and R 5 each independently represent a hydrogen atom or a C1-C6 alkyl group.
  • R 6 is a hydrogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, an amino group, a C1-C6 alkylamino group, an aminocarbonylamino group, or a phenylamino group (the group is a halogen atom, a C1-C6 (May be mono- or polysubstituted by an alkyl group or a C1-C6 haloalkyl group.)
  • R 1 each independently represents a phenyl group (the group may be mono- or polysubstituted with a halogen atom, a C1-C6 alkyl group, or a C1-C6 haloalkyl group), a C7-C11 aralkyl group (the group may be mono- or polysubstituted with a halogen atom, cyano group, nitro group, C1-C6 alkyl group, C1-C6 haloalkyl group, C1-C6 alkoxy group, or C1-C6 haloalkoxy group), heterocycle C1-C6 alkyl group (the group may be mono- or polysubstituted with a halogen atom, a C1-C6 alkyl group, or a C1-C6 haloalkyl group), a phenoxy C1-C6 alkyl group (the group may be monosubstituted or polysubstituted with a
  • R 2 and R 3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 alkoxy C1-C6 alkoxy group, a C1-C6 Represents an alkylthiothiocarbonyloxy group or a C1-C6 haloalkylsulfonyloxy group, at least one of which is a substituent other than a hydrogen atom, and two adjacent substituents R 2 and R 3 are bonded together.
  • X represents an oxygen atom
  • R 4 and R 5 each independently represent a hydrogen atom or a C1-C6 alkyl group
  • R 6 is a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, an amino group, a C1-C6 alkylamino group, an aminocarbonylamino group, or a phenylamino group (the group is a halogen atom, a C1-C6 alkyl group, or may be mono- or polysubstituted with a C1-C6 haloalkyl group.)
  • the 1,4-cineole derivative according to [1].
  • R 1a each independently represents a hydrogen atom or a triC1-C6 alkylsilyl group, which may be the same or different.
  • R 2a and R 3a each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 alkoxy C1-C6 alkoxy group, a C1-C6 represents an alkylcarbonyloxy group, a C1-C6 alkoxycarbonyloxy group, a C1-C6 alkylthiocarbonyloxy group, a C1-C6 alkylthiothiocarbonyloxy group, a C1-C6 alkylsulfonyloxy group, or a C1-C6 haloalkylsulfon
  • the two adjacent substituents R 2a and R 3a together with the carbon to which they are bonded form a 3- to 6-membered carbon ring, or independently from the oxygen, sulfur, and nitrogen atoms.
  • a 3- to 6-membered heterocycle having 1 to 4 selected heteroatoms is formed, and the ring formed here may have one or more substituents.
  • X a represents an oxygen atom, a sulfur atom, CR 4a R 5a or NR 6a .
  • R 4a and R 5a each independently represent a hydrogen atom or a C1-C6 alkyl group.
  • R 6a is a hydrogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, an amino group, a C1-C6 alkylamino group, an aminocarbonylamino group, or a phenylamino group (the group is a halogen atom, a C1-C6 (May be mono- or polysubstituted by an alkyl group or a C1-C6 haloalkyl group.)
  • R 1a each independently represents a hydrogen atom or a triC1-C6 alkylsilyl group, which may be the same or different;
  • R 2a and R 3a each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 alkoxy C1-C6 alkoxy group, a C1-C6 Represents an alkylthiothiocarbonyloxy group or a C1-C6 haloalkylsulfonyloxy group, at least one of which is a substituent other than a hydrogen atom, and two adjacent substituents R 2a and R 3a are bonded together.
  • 3-6 membered carbocycle or 3-6 membered heterocycle having 1-4 heteroatoms independently selected from oxygen, sulfur and nitrogen atoms and the ring formed here may have one or more substituents
  • X a represents an oxygen atom
  • R 4a and R 5a each independently represent a hydrogen atom or a C1-C6 alkyl group
  • R 6a is a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, an amino group, a C1-C6 alkylamino group, an aminocarbonylamino group, or a phenylamino group (the group is a halogen atom, a C1-C6 alkyl group, or may be mono- or polysubstituted with a C1-C6 haloalkyl group.)
  • [5] A herbicide containing the 1,4-cineole derivative according to [1] or [2] as an active ingredient.
  • the herbicide according to [5] which is used for farmland, pasture, lawn, or non-agricultural land.
  • a method for preparing an agrochemical composition the method comprising the step of mixing the herbicide according to [5] with at least one selected from fillers and surfactants.
  • the present invention it is possible to provide 1,4-cineole derivatives and intermediates thereof, as well as herbicides having excellent herbicidal activity and crop selectivity.
  • the novel 1,4-cineole derivative of the present invention represented by the general formula (1), (1'), (2) or (2') exhibits excellent herbicidal effects. Further, according to the present invention, a method for using a herbicide and a method for preparing an agrochemical composition can be provided.
  • 1,4-cineole derivatives related to the compounds of the present invention, the intermediates of the present invention, and herbicides containing the derivatives as active ingredients will be specifically explained.
  • the 1,4-cineole derivative of the present invention represented by the above general formula (1), (1'), (2) or (2'), the above general formula (1a), (1a'), (2a) or In the synthetic intermediate represented by (2a') and the substrates, reaction substrates, and products described in the production method described below, R 2 , R 3 , R 2a , R 3a , Y, or Z
  • the halogen atom or the halogen atom as a substituent include fluorine, chlorine, bromine, and iodine.
  • the number of halogen atoms as a substituent may be 1 or 2 or more, and in the case of 2 or more, each halogen atom may be the same or different.
  • the halogen atom may be substituted at any position.
  • C1-C6 alkyl group or substitution represented by R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 2a , R 3a , R 4a , R 5a , R 6a , R 8 , or R 9
  • Examples of the C1-C6 alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, and neopentyl group.
  • C1-C6 alkyl groups as a substituent may be 1 or 2 or more, and in the case of 2 or more, each C1-C6 alkyl group may be the same or different. Furthermore, the C1-C6 alkyl group may be substituted at any position.
  • Examples of the C1-C6 haloalkyl group represented by R 1 , R 2 , R 3 , R 2a , R 3a , or R 8 or the C1-C6 haloalkyl group as a substituent include a monofluoromethyl group, a difluoromethyl group, and a trifluoromethyl group. Examples include fluoromethyl group, 2,2,2-trifluoroethyl group, 2-chloroethyl group, trichloromethyl group, 1-fluoroethyl group, 2-fluoroethyl group, 6-fluorohexyl group, monobromomethyl group, etc. be able to.
  • the C2-C6 alkenyl group represented by R 1 includes vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group. , 2-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 3- Examples include methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, and 5-hexenyl group.
  • Examples of the C2-C6 alkynyl group represented by R 1 include ethynyl group, 1-propynyl group, propargyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-propynyl group, 2 -Methyl-3-butynyl group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-methyl-2-butynyl group, 2-methyl-3-pentynyl group, 1-hexynyl group , 1,1-dimethyl-2-butynyl group and the like.
  • Examples of the C3-C6 cycloalkyl group represented by R 1 include cyclopropyl group, 1-methylcyclopropyl group, 2-methylcyclopropyl group, 2,2-dimethylpropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc. can be exemplified.
  • the C3-C6 cycloalkyl C1-C6 alkyl group represented by R 1 includes a cyclopropylmethyl group, a cyclopropylethyl group, a 1-methylcyclopropylmethyl group, a 2-methylcyclopropylmethyl group, and a 2,2-dimethyl group. Examples include a cyclopropylmethyl group, a cyclobutylmethyl group, a cyclopentylmethyl group, and a cyclohexylmethyl group.
  • the C1-C6 alkoxy C1-C6 alkyl group represented by R 1 or R 9 includes methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, sec-butoxy Methyl group, tert-butoxymethyl group, 1-pentyloxymethyl group, 1-hexyloxymethyl group, 2-methoxyethyl group, 1-ethoxyethyl group, 2-ethoxyethyl group, 2-isopropoxyethyl group, 2- Examples include isobutoxyethyl group, 3-methoxypropyl group, 2-methoxypropyl group, and 2-methoxy-1-methylethyl group.
  • the heterocycle represented by R 1 includes 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-thienyl group, 3-thienyl group, 2-furyl group, 3-furyl group, 2-pyrimidyl group. , 4-pyrimidyl group, 5-pyrimidyl group, 6-pyrimidyl group, 2-tetrahydrofuryl group, 3-tetrahydrofuryl group, 2-tetrahydropyranyl group, 3-tetrahydropyranyl group, 4-tetrahydropyranyl group, etc. I can give an example.
  • Examples of the C7-C11 aralkyl group represented by R 1 or R 7 include benzyl group, 1-phenethyl group, 2-phenethyl group, 1-phenylpropyl group, 2-phenylpropyl group, 3-phenylpropyl group, 1 Examples include -phenyl-2-methylpropyl group, 1-phenylbutyl group, and 1-phenylpentyl group.
  • the heterocyclic C1-C6 alkyl group represented by R 1 or R 7 includes 2-pyridylmethyl group, 3-pyridylmethyl group, 4-pyridylmethyl group, 2-thienylmethyl group, 3-thienylmethyl group, 2-furfuryl group, 3-furfuryl group, 2-pyrimidylmethyl group, 4-pyrimidylmethyl group, 5-pyrimidylmethyl group, 6-pyrimidylmethyl group, 4-pyrazolylmethyl group, 2-tetrahydrofurfuryl group, 3-tetrahydrofurfuryl group, etc. can be exemplified.
  • the phenoxy C1-C6 alkyl group represented by R 1 includes phenoxymethyl group, 2-phenoxyethyl group, 2-phenoxypropyl group, 3-phenoxypropyl group, 2-phenoxybutyl group, 3-phenoxybutyl group, 4 -Phenoxybutyl group, etc. can be exemplified.
  • the C7-C11 aralkyloxy C1-C6 alkyl group represented by R 1 includes benzyloxymethyl group, 1-phenethyloxymethyl group, 2-phenethyloxymethyl group, 1-phenylpropoxymethyl group, 2-phenylpropoxymethyl group. Examples include a 3-phenylpropoxymethyl group, a benzyloxyethyl group, and the like.
  • Examples of the benzoyl C1-C6 alkyl group represented by R 1 include phenacyl group, 2-oxo-2-phenylethyl group, and the like.
  • the C1-C6 alkoxy group represented by R 2 , R 3 , R 6 , R 2a , R 3a or R 6a or the C1-C6 alkoxy group as a substituent includes a methoxy group, an ethoxy group, an n-propoxy group , isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group and the like.
  • the number of C1-C6 alkoxy groups as a substituent may be 1 or 2 or more, and in the case of 2 or more, each C1-C6 alkoxy group may be the same or different.
  • the C1-C6 alkoxy group may be substituted at any position.
  • the C1-C6 alkoxy C1-C6 alkoxy group represented by R 2 , R 3 , R 2a or R 3a includes methoxymethoxy group, ethoxymethoxy group, 1-ethoxyethoxy group, n-propoxymethoxy group, isopropoxy Examples include methoxy group, n-butoxymethoxy group, sec-butoxymethoxy group, tert-butoxymethoxy group, 1-pentyloxymethoxy group, and 1-hexyloxymethoxy group.
  • the C1-C6 alkylcarbonyloxy group represented by R 2 , R 3 , R 2a or R 3a includes acetyloxy group, ethylcarbonyloxy group, n-propylcarbonyloxy group, isopropylcarbonyloxy group, n-butyl Examples include carbonyloxy group, isobutylcarbonyloxy group, sec-butylcarbonyloxy group, tert-butylcarbonyloxy group, 1-pentylcarbonyloxy group, and 1-hexylcarbonyloxy group.
  • the C1-C6 alkoxycarbonyloxy group represented by R 2 , R 3 , R 2a or R 3a includes methoxycarbonyloxy group, ethoxycarbonyloxy group, n-propoxycarbonyloxy group, isopropoxycarbonyloxy group, n Examples include -butoxycarbonyloxy group, sec-butoxycarbonyloxy group, and tert-butoxycarbonyloxy group.
  • the C1-C6 alkylthiocarbonyloxy group represented by R 2 , R 3 , R 2a or R 3a includes methylthiocarbonyloxy group, ethylthiocarbonyloxy group, n-propylthiocarbonyloxy group, isopropylthiocarbonyloxy group , n-butylthiocarbonyloxy group, sec-butylthiocarbonyloxy group, tert-butylthiocarbonyloxy group, 1-pentylthiocarbonyloxy group, 1-hexylthiocarbonyloxy group, and the like.
  • the C1-C6 alkylthiothiocarbonyloxy group represented by R 2 , R 3 , R 2a or R 3a includes methylthiothiocarbonyloxy group, ethylthiothiocarbonyloxy group, n-propylthiothiocarbonyloxy group, isopropyl Thiothiocarbonyloxy group, n-butylthiothiocarbonyloxy group, sec-butylthiothiocarbonyloxy group, tert-butylthiothiocarbonyloxy group, 1-pentylthiothiocarbonyloxy group, 1-hexylthiothiocarbonyloxy group etc. can be exemplified.
  • Examples of the C1-C6 alkylsulfonyloxy group represented by R 2 , R 3 , R 2a , or R 3a include methanesulfonyloxy group, ethanesulfonyloxy group, n-propanesulfonyloxy group, isopropanesulfonyloxy group, n -butanesulfonyloxy group, isobutanesulfonyloxy group, sec-butanesulfonyloxy group, tert-butanesulfonyloxy group, n-pentanesulfonyloxy group, and the like.
  • Examples of the C1-C6 haloalkylsulfonyloxy group represented by R 2 , R 3 , R 2a , or R 3a include monofluoromethylsulfonyloxy group, difluoromethylsulfonyloxy group, trifluoromethylsulfonyloxy group, and monochloromethylsulfonyloxy group. Examples include a trichloromethylsulfonyloxy group, a 2,2,2-trifluoroethylsulfonyloxy group, and the like.
  • the C1-C6 alkylamino group represented by R 6 or R 6a includes methylamino group, ethylamino group, n-propylamino group, isopropylamino group, n-butylamino group, isobutylamino group, sec-butyl Examples include an amino group and a tert-butylamino group.
  • Examples of the C1-C6 haloalkoxy group as a substituent include difluoromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2-chloroethoxy group, trichloromethoxy group, 1-fluoroethoxy group, 2 -Fluoroethoxy group, etc. can be exemplified.
  • the triC1-C6 alkylsilyl group which may be the same or different and is represented by R 1a , R 7 or R 10 includes trimethylsilyl group, triethylsilyl group, triisopropylsilyl group, dimethylisopropylsilyl group, diethylisopropylsilyl group. , dimethylhexylsilyl group, tert-butyldimethylsilyl group, di-tert-butylmethylsilyl group, and the like.
  • Examples of the C1-C6 alkylcarbonyl group represented by R 9 include acetyl group, ethylcarbonyl group, n-propylcarbonyl group, isopropylcarbonyl group, n-butylcarbonyl group, isobutylcarbonyl group, sec-butylcarbonyl group, tert- Examples include butylcarbonyl group, 1-pentylcarbonyl group, and 1-hexylcarbonyl group.
  • the C1-C6 alkoxycarbonyl group represented by R 9 includes a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, a sec-butoxycarbonyl group, and a tert-butoxycarbonyl group. Examples include groups.
  • Examples of the C1-C6 alkylthiocarbonyl group represented by R9 include methylthiocarbonyl group, ethylthiocarbonyl group, n-propylthiocarbonyl group, isopropylthiocarbonyl group, n-butylthiocarbonyl group, sec-butylthiocarbonyl group, Examples include tert-butylthiocarbonyl group, 1-pentylthiocarbonyl group, and 1-hexylthiocarbonyl group.
  • the C1-C6 alkylthiothiocarbonyl group represented by R9 includes methylthiothiocarbonyl group, ethylthiothiocarbonyl group, n-propylthiothiocarbonyl group, isopropylthiothiocarbonyl group, n-butylthiothiocarbonyl group, sec Examples include -butylthiothiocarbonyl group, tert-butylthiothiocarbonyl group, 1-pentylthiothiocarbonyl group, and 1-hexylthiothiocarbonyl group.
  • the C1-C6 alkylsulfonyl group represented by R 9 includes a methanesulfonyl group, ethanesulfonyl group, n-propanesulfonyl group, isopropanesulfonyl group, n-butanesulfonyl group, isobutanesulfonyl group, sec-butanesulfonyl group, Examples include tert-butanesulfonyl group and n-pentanesulfonyl group.
  • the C1-C6 haloalkylsulfonyl group represented by R 9 includes monofluoromethylsulfonyl group, difluoromethylsulfonyl group, trifluoromethylsulfonyl group, monochloromethylsulfonyl group, trichloromethylsulfonyl group, 2,2,2-trifluoro Examples include ethylsulfonyl group.
  • R 1 each independently represents a phenyl group (the group may be mono- or polysubstituted with a halogen atom, a C1-C6 alkyl group, or a C1-C6 haloalkyl group), a C7-C11 aralkyl group (the group may be mono- or polysubstituted with a halogen atom, cyano group, nitro group, C1-C6 alkyl group, C1-C6 haloalkyl group, C1-C6 alkoxy group, or C1-C6 haloalkoxy group), heterocycle C1-C6 alkyl group (the group may be mono- or polysubstituted with a halogen atom, a C1-C6 alkyl group, or a C1-C6 haloalkyl group), a phenoxy C1-C6 alkyl
  • R 2 and R 3 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 alkoxy C1-C6 alkoxy group, a C1-C6 Represents an alkylthiothiocarbonyloxy group or a C1-C6 haloalkylsulfonyloxy group, at least one of which is a substituent other than a hydrogen atom, and two adjacent substituents R 2 and R 3 are bonded together.
  • X represents an oxygen atom
  • R 4 and R 5 each independently represent a hydrogen atom or a C1-C6 alkyl group
  • R 6 is a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, an amino group, a C1-C6 alkylamino group, an aminocarbonylamino group, or a phenylamino group (the group is a halogen atom, a C1-C6 alkyl group, or may be mono- or polysubstituted by a C1-C6 haloalkyl group.
  • R 1a each independently represents a hydrogen atom or a triC1-C6 alkylsilyl group, which may be the same or different
  • R 2a and R 3a each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, a C1-C6 alkoxy C1-C6 alkoxy group, a C1-C6 Represents an alkylthiothiocarbonyloxy group or a C1-C6 haloalkylsulfonyloxy group, at least one of which is a substituent other than a hydrogen atom, and two adjacent substituents
  • X a represents an oxygen atom
  • R 4a and R 5a each independently represent a hydrogen atom or a C1-C6 alkyl group
  • R 6a is a hydroxyl group, a C1-C6 alkyl group, a C1-C6 alkoxy group, an amino group, a C1-C6 alkylamino group, an aminocarbonylamino group, or a phenylamino group (the group is a halogen atom, a C1-C6 alkyl group, or may be mono- or polysubstituted by a C1-C6 haloalkyl group.
  • 1,4-cineole derivatives represented by general formula (1) or (1') are shown in Table 1 below. Representative examples of the derivatives are summarized in Table 2 below, but are not limited to these compounds. These compounds include optical isomers, E-forms, and Z-forms. Compound numbers are referenced in the following description.
  • H is a hydrogen atom
  • Me is a methyl group
  • Et is an ethyl group
  • iPr is an isopropyl group
  • cPr is a cyclopropyl group
  • nBu is a normal butyl group
  • iBu is a An isobutyl group
  • tBu represents a tert-butyl group
  • cHex represents a cyclohexyl group
  • Ph represents a phenyl group
  • TPP represents a tetrahydropyranyl group.
  • Stepochemistry at C-3 position in Table 1 refers to the carbon atom substituted with a methyl group in the 1,4-cineole derivative represented by general formula (1) or (1'). This figure shows the optical isomerism when focusing on the C3 position when the C1 position is set.
  • R 1 in the compounds of Table 1 and Table 2 is a hydrogen atom
  • trimethylsilyl examples include compounds substituted with a triethylsilyl group, a triisopropylsilyl group, a dimethylisopropylsilyl group, a diethylisopropylsilyl group, a dimethylhexylsilyl group, a tert-butyldimethylsilyl group, or a ditert-butylmethylsilyl group. be able to.
  • Step-1 is a step of producing a diol derivative (4) by subjecting ⁇ -terpinene represented by formula (3) to an oxidation reaction.
  • ⁇ -Terpinene represented by formula (3) is known and can be obtained from Tokyo Kasei Kogyo Co., Ltd., etc.
  • Oxidation methods in this step include methods using oxidizing agents such as osmium tetroxide, potassium osmate, lead tetraacetate, potassium permanganate, sodium periodate and ruthenium chloride, iodine and silver acetate, potassium ferricyanide, N Examples include oxidation in the presence of a reoxidizing agent such as -methylmorpholine N-oxide and tert-butyl hydroperoxide. Among these oxidation methods, methods using osmium tetroxide and potassium osmate are preferred in terms of good yields.
  • This reaction may be carried out in the presence of a base
  • examples of the base include triethylamine, diisopropylethylamine, tributylamine, propylamine, butylamine, tert-butylamine, benzylamine, N-methylmorpholine, N,N-dimethylaniline, N, Organic bases such as N-diethylaniline, 4-tert-butyl-N,N-dimethylaniline, pyridine, 4-dimethylaminopyridine, picoline, lutidine, pyrazine, imidazole, N-methylimidazole, sodium carbonate, potassium carbonate, carbonic acid Sodium hydrogen, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium hydride, potassium hydride, sodium amide, butyl lithium, tert-butyl lithium, sec-butyl lithium , lithium diiso
  • the base can be used in an amount of 0.01 to 10 equivalents based on ⁇ -terpinene (3) without adversely affecting the progress of the reaction, but in order to obtain the target product in a good yield, It is more preferable to use the amount in an amount of 0.05 to 0.05 equivalents.
  • This reaction is preferably carried out in a solvent.
  • a solvent any solvent that does not harm the reaction can be used, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; Ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, halogen solvents such as chloroform and dichloromethane, acetonitrile, and propionic solvents.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene
  • aliphatic hydrocarbon solvents such
  • Nitrile solvents such as nitrile, ester solvents such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, methanol , alcoholic solvents such as ethanol, 1-propanol, 2-propanol, and tert-butanol, dimethyl sulfoxide, water, hydrochloric acid, acetic acid, or a mixed solvent thereof.
  • the reaction varies depending on the oxidizing agent and reaction conditions used, it can be carried out at an appropriately selected temperature from the range of -90°C to 100°C, but the yield is best in the range of -20 to 100°C. This is preferable in this respect.
  • the desired product can be obtained by ordinary post-treatment operations, but if necessary, it can also be purified by column chromatography, recrystallization, etc. In this step, both isomers can also be obtained individually by performing an asymmetric reaction using an asymmetric ligand such as (DHQ) 2 PHAL or (DHQD) 2 PHAL.
  • R 7 is a C7-C11 aralkyl group (the group is a halogen atom, a cyano group, a nitro group, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C1-C6 alkoxy group, or a C1-C6 haloalkoxy group) ), a heterocyclic C1-C6 alkyl group (the group may be mono- or polysubstituted with a halogen atom, a C1-C6 alkyl group, or a C1-C6 haloalkyl group), represents a benzoyl group (which group may be mono- or polysubstituted by a halogen atom, a C1-C6 alkyl group, or a C1-C6 haloalkyl group), or a triC1-C6 alkylsilyl group, which may be the same or different (Y represents a halogen
  • Step-2 is a diol derivative represented by formula (4) (hereinafter also referred to as substrate (4) or diol (4)) and formula (5) (hereinafter also referred to as reaction substrate (5)).
  • This is a step of producing a monosubstituted product (6) by reacting a compound in the presence of a base.
  • This reaction may be carried out in the presence of a base
  • examples of the base include triethylamine, diisopropylethylamine, tributylamine, propylamine, butylamine, tert-butylamine, benzylamine, N-methylmorpholine, N,N-dimethylaniline, N, Organic bases such as N-diethylaniline, 4-tert-butyl-N,N-dimethylaniline, pyridine, 4-dimethylaminopyridine, picoline, lutidine, pyrazine, imidazole, N-methylimidazole, sodium carbonate, potassium carbonate, carbonic acid Sodium hydrogen, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium hydride, potassium hydride, sodium amide, butyl lithium, tert-butyl lithium, sec-butyl lithium , lithium diiso
  • the base can be used in an amount of 0.1 to 5 equivalents based on the substrate (4) without adversely affecting the progress of the reaction, but in order to obtain the target product in a good yield, it is necessary to use a base in an amount of 0.5 to 3 equivalents. It is preferably used in a range of 1 to 1.5 equivalents, and more preferably in a range of 1 to 1.5 equivalents.
  • Reaction substrate (5) can be used in an amount of 0.5 to 5 equivalents relative to substrate (4) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is necessary to use 1 to 5 equivalents. It is preferably used in a range of 3 equivalents, more preferably in a range of 1.1 to 1.5 equivalents.
  • the desired product may be obtained in good yield by using a reoxidizing agent, and N-methylmorpholine oxide, trimethylamine oxide, tert-butyl hydroperoxide, potassium ferricyanide, etc. can be used as the reoxidizing agent.
  • the reoxidizing agent can be used in an amount of 0.1 to 20 equivalents based on the substrate (4) without adversely affecting the progress of the reaction, but in order to obtain the target product in a good yield, it is necessary to use a reoxidizing agent in an amount of 1 to 10 equivalents. It is preferably used in a range of 1.5 to 5 equivalents, more preferably in a range of 1.5 to 5 equivalents.
  • This reaction is preferably carried out in a solvent.
  • a solvent any solvent that does not harm the reaction can be used, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; Ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, halogen solvents such as chloroform and dichloromethane, acetonitrile, and propionic solvents.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene
  • aliphatic hydrocarbon solvents such
  • Nitrile solvents such as nitrile, ester solvents such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, methanol , alcoholic solvents such as ethanol, 1-propanol, 2-propanol, and tert-butanol, dimethyl sulfoxide, water, or a mixed solvent thereof can be used.
  • the reaction can be carried out at an appropriately selected temperature from the range of -90°C to 200°C, although it varies depending on the base used and reaction conditions. preferable.
  • the desired product can be obtained by ordinary post-treatment operations, but if necessary, it can also be purified by column chromatography, recrystallization, etc.
  • 1S,2R-(4) and 1R,2S-(4) in place of diol (4), both isomers can be obtained while maintaining their stereochemistry.
  • Step-3 is a step of producing an epoxy derivative (7) by subjecting the olefin derivative represented by formula (6) (hereinafter also referred to as substrate (6)) to an oxidation reaction.
  • the obtained epoxy derivative (7) is a mixture of 1R,6R-(7) and 1S,6S-(7), and can be easily separated and purified by column chromatography or the like.
  • the oxidizing agents used in this reaction include hydrogen peroxide, m-chloroperbenzoic acid, peracetic acid, tert-butyl hydroperoxide, sodium periodate, and OXONE (trade name of EI DuPont; peroxosulfuric acid).
  • Peroxides such as potassium hydrogen-containing substances), N-chlorosuccinimide, N-bromosuccinimide, tert-butyl dichlorite, sodium hypochlorite, oxygen, etc. can be used.
  • the oxidizing agent can be used in an amount of 0.1 to 10 equivalents based on the substrate (6) without adversely affecting the progress of the reaction, but in order to obtain the target product in a good yield, it is necessary to use an oxidizing agent of 0.5 to 5 equivalents. It is preferably used in an equivalent range, more preferably in a range of 1 to 3 equivalents.
  • the desired product may be synthesized in good yield.
  • the catalyst used in this reaction include molybdenum oxide, boric acid, tris(acetylacetone)iron, and sodium tungstate. Among these catalysts, sodium tungstate and the like are preferred in terms of good yield. These catalysts can be used in the range of 0.01 to 30 mol % based on the substrate (6) without adversely affecting the progress of the reaction. ) is preferably used in a range of 0.1 to 10 mol %, more preferably 0.5 to 1 mol %.
  • This reaction is preferably carried out in a solvent.
  • a solvent any solvent that does not harm the reaction can be used, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; Ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; halogen solvents such as chloroform and dichloromethane; water; Mixed solvents can be used.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene
  • aliphatic hydrocarbon solvents such as pentane
  • the reaction can be carried out at an appropriately selected temperature from the range of -90°C to 200°C, although it varies depending on the oxidizing agent and reaction conditions used, but the yield is best in the range of -10 to 50°C. This is preferable in this respect.
  • the desired product can be obtained by ordinary post-treatment operations, but if necessary, it can also be purified by column chromatography, recrystallization, etc.
  • Step-2 is carried out using 1S,2R-(4) and 1R,2S-(4) obtained by carrying out the asymmetric reaction in Step-1 as raw materials instead of the olefin derivative (6).
  • the olefin derivative (6) of both isomers each of the isomers can be obtained while maintaining its stereochemistry.
  • Step-4 is to ring-open the epoxy derivative represented by formula (7) (hereinafter also referred to as substrate (7)) using an acid, and simultaneously perform intramolecular cyclization to form a 1,4-cineole derivative ( This is the process of manufacturing 8).
  • Acids used in this reaction include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, trifluoroacetic acid, p-tosylic acid, pyridinium p-toluenesulfonate, methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, benzenesulfonic acid, and fluorosulfonic acid.
  • Organic acids and inorganic acids such as acid, chloric acid, bromic acid, iodic acid, perbromic acid, thiocyanic acid, metaperiodic acid, hexafluorophosphoric acid, tetrafluoroboric acid, chlorobenzoic acid, and fluorobenzoic acid are used. be able to.
  • the acid can be used in an amount of 0.1 to 5 equivalents based on the substrate (7) without adversely affecting the progress of the reaction, but in order to obtain the target product in a good yield, it is necessary to use an acid in an amount of 0.5 to 3 equivalents. It is preferably used in a range of 1 to 1.5 equivalents, and more preferably in a range of 1 to 1.5 equivalents.
  • This reaction is preferably carried out in a solvent.
  • a solvent any solvent that does not harm the reaction can be used, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; Ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, halogen solvents such as chloroform and dichloromethane, acetonitrile, and propionic solvents.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene
  • aliphatic hydrocarbon solvents such
  • Nitrile solvents such as nitrile, ester solvents such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, methanol , alcoholic solvents such as ethanol, 1-propanol, 2-propanol, and tert-butanol, dimethyl sulfoxide, water, hydrochloric acid, acetic acid, or a mixed solvent thereof.
  • the reaction can be carried out at an appropriately selected temperature from the range of -90°C to 200°C, although it varies depending on the acid used and reaction conditions. preferable.
  • the desired product can be obtained by ordinary post-treatment operations, but if necessary, it can also be purified by column chromatography, recrystallization, or the like.
  • 1S,2R-(4) and 1R,2S-(4) obtained by carrying out the asymmetric reaction in Step-1 instead of the epoxy derivative (7) are used as raw materials in Step-2 and Step-2.
  • the epoxy derivatives (7) of each isomer subjected to -3 each isomer can be obtained while maintaining its stereochemistry.
  • Step-5 is a step of producing a ketone derivative (9) by subjecting the 1,4-cineole derivative represented by formula (8) (hereinafter also referred to as substrate (8)) to an oxidation reaction.
  • the oxidation reactions used in this reaction include Swern oxidation using dimethyl sulfoxide, oxalyl chloride, and triethylamine, PCC oxidation and PDC oxidation using pyridinium chlorochromate and pyridinium dichromate, and Dess-Martin periodinane and 2-iodoxybenzoic acid.
  • IBX TPAP oxidation using tetrapropylammonium perruthenate, 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO), 2-azaadamantane-N-oxyl ( AZADO) Oxidation using nitroxy radicals such as 2-hydroxy-2-azadamantane (AZADOL), iodobenzenediacetate (PIDA), 1-acetoxy-1,2-benzyodoxol-3(1H)- (ABX), oxidation using hypervalent iodine such as 1-(tert-butylperoxy)-1,2-benzoiodoxol-3-one, and using N-tert-butylbenzenesulfimidoyl chloride.
  • TEMPO 2,2,6,6-tetramethylpiperidine-1-oxyl radical
  • AZADO 2-azaadamantane-N-oxyl
  • AZADO 2-azaadamantane-N-oxyl
  • AZADOL 2-hydroxy-2-
  • the oxidizing agent can be used in an amount of 0.1 to 10 equivalents based on the substrate (8) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is necessary to use 0.5 to 3 equivalents. It is preferably used in an equivalent range, more preferably in a range of 1 to 1.5 equivalents.
  • This reaction is preferably carried out in a solvent.
  • a solvent any solvent that does not harm the reaction can be used, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; Ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane; ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; halogen solvents such as chloroform and dichloromethane; water; Mixed solvents can be used.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene
  • aliphatic hydrocarbon solvents such as pentane
  • the reaction can be carried out at an appropriately selected temperature from the range of -90°C to 200°C, although it varies depending on the oxidizing agent and reaction conditions used, but a temperature range of 0 to 100°C gives a good yield. It is preferable.
  • the desired product can be obtained by ordinary post-treatment operations, but if necessary, it can also be purified by column chromatography, recrystallization, or the like.
  • 1S,2R-(4) and 1R,2S-(4) obtained by carrying out the asymmetric reaction in Step-1 instead of the 1,4-cineole derivative (8) are used as raw materials in the step.
  • the 1,4-cineole derivative (8) of each isomer obtained by carrying out Step-2, Step-3 and Step-4 each isomer can be obtained while maintaining its stereochemistry.
  • Step-6 is a Wittig reaction of the ketone derivative represented by formula (9) (hereinafter also referred to as substrate (9)) with phosphonium ylide (10) (hereinafter also referred to as reaction substrate (10)) to produce an olefin derivative.
  • substrate (9) a ketone derivative represented by formula (9)
  • phosphonium ylide (10) hereinafter also referred to as reaction substrate (10)
  • the reaction substrate (10) can be used in the range of 0.5 to 5 equivalents relative to the substrate (9) without adversely affecting the progress of the reaction, but in order to obtain the target product in a good yield, it is necessary to use 1 to 5 equivalents. It is preferably used in a range of 3 equivalents, more preferably in a range of 1.1 to 1.5 equivalents.
  • This reaction may be carried out in the presence of a base
  • examples of the base include sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, potassium tert-butoxide, Sodium hydride, potassium hydride, sodium amide, butyl lithium, tert-butyl lithium, sec-butyl lithium, lithium diisopropylamide, trimethylsilyl lithium, sodium hexamethyl disilazide, potassium hexamethyl disilazide, lithium hexamethyl disilazide Alkali metal salts such as dide can be used.
  • the base can be used in an amount of 0.1 to 5 equivalents based on the substrate (9) without adversely affecting the progress of the reaction, but in order to obtain the target product in a good yield, it is necessary to use a base in an amount of 0.5 to 3 equivalents. It is preferably used in a range of 1 to 1.5 equivalents, and more preferably in a range of 1 to 1.5 equivalents.
  • This reaction is preferably carried out in a solvent.
  • a solvent any solvent that does not harm the reaction can be used, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; Ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane, halogen solvents such as chloroform and dichloromethane, nitrile solvents such as acetonitrile and propionitrile, ethyl acetate, and acetic acid.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene
  • aliphatic hydrocarbon solvents such as pentane, hexan
  • Ester solvents such as propyl, butyl acetate, methyl propionate, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, methanol, ethanol, 1-propanol, 2-propanol, An alcoholic solvent such as tert-butanol, dimethyl sulfoxide, water, or a mixed solvent thereof can be used.
  • the reaction can be carried out at an appropriately selected temperature from the range of -90°C to 200°C, although it varies depending on the base used and reaction conditions. preferable.
  • the desired product can be obtained by ordinary post-treatment operations, but if necessary, it can also be purified by column chromatography, recrystallization, etc.
  • 1S,2R-(4) and 1R,2S-(4) obtained by carrying out the asymmetric reaction in Step-1 are used as raw materials, and Step-2 and Step-2 are carried out.
  • the ketone derivatives (9) of each isomer after carrying out Step-3, Step-4 and Step-5, each isomer can be obtained while maintaining its stereochemistry.
  • Step-7 is to react the ketone derivative represented by formula (9) with an organic metal represented by formula (12) or formula (13) (hereinafter also referred to as reaction substrates (12) and (13), respectively). This is a step for producing a 1,4-cineole derivative (14).
  • Reaction substrate (12) or (13) can be used in an amount of 0.5 to 5 equivalents relative to substrate (9) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, It is preferably used in a range of 1 to 3 equivalents, more preferably in a range of 1.1 to 1.5 equivalents.
  • This reaction is preferably carried out in a solvent.
  • a solvent any solvent that does not harm the reaction can be used, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; Ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, 1,4-dioxane, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, halogen solvents such as chloroform, dichloromethane, or mixed solvents thereof.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene
  • aliphatic hydrocarbon solvents such as pentane, hexan
  • the reaction can be carried out at a temperature appropriately selected from the range of -90°C to 200°C, although it varies depending on the reaction conditions, but a temperature in the range of -20 to 100°C is preferred in terms of good yield.
  • the desired product can be obtained by ordinary post-treatment operations, but if necessary, it can also be purified by column chromatography, recrystallization, etc.
  • 1S,2R-(4) and 1R,2S-(4) obtained by carrying out the asymmetric reaction in Step-1 are used as raw materials, and Step-2 and Step-2 are carried out.
  • the ketone derivatives (9) of each isomer after carrying out Step-3, Step-4 and Step-5, each isomer can be obtained while maintaining its stereochemistry.
  • Step-8 is to produce an imine derivative (16) by reacting an amine compound represented by formula (15) (hereinafter also referred to as reaction substrate (15)) with a ketone derivative represented by formula (9). It is a process.
  • the amine compound (15) used in this reaction can also be used as a salt, and as the salt, hydrochloride, sulfate, carbonate, etc. can be used.
  • the reaction substrate (15) can be used in an amount of 0.5 to 5 equivalents relative to the substrate (9) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is necessary to use 1 to 5 equivalents. It is preferably used in a range of 3 equivalents, more preferably in a range of 1.1 to 1.5 equivalents.
  • This reaction may be carried out in the presence of an acid or a base, and examples of the acid include hydrochloric acid, sulfuric acid, acetic acid, etc., and examples of the base include triethylamine, diisopropylethylamine, tributylamine, propylamine, butylamine, and tert-butylamine.
  • benzylamine N-methylmorpholine, N,N-dimethylaniline, N,N-diethylaniline, 4-tert-butyl-N,N-dimethylaniline, pyridine, 4-dimethylaminopyridine, picoline, lutidine, pyrazine,
  • Organic bases such as imidazole, N-methylimidazole, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, potassium-tert-butoxide, sodium hydride, hydrogen Alkali metal salts such as potassium dichloride, sodium amide, butyllithium, tert-butyllithium, lithium diisopropylamide, trimethylsilyllithium, lithium hexamethyldisilazide, etc.
  • the acid or base can be used in an amount of 0.1 to 10 equivalents based on the substrate (9) without adversely affecting the progress of the reaction, but in order to obtain the target product in a good yield, it is necessary to use an amount of 0.5 to 10 equivalents. It is preferably used in a range of 5 equivalents, and more preferably in a range of 1 to 3 equivalents.
  • This reaction is preferably carried out in a solvent.
  • a solvent any solvent that does not harm the reaction can be used, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; Ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane, halogen solvents such as chloroform and dichloromethane, nitrile solvents such as acetonitrile and propionitrile, ethyl acetate, and acetic acid.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene
  • aliphatic hydrocarbon solvents such as pentane, hexan
  • Ester solvents such as propyl, butyl acetate, methyl propionate, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, methanol, ethanol, 1-propanol, 2-propanol, An alcoholic solvent such as tert-butanol, dimethyl sulfoxide, water, or a mixed solvent thereof can be used.
  • the reaction can be carried out at an appropriately selected temperature from the range of 0°C to 200°C, although it varies depending on the base used and reaction conditions, but a temperature range of 20 to 100°C is preferred in terms of good yield. .
  • the desired product can be obtained by ordinary post-treatment operations, but if necessary, it can also be purified by column chromatography, recrystallization, etc.
  • 1S,2R-(4) and 1R,2S-(4) obtained by carrying out the asymmetric reaction in Step-1 are used as raw materials, and Step-2 and Step-2 are carried out.
  • the ketone derivatives (9) of each isomer after carrying out Step-3, Step-4 and Step-5 each isomer can be obtained while maintaining its stereochemistry.
  • Step-9 is by reacting the compound represented by formula (17) (hereinafter also referred to as reaction substrate (17)) on the 3-position hydroxyl group of the 1,4-cineole derivative represented by formula (8). , is a step for producing a 1,4-cineole derivative (18).
  • the reaction substrate (17) can be used in an amount of 0.5 to 5 equivalents relative to the substrate (8) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is necessary to use 1 to 5 equivalents. It is preferably used in a range of 3 equivalents, more preferably in a range of 1.1 to 1.5 equivalents.
  • This reaction may be carried out in the presence of a base
  • examples of the base include triethylamine, diisopropylethylamine, tributylamine, propylamine, butylamine, tert-butylamine, benzylamine, N-methylmorpholine, N,N-dimethylaniline, N, Organic bases such as N-diethylaniline, 4-tert-butyl-N,N-dimethylaniline, pyridine, 4-dimethylaminopyridine, picoline, lutidine, pyrazine, imidazole, N-methylimidazole, sodium carbonate, potassium carbonate, carbonic acid Sodium hydrogen, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium hydride, potassium hydride, sodium amide, butyl lithium, tert-butyl lithium, sec-butyl lithium , lithium diiso
  • the base can be used in an amount of 0.1 to 10 equivalents based on the substrate (8) without adversely affecting the progress of the reaction, but in order to obtain the target product in a good yield, it is necessary to use a base in an amount of 0.5 to 3 equivalents. It is preferably used in a range of 1 to 1.5 equivalents, and more preferably in a range of 1 to 1.5 equivalents.
  • any solvent that does not harm the reaction can be used, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene, and aliphatic solvents such as pentane, hexane, and octane.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene
  • aliphatic solvents such as pentane, hexane, and octane.
  • Hydrocarbon solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, and halogen solvents such as chloroform and dichloromethane.
  • ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane
  • ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone
  • halogen solvents such as chloroform and dichloromethane.
  • nitrile solvents such as acetonitrile, propionitrile, ester solvents such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.
  • An amide solvent, an alcohol solvent such as methanol, ethanol, 1-propanol, 2-propanol, and tert-butanol, dimethyl sulfoxide, water, or a mixed solvent thereof can be used.
  • the reaction can be carried out at an appropriately selected temperature from the range of 0°C to 200°C, although it varies depending on the base used and reaction conditions, but a temperature range of 20 to 100°C is preferred in terms of good yield. .
  • the desired product can be obtained by ordinary post-treatment operations, but if necessary, it can also be purified by column chromatography, recrystallization, etc.
  • 1S,2R-(4) and 1R,2S-(4) obtained by carrying out the asymmetric reaction in Step-1 are used as raw materials in place of the 1,4-cineole derivative (8).
  • the 1,4-cineole derivative (8) of each isomer obtained by carrying out Step-2, Step-3 and Step-4 each isomer can be obtained while maintaining its stereochemistry.
  • step-10 the 1,4-cineole derivative represented by formula (8) is reacted with ethyl vinyl ether (19) (hereinafter also referred to as reaction substrate (19)) under an acid catalyst to form a product represented by formula (20).
  • reaction substrate (19) can be used in an amount of 0.5 to 5 equivalents relative to the substrate (8) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is necessary to use 1 to 5 equivalents. It is preferably used in a range of 3 equivalents, more preferably in a range of 1.1 to 1.5 equivalents.
  • organic acids or inorganic acids such as hydrochloric acid, sulfuric acid, acetic acid, p-tosylic acid, and pyridinium p-toluenesulfonate can be used.
  • the acid can be used in an amount of 0.001 to 1 equivalent relative to the substrate (8) without adversely affecting the progress of the reaction, but in order to obtain the target product in a good yield, it should be used in an amount of 0.005 to 0. It is preferably used in a range of 5 equivalents, more preferably in a range of 0.05 to 0.1 equivalents.
  • This reaction is preferably carried out in a solvent.
  • a solvent any solvent that does not harm the reaction can be used, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; Ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, halogen solvents such as chloroform and dichloromethane, acetonitrile, and propionic solvents.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene
  • aliphatic hydrocarbon solvents such
  • Nitrile solvents such as nitrile, ester solvents such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, methanol , alcoholic solvents such as ethanol, 1-propanol, 2-propanol, and tert-butanol, dimethyl sulfoxide, water, or a mixed solvent thereof can be used.
  • the reaction can be carried out at an appropriately selected temperature from the range of 0°C to 200°C, although it varies depending on the acid used and reaction conditions, but a temperature range of 20 to 100°C is preferred in terms of good yield. .
  • the desired product can be obtained by ordinary post-treatment operations, but if necessary, it can also be purified by column chromatography, recrystallization, or the like.
  • 1S,2R-(4) and 1R,2S-(4) obtained by carrying out the asymmetric reaction in Step-1 instead of the 1,4-cineole derivative (8) are used as raw materials in the step.
  • the 1,4-cineole derivative (8) of each isomer obtained by carrying out Step-2, Step-3 and Step-4 each isomer can be obtained while maintaining its stereochemistry.
  • Step-11 is to deprotect the silyl ether derivative represented by formula (21) (hereinafter also referred to as substrate (21)) in the presence of an acid or fluoride ion to obtain 1,4 represented by formula (22). - This is a process for producing cineole derivatives.
  • Acids used in this reaction include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, trifluoroacetic acid, p-tosylic acid, pyridinium paratoluenesulfonate, methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, benzenesulfonic acid, and fluorosulfonic acid. , chloric acid, bromic acid, iodic acid, perbromic acid, thiocyanic acid, metaperiodic acid, hexafluorophosphoric acid, tetrafluoroboric acid, chlorobenzoic acid, fluorobenzoic acid, and other organic acids and inorganic acids.
  • the acid can be used in an amount of 0.1 to 10 equivalents based on the substrate (21) without adversely affecting the progress of the reaction, but in order to obtain the target product in a good yield, it is necessary to use an acid in an amount of 0.5 to 3 equivalents. It is preferably used in a range of 1 to 1.5 equivalents, and more preferably in a range of 1 to 1.5 equivalents.
  • the fluoride ion used in this reaction potassium fluoride, cesium fluoride, hydrofluoric acid and its salts, tetrabutylammonium fluoride, etc. can be used.
  • Fluoride ions can be used in an amount of 0.1 to 10 equivalents relative to the substrate (21) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, fluoride ions can be used in an amount of 0.1 to 10 equivalents. It is preferably used in a range of 3 equivalents, more preferably in a range of 1 to 1.5 equivalents.
  • This reaction is preferably carried out in a solvent.
  • a solvent any solvent that does not harm the reaction can be used, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; Ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, halogen solvents such as chloroform and dichloromethane, acetonitrile, and propionic solvents.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene
  • aliphatic hydrocarbon solvents such
  • Nitrile solvents such as nitrile, ester solvents such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, methanol , alcoholic solvents such as ethanol, 1-propanol, 2-propanol, and tert-butanol, dimethyl sulfoxide, water, or a mixed solvent thereof can be used.
  • the reaction can be carried out at an appropriately selected temperature from the range of 0°C to 200°C, although it varies depending on the acid used and reaction conditions, but a temperature range of 20 to 100°C is preferred in terms of good yield. .
  • the desired product can be obtained by ordinary post-treatment operations, but if necessary, it can also be purified by column chromatography, recrystallization, or the like.
  • Step-12 is to deprotect the silyl ether derivative represented by formula (23) (hereinafter also referred to as substrate (23)) in the presence of an acid or fluoride ion to obtain 1,4 represented by formula (24).
  • substrate (23) an acid or fluoride ion
  • 1,4 represented by formula (24) This is a process for producing cineole derivatives.
  • Acids used in this reaction include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, trifluoroacetic acid, p-tosylic acid, pyridinium para-toluenesulfonate, methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, benzenesulfonic acid, and fluorosulfonic acid. , chloric acid, bromic acid, iodic acid, perbromic acid, thiocyanic acid, metaperiodic acid, hexafluorophosphoric acid, tetrafluoroboric acid, chlorobenzoic acid, fluorobenzoic acid, and other organic acids and inorganic acids.
  • the acid can be used in an amount of 0.1 to 10 equivalents based on the substrate (23) without adversely affecting the progress of the reaction, but in order to obtain the target product in a good yield, it is necessary to use an acid in an amount of 0.5 to 3 equivalents. It is preferably used in a range of 1 to 1.5 equivalents, and more preferably in a range of 1 to 1.5 equivalents.
  • fluoride ion used in this reaction sodium fluoride, potassium fluoride, cesium fluoride, hydrofluoric acid and its salts, tetrabutylammonium fluoride, etc. can be used.
  • Fluoride ions can be used in an amount of 0.1 to 10 equivalents relative to the substrate (23) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, fluoride ions can be used in an amount of 0.1 to 10 equivalents. It is preferably used in a range of 3 equivalents, more preferably in a range of 1 to 1.5 equivalents.
  • This reaction is preferably carried out in a solvent.
  • a solvent any solvent that does not harm the reaction can be used, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; Ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, halogen solvents such as chloroform and dichloromethane, acetonitrile, and propionic solvents.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene
  • aliphatic hydrocarbon solvents such
  • Nitrile solvents such as nitrile, ester solvents such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, methanol , alcoholic solvents such as ethanol, 1-propanol, 2-propanol, and tert-butanol, dimethyl sulfoxide, water, or a mixed solvent thereof can be used.
  • reaction varies depending on the acid used and reaction conditions, it can be carried out at an appropriately selected temperature from the range of 0°C to 200°C, but a temperature range of 20 to 100°C is preferred in terms of good yield. .
  • the desired product can be obtained by ordinary post-treatment operations, but if necessary, it can also be purified by column chromatography, recrystallization, etc.
  • Step-13 is a step of producing a 1,4-cineole derivative (26) by reducing the olefin derivative represented by formula (25) (hereinafter also referred to as substrate (25)).
  • the obtained 1,4-cineole derivative (26) is a mixture of 3R-(26) and 3S-(26), and can be easily separated and purified by column chromatography or the like.
  • Reduction methods in this reaction include a method using a reducing agent such as zinc powder, reduced iron, tin powder, stannous chloride, titanium chloride, etc., a method using a hydrogen donor such as hydrazine in the presence of Raney nickel, a method using Raney nickel, palladium carbon, etc. , catalytic hydrogen reduction in the presence of a catalyst such as palladium hydroxide, platinum oxide, rhodium on carbon, or catalytic hydrogen transfer reduction.
  • a reducing agent such as zinc powder, reduced iron, tin powder, stannous chloride, titanium chloride, etc.
  • This reaction is preferably carried out in a solvent.
  • a solvent any solvent that does not harm the reaction can be used, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; Ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, halogen solvents such as chloroform and dichloromethane, acetonitrile, and propionic solvents.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene
  • aliphatic hydrocarbon solvents such
  • Nitrile solvents such as nitrile, ester solvents such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, methanol , alcoholic solvents such as ethanol, 1-propanol, 2-propanol, and tert-butanol, dimethyl sulfoxide, water, or a mixed solvent thereof can be used.
  • the reaction can be carried out at a temperature appropriately selected from the range of 0°C to 200°C, although it varies depending on the reaction conditions, but a temperature range of 20 to 100°C is preferred in terms of good yield.
  • the desired product can be obtained by ordinary post-treatment operations, but if necessary, it can also be purified by column chromatography, recrystallization, or the like.
  • 1S,2R-(4) and 1R,2S-(4) obtained by carrying out the asymmetric reaction in Step-1 are used as raw materials, and Step-2 and Step-2 are carried out.
  • -3 By using the isomeric olefin derivatives (25) obtained through Step-4, Step-5, Step-6 and Step-12, each isomer can be obtained while maintaining its stereochemistry. can.
  • reaction substrate (22) a compound represented by formula (27)
  • substrate (22) is added onto the 2-position hydroxyl group of the 1,4-cineole derivative represented by formula (22) (hereinafter also referred to as substrate (22)).
  • substrate (22) This is a step for producing a 1,4-cineole derivative (28) by reacting the 1,4-cineole derivative (27).
  • the reaction substrate (27) can be used in an amount of 0.5 to 5 equivalents relative to the substrate (22) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is necessary to use 1 to 5 equivalents.
  • This reaction may be carried out in the presence of a base, and examples of the base include triethylamine, diisopropylethylamine, tributylamine, propylamine, butylamine, tert-butylamine, benzylamine, N-methylmorpholine, N,N-dimethylaniline, N, Organic bases such as N-diethylaniline, 4-tert-butyl-N,N-dimethylaniline, pyridine, 4-dimethylaminopyridine, picoline, lutidine, pyrazine, imidazole, N-methylimidazole, sodium carbonate, potassium carbonate, carbonic acid Sodium hydrogen, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium hydride, potassium hydride, sodium hydride, potassium hydride, sodium
  • the base can be used in an amount of 0.1 to 10 equivalents based on the substrate (22) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is necessary to use a base in an amount of 0.5 to 3 equivalents. It is preferably used in a range of 1 to 1.5 equivalents, and more preferably in a range of 1 to 1.5 equivalents.
  • any solvent that does not harm the reaction can be used, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene, and aliphatic solvents such as pentane, hexane, and octane.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene
  • aliphatic solvents such as pentane, hexane, and octane.
  • Hydrocarbon solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, and halogen solvents such as chloroform and dichloromethane.
  • ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane
  • ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone
  • halogen solvents such as chloroform and dichloromethane.
  • nitrile solvents such as acetonitrile, propionitrile, ester solvents such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.
  • An amide solvent, an alcohol solvent such as methanol, ethanol, 1-propanol, 2-propanol, tert-butanol, dimethyl sulfoxide, water, or a mixed solvent thereof can be used.
  • the reaction can be carried out at a temperature appropriately selected from the range of 0°C to 200°C, although it varies depending on the base used and reaction conditions, but a temperature range of 20 to 100°C is preferred in terms of good yield. .
  • the desired product can be obtained by ordinary post-treatment operations, but if necessary, it can also be purified by column chromatography, recrystallization, or the like.
  • Step-15 is by reacting the compound represented by formula (27) on the 2-position hydroxyl group of the 1,4-cineole derivative represented by formula (24) (hereinafter also referred to as substrate (24)), This is a step for producing a 1,4-cineole derivative (29).
  • the reaction substrate (27) can be used in an amount of 0.5 to 5 equivalents relative to the substrate (24) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is necessary to use 1 to 5 equivalents. It is preferably used in a range of 3 equivalents, more preferably in a range of 1.1 to 1.5 equivalents.
  • This reaction may be carried out in the presence of a base
  • examples of the base include triethylamine, diisopropylethylamine, tributylamine, propylamine, butylamine, tert-butylamine, benzylamine, N-methylmorpholine, N,N-dimethylaniline, N, Organic bases such as N-diethylaniline, 4-tert-butyl-N,N-dimethylaniline, pyridine, 4-dimethylaminopyridine, picoline, lutidine, pyrazine, imidazole, N-methylimidazole, sodium carbonate, potassium carbonate, carbonic acid Sodium hydrogen, potassium hydrogen carbonate, sodium acetate, potassium acetate, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium hydride, potassium hydride, sodium amide, butyl lithium, tert-butyl lithium, sec-butyl lithium , lithium diiso
  • the base can be used in an amount of 0.1 to 10 equivalents based on the substrate (24) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is necessary to use a base in an amount of 0.5 to 3 equivalents. It is preferably used in a range of 1 to 1.5 equivalents, and more preferably in a range of 1 to 1.5 equivalents.
  • any solvent that does not harm the reaction can be used, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene, and aliphatic solvents such as pentane, hexane, and octane.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene
  • aliphatic solvents such as pentane, hexane, and octane.
  • Hydrocarbon solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, and halogen solvents such as chloroform and dichloromethane.
  • ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane
  • ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone
  • halogen solvents such as chloroform and dichloromethane.
  • nitrile solvents such as acetonitrile, propionitrile, ester solvents such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.
  • An amide solvent, an alcohol solvent such as methanol, ethanol, 1-propanol, 2-propanol, tert-butanol, dimethyl sulfoxide, water, or a mixed solvent thereof can be used.
  • the reaction can be carried out at an appropriately selected temperature from the range of 0°C to 200°C, although it varies depending on the base used and reaction conditions, but a temperature range of 20 to 100°C is preferred in terms of good yield. .
  • the desired product can be obtained by ordinary post-treatment operations, but if necessary, it can also be purified by column chromatography, recrystallization, etc.
  • 1S,2R-(4) and 1R,2S-(4) obtained by performing the asymmetric reaction in Step-1 were used as raw materials instead of the 1,4-cineole derivative (24), and then By using each isomer of the 1,4-cineole derivative (24) subjected to the step described above, each isomer can be obtained while maintaining its stereochemistry.
  • Step-16 is a step of producing a 1,4-cineole derivative represented by formula (30) by halogenating an alcohol derivative represented by formula (8) (hereinafter also referred to as substrate (8)).
  • halogenating reagents used in this reaction include fluorinating reagents such as DAST, bromine trifluoride, and cesium fluoride, and chlorinating reagents such as chlorine, thionyl chloride, oxalyl chloride, phosphorus pentachloride, phosphoryl chloride, and N-chlorosuccinimide.
  • Brominating reagents such as , bromine, thionyl bromide, oxalyl bromide, phosphorous pentabromide, phosphoryl bromide, N-bromosuccinimide, and iodinating reagents such as iodine and N-iodosuccinimide can be used.
  • the halogenating agent can be used in an amount of 0.1 to 10 equivalents based on the substrate (8) without adversely affecting the progress of the reaction. It is preferably used in a range of 3 equivalents, more preferably in a range of 1 to 1.5 equivalents.
  • This reaction is preferably carried out in a solvent.
  • a solvent any solvent that does not harm the reaction can be used, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; Ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, halogen solvents such as chloroform and dichloromethane, acetonitrile, and propionic solvents.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene
  • aliphatic hydrocarbon solvents such
  • Nitrile solvents such as nitrile, ester solvents such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, methanol , alcoholic solvents such as ethanol, 1-propanol, 2-propanol, and tert-butanol, pyridine, dimethyl sulfoxide, water, or a mixed solvent thereof can be used.
  • ester solvents such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate
  • amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone
  • methanol alcoholic solvents such as ethanol, 1-propanol, 2-propanol, and tert-butanol, pyr
  • the reaction can be carried out at an appropriately selected temperature from the range of 0°C to 200°C, although it varies depending on the halogenating agent and reaction conditions used. However, a temperature range of 20 to 100°C gives a good yield. It is preferable.
  • the desired product can be obtained by ordinary post-treatment operations, but if necessary, it can also be purified by column chromatography, recrystallization, or the like.
  • 1S,2R-(4) and 1R,2S-(4) obtained by carrying out the asymmetric reaction in Step-1 instead of the alcohol derivative (8) are used as raw materials in Step-2 and Step-2.
  • Step-17 is a step of producing an alcohol derivative represented by formula (32) by deprotecting the ether derivative represented by formula (31) (hereinafter also referred to as substrate (31)) in the presence of an acid.
  • Acids used in this reaction include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, trifluoroacetic acid, p-tosylic acid, pyridinium paratoluenesulfonate, methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, benzenesulfonic acid, and fluorosulfonic acid.
  • the acid can be used in an amount of 0.1 to 10 equivalents based on the substrate (31) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is necessary to use 0.5 to 5 equivalents. It is preferable to use it in the range of 1 to 3 equivalents, and more preferably in the range of 1 to 3 equivalents.
  • This reaction is preferably carried out in a solvent.
  • a solvent any solvent that does not harm the reaction can be used, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; Ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, halogen solvents such as chloroform and dichloromethane, acetonitrile, and propionic solvents.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene
  • aliphatic hydrocarbon solvents such
  • Nitrile solvents such as nitrile, ester solvents such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, methanol , alcoholic solvents such as ethanol, 1-propanol, 2-propanol, and tert-butanol, dimethyl sulfoxide, water, or a mixed solvent thereof can be used.
  • the reaction varies depending on the acid used and reaction conditions, it can be carried out at an appropriately selected temperature from the range of 0°C to 200°C, but a temperature range of 20 to 100°C is preferred in terms of good yield. .
  • the desired product can be obtained by ordinary post-treatment operations, but if necessary, it can also be purified by column chromatography, recrystallization, etc.
  • 1S,2R-(4) and 1R,2S-(4) obtained by carrying out the asymmetric reaction in Step-1 are used as raw materials, and Step-2 and Step-2 are carried out.
  • -3 By using the isomeric ether derivatives (31) obtained through Step-4, Step-10, Step-11 and Step-14, each isomer can be obtained while maintaining its stereochemistry. can.
  • Step-18 is a step of producing a 1,4-cineole derivative represented by formula (33) by halogenating an alcohol derivative represented by formula (32) (hereinafter also referred to as substrate (32)).
  • halogenating reagents used in this reaction include fluorinating reagents such as DAST, bromine trifluoride, and cesium fluoride, and chlorinating reagents such as chlorine, thionyl chloride, oxalyl chloride, phosphorus pentachloride, phosphoryl chloride, and N-chlorosuccinimide.
  • Brominating reagents such as , bromine, thionyl bromide, oxalyl bromide, phosphorous pentabromide, phosphoryl bromide, N-bromosuccinimide, and iodinating reagents such as iodine and N-iodosuccinimide can be used.
  • the halogenating agent can be used in an amount of 0.1 to 10 equivalents based on the substrate (32) without adversely affecting the progress of the reaction, but in order to obtain the target product in good yield, it is necessary to use 0.1 to 10 equivalents. It is preferably used in a range of 3 equivalents, more preferably in a range of 1 to 1.5 equivalents.
  • This reaction is preferably carried out in a solvent.
  • a solvent any solvent that does not harm the reaction can be used, including aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and octane; Ether solvents such as diethyl ether, diisopropyl ether, cyclopentyl methyl ether, tetrahydrofuran, dimethoxyethane, and 1,4-dioxane, ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone, halogen solvents such as chloroform and dichloromethane, acetonitrile, and propionic solvents.
  • aromatic hydrocarbon solvents such as benzene, toluene, xylene, and chlorobenzene
  • aliphatic hydrocarbon solvents such
  • Nitrile solvents such as nitrile, ester solvents such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate, amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, methanol , alcoholic solvents such as ethanol, 1-propanol, 2-propanol, and tert-butanol, pyridine, dimethyl sulfoxide, water, or a mixed solvent thereof can be used.
  • ester solvents such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate
  • amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone
  • methanol alcoholic solvents such as ethanol, 1-propanol, 2-propanol, and tert-butanol, pyr
  • the reaction can be carried out at an appropriately selected temperature from the range of 0°C to 200°C, although it varies depending on the halogenating agent used and reaction conditions. It is preferable.
  • the desired product can be obtained by ordinary post-treatment operations, but if necessary, it can also be purified by column chromatography, recrystallization, etc.
  • 1S,2R-(4) and 1R,2S-(4) obtained by carrying out the asymmetric reaction in Step-1 are used as raw materials, and Step-2 is carried out.
  • Step-2 is carried out.
  • the alcohol derivatives (32) of each isomer obtained through Step-4, Step-10, Step-11, Step-14 and Step-17 each isomer can be obtained while maintaining its stereochemistry. You can also get
  • the compound of the present invention and the intermediate of the present invention can be analyzed, confirmed, and identified by melting point, infrared absorption spectrum, 1 H-NMR, 13 C-NMR, mass spectrometry, X-ray structural analysis, etc., as necessary.
  • the compound of the present invention is not limited to the above-mentioned manufacturing method, and can be manufactured by any organic synthesis method.
  • the present invention also relates to a herbicide containing the compound of the present invention as an active ingredient (hereinafter also referred to as "the herbicide of the present invention").
  • the herbicide of the present invention is preferably used for farmland, pasture, lawn, or non-agricultural land. Examples of farmland include fields, rice fields, orchards, fallow land, and uncultivated land.
  • the compound of the present invention exhibits excellent herbicidal activity and also exhibits excellent selective herbicidal activity between the following weeds and crops. It can be used for a wide range of subjects. Specific examples of weeds include the following:
  • Echinochloa crus-galli Echinochloa oryzicola, Echinochloa crus-galli var. aria sanguinalis, Digitalia ischaem, Digitalia adscendens, Digitalia microbachne, Digitalia horizontalis) , Setaria Viridis, Setaria faberi, Setaria lutescens, Eleusine indica, Avena fatua, Sor ghum halepense), barley (Aropyron repens), velvet millet (Brachiaria plantaginea) , Panicum maximum, Panicum purpurascens, Panicum dichotomiflorum, Leptochloroa chinensis, Leptochloro a panicea), Poa annua, Alopecurus aequalis, Alopecurus myosuroides, Agropyron tsukushiense, Brachiaria platyphylla, Cench
  • cyperaceae such as Sagittaria pygmaea, Sagittaria trifolia, Alisma canaliculatum; ); Monochoria vaginalis, American monochoria (Heteranthera limosa), water mallow pontderiaceae such as Monochoria kosakowii; linderniaceae such as Lindernia pyxidaria; Plantago asiatica, Plantago asiatica (Gratiola japonica), Dopatrium junceum, Veronica Weeds of the plantaginaceae family (plantaginaceae) such as P.
  • Monochoria vaginalis American monochoria (Heteranthera limosa), water mallow pontderiaceae such as Monochoria kosakowii; linderniaceae such as Lindernia pyxidaria; Plantago asiatica, Plantago asiatica (Gratiola japonica),
  • weeds of the family Lythraceae (lythraceae) such as Rotala india and Ammannia multiflora; Elatine triand Weeds of the Elatinaceae family (elatinaceae) such as ra); malvaceae such as Xantium strumarim, Ambrosia elatioor, Breea sero sa), Chamomile (Galinsoga ciliata), Chamomile (Matricaria) Chamomilla), Taraxacum officinale, Erigeron canadensis, Bidens frondosa, Bidens pilosa, Bide Asteraceae weeds such as Gnaphalium affine (Gnaphalium affine), Senecio vulgaris (Senecio vulgaris) (compositae); Lamiaceae weeds such as Lamium amplexinale weber; Solanaceae weeds such as Solanum nigrum and D
  • various harmful weeds such as Zygnemataceae can be controlled. Therefore, for example, useful crops, for example, rice (Oryza SATIVA L.), corn (ZEA MAYS), D solid (Glycine Max), Wata (GOSSYPIUM SPP.), Komugi (Triticum SPP.) VULGARE), Limige (Secalecereale), Oat (Avena sativa), Sorghum (Sorghum bicolor), Brassica napus (Brassica napus), Sunflower (Helianthus annuus), Sugar beet (Beta Vulgaris), Sugarcane (Sacc) harum officinarum), grass (Zoysia japonicaa), peanut (Arachis hypogaea) It is effectively used to control noxious weeds in the cultivation of , Linum usitatissmum, tobacco (Nicotiana tabacum), coffee (Coffea spp.), etc. Note that the application of the herbicide of the present invention is not limited
  • the compound of the present invention may be used as necessary in formulation or spraying with other herbicides, various insecticides, acaricides, nematicides, fungicides (fungicides, bactericides, antiviral agents, plant resistance induction agents, etc.). It may also be applied in a mixed formulation with a bird repellent, a plant growth regulator, a safener, a fertilizer, a soil conditioner, or a synergist, or in a tank mix at the time of spraying. In particular, by applying the herbicide in combination with other herbicides, the amount of herbicide used can be reduced and labor can be saved. Furthermore, the synergistic action of both herbicides allows the herbicide to be applied to different herbicides (herbicidal spectrum). It is expected that the effects of the two drugs will be expanded and that even stronger effects will be obtained due to the synergistic action of both drugs. At this time, a combination of a plurality of known herbicides and safeners can be added at the same time.
  • herbicides are shown below, but the present invention is not limited to these.
  • Quaternary ammonium salt compounds such as paraquat and diquat, which themselves become free radicals in the plant body and generate active oxygen, thereby exhibiting rapid herbicidal efficacy.
  • Pyridazinone compounds such as norflurazon, chloridazon, metflurazon; pyrazolinate, pyrazoxyfen, benzofenap nzofenap), topramezone, pyrasulfotol Pyrazole compounds such as pyrasulfotole, tolpyralate, tripyrasulfone, fenpyrazone, bipyrazone; others, amitrole, fluridone done), flurtamone, diflufenican, methoxyphenone, clomazone, bixlozone, sulcotrione, mesotrione, tembotr ione), tefuryltrione, fenquinotrione , lancotrione, dioxopyritrone, benquitrione, cyclopyrimorate, isoxaflutole, difenzo difenzoquat), difenzoquat methyl sulfate (dife)
  • chloroacetamide type compound molinate , dimepiperate, pyributicarb, EPTC, butylate, vernolate, cycloate, prosulfocarb, esprocarb ), thiobencarb, diallate , tri-allate, orbencarb; others, etobenzanide, mefenacet, flufenacet, tridiphane, cafenstrol enstrole ), fentrazamide, ipfencarbazone, oxaziclomefone, indanofan, benfuresate, pyroxasu lfone), phenoxasulfone, methiozolin
  • Herbicidal efficacy is achieved by inhibiting protein biosynthesis or lipid biosynthesis in plants, such as , dalapon, dalapon-sodium, TCA-sodium, and trichloroacetic acid.
  • the compound of the present invention when using the compound of the present invention as a herbicide, it can be used as it is, but it can also be used in the form of a formulation.
  • a formulation use appropriate carriers, adjuvants, surfactants, binders, and stabilizers as described in the Pesticide Formulation Guide (edited by the Japanese Society of Pesticide Application Methods, published by the Japan Plant Protection Association, 1997). Agents etc. may be added.
  • the herbicide containing the compound of the present invention can be formulated into any commonly used dosage form, such as granules, fine granules, fine granules, wettable powders, hydrated granules (dry Forms such as flowable agents, emulsions, aqueous solutions, sol agents (flowable agents), liquid agents, powder agents, coarse powder agents, DL (driftless) powder agents, flow dust agents, oil agents, microcapsules, paste agents, jumbo agents, etc. It can be used, but is not limited to:
  • any solid or liquid carrier that is commonly used for agricultural chemical formulations can be used.
  • solid carriers include mineral powders (kaolin, bentonite, clay, montmorillonite, talc, diatomaceous earth, mica, vermiculite, quartz, calcium carbonate, apatite, white carbon, slaked lime, silica sand, acid clay, zeolite, sepiolite, expanded perlite products, shirasu balloons, alumina balloons, microspheres made of phenolic resin, epoxy resin, polyacrylonitrile, polyurethane, etc.), vegetable powders (soybean flour, wheat flour, wood flour, tobacco flour, starch, crystalline cellulose, etc.) ), polymer compounds (petroleum resins, polyvinyl chloride, ketone resins, etc.), alumina, silicates, glucose, sucrose, lactose, sugar polymers, am
  • liquid carriers examples include water, alcohols (methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, butanol, ethylene glycol, benzyl alcohol, etc.), aromatic hydrocarbons (toluene, benzene, xylene, ethylbenzene, etc.).
  • alcohols methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, butanol, ethylene glycol, benzyl alcohol, etc.
  • aromatic hydrocarbons toluene, benzene, xylene, ethylbenzene, etc.
  • ethers ethyl ether, ethylene oxide, dioxane, tetrahydrofuran, etc.
  • ketone solvents acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, isophorone, etc.
  • esters ethyl acetate, butyl acetate, ethylene glycol acetate, amyl acetate, etc.
  • acid amides dimethylformamide, dimethylacetamide, etc.
  • nitriles acetonitrile, propionitrile, acrylonitrile, etc.
  • sulfoxides dimethyl sulfoxide, etc.
  • alcohol ethers ethylene glycol monomethyl ether, ethylene glycol monomethyl ether, etc.
  • aliphatic or alicyclic hydrocarbons n-hexane, cyclohexane,
  • surfactants when formulating herbicides into emulsions, wettable powders, flowables, etc., various surfactants are added for the purposes of emulsification, dispersion, solubilization, wetting, foaming, lubrication, spreading, etc. be done.
  • surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, polyoxyethylene alkylaryl ether, polyoxyethylene polyoxypropylene block polymer, and polyoxyethylene styryl.
  • Nonionic surfactants such as phenyl ether, alkylbenzene sulfonate, alkyl sulfosuccinate, alkyl sulfate, polyoxyethylene alkyl sulfate, aryl sulfonate, alkylnaphthalene sulfonate, polyoxyethylene styrylphenyl ether sulfate, lignin sulfonate, Anionic surfactants such as naphthalene sulfonic acid formaldehyde condensates, polycarboxylate salts, alkylamines (laurylamine, stearyltrimethylammonium chloride, etc.), polyoxyethylenealkylamines, alkylpyridinium salts, alkyltrimethylammonium salts, Examples include cationic surfactants such as alkyldimethylammonium salts, amphoteric surfactants such as carboxylic acid (betaine type), and sulfuric acid
  • various adjuvants include polyvinyl alcohol (PVA), carboxymethyl cellulose (CMC), gum arabic, polyvinyl acetate, sodium alginate, gelatin, gum tragacanth, dextrin, hydroxypropyl methyl cellulose (HPMC), and methyl cellulose (MC). , additives, etc. can be used.
  • PVA polyvinyl alcohol
  • CMC carboxymethyl cellulose
  • HPMC hydroxypropyl methyl cellulose
  • MC methyl cellulose
  • additives, etc. can be used.
  • Preferred methods of using the herbicide containing the compound of the present invention as an active ingredient include soil treatment, water surface treatment, foliage treatment, etc., and particularly excellent effects can be achieved by application before the germination of weeds to be controlled or when they are young. Can be done.
  • the amount of the compound of the present invention to be applied as a herbicide varies depending on the application situation, application time, application method, target weeds, cultivated crops, etc., but in general, the amount of active ingredient is 0.001 to 10 kg per hectare (ha). A suitable amount is preferably about 0.01 to 1 kg.
  • the present invention also relates to a method of using the herbicide of the present invention, which comprises applying an effective amount of the compound of the present invention to at least one selected from weed foliage, soil, and water surface.
  • Weeds are not particularly limited, but include, for example, the above-mentioned weeds. It is preferable that the above-mentioned soil is a field or paddy farmland where agricultural and horticultural plants are cultivated.
  • the water surface refers to the water surface in the soil under flooding.
  • the processing steps are not particularly limited. For example, a step of spraying an effective amount of the compound of the present invention onto at least one selected from the foliage of weeds, soil, and water surface can be mentioned.
  • the present invention provides a method for preparing an agrochemical composition, which includes the step of mixing a herbicide containing the compound of the present invention as an active ingredient with at least one selected from fillers and surfactants. It also relates to methods. Extending agents include, but are not particularly limited to, clay, quartz, calcite, sepiolite, dolomite, chalk, kaolin, pyrophyllite, sericite, hallosite, metahallosite, kibushi clay, frog's eye clay, and ceramics.
  • Natural minerals such as stone, ziecrite, allophane, shirasu, kira, talc, pumice, hectorite, zeolite and diatomaceous earth, such as calcined clay, perlite, shirasu balloon, vermiculite, attapulgus clay and calcined diatomaceous earth.
  • Calcined products such as magnesium carbonate, calcium carbonate, sodium carbonate, sodium bicarbonate, ammonium sulfate, sodium sulfate, magnesium sulfate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and potassium chloride, inorganic salts such as glucose, fructose, Sugars such as sucrose and lactose, polysaccharides such as starch, powdered cellulose and dextrins, organic substances such as urea, urea derivatives, benzoic acid and salts of benzoic acid, such as wood flour, corn cobs, walnut shells and tobacco stalks, etc. Examples include plants, fly ash, white carbon, water, etc.
  • the surfactant is not particularly limited, but includes, for example, those similar to the surfactants described in the above-mentioned formulation of herbicides. Mixing of the herbicide containing the compound of the present invention as an active ingredient and at least one selected from extenders and surfactants is not particularly limited, and known methods can be used.
  • the compound of the present invention has excellent safety in paddy rice.
  • Synthesis example 2 Synthesis of (1S,2R,3R,4S)-3-(benzyloxy)-1-isopropyl-4-methyl-7-oxabicyclo[2.2.1]heptan-2-ol(1-22) (1R,2R ,3S,6R)-2-(benzyloxy)-6-isopropyl-3-methyl-7-oxabicyclo[4.1.0]heptan-3-ol (828 mg, 3.00 mmol) in tetrahydrofuran solution (30 mL). -Toluenesulfonic acid monohydrate (611 mg, 3.19 mmol) was added, and the mixture was stirred at room temperature for 7 hours.
  • Synthesis example 17 (1S,2R,3R,4S)-2-[(2-fluorobenzyl)oxy]-4-isopropyl-3-methoxy-1-methyl-7-oxabicyclo[2.2.1]heptane (1-146)
  • Synthesis Example 15 2-Fluorobenzyl bromide was used instead of 2-Methylbenzyl bromide, and the same reaction and treatment were performed to obtain the title compound as a colorless liquid (yield 25%).
  • Synthesis example 24 (1S,2R,3R,4S)-2-(1-ethoxyethoxy)-1-isopropyl-3-[(2-methoxybenzyl)oxy]-4-methyl-7-oxabicyclo[2.2.1]heptane(1 Synthesis of -173)
  • 2-Methoxybenzyl bromide was used instead of 2-Chlorobenzyl bromide, and the same reaction and treatment were performed to obtain the title compound (yield: 83%) as a colorless liquid.
  • Synthesis example 25 (1S,2R,3R,4S)-2-(1-ethoxyethoxy)-3-[(2-fluorobenzyl)oxy]-1-isopropyl-4-methyl-7-oxabicyclo[2.2.1]heptane(1 Synthesis of -175)
  • 2-Fluorobenzyl bromide was used instead of 2-Chlorobenzyl bromide, and the same reaction and treatment were performed to obtain the title compound as a colorless liquid (yield: 85%).
  • Synthesis example 40 (1S,3R,4S)-3-[(2,6-difluorobenzyl)oxy]-1-isopropyl-2,4-dimethyl-7-oxabicyclo[2.2.1]heptan-2-ol(1-256 )
  • Synthesis of Synthesis Example 37 using 2,6-Difluorobenzyl bromide instead of 1-(iodomethyl)-2-methoxybenzene and carrying out the same reaction and treatment, the title compound as a colorless liquid (yield 22%) was obtained. ) was obtained.
  • Synthesis example 41 (1S,3R,4S)-3-[(2,6-dichlorobenzyl)oxy]-1-isopropyl-2,4-dimethyl-7-oxabicyclo[2.2.1]heptan-2-ol(1-258 )
  • Synthesis of Synthesis Example 37 using 2,6-Dichlorobenzyl bromide in place of 1-(iodomethyl)-2-methoxybenzene and carrying out the same reaction and treatment, the title compound as a colorless liquid (yield 83%) was obtained. ) was obtained.
  • Synthesis example 45 Synthesis of (1S,3R,4S)-3-(benzyloxy)-2-butyl-1-isopropyl-4-methyl-7-oxabicyclo[2.2.1]heptan-2-ol (1-273) (1S ,3S,4S)-3-(benzyloxy)-1-isopropyl-4-methyl-7-oxabicyclo[2.2.1]heptan-2-one (250 mg, 0.911 mmol) in tetrahydrofuran solution (10 mL). -Butyllithium (1.58 M hexane solution, 0.69 mL, 1.1 mmol) was added, and the mixture was stirred at room temperature for 1 hour.
  • Synthesis example 48 Synthesis of (1S,3R,4S)-1-isopropyl-3-[(2-methoxybenzyl)oxy]-2,4-dimethyl-7-oxabicyclo[2.2.1]heptane (1-80) Synthesis Example 44 By performing the same reaction and treatment using 1-(iodomethyl)-2-methoxybenzene instead of 2-Methylbenzyl bromide, the title compound as a colorless liquid (yield 50%) was obtained.
  • Synthesis example 49 Synthesis of (1S,2R,4S)-2-[(2-fluorobenzyl)oxy]-4-isopropyl-1,3-dimethyl-7-oxabicyclo[2.2.1]heptane (1-82) Synthesis Example 44 By performing the same reaction and treatment using 2-fluorolbenzyl bromide instead of 2-methylbenzyl bromide, the title compound as a colorless liquid (yield 59%) was obtained.
  • Synthesis example 50 Synthesis of (1S,2R,4S)-2-[(2,3-difluorobenzyl)oxy]-4-isopropyl-1,3-dimethyl-7-oxabicyclo[2.2.1]heptane (1-95)
  • 2,3-Difluorolbenzyl bromide was used instead of 2-Methylbenzyl bromide, and the same reaction and treatment were carried out to obtain the title compound as a colorless liquid (yield 56%).
  • Synthesis example 53 Synthesis of (1S,2R,4S)-2-[(2,6-difluorobenzyl)oxy]-4-isopropyl-1,3-dimethyl-7-oxabicyclo[2.2.1]heptane (1-101)
  • 2,6-Difluorolbenzyl bromide was used instead of 2-Methylbenzyl bromide, and the same reaction and treatment were performed to obtain the title compound as a colorless liquid (yield 44%).
  • Synthesis example 54 Synthesis of (1S,2R,4S)-2-[(3,5-difluorobenzyl)oxy]-4-isopropyl-1,3-dimethyl-7-oxabicyclo[2.2.1]heptane (1-107)
  • 3,5-Difluorolbenzyl bromide was used instead of 2-Methylbenzyl bromide, and the same reaction and treatment were performed to obtain the title compound as a colorless liquid (yield 18%).
  • Synthesis example 55 Synthesis of (1S,2R,4S)-2-[(2-chlorobenzyl)oxy]-4-isopropyl-1,3-dimethyl-7-oxabicyclo[2.2.1]heptane (1-88) Synthesis Example 44 By performing the same reaction and treatment using 2-Chlorobenzyl bromide instead of 2-Methylbenzyl bromide, the title compound as a colorless liquid (yield 69%) was obtained.
  • Synthesis example 58 Synthesis of (1S,3R,4S)-1-isopropyl-4-methyl-3-[(2-methylbenzyl)oxy]-2-methylene-7-oxabicyclo[2.2.1]heptane (2-72) ( A dimethylformamide solution (4. Sodium hydride (55% dispersion in mineral oil, 29.7 mg, 0.681 mmol) was added to the solution (5 mL) and stirred at 0° C. for 1 hour. 2-Methylbenzyl bromide (0.061 mL, 0.46 mmol) was added to the reaction mixture, and the mixture was stirred at room temperature for 12 hours.
  • Synthesis example 60 Synthesis of (1S,3R,4S)-1-isopropyl-4-methyl-3-[(4-methylbenzyl)oxy]-2-methylene-7-oxabicyclo[2.2.1]heptane (2-76) The same reaction and treatment as in Example 58 was carried out using 4-Methylbenzyl chloride in place of 2-Methylbenzyl bromide to obtain the title compound as a colorless liquid (yield 91%).
  • Synthesis example 63 Synthesis of (1S,3R,4S)-1-isopropyl-3-[(2-methoxybenzyl)oxy]-4-methyl-2-methylene-7-oxabicyclo[2.2.1]heptane (2-82) The same reaction and treatment as in Example 58 was carried out using 2-Methylbenzyl iodide in place of 2-Methylbenzyl bromide to obtain the title compound as a colorless liquid (yield 89%).
  • Synthesis example 64 Synthesis of (1S,3R,4S)-1-isopropyl-3-[(3-methoxybenzyl)oxy]-4-methyl-2-methylene-7-oxabicyclo[2.2.1]heptane (2-84) The same reaction and treatment as in Example 58 was performed using 3-Methylbenzyl bromide in place of 2-Methylbenzyl bromide to obtain the title compound as a colorless liquid (yield 91%).
  • Synthesis example 65 Synthesis of (1S,3R,4S)-1-isopropyl-3-[(4-methoxybenzyl)oxy]-4-methyl-2-methylene-7-oxabicyclo[2.2.1]heptane (2-86) The same reaction and treatment as in Example 58 was carried out using 4-Methylbenzyl bromide in place of 2-Methylbenzyl bromide to obtain the title compound as a colorless liquid (yield 100%).
  • Synthesis example 70 (1S,2R,4S)-2-[(2,3-difluorobenzyl)oxy]-4-isopropyl-1-methyl-3-methylene-7-oxabicyclo[2.2.1]heptane (2-98) Synthesis The title compound (yield: 69%) as a colorless liquid was obtained by performing the same reaction and treatment as in Synthesis Example 58, using 2,3-difluorolbenzyl bromide instead of 2-Methylbenzyl bromide.
  • Synthesis example 72 (1S,2R,4S)-2-[(2,5-difluorobenzyl)oxy]-4-isopropyl-1-methyl-3-methylene-7-oxabicyclo[2.2.1]heptane (2-102) Synthesis The same reaction and treatment as in Synthesis Example 58 was performed using 2,5-difluorolbenzyl bromide instead of 2-Methylbenzyl bromide to obtain the title compound as a colorless liquid (yield 71%).
  • Synthesis example 75 (1S,2R,4S)-2-[(2,6-dichlorobenzyl)oxy]-4-isopropyl-1-methyl-3-methylene-7-oxabicyclo[2.2.1]heptane (2-110) Synthesis The title compound as a colorless liquid (yield 94%) was obtained by performing the same reaction and treatment as in Synthesis Example 58, using 2,6-dichlorobenzyl bromide instead of 2-Methylbenzyl bromide.
  • Synthesis example 78 (1S,3R,4S)-1-isopropyl-4-methyl-2-methylene-3-[[3-(trifluoromethyl)benzyl]oxy]-7-oxabicyclo[2.2.1]heptane (2-118)
  • Synthesis of Synthesis Example 58 using 3-(trifluoromethyl)benzyl bromide instead of 2-Methylbenzyl bromide, and performing the same reaction and treatment to obtain the title compound as a colorless liquid (yield: 83%).
  • Synthesis example 80 (1S,2R,4S)-2-[[2-fluoro-6-(trifluoromethyl)benzyl]oxy]-4-isopropyl-1-methyl-3-methylene-7-oxabicyclo[2.2.1]heptane ( Synthesis of 2-122)
  • 2-Fluoro-6-(trifluoromethyl)-benzyl bromide instead of 2-Methylbenzyl bromide, the colorless liquid title compound ( A yield of 96% was obtained.
  • Synthesis example 81 (1S,3R,4S)-1-isopropyl-4-methyl-2-methylene-3-[[2-(trifluoromethoxy)benzyl]oxy]-7-oxabicyclo[2.2.1]heptane (2-124)
  • Synthesis of Synthesis Example 58 using 2-(Trifluoromethoxy)benzyl bromide instead of 2-Methylbenzyl bromide, and carrying out the same reaction and treatment to obtain the title compound as a colorless liquid (yield 69%).
  • Synthesis example 84 Synthesis of (1S,3S,4S)-1-isopropyl-4-methyl-3-[(2-methylbenzyl)oxy]-7-oxabicyclo[2.2.1]heptan-2-one (2-3) 1S,2R,3R,4S)-1-isopropyl-4-methyl-3-[(2-methylbenzyl)oxy)-7-oxabicyclo[2.2.1]heptan-2-ol (964mg, 3.32mmol) To a dichloromethane solution (11 mL) were added pyridinium chlorochromate (1.07 g, 4.98 mmol) and Celite (1.61 g), and the mixture was stirred at room temperature for 11 hours.
  • Synthesis example 85 Synthesis of (1S,3S,4S)-3-(benzyloxy)-1-isopropyl-4-methyl-7-oxabicyclo[2.2.1]heptan-2-one (2-1)
  • Synthesis Example 84 ( (1S,2R,3R,4S)-1-isopropyl-4-methyl-3-[(2-methylbenzyl)oxy)-7-oxabicyclo[2.2.1]heptan-2-ol instead of (1S,2R ,3R,4S)-3-(benzyloxy)-1-isopropyl-4-methyl-7-oxabicyclo[2.2.1]heptan-2-ol by performing similar reaction and treatment The liquid title compound (yield 88%) was obtained.
  • the reaction mixture was extracted with ethyl acetate, and the extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure.
  • the concentrate was purified by silica gel column chromatography (extractant: ethyl acetate/n-hexane) to obtain the title compound (107 mg, 67%) as a colorless liquid.
  • Synthesis example 100 Synthesis of (1S,3R,4S)-1-isopropyl-3-[(2-methoxybenzyl)oxy]-4-methyl-7-oxabicyclo[2.2.1]heptan-2-one oxime (2-195)
  • Synthesis Example 98 instead of (1S,3S,4S)-1-isopropyl-4-methyl-3-[(2-methylbenzyl)oxy]-7-oxabicyclo[2.2.1]heptan-2-one A similar reaction and The treatment gave the title compound as a colorless liquid (yield 96%).
  • Synthesis example 101 Synthesis of (1S,3R,4S)-3-[(2-fluorobenzyl)oxy]-1-isopropyl-4-methyl-7-oxabicyclo[2.2.1]heptan-2-one oxime (2-197)
  • Synthesis Example 98 instead of (1S,3S,4S)-1-isopropyl-4-methyl-3-[(2-methylbenzyl)oxy]-7-oxabicyclo[2.2.1]heptan-2-one A similar reaction and The treatment gave the title compound as a colorless liquid (yield 92%).
  • Synthesis example 102 Synthesis of (1S,3R,4S)-3-[(2-chlorobenzyl)oxy]-1-isopropyl-4-methyl-7-oxabicyclo[2.2.1]heptan-2-one oxime (2-199)
  • Synthesis Example 98 instead of (1S,3S,4S)-1-isopropyl-4-methyl-3-[(2-methylbenzyl)oxy]-7-oxabicyclo[2.2.1]heptan-2-one A similar reaction and The treatment gave the title compound as a colorless liquid (yield 98%).
  • Synthesis example 108 Synthesis of (1S,3R,4S)-1-isopropyl-4-methyl-3-[(perfluorophenyl)methoxy]-7-oxabicyclo[2.2.1]heptan-2-one oxime (2-211)
  • Synthesis example 98 (1S,3S,4S)-1-isopropyl-4-methyl-3-[(2-methylbenzyl)oxy]-7-oxabicyclo[2.2.1]heptan-2-one , 3S, 4S) -1-isopropyl-4-methyl-3-[(perfluorophenyl)methoxy]-7-oxabicyclo[2.2.1]heptan-2-one to perform similar reactions and treatments.
  • the title compound (yield 99%) was obtained as a colorless liquid.
  • the reaction mixture was concentrated under reduced pressure, and the concentrate was purified by silica gel column chromatography (extractant: ethyl acetate/n-hexane) to obtain the title compound (128 mg, 74%) as a colorless liquid.
  • Synthesis example 120 Synthesis of (tert-butyl(((1S,2R,4S)-4-isopropyl-1-methyl-3-methylene-7-oxabicyclo[2.2.1]heptan-2-yl)oxy)dimethylsilane Methyltriphenyl
  • phosphonium bromide 536 mg, 1.50 mmol
  • n-butyllithium 0.87 mL, 1.56 mol/L hexane solution, 1.4 mmol
  • Synthesis example 121 Synthesis of (1S,2R,4S)-4-isopropyl-1-methyl-3-methylene-7-oxabicyclo[2.2.1]heptan-2-ol (tert-butyl((1S,2R,4S) -4-isopropyl-1-methyl-3-methylene-7-oxabicyclo[2.2.1]heptan-2-yl)oxy)dimethylsilane (214 mg, 0.722 mmol) in tetrahydrofuran solution (3 mL) was added with tetrabutylammonium fluoride. (0.94 mL, 1 mol/L tetrahydrofuran solution, 0.94 mmol) was added and stirred at room temperature for 13 hours.
  • Synthesis example 122 Synthesis of (1S,2R,4S)-4-isopropyl-1,3-dimethyl-7-oxabicyclo[2.2.1]heptan-2-ol (1S,2R,4S)-4-isopropyl-1-methyl Palladium on carbon (67.8 mg, 55 wt% water content) was added to a methanol solution (6 mL) of -3-methylene-7-oxabicyclo[2.2.1]heptan-2-ol (104 mg, 0.571 mmol), and hydrogen The mixture was stirred at room temperature under atmosphere for 2 hours. The reaction mixture was filtered through Celite and then concentrated under reduced pressure.
  • Synthesis example 123 Synthesis of tert-butyl(((1S,2R,3R,4S)-4-isopropyl-3-methoxy-1-methyl-7-oxabicyclo[2.2.1]heptan-2-yl)oxy)dimethylsilane (1S ,2R,3R,4S)-3-((tert-butyldimethylsilyl)oxy)-1-isopropyl-4-methyl-7-oxabicyclo[2.2.1]heptan-2-ol (139mg, 0.464mmol) Sodium hydride (55% dispersion in tetrahydrofuran solution (5 mL)) mineral oil, 40.4 mg, 0.927 mmol) was added thereto, and the mixture was stirred at 0°C for 1 hour.
  • Synthesis example 124 Synthesis of (1S,2R,3R,4S)-4-isopropyl-3-methoxy-1-methyl-7-oxabicyclo[2.2.1]heptan-2-ol tert-butyl(((1S,2R,3R , 4S)-4-isopropyl-3-methoxy-1-methyl-7-oxabicyclo[2.2.1]heptan-2-yl)oxy)dimethylsilane (410 mg, 1.30 mmol) in tetrahydrofuran solution (4 mL).
  • Butylammonium fluoride (1.70 mL, 1 mol/L tetrahydrofuran solution, 1.70 mmol) was added, and the mixture was stirred at room temperature for 22 hours and 30 minutes. A saturated aqueous ammonium chloride solution was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (extractant: ethyl acetate/n-hexane) to obtain the title compound (231 mg, 88% yield) as a colorless liquid.
  • Synthesis example 125 (1S,2R,3R,4S)-4-isopropyl-1,3-dimethyl-7-oxabicyclo[2.2.1]heptan-2-ol and (1S,2R,3S,4S)-4-isopropyl- Synthesis of 1,3-dimethyl-7-oxabicyclo[2.2.1]heptan-2-ol
  • Synthesis Example 122 by purifying by silica gel column chromatography (extractant: ethyl acetate/n-hexane), Colorless liquid (1S,2R,3R,4S)-4-isopropyl-1,3-dimethyl-7-oxabicyclo[2.2.1]heptan-2-ol (yield 25%) and white solid (1S , 2R, 3S, 4S)-4-isopropyl-1,3-dimethyl-7-oxabicyclo[2.2.1]heptan-2-ol (yield 43%) was obtained.
  • Synthesis example 128 Synthesis of (1S,2R,3S,4S)-2-[(2-fluorobenzyl)oxy]-4-isopropyl-1,3-dimethyl-7-oxabicyclo[2.2.1]heptane (1-83)
  • (1S,2R,3S,4S)-4 instead of (1S,2R,4S)-4-isopropyl-1,3-dimethyl-7-oxabicyclo[2.2.1]heptan-2-ol -Isopropyl-1,3-dimethyl-7-oxabicyclo[2.2.1]heptan-2-ol was used to produce the title compound (80% yield) as a colorless liquid by carrying out the same reaction and treatment. Obtained.
  • Synthesis example 130 Synthesis of (1S,2R,3R,4S)-2-[(2-chlorobenzyl)oxy]-4-isopropyl-1,3-dimethyl-7-oxabicyclo[2.2.1]heptane (1-90)
  • (1S,2R,3R,4S)-4 instead of (1S,2R,4S)-4-isopropyl-1,3-dimethyl-7-oxabicyclo[2.2.1]heptan-2-ol -Isopropyl-1,3-dimethyl-7-oxabicyclo[2.2.1]heptan-2-ol was used to produce the title compound (yield 72%) as a colorless liquid by carrying out the same reaction and treatment. Obtained.
  • Synthesis example 132 (1S,2R,3R,4S)-2-[(2,6-difluorobenzyl)oxy]-4-isopropyl-1,3-dimethyl-7-oxabicyclo[2.2.1]heptane (1-103) Synthesis In Synthesis Example 53, (1S, 2R, 3R, 4S) was used instead of (1S, 2R, 4S)-4-isopropyl-1,3-dimethyl-7-oxabicyclo[2.2.1]heptan-2-ol.
  • Synthesis example 133 Synthesis of (1S,2R,3R,4S)-1-isopropyl-4-methyl-3-(pyridin-3-ylmethoxy)-7-oxabicyclo[2.2.1]heptan-2-ol (1-53)
  • Synthesis example 135 Synthesis of (1S,2R,3R,4S)-1-isopropyl-4-methyl-3-(thiophen-2-ylmethoxy)-7-oxabicyclo[2.2.1]heptan-2-ol (1-57)
  • Synthesis Example 3 (1S,2R,3R,4S)-2-[(2-chlorobenzyl)oxy]-3-(1-ethoxyethoxy)-4-isopropyl-1-methyl-7-oxabicyclo[2.2.
  • Synthesis example 136 Synthesis of (1S,3S,4S)-1-isopropyl-4-methyl-3-(pyridin-3-ylmethoxy)-7-oxabicyclo[2.2.1]heptan-2-one (2-32)
  • Synthesis example 84 instead of (1S,2R,3R,4S)-1-isopropyl-4-methyl-3-[(2-methylbenzyl)oxy]-7-oxabicyclo[2.2.1]heptan-2-ol
  • the title compound (yield: 50%) was obtained as a colorless liquid.
  • Synthesis example 137 Synthesis of (1S,3S,4S)-1-isopropyl-4-methyl-3-(pyridin-4-ylmethoxy)-7-oxabicyclo[2.2.1]heptan-2-one (2-34)
  • Synthesis example 84 instead of (1S,2R,3R,4S)-1-isopropyl-4-methyl-3-[(2-methylbenzyl)oxy]-7-oxabicyclo[2.2.1]heptan-2-ol
  • the title compound (yield: 37%) was obtained as a colorless liquid.
  • Synthesis example 138 Synthesis of (1S,3S,4S)-1-isopropyl-4-methyl-3-(thiophen-2-ylmethoxy)-7-oxabicyclo[2.2.1]heptan-2-one (2-36)
  • Synthesis example 84 instead of (1S,2R,3R,4S)-1-isopropyl-4-methyl-3-[(2-methylbenzyl)oxy]-7-oxabicyclo[2.2.1]heptan-2-ol
  • the title compound (yield: 83%) was obtained as a colorless liquid.
  • Synthesis example 140 (1S,3R,4S,E)-1-isopropyl-4-methyl-3-(pyridin-4-ylmethoxy)-7-oxabicyclo[2.2.1]heptan-2-one oxime (2-221) Synthesis In Synthesis Example 98, instead of (1S,3S,4S)-1-isopropyl-4-methyl-3-[(2-methylbenzyl)oxy]-7-oxabicyclo[2.2.1]heptan-2-one A similar reaction and The treatment gave the title compound as a colorless liquid (yield 100%).
  • the concentrate was purified by silica gel column chromatography (extractant: ethyl acetate/n-hexane) to obtain a colorless liquid tert-Butyl[[(1S,2R,3R,4S)-3-(1-ethoxyethoxy)-4-isopropyl -1-methyl-7-oxabicyclo[2.2.1]heptan-2-yl]oxy]dimethylsilane (2.39 g, 94%) was obtained.
  • Synthesis example 143 Synthesis of (1S,2R,3R,4S)-3-(1-ethoxyethoxy)-4-isopropyl-1-methyl-7-oxabicyclo[2.2.1]heptan-2-ol tert-Butyl[[(1S , 2R, 3R, 4S)-3-(1-ethoxyethoxy)-4-isopropyl-1-methyl-7-oxabicyclo[2.2.1]heptan-2-yl]oxy]dimethylsilane (2.28g, 6.
  • Tetrabutylammonium fluoride (9.2 mL, 1 mol/L tetrahydrofuran solution, 9.2 mmol) was added to a tetrahydrofuran solution (20 mL) of 13 mmol), and the mixture was stirred at room temperature for 15 hours. A saturated aqueous ammonium chloride solution was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was dried over anhydrous magnesium sulfate and concentrated under reduced pressure.
  • the concentrate was purified by silica gel column chromatography (extractant: ethyl acetate/n-hexane) to obtain a colorless liquid (1S, 2R, 3R, 4S)-3-(1-ethoxyethoxy)-4-isopropyl-1-methyl- 7-oxabicyclo[2.2.1]heptan-2-ol (1.49 g, 94%) was obtained.
  • Synthesis example 147 Synthesis of tert-Butyl[[(1S,2S,3R,4S)-3-chloro-4-isopropyl-1-methyl-7-oxabicyclo[2.2.1]heptan-2-yl]oxy]dimethylsilane (1S ,2R,3R,4S)-3-((tert-butyldimethylsilyl)oxy)-1-isopropyl-4-methyl-7-oxabicyclo[2.2.1]heptan-2-ol (235mg, 0.782mmol) Thionyl chloride (0.17 mL, 0.24 mmol) was added to a dichloromethane solution (2.6 mL), and the mixture was stirred under heating under reflux for 15 hours.
  • Synthesis example 148 Synthesis of (1S,2S,3R,4S)-3-Chloro-4-isopropyl-1-methyl-7-oxabicyclo[2.2.1]heptan-2-ol tert-Butyl[[(1S,2S,3R ,4S)-3-chloro-4-isopropyl-1-methyl-7-oxabicyclo[2.2.1]heptan-2-yl]oxy]dimethylsilane (176mg, 0.552mmol) in tetrahydrofuran solution (1.8mL) Tetrabutylammonium fluoride (0.83 mL, 0.83 mmol) was added to the mixture, and the mixture was stirred at room temperature for 2 hours.
  • Synthesis example 150 (1S,2R,3S,4S)-2-chloro-3-[(2-fluorobenzyl)oxy]-1-isopropyl-4-methyl-7-oxabicyclo[2.2.1]heptane (1-12)
  • Synthesis A colorless and transparent title compound (97%) was obtained by performing the same reaction and treatment as in Synthesis Example 149, using 2-Fluoro benzyl bromide instead of 2-Methyl benzyl bromide.
  • Synthesis example 151 Synthesis of (1S,2R,4S)-2-(1-ethoxyethoxy)-4-isopropyl-1-methyl-3-methylene-7-oxabicyclo[2.2.1]heptane (2-270) (1S,2R ,4S)-4-isopropyl-1-methyl-3-methylene-7-oxabicyclo[2.2.1]heptan-2-ol (54.8 mg, 0.301 mmol) in dichloromethane solution (1 mL) was added with pyridinium-p-toluene.
  • Synthesis example 153 Synthesis of (1S,3R,4S)-1-isopropyl-4-methyl-2-methylene-3-phenoxy-7-oxabicyclo[2.2.1]heptane (2-61) (1S,2R,4S)- Potassium phosphate (170 mg) was added to a toluene solution (0.4 mL) of 4-isopropyl-1-methyl-3-methylene-7-oxabicyclo[2.2.1] heptan-2-ol (71.4 mg, 0.392 mmol).
  • Synthesis example 154 Synthesis of (1S,3R,4S)-1-isopropyl-4-methyl-2-methylene-3-(o-tolyloxy)-7-oxabicyclo[2.2.1]heptane (2-62) In Synthesis Example 153 By performing the same reaction and treatment using 2-iodotoluene instead of iodobenzene, the title compound (yield 86%) as a colorless liquid was obtained.
  • Synthesis example 155 Synthesis of (1S,2R,4S)-2-(2-fluorophenoxy)-4-isopropyl-1-methyl-3-methylene-7-oxabicyclo[2.2.1]heptane (2-63)
  • Synthesis Example 153 By performing the same reaction and treatment using 1-fluoro-2-iodobenzene instead of iodobenzene, the title compound (yield 53%) as a colorless liquid was obtained.
  • Synthesis example 156 Synthesis of (1S,3R,4S)-1-isopropyl-2,4-dimethyl-3-phenoxy-7-oxabicyclo[2.2.1]heptane (1-305) (1S,2R,4S)-4- Potassium phosphate (83.2 mg, 0 .392 mmol), copper iodide (3.7 mg, 0.019 mmol), 4-pyrrolidinopyridine (34.8 mg, 0.235 mmol), and iodobenzene (0.022 mL, 0.20 mmol) were added, and the mixture was heated at 140°C. The mixture was stirred for 23 hours. Hexane was poured into the reaction mixture, and after filtration, the filtrate was concentrated under reduced pressure.
  • the concentrate was purified by silica gel column chromatography (extractant: ethyl acetate/n-hexane) to obtain a colorless liquid (1S, 3R, 4S)-1-isopropyl-2,4-dimethyl-3-phenoxy-7-oxabicyclo[ 2.2.1] heptane (31.8 mg, 62%) was obtained.
  • Synthesis example 157 Synthesis of (1S,3R,4S)-1-isopropyl-2,4-dimethyl-3-(o-tolyloxy)-7-oxabicyclo[2.2.1]heptane (1-306)
  • Synthesis Example 156 iodine
  • Synthesis example 158 Synthesis of (1S,2R,4S)-2-(2-fluorophenoxy)-4-isopropyl-1,3-dimethyl-7-oxabicyclo[2.2.1]heptane (1-307)
  • Synthesis Example 156 iodine
  • the title compound Yield 53%) as a colorless liquid was obtained.
  • Synthesis example 160 (1S,3R,4S)-3-ethoxy-1-isopropyl-4-methyl-2-methylene-7-oxabicyclo(2.2.1) Synthesis of heptane (2-46) In Synthesis Example 58, 2-Methylbenzyl The title compound (yield 23%) as a yellow liquid was obtained by performing the same reaction and treatment using Iodoethane instead of bromide.
  • Synthesis example 161 Synthesis of (1S,3R,4S)-1-isopropyl-4-methyl-2-methylene-3-(2,2,2-trifluoroethoxy)-7-oxabicyclo(2.2.1)heptane (2-51)
  • the same reaction and treatment as in Synthesis Example 58 was carried out using 2,2,2-trifluoroethyl trifluoromethanesulfonate instead of 2-Methylbenzyl bromide to obtain the title compound as a yellow liquid (yield 20%).
  • Synthesis example 163 Synthesis of (1S,3R,4S)-1-isopropyl-4-methyl-2-methylene-3-prop-2-ynoxy-7-oxabicyclo (2.2.1) heptane (2-53)
  • Synthesis Example 58 2-Methylbenzyl bromide in place of propargyl bromide, and the same reaction and treatment was performed to obtain the title compound as a colorless liquid (yield 98%).
  • Synthesis example 164 Synthesis of (1S,3R,4S)-3-(cyclopropylmethoxy)-1-isopropyl-4-methyl-2-methylene-7-oxabicyclo(2.2.1)heptane (2-56)
  • Synthesis Example 58 2 -
  • the title compound Yield 44%) as a yellow liquid was obtained.
  • Synthesis example 165 Synthesis of (1S,3R,4S)-1-isopropyl-3-(methoxymethoxy)-4-methyl-2-methylene-7-oxabicyclo (2.2.1) heptane (2-58) In Synthesis Example 58, 2 - By performing the same reaction and treatment using chloro(methoxy)methane in place of methylbenzyl bromide, the title compound as a yellow liquid (yield 27%) was obtained.
  • Synthesis example 167 Synthesis of 2-(((1S,2R,4S)-4-isopropyl-1-methyl-3-methylene-7-oxabicyclo(2.2.1)heptan-2-yl)oxymethyl)benzonitrile (2-114)
  • the same reaction and treatment as in Synthesis Example 58 was carried out using 2-(bromomethyl)benzonitrile instead of 2-Methylbenzyl bromide to obtain the title compound as a pale yellow liquid (yield 47%).
  • Synthesis example 168 Synthesis of (1S,3R,4S)-1-isopropyl-4-methyl-2-methylene-3-(3-phenylpropoxy)-7-oxabicyclo(2.2.1)heptane (2-135)
  • Synthesis Example 58 3-bromopropylbenzene was used in place of 2-Methylbenzyl bromide, and the same reaction and treatment were performed to obtain the title compound as a pale yellow liquid (yield: 44%).
  • Synthesis example 170 3-(((1S,2R,4S)-4-isopropyl-1-methyl-3-methylene-7-oxabicyclo(2.2.1)heptan-2-yl)oxymethyl)-2-methyl-pyridine(2 -146) Synthesis In Synthesis Example 58, the title compound (yield 25%).
  • Synthesis example 171 Synthesis of (1S,3R,4S)-1-isopropyl-4-methyl-2-methylene-3-(2-phenoxyethoxy)-7-oxabicyclo(2.2.1)heptane (2-157)
  • Synthesis Example 58 2-Methylbenzyl bromide was replaced with 2-bromoethoxybenzene and the same reaction and treatment was performed to obtain the title compound as a yellow liquid (yield 9%).
  • Synthesis example 172 Synthesis of (1S,3R,4S)-3-(2-benzyloxyethoxy)-1-isopropyl-4-methyl-2-methylene-7-oxabicyclo(2.2.1)heptane (2-162)
  • Synthesis Example 58 2-Methylbenzyl bromide was replaced with 2-bromoethoxymethylbenzene and the same reaction and treatment was performed to obtain the title compound as a yellow liquid (yield 18%).
  • Synthesis example 173 (1S,3R,4S)-3-butoxy-1-isopropyl-4-methyl-2-methylene-7-oxabicyclo(2.2.1) Synthesis of heptane (2-267) In Synthesis Example 58, 2-Methylbenzyl By performing the same reaction and treatment using 1-iodobutane instead of bromide, the title compound (yield 86%) as a colorless liquid was obtained.
  • Synthesis example 174 Synthesis of (1S,3R,4S)-1-isopropyl-4-methyl-3-(3-methylbut-2-enoxy)-2-methylene-7-oxabicyclo(2.2.1)heptane (2-268) By performing the same reaction and treatment as in Synthesis Example 58 using 1-bromo-3-methyl-2-butene instead of 2-Methylbenzyl bromide, the title compound as a colorless liquid (yield 85%) was obtained. .
  • Tables 3 and 4 show the 1 HNMR spectrum (CDCl 3 ) ⁇ (ppm) value, melting point (° C.), etc. of the compound according to the present invention produced based on the above synthesis example and the above production method.
  • 1 HNMR data was measured using a JNM-ECS400 spectrometer (manufactured by JEOL Ltd.) or the like.
  • the reference examples show synthesis examples in which the starting materials for the above synthesis are synthesized from commercially available products, but the present invention is not limited thereto.
  • Formulation example 1 (granules) Add 15 parts of water to 1 part of the compound of Synthesis Example 1, 1 part of calcium lignin sulfonate, 1 part of lauryl sulfate, 30 parts of bentonite and 67 parts of talc, knead with a kneader, and then granulate with an extrusion granulator. did. This can be dried in a fluidized bed dryer to obtain granules containing 1% herbicidal active ingredient. Furthermore, granules can be obtained by the same method except that each compound listed in Tables 1 and 2 is used in place of the compound of Synthesis Example 1.
  • Formulation example 2 (flowable agent) 20.0 parts of the compound of Synthesis Example 1, 2.0 parts of sulfosuccinic acid di-2-ethylhexyl ester sodium salt, 2.0 parts of polyoxyethylene nonylphenyl ether, 5.0 parts of propylene glycol, 0.5 parts of antifoaming agent.
  • a flowable agent containing 20% of herbicidal active ingredient can be obtained by uniformly mixing and pulverizing the mixture and 70.5 parts of water using a wet ball mill.
  • each flowable agent can be obtained by the same method except that each compound listed in Tables 1 and 2 is used in place of the compound of Synthesis Example 1.
  • Formulation example 3 75 parts of the compound of Synthesis Example 1, 10 parts of naphthalene sulfonic acid formaldehyde condensate, 5 parts of sodium lauryl sulfate, 5 parts of white carbon, and 5 parts of clay were uniformly mixed and pulverized to produce a dry flowable containing 75% of herbicidal active ingredients. (granule hydration) agent can be obtained. Further, dry flowable (granule hydrated) agents can be obtained by the same method except that each compound listed in Tables 1 and 2 is used in place of the compound of Synthesis Example 1.
  • Formulation example 4 (hydrating powder) 15 parts of the compound of Synthesis Example 1, 15 parts of white carbon, 3 parts of calcium lignin sulfonate, 2 parts of polyoxyethylene alkyl ether, 5 parts of diatomaceous earth, and 60 parts of clay were uniformly mixed using a grinding mixer to obtain the herbicidal active ingredient. It is possible to obtain a hydrating agent containing 15% of Furthermore, hydrating agents can be obtained by the same method except that each compound listed in Tables 1 and 2 is used in place of the compound of Synthesis Example 1.
  • Formulation example 5 (emulsion) By mixing 20 parts of the compound of Synthesis Example 1, 18 parts of polyoxyethylene styryl phenyl ether, 2 parts of calcium dodecylbenzenesulfonate and 60 parts of xylene, an emulsion containing 20% of herbicidal active ingredient can be obtained. Further, emulsions can be obtained in the same manner except that the compounds listed in Tables 1 and 2 are used in place of the compound in Synthesis Example 1.
  • Formulation example 6 (powder) 0.5 parts of the compound of Synthesis Example 1, 0.5 parts of white carbon, 0.5 parts of calcium stearate, 50.0 parts of clay, and 48.5 parts of talc were uniformly mixed and ground to obtain 0.5 parts of herbicidal active ingredient. It is possible to obtain a powder containing %. Further, powders can be obtained in the same manner, except that the compounds listed in Tables 1 and 2 are used in place of the compound in Synthesis Example 1.
  • Formulation example 7 (jumbo drug) After mixing 15 parts of the compound of Synthesis Example 1, 2 parts of sodium lauryl sulfate, 5 parts of sulfosuccinic acid di-2-ethylhexyl ester sodium salt, 5 parts of carboxymethyl cellulose sodium salt, 35 parts of Shirasu balloon, 10 parts of lactose and 28 parts of expanded perlite. After adding 35 parts of water and kneading with a kneader, the mixture was granulated with an extrusion type granulator. This can be dried in a fluidized bed dryer to obtain a jumbo agent containing 15% of herbicidal active ingredient. Further, jumbo preparations can be obtained by the same method except that each compound listed in Tables 1 and 2 is used in place of the compound of Synthesis Example 1.
  • the above compound numbers 1-24, 1-25, 1-30, 1-35, 1-37, 1-41, 1-45, 1-61, 1-74, 1-75, 1-83 , 1-97, 1-101, 1-102, 1-103, 1-247, 2-11, 2-20, 2-26, 2-76, 2-78, 2-82, 2-88, 2 -90, 2-94, 2-96, 2-112, 2-191, 2-197, 2-199, 2-201, 2-203, 2-207, 2-213, 2-227, 2-240
  • the compound showed a weed suppression rate of 80% or more against Azena.
  • Compounds -96, 2-112, 2-191, 2-197, 2-203, 2-205, 2-207, 2-213, 2-227, and 2-240 have a weed control rate of 80% or more against Azena. showed that.
  • Test example 3 Herbicidal effect test by field crop soil treatment Fill a 36cm2 pot with field soil (alluvial loam), uniformly mix 1cm of the soil with 20 seeds of each weed of crabgrass, goldenweed, whiteweed, and blueberry. was pressed lightly. One day after sowing, an emulsion prepared according to Formulation Example 5 using the compound shown below was diluted with water, and the water-diluted chemical solution was sprayed onto the soil surface at a rate of 100 liters per 10 are. The applied amount of the active ingredient was equivalent to 120 g per 10 are. Fourteen days after the chemical treatment, the herbicidal effect was evaluated using the same criteria as Test Example 1.
  • the above compound numbers 1-25, 1-62, 1-82, 1-291, 2-3, 2-11, 2-72, 2-90, 2-191, 2-199, 2-227 , 2-247, and 2-267 showed a weed suppression rate of 80% or more against Shiroza.
  • the above compound numbers 1-25, 1-62, 1-82, 1-146, 1-148, 1-291, 2-3, 2-11, 2-72, 2-90, 2-94 , 2-191, 2-199, 2-227, 2-247, and 2-267 showed a weed suppression rate of 80% or more against blueberry.
  • Test example 4 Weeding effect test by field crop foliage treatment Fill a 36 cm 2 pot with field soil (alluvial loam), uniformly mix 1 cm of the soil with 20 seeds of each weed species of crabgrass, golden weed, white locust, and blueberry, and was pressed lightly. Seven days after sowing, an emulsion prepared according to Formulation Example 5 using the compound shown below was diluted with water, and the water-diluted chemical solution was sprayed onto the soil surface at a rate of 100 liters per 10 are. The applied amount of the active ingredient was equivalent to 120 g per 10 are. Fourteen days after the chemical treatment, the herbicidal effect was evaluated using the same criteria as Test Example 1.
  • the compounds No. 1-101, 1-247, 2-11, 2-195, and 2-199 exhibited a weed suppression rate of 80% or more against Shiroza.
  • the compounds Nos. 2-3 and 2-11 exhibited a weed suppression rate of 80% or more against blueberry.
  • the compounds of the present invention have excellent herbicidal activity, have a low growth inhibition rate against rice, and are excellent in safety for paddy rice.
  • the present invention it is possible to provide a novel 1,4-cineole derivative having excellent herbicidal activity, a synthetic intermediate thereof, and a herbicide containing the above-mentioned 1,4-cineole derivative. Further, according to the present invention, a method for using a herbicide and a method for preparing an agrochemical composition can be provided.

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Abstract

La présente invention concerne un dérivé de 1,4-cinéol représenté par la formule générale (1), (1'), (2) ou (2') qui présente une excellente activité herbicide, un intermédiaire de celui-ci, un herbicide caractérisé en ce qu'il contient le dérivé en tant que principe actif, etc. Dans les formules générales (1), (1'), (2) et (2'), R1 à R3 et X représentent chacun un substituant spécifique.　
PCT/JP2023/024517 2022-06-30 2023-06-30 Dérivé de 1,4-cinéol et intermédiaire de celui-ci, herbicide le contenant en tant que principe actif, procédé d'utilisation d'un herbicide et procédé de préparation d'une composition agrochimique Ceased WO2024005209A1 (fr)

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US4525203A (en) * 1984-06-15 1985-06-25 Shell Oil Company ((3,4,5,6-Tetrahydro-2H-pyran-2-yl)methoxy)oxabicycloalkane herbicides
JPS62249980A (ja) * 1986-04-14 1987-10-30 シエル・インタ−ナシヨネイル・リサ−チ・マ−チヤツピイ・ベ−・ウイ ハロゲン化複素環式エ−テル除草剤
JPH03504380A (ja) * 1988-05-23 1991-09-26 イー・アイ・デユポン・デ・ニモアス・アンド・カンパニー 除草性オキサビシクロアルカンエーテル

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